Compounds, polymers, compositions, rust inhibitors, adhesives, and coatings

Abstract

This compound is represented by formula (1). (In formula (1), R1 represents a hydrogen atom, a methyl group, an ethyl group, a methacryloyloxymethyl group, or an acryloyloxymethyl group. R2 represents a hydrogen atom or a methyl group. R3 represents a hydrogen atom or a hydroxyl group. n represents 0 or 1, and m represents an integer of 0-4, but excluding the case where m and n both represent 0.)

Description

[Technical Field]

[0001] The present invention relates to compounds, polymers, compositions, rust inhibitors, adhesives, and coatings. [Background technology]

[0002] BACKGROUND ART Rust inhibitors containing polymers of polymerization components containing compounds having catechol or gallol groups have been known as adhesives and coating agents used on metals.

[0003] As such a rust inhibitor, for example, a rust inhibitor containing a (meth)acrylic resin containing 10-(methacryloyloxy)decyl 3,4,5-trihydroxybenzoate (a compound having a gallol group) as a polymerization unit has been proposed (see, for example, Example 1 of Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2021-155537 Summary of the Invention [Problem to be solved by the invention]

[0005] On the other hand, the rust inhibitor is required to have excellent rust prevention properties.

[0006] Furthermore, when the rust inhibitor is applied to a metal, it is required to have excellent adhesion to the metal.

[0007] The present invention provides a novel compound that exhibits adhesion and rust prevention properties, a polymer obtained by polymerizing a polymerization component containing the compound, a polymer of a polymerization component containing the compound, and / or a composition containing the compound, a rust inhibitor containing the composition, an adhesive containing the composition, and a coating agent containing the composition. [Means for solving the problem]

[0008] The present invention [1] is a compound represented by the following formula (1). [ka] (In the above formula (1), R 1 represents a hydrogen atom, a methyl group, an ethyl group, a methacryloyloxymethyl group, or an acryloyloxymethyl group. 2 represents a hydrogen atom or a methyl group. 3 represents a hydrogen atom or a hydroxyl group. n represents 0 or 1. m represents an integer of 0 or more and 4 or less, except when both m and n are 0.

[0009] The present invention [2] is 1 represents a hydrogen atom, a methyl group, or an ethyl group.

[0010] The present invention [3] includes the compound according to the above [1], wherein n is 0 and m is 1, or n is 0 and m is 4, or n is 1 and m is 1.

[0011] The present invention [4] is 1 indicates a hydrogen atom, and R 2 indicates a methyl group, and R 3 represents a hydrogen atom, n represents 0, and m represents 1.

[0012] The present invention [5] is 1 indicates a hydrogen atom, and R 2 indicates a methyl group, and R 3 represents a hydroxyl group, n represents 0, and m represents 1.

[0013] The present invention [6] is 1 indicates a hydrogen atom, and R 2 represents a methyl group, R3 represents a hydrogen atom, n represents 0, and m represents 4, the compound according to [1] above is included.

[0014] The present invention [7] is 1 indicates a methyl group, and R 2 indicates a hydrogen atom, and R 3 represents a hydroxyl group, n represents 1, and m represents 1, the compound according to [1] above is included.

[0015] The present invention [8] is 1 indicates an ethyl group, and R 2 indicates a hydrogen atom, and R 3 represents a hydrogen atom, n represents 1, and m represents 1.

[0016] The present invention [9] includes a polymer obtained by polymerizing a polymerization component containing the compound according to any one of the above [1] to [8].

[0017] The present invention

[10] includes a polymer of a polymerization component containing the compound according to any one of the above [1] to [8], and / or a composition containing the polymerization component.

[0018] The present invention

[11] is a rust inhibitor comprising the composition according to the above

[10] .

[0019] The present invention

[12] is an adhesive comprising the composition

[10] above.

[0020] The present invention

[13] relates to a coating agent comprising the composition of the above

[10] .

[0021] The present invention

[14] is a compound represented by the following formula (2). [ka] (In the above formula (2), R 1 , R 2 , m, and n are R in the above formula (1). 1 , R 2 , m, and n. 4 and R 5 represents a protecting group for a hydroxyl group, or R 4and R 5 R may be combined with each other to form a 5-membered ring, and the ring may be substituted with alkyl having 1 to 6 carbon atoms or alkoxy having 1 to 6 carbon atoms. 8 represents a protecting group for a hydrogen atom or a hydroxyl group.

[0022] The present invention

[15] is 1 represents a hydrogen atom, a methyl group, or an ethyl group.

[0023] The present invention

[16] includes the compound according to the above

[14] , wherein n is 0 and m is 1, or n is 0 and m is 4, or n is 1 and m is 1.

[0024] The present invention

[17] includes the compound described in the above

[14] , which is represented by the following formula (2-1). [ka]

[0025] The present invention

[18] includes the compound described in the above

[14] , which is represented by the following formula (2-2). [ka]

[0026] The present invention

[19] includes the compound described in the above

[14] , which is represented by the following formula (2-3). [ka]

[0027] The present invention

[20] includes the compound described in the above

[14] , which is represented by the following formula (2-4). [ka]

[0028] The present invention

[21] includes the compound described in the above

[14] , which is represented by the following formula (2-5). [ka] [Effects of the Invention]

[0029] The compound of the present invention is represented by the following formula (1): Therefore, due to the chemical structure represented by the following formula (1), the compound exhibits adhesion and rust prevention properties. [ka] (In the above formula (1), R 1 represents a hydrogen atom, a methyl group, an ethyl group, a methacryloyloxymethyl group, or an acryloyloxymethyl group. 2 represents a hydrogen atom or a methyl group. 3 represents a hydrogen atom or a hydroxyl group. n represents 0 or 1. m represents an integer of 0 or more and 4 or less, except when both m and n are 0.

[0030] The compound of the present invention is represented by the following formula (2): [ka] (In the above formula (2), R 1 , R 2 , m, and n are R in the above formula (1). 1 , R 2 , m, and n. 4 and R 5 represents a protecting group for a hydroxyl group, or R 4 and R 5 R may be combined with each other to form a 5-membered ring, and the ring may be substituted with alkyl having 1 to 6 carbon atoms or alkoxy having 1 to 6 carbon atoms. 8 represents a protecting group for a hydrogen atom or a hydroxyl group.

[0031] The compound represented by the formula (2) can be suitably produced according to the formula (1).

[0032] The polymer of the present invention is obtained by polymerizing a polymerization component containing the compound of the present invention, and therefore has excellent adhesion (to metals) and rust prevention properties.

[0033] The composition of the present invention contains a polymer of a polymerization component containing the compound of the present invention and / or the compound, and therefore has excellent adhesion (to metals) and rust prevention properties.

[0034] The rust inhibitor of the present invention includes the composition of the present invention, and therefore has excellent adhesion (to metals) and rust prevention properties.

[0035] The adhesive of the present invention contains the composition of the present invention, and therefore has excellent adhesion (to metals) and rust prevention properties.

[0036] The coating agent of the present invention contains the composition of the present invention, and therefore has excellent adhesion (to metals) and rust prevention properties. DETAILED DESCRIPTION OF THE INVENTION

[0037] <Compound> The compound of the present invention is represented by the following formula (1): In the following explanation, the compound represented by the following formula (1) may be referred to as compound (1). [ka]

[0038] In the above formula (1), R 1 represents a hydrogen atom, a methyl group, an ethyl group, a methacryloyloxymethyl group, or an acryloyloxymethyl group.

[0039] In addition, in the above formula (1), R 2 represents a hydrogen atom or a methyl group.

[0040] In addition, in the above formula (1), R3 represents a hydrogen atom or a hydroxyl group.

[0041] In the above formula (1), n ​​represents 0 or 1. Specifically, when n is 0, compound (1) is represented by the following formula (3-1). When n is 1, compound (1) is represented by the following formula (3-2). [ka]

[0042] Furthermore, m represents an integer of 0 or more and 4 or less. Specifically, when m is 0, compound (1) is represented by the following formula (3-3). When m is 1, compound (1) is represented by the following formula (3-4). When m is 2, compound (1) is represented by the following formula (3-5). When m is 3, compound (1) is represented by the following formula (3-6). When m is 4, compound (1) is represented by the following formula (3-7). [ka]

[0043] Also, the case where both m and n are 0 is excluded. In other words, compound (1) does not include a compound represented by the following formula (4). [ka]

[0044] Examples of compound (1) include a first compound in which n is 1 and m is 0, a second compound in which n is 0 and m is 1, a third compound in which n is 0 and m is 2, a fourth compound in which n is 0 and m is 4, and a fifth compound in which n is 1 and m is 1.

[0045] The first compound is a compound represented by the following formula (5-1) (R 1 : Hydrogen atom, R 2 : Methyl group, two R 3 : hydrogen atom, n=1, m=0), a compound represented by the following formula (5-2) (R1 : Hydrogen atom, R 2 : Hydrogen atom, two R 3 : hydrogen atom, n=1, m=0), a compound represented by the following formula (5-3) (R 1 : Hydrogen atom, R 2 : Methyl group, two R 3 hydroxyl group, n=1, m=0), and a compound represented by the following formula (5-4) (R 1 : Hydrogen atom, R 2 : Hydrogen atom, two R 3 : hydroxyl group, n=1, m=0). [ka]

[0046] The second compound is a compound represented by the following formula (6-1) (R 1 : Hydrogen atom, R 2 : Methyl group, two R 3 : hydrogen atom, n=0, m=1), a compound represented by the following formula (6-2) (R 1 : Hydrogen atom, R 2 : Hydrogen atom, two R 3 : hydrogen atom, n=0, m=1), a compound represented by the following formula (6-3) (R 1 : Hydrogen atom, R 2 : Methyl group, two R 3 hydroxyl group, n=0, m=1), and a compound represented by the following formula (6-4) (R 1 : Hydrogen atom, R 2 : Hydrogen atom, two R 3 hydroxyl group, n=0, m=1). Preferred examples of the second compound include the compound represented by the above formula (6-1) (3-(methacryloyloxy)propane-1,2-dyl bis(3,4-dihydroxybenzoate)) and the compound represented by the above formula (6-3) (3-(methacryloyloxy)propane-1,2-dyl bis(3,4,5-trihydroxybenzoate)). More preferred examples of the second compound include the compound represented by the above formula (6-1). [ka]

[0047] The third compound is a compound represented by the following formula (7-1) (R 1 : Hydrogen atom, R 2 : Methyl group, two R 3 : hydrogen atom, n=0, m=2), a compound represented by the following formula (7-2) (R 1 : Hydrogen atom, R 2 : Hydrogen atom, two R 3 : hydrogen atom, n=0, m=2), a compound represented by the following formula (7-3) (R 1 : Hydrogen atom, R 2 : Methyl group, two R 3 hydroxyl group, n=0, m=2), and a compound represented by the following formula (7-4) (R 1 : Hydrogen atom, R 2 : Hydrogen atom, two R 3 : hydroxyl group, n=0, m=2). [ka]

[0048] The fourth compound is a compound represented by the following formula (8-1) (R 1 : Hydrogen atom, R 2 : Methyl group, two R 3 : hydrogen atom, n=0, m=4), a compound represented by the following formula (8-2) (R 1 : Hydrogen atom, R 2 : Hydrogen atom, two R 3 : hydrogen atom, n=0, m=4), a compound represented by the following formula (8-3) (R 1 : Hydrogen atom, R 2 : Methyl group, two R 3 hydroxyl group, n=0, m=4), and a compound represented by the following formula (8-4) (R 1 : Hydrogen atom, R 2 : Hydrogen atom, two R 3 hydroxyl group, n=0, m=4). A preferred example of the fourth compound is a compound represented by the following formula (8-1) (6-(methacryloyloxy)hexane-1,2-diyl bis(3,4-dihydroxybenzoate)). [ka]

[0049] The fifth compound is a compound represented by the following formula (9-1) (R 1 : methacryloyloxymethyl group, R 2 : Methyl group, two R 3 : hydrogen atom, n=1, m=1), a compound represented by the following formula (9-2) (R 1 : methacryloyloxymethyl group, R 2 : Hydrogen atom, two R 3 : hydrogen atom, n=1, m=1), a compound represented by the following formula (9-3) (R 1 : methacryloyloxymethyl group, R 2 : Methyl group, two R 3 hydroxyl group, n=1, m=1), a compound represented by the following formula (9-4) (R 1 : methacryloyloxymethyl group, R 2 : Hydrogen atom, two R 3 hydroxyl group, n=1, m=1), a compound represented by the following formula (9-5) (R 1 : Hydrogen atom, R 2 : Methyl group, two R 3 : hydrogen atom, n=1, m=1), a compound represented by the following formula (9-6) (R 1 : Hydrogen atom, R 2 : Hydrogen atom, two R 3 : hydrogen atom, n=1, m=1), a compound represented by the following formula (9-7) (R 1 : Hydrogen atom, R 2 : Methyl group, two R 3 hydroxyl group, n=1, m=1), a compound represented by the following formula (9-8) (R 1 : Hydrogen atom, R 2 : Hydrogen atom, two R 3 hydroxyl group, n=1, m=1), a compound represented by the following formula (9-9) (R 1 : Methyl group, R 2 : Methyl group, two R 3 : hydrogen atom, n=1, m=1), a compound represented by the following formula (9-10) (R 1 : Methyl group, R 2 : Hydrogen atom, two R3 : hydrogen atom, n=1, m=1), a compound represented by the following formula (9-11) (R 1 : Methyl group, R 2 : Methyl group, two R 3 hydroxyl group, n=1, m=1), a compound represented by the following formula (9-12) (R 1 : Methyl group, R 2 : Hydrogen atom, two R 3 hydroxyl group, n=1, m=1), a compound represented by the following formula (9-13) (R 1 : ethyl group, R 2 : Methyl group, two R 3 : hydrogen atom, n=1, m=1), a compound represented by the following formula (9-14) (R 1 : ethyl group, R 2 : Hydrogen atom, two R 3 : hydrogen atom, n=1, m=1), a compound represented by the following formula (9-15) (R 1 : ethyl group, R 2 : Methyl group, two R 3 hydroxyl group, n=1, m=1), and a compound represented by the following formula (9-16) (R 1 : ethyl group, R 2 : Hydrogen atom, two R 3 hydroxyl group, n=1, m=1). Preferred examples of the fifth compound include a compound represented by the following formula (9-12) (2-((acryloyloxy)methyl)-2-methylpropane-1,3-dyl bis(3,4,5-trihydroxybenzoate)) and a compound represented by the following formula (9-14) (2-((acryloyloxy)methyl)-2-ethylpropane-1,3-dyl bis(3,4-dihydroxybenzoate). [ka] [ka]

[0050] The compound (1) is preferably the second compound.

[0051] <Method for synthesizing compounds> Compound (1) is synthesized by reacting a compound represented by the following formula (10) (hereinafter referred to as compound (10)) with a compound represented by the following formula (11) (hereinafter referred to as compound (11)) to synthesize a compound represented by the following formula (12) (hereinafter referred to as compound (12)), and then reacting compound (12) with an acid. [ka] R in the above formulas (10) to (12) 1 , R 2 , R 4 , R 5 , R 8 , m and n will be described later.

[0052] That is, the method for synthesizing compound (1) includes a first step of synthesizing compound (10), a second step of synthesizing compound (11), a third step of reacting compound (10) with compound (11) to synthesize compound (12), and a fourth step of reacting compound (12) with an acid to synthesize compound (1).

[0053] [1st step] In the first step, compound (10) is synthesized.

[0054] To synthesize compound (10), for example, first, a compound represented by the following formula (13) (hereinafter referred to as compound (13)) is reacted with a compound represented by the following formula (14) (hereinafter referred to as compound (14)) in the presence of a base to synthesize a compound represented by the following formula (15) (hereinafter referred to as compound (15)). [ka]

[0055] In the above formula (13), R 6 and R 7 are the same or different and represent a hydrogen atom, a methyl group, or a phenyl group. 9represents a hydrogen atom, a methyl group, an ethyl group, or a hydroxymethyl group. In the above formula (13), m and n have the same meanings as m and n in the above formula (1).

[0056] Compound (13) can be obtained, for example, by cyclic acetalization of two hydroxyl groups in a trihydric alcohol (for example, 1,2,6-hexanetriol).

[0057] In the above formula (14), R 2 is R in the above formula (1). 2 In the above formula (14), X represents a halogen atom, a hydroxyl group, a methacryloyloxy group, or an acryloyloxy group.

[0058] In the above formula (15), R 1 , R 2 , m and n are R in the above formula (1). 1 , R 2 , m and n are synonymous. In the above formula (15), R 6 and R 7 is R in the above formula (13). 6 and R 7 is synonymous with.

[0059] The base is not particularly limited, and examples thereof include alkali metal carbonates, alkali metal bicarbonates, organic bases, metal hydrides, and metal alkoxides. Examples of alkali metal carbonates include sodium carbonate and potassium carbonate. Examples of alkali metal bicarbonates include sodium bicarbonate and potassium bicarbonate. Examples of organic bases include triethylamine, N,N-dimethylaniline, pyridine, and 4-dimethylaminopyridine. Examples of metal hydrides include sodium hydride and potassium hydride. Examples of metal alkoxides include sodium methoxide, sodium ethoxide, and potassium tert-butoxide. A preferred base is triethylamine.

[0060] A commercially available product can also be used as compound (13). Specifically, an example of a compound in which n is 0 and m is 1 in the above formula (13) (hereinafter referred to as compound (13) (n = 0, m = 1)). In the following explanation, a compound in which n is a and m is b in the above formula (13) (n = a, m = b)) is 2,2-dimethyl-1,3-dioxolane-4-methanol.

[0061] Compound (13) can be synthesized by known methods. Specifically, compound (13) (n = 0, m = 2) can be produced according to the method described in Journal of Organic Chemistry, 1996, vol. 61, pp. 831-837. Compound (13) (n = 0, m = 3) can be synthesized according to the method described in Journal of Organic Chemistry, 1987, vol. 52, pp. 819-827. Compound (13) (n = 0, m = 4) can be synthesized according to the method described in Tetrahedron Letters, 1996, vol. 37, pp. 9369-9372. Compound (13) (n = 1, m = 0) can be synthesized according to the method described in Synthesis, 1998, pp. 879-882. Compound (13) (n = 1, m = 1) can be synthesized according to the method described in Journal of the Chemical Society, Perkin Transactions II, 1995, pp. 1761-1770, and Tetrahedron, 2002, vol. 58, pp. 4053-4059. Compound (13) (n = 1, m = 2) can be synthesized according to the method described in European Journal of Medicinal Chemistry, 2011, vol. 46, pp. 1153-1164. Compound (13) (n = 1, m = 3) can be synthesized according to the method described in U.S. Patent Application Publication No. 567743. Compound (13) (n = 1, m = 4) can be synthesized according to the method described in U.S. Patent Application Publication No. 567743.

[0062] As the compound (13), preferably, in the above formula (13), R 6 indicates a methyl group, and R 7 indicates a methyl group, and R 9 represents a hydrogen atom, n represents 0, and m represents 1.

[0063] As the compound (14), preferably, in the above formula (14), R 3 represents a hydrogen atom and X represents a chlorine atom.

[0064] The compound (14) is added in an amount of, for example, 1 mole or more and, for example, 5 moles or less per mole of compound (13).

[0065] In the above reaction, an organic solvent can be added.

[0066] The organic solvent is not particularly limited, and examples thereof include ethers, aromatic hydrocarbons, aliphatic hydrocarbons, and halogenated hydrocarbons. Ethers include, for example, diethyl ether, dimethoxyethane, tetrahydrofuran, and 1,4-dioxane. Aromatic hydrocarbons include, for example, benzene, toluene, and xylene. Aliphatic hydrocarbons include, for example, cyclohexane and heptane. Halogenated hydrocarbons include, for example, dichloromethane, 1,2-dichloroethane, and chloroform.

[0067] The organic solvents can be used alone or in combination of two or more kinds.

[0068] In the above reaction, the reaction temperature is −20° C. or higher, preferably −10° C. or higher, and, for example, 50° C. or lower. The reaction time is, for example, 0.5 hours or longer, and, for example, 48 hours or shorter, preferably 24 hours or shorter.

[0069] As a result, the compound (13) reacts with the compound (14) to synthesize the compound (15).

[0070] Next, the compound (15) is reacted with an acid to synthesize the compound (10). [ka]

[0071] In the above formula (10), R 1 , R 2 , m and n are R in the above formula (1). 1 , R 2 , m and n.

[0072] Examples of acids include organic acids, inorganic acids, and solid acids. Examples of organic acids include sulfonic acids and carboxylic acids. Examples of sulfonic acids include methanesulfonic acid, paratoluenesulfonic acid, and camphorsulfonic acid. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, benzoic acid, and trifluoroacetic acid. Examples of inorganic acids include hydrochloric acid, sulfuric acid, perchloric acid, and phosphoric acid. Examples of solid acids include strongly acidic ion exchange resins, H type. Examples of strongly acidic ion exchange resins, H type, include Dowex 50wx2 and Amberlyst 15.

[0073] The proportion of the acid to be added relative to compound (15) is, for example, 0.001 equivalents or more, preferably 0.1 equivalents or more, and for example, 100 equivalents or less, preferably 50 equivalents or less.

[0074] This causes the compound (15) to react with the acid to synthesize the compound (10).

[0075] As the compound (10), preferably, glycerol monomethacrylate (in the above formula (10), R 1 indicates a hydrogen atom, and R 2 represents a methyl group, m represents 1, and n represents 0), 5,6-dihydroxyhexyl methacrylate (a compound in which R 1 indicates a hydrogen atom, and R2 represents a methyl group, m represents 4, and n represents 0), and 2,2-bis(hydroxymethyl)butyl acrylate (a compound represented by the above formula (10), 1 indicates an ethyl group, and R 2 represents a hydrogen atom, m represents 1, and n represents 1), and 3-hydroxy-2-(hydroxymethyl)-2-methylpropyl acrylate (a compound represented by the above formula (10), 1 indicates a methyl group, and R 2 represents a hydrogen atom, m represents 1, and n represents 1).

[0076] [Second process] In the second step, compound (11) is synthesized.

[0077] To synthesize compound (11), for example, a hydroxyl group in a compound represented by the following formula (16) (hereinafter referred to as compound (16)) is acetalized or etherified to produce a compound represented by the following formula (17) (hereinafter referred to as compound (17)). [ka]

[0078] In the above formula (16), R 3 is R in the above formula (1). 3 It is synonymous with R. 10 represents a hydrogen atom or an alkyl group (for example, a methyl group or an ethyl group).

[0079] In the above formula (17), R 4 and R 5 represents a protecting group for a hydroxyl group. Examples of the protecting group for a hydroxyl group include an acetal protecting group and an ether protecting group.

[0080] Examples of acetal-based protecting groups include alkoxymethyl groups and tetrahydro-2H-pyran-2-yl groups. Examples of alkoxymethyl groups include methoxymethyl groups, ethoxymethyl groups, methoxyethoxymethyl groups, and 1-ethoxyethyl groups.

[0081] Examples of ether-based protecting groups include a methyl group, an ethyl group, a propyl group, a t-butyl group, a benzyl group, a para-methoxybenzyl group, and a trityl group.

[0082] Also, R 4 and R 5 are taken together to form a 5-membered ring, and the ring may be substituted with an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group), an alkoxy group having 1 to 6 carbon atoms (e.g., a methoxy group, an ethoxy group), or a phenyl group. Specific examples include 2-methoxy-1,3-dioxolane and 2-ethoxy-1,3-dioxolane. In addition, in the above formula (17), R 8 represents a hydrogen atom or the above-mentioned hydroxyl-protecting group.

[0083] R 4 and R 5 As the hydroxyl group, preferably, an alkoxymethyl group and 2-ethoxy-1,3-dioxolane are mentioned. That is, as will be described in detail later, preferably, the hydroxyl groups in compound (16) are acetalized. Specifically, the hydroxyl groups in compound (16) are acetalized individually, or two hydroxyl groups are simultaneously acetalized to form a ring (cyclic acetalization).

[0084] Examples of compound (16) include carboxylic acids and carboxylic acid esters. Examples of carboxylic acids include 3,4-dihydroxybenzoic acid. Examples of carboxylic acid esters include methyl 3,4,5-trihydroxybenzoate.

[0085] Specifically, the acetalization or etherification of the hydroxyl group in compound (16) is a two-step reaction. That is, first, the hydroxyl group in compound (16) is protected by the above-mentioned protecting group (specifically, R 4 and R 5 ) is introduced to obtain a compound represented by the following formula (17-2). Then, hydrolysis with an alkaline aqueous solution (specifically, the -COOR 10 is converted to -COOH.) to obtain compound (17). [ka] In the above formula (17-2), R 4 , R 5 and R 8 is R in the above formula (17) 4 , R 5 and R 8 In addition, in the above formula (17-2), R 10 is R in the above formula (16). 10 is synonymous with.

[0086] Next, the method for cyclic acetalization of the hydroxyl group in compound (16) will be described in detail below.

[0087] To convert the hydroxyl group in compound (16) into a cyclic acetal, for example, compound (16) is mixed with an orthoester (e.g., triethyl orthoformate) under acidic conditions and heated, for example, at 40°C or higher and 130°C or lower for 0.5 hours to 6 hours.

[0088] The mixing ratio of the orthoester is, for example, 1 mole or more and, for example, 10 moles or less per mole of compound (16).

[0089] The orthoesters can be used alone or in combination of two or more.

[0090] To acetalize each hydroxyl group in compound (16) individually, for example, compound (16) and chloromethyl ethyl ether are mixed and stirred under basic conditions.

[0091] The mixing ratio of chloromethyl ethyl ether is, for example, 2.0 moles or more and, for example, 10.0 moles or less per mole of compound (16).

[0092] This produces compound (17).

[0093] When compound (16) is a carboxylic acid ester, the ester is hydrolyzed after the acetalization by treating the compound with alkaline water (e.g., aqueous sodium hydroxide solution) in a water-soluble organic solvent to hydrolyze the ester into a carboxylic acid, thereby producing compound (17).

[0094] Next, the carboxyl group of the compound (17) is halogenated to synthesize the compound (11). [ka]

[0095] In the above formula (11), R 4 , R 5 and R 8 is R in the above formula (17) 4 , R 5 and R 8 In the above formula (11), Y represents a halogen atom (for example, a chlorine atom).

[0096] To halogenate the carboxyl group of compound (17), a halogen compound such as carbon tetrachloride is added in the presence of triphenylphosphine.

[0097] The mixing ratio of the halogen compound is, for example, 0.5 moles or more and, for example, 5 moles or less per mole of compound (17).

[0098] The halogen compounds can be used alone or in combination of two or more kinds.

[0099] This results in the synthesis of compound (11).

[0100] As such a compound (11), 2-ethoxybenzo[d][1,3]dioxole-5-carbonyl chloride (in the above formula (11), R 4 and R 5 indicates 2-ethoxy-1,3-dioxolane, and R 8 represents a hydrogen atom, and Y represents a chlorine atom), and 3,4,5-tris(ethoxymethoxy)benzoyl chloride (in the above formula (11), R 4 , R 5 and R 8 represents an ethoxymethoxymethyl group, and Y represents a chlorine atom.) More preferably, compound (11) is 2-ethoxybenzo[d][1,3]dioxole-5-carbonyl chloride.

[0101] [3rd step] In the third step, compound (10) is reacted with compound (11) in the presence of a base to synthesize compound (12). [ka]

[0102] In the above formula (12), R 4 , R 5 and R 8 is R in the above formula (17) 4 , R 5 and R 8 In addition, in the above formula (12), R 1 , R 2 , m and n are R in the above formula (1). 1 , R 2 , m and n.

[0103] Examples of the base include the bases exemplified in the above Step 1. A preferred example of the base is triethylamine.

[0104] In the above reaction, an antioxidant (for example, 2,6-di-tert-butyl-p-cresol) can also be added.

[0105] The compound (11) is added in an amount of, for example, 2 moles or more and, for example, 10 moles or less per mole of compound (10).

[0106] This synthesizes the compound (12). Preferred examples of such compound (12) include compounds represented by the following formulae (12-1) to (12-5). [ka]

[0107] The compounds represented by the above formulas (12-1) to (12-5) can exhibit the same effects as compound (1) (specifically, improved adhesion (adhesion to metals) and rust prevention) by carrying out a known deprotection operation after polymerization.

[0108] [4th step] In the fourth step, the compound (12) is reacted with an acid to synthesize the compound (1). [ka]

[0109] Examples of the acid include the acids exemplified in the above step 1. Preferred examples of the acid include hydrochloric acid and Dowex50wx2.

[0110] The proportion of the acid to be added relative to compound (15) is, for example, 0.001 equivalents or more, preferably 0.1 equivalents or more, and for example, 100 equivalents or less, preferably 50 equivalents or less.

[0111] In this way, compound (1) is synthesized.

[0112] In the above description, compound (10) is reacted with compound (11) to synthesize compound (12) in the third step. However, compound (10) can also be reacted with compound (17) to synthesize compound (12).

[0113] In such a case, in the second step, the carboxyl group of compound (17) is not halogenated to synthesize compound (11), but compound (10) is reacted with compound (17) as it is.

[0114] In the reaction of compound (10) with compound (17), a condensing agent and a base (the base exemplified in the above step 3) are added together with compound (10) and compound (17). Examples of the condensing agent include N,N'-dicyclohexylcarbodiimide, N-(3-dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride, 2-chloro-4,6-dimethoxy-1,3,5-triazine, and diphenylphosphoric acid azide.

[0115] Compound (1) exhibits adhesiveness (adhesion to metals) and rust prevention properties due to its chemical structure.

[0116] Furthermore, compound (1) has a polymerizable double bond (acryloyl group) and is therefore radically polymerizable, and can be used as a polymerization component (monomer component) in the following first to third embodiments.

[0117] Compound (1) can also be used as an additive as it is. Also, a polymer of a polymerization component containing compound (1), which will be described later, can also be used as an additive. Such a polymer can improve adhesion (to metals) and rust prevention.

[0118] <Composition> The composition contains a polymer of a polymerization component containing compound (1) and / or a polymerization component containing compound (1). That is, the composition contains a polymer of a polymerization component containing compound (1), a polymerization component containing compound (1), or a polymerization component containing compound (1) and a polymerization component containing compound (1).

[0119] In the following description, a first embodiment in which the composition contains a polymer of a polymerization component containing compound (1), a second embodiment in which the composition contains a polymerization component containing compound (1), and a third embodiment in which the composition contains a polymer of a polymerization component containing compound (1) and a polymerization component containing compound (1) will be described in detail.

[0120] [First embodiment] In a first embodiment, the composition contains a polymer of a polymerization component containing compound (1).

[0121] Examples of the polymer include (meth)acrylic resins (methacrylic resins and / or acrylic resins).

[0122] The (meth)acrylic resin can be obtained, for example, as a polymer of polymerization components containing compound (1) and a (meth)acrylic acid alkyl ester (a methacrylic acid alkyl ester and / or an acrylic acid alkyl ester).

[0123] Examples of (meth)acrylic acid alkyl esters include (meth)acrylic acid alkyl esters having an alkyl moiety with 1 to 12 carbon atoms. Examples of (meth)acrylic acid alkyl esters having an alkyl moiety with 1 to 12 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate.

[0124] The (meth)acrylic acid alkyl ester is appropriately selected from the viewpoint of adjusting the glass transition temperature of the polymer and obtaining excellent adhesiveness.

[0125] Preferred examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate and alkyl acrylate esters having 2 to 8 carbon atoms. More preferred examples of the (meth)acrylic acid alkyl ester include methyl methacrylate and alkyl acrylate esters having 3 to 5 carbon atoms. Even more preferred examples of the (meth)acrylic acid alkyl ester include methyl methacrylate and n-butyl acrylate.

[0126] When methyl methacrylate is used as the (meth)acrylic acid alkyl ester, the proportion of methyl methacrylate is, for example, 1 mol or more, preferably 5 mol or more, and for example, 120 mol or less, preferably 60 mol or less, relative to 1 mol of compound (1).

[0127] When n-butyl acrylate is used as the (meth)acrylic acid alkyl ester, the proportion of n-butyl acrylate is, for example, 1 mole or more, preferably 2 moles or more, and for example, 60 moles or less, preferably 30 moles or less, relative to 1 mole of compound (1).

[0128] In the polymerization components, the proportion (total amount) of the (meth)acrylic acid alkyl ester is, for example, 1 mole or more, preferably 5 moles or more, and for example, 180 moles or less, preferably 90 moles or less, relative to 1 mole of compound (1).

[0129] The type and proportion of the (meth)acrylic acid alkyl ester are not limited to those mentioned above, and may be appropriately determined depending on the purpose and application.

[0130] The (meth)acrylic acid alkyl esters can be used alone or in combination of two or more kinds.

[0131] The polymerization components may also contain a copolymerizable monomer that is copolymerizable with compound (1) and / or an alkyl (meth)acrylate ester.

[0132] Examples of copolymerizable monomers include functional group-containing vinyl monomers, aromatic vinyl monomers, N-substituted unsaturated carboxylic acid amides, heterocyclic vinyl compounds, vinylidene halide compounds, α-olefins, and dienes.

[0133] Examples of functional group-containing vinyl monomers include carboxy group-containing vinyl monomers, hydroxy group-containing vinyl monomers, amino group-containing vinyl monomers, glycidyl group-containing vinyl monomers, cyano group-containing vinyl monomers, sulfonic acid group-containing vinyl monomers and salts thereof, acetoacetoxy group-containing vinyl monomers, phosphoric acid group-containing compounds, and amide group-containing vinyl monomers.

[0134] Examples of carboxy group-containing vinyl monomers include (meth)acrylic acid, maleic anhydride, maleic acid, fumaric acid, itaconic acid, and crotonic acid.

[0135] Examples of hydroxyl group-containing vinyl monomers include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

[0136] Examples of amino group-containing vinyl monomers include 2-aminoethyl (meth)acrylate, 2-(N-methylamino)ethyl (meth)acrylate, and 2-(N,N-dimethylamino)ethyl (meth)acrylate.

[0137] An example of the glycidyl group-containing vinyl monomer is glycidyl (meth)acrylate.

[0138] An example of the cyano group-containing vinyl monomer is (meth)acrylonitrile.

[0139] Examples of sulfonic acid group-containing vinyl monomers include allyl sulfonic acid and methallyl sulfonic acid. Examples of salts thereof include alkali metal salts (e.g., sodium salts and potassium salts) of the sulfonic acid group-containing vinyl monomers, such as ammonium salts. Specific examples include sodium allyl sulfonate, sodium methallyl sulfonate, and ammonium methallyl sulfonate.

[0140] Examples of the acetoacetoxy group-containing vinyl monomer include acetoacetoxyethyl (meth)acrylate.

[0141] An example of the phosphate group-containing compound is 2-methacryloyloxyethyl acid phosphate.

[0142] An example of the amide group-containing vinyl monomer is (meth)acrylamide.

[0143] An example of the vinyl esters is vinyl propionate.

[0144] Examples of aromatic vinyl monomers include styrene, α-methylstyrene, and divinylbenzene.

[0145] An example of the N-substituted unsaturated carboxylic acid amide is N-methylol (meth)acrylamide.

[0146] An example of the heterocyclic vinyl compound is vinylpyrrolidone.

[0147] Examples of vinylidene halide compounds include vinylidene chloride and vinylidene fluoride.

[0148] Examples of the α-olefins include ethylene and propylene.

[0149] An example of the dienes is butadiene.

[0150] Further, the copolymerizable monomer may be a crosslinkable vinyl monomer.

[0151] Examples of crosslinkable vinyl monomers include compounds containing two or more vinyl groups, such as methylenebis(meth)acrylamide, divinylbenzene, and polyethylene glycol chain-containing di(meth)acrylate.

[0152] As the copolymerizable monomer, from the viewpoint of adjusting the glass transition temperature and improving the adhesiveness, preferably, an aromatic vinyl monomer is used, and more preferably, styrene is used.

[0153] When an aromatic vinyl monomer is used as the copolymerizable monomer, the proportion of the aromatic vinyl monomer is, for example, 1 mole or more, preferably 5 moles or more, and for example, 120 moles or less, preferably 60 moles or less, relative to 1 mole of compound (1).

[0154] In addition, the proportion (total amount) of the copolymerizable monomer in the polymerization components is, for example, 1 mole or more, preferably 5 moles or more, and for example, 150 moles or less, preferably 140 moles or less, relative to 1 mole of compound (1).

[0155] The types and proportions of the copolymerizable monomers are not limited to those mentioned above, and may be appropriately determined depending on the purpose and application.

[0156] The copolymerizable monomers can be used alone or in combination of two or more kinds.

[0157] The polymerization method for the polymerization components is not particularly limited, and any known polymerization method may be used.

[0158] As a method for polymerizing the polymerization components, the polymerization components are preferably radically polymerized in a solvent (e.g., butyl acetate). In this method, for example, the polymerization components and a polymerization initiator are mixed in a solvent and polymerized in the solvent.

[0159] The polymerization initiator is not particularly limited. Examples of the polymerization initiator include persulfates, organic peroxides, and azo compounds. Preferably, the polymerization initiator is an azo compound. Examples of the azo compound include azobisisobutyronitrile (AIBN).

[0160] The blending ratio of the polymerization initiator is appropriately set depending on the purpose and application.

[0161] The polymerization initiators can be used alone or in combination of two or more kinds.

[0162] In the polymerization, a molecular weight modifier may be added as needed.

[0163] Examples of molecular weight regulators include mercaptans, allyl compounds, and low-molecular-weight halogen compounds. Examples of mercaptans include t-dodecyl mercaptan and n-dodecyl mercaptan. Examples of allyl compounds include allyl sulfonic acid, methallyl sulfonic acid, and sodium salts thereof.

[0164] The blending ratio of the molecular weight modifier is appropriately set depending on the purpose and application.

[0165] The molecular weight regulator can be used alone or in combination of two or more kinds.

[0166] The polymerization conditions are, under normal pressure, a polymerization temperature of, for example, 30° C. or more, preferably 50° C. or more, and for example, 150° C. or less, preferably 120° C. or less, and a polymerization time of, for example, 1 hour or more, preferably 2 hours or more, and for example, 30 hours or less, preferably 20 hours or less.

[0167] This gives a polymer of a polymerization component containing the compound (1), that is, a polymer containing polymerization units derived from the compound (1).

[0168] When the polymer is a (meth)acrylic resin, the main component of the polymerization components is a (meth)acrylic acid alkyl ester.

[0169] The proportion of polymerization units derived from the (meth)acrylic acid alkyl ester, relative to the total amount of the polymer, is, for example, 50 mol% or more, preferably 55 mol% or more, and for example, 90 mol% or less, preferably 85 mol% or less, more preferably 80 mol% or less, and even more preferably 75 mol% or less.

[0170] The content of the polymerized units derived from compound (1) is, for example, 1 mol% or more, preferably 2 mol% or more, and for example, 10 mol% or less, preferably 8 mol% or less, more preferably 6 mol% or less, relative to the total amount of the polymer.

[0171] The amount of polymerized units derived from the copolymerizable monomer is, for example, 0 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more, and for example, 49 mol% or less, preferably 45 mol% or less, more preferably 40 mol% or less, relative to the total amount of the polymer.

[0172] The proportion of each polymer unit to the total amount of the polymer can be calculated as the proportion of the monomer for obtaining each polymer unit to the total amount of the polymerization components (raw materials).

[0173] In addition, in the production of the polymer, known additives such as surfactants, pH adjusters, and sequestering agents such as ethylenediaminetetraacetic acid and salts thereof may be blended in appropriate proportions in order to improve production stability.

[0174] The molecular weight of the resulting polymer is not particularly limited and is adjusted appropriately depending on the purpose and application.

[0175] For example, when the resulting polymer is applied, the weight average molecular weight of the polymer is, in terms of standard polystyrene measured by gel permeation chromatography (GPC), for example, 5,000 or more, preferably 20,000 or more, and for example, 200,000 or less, preferably 100,000 or less.

[0176] The glass transition temperature of the resulting polymer is not particularly limited and may be adjusted appropriately depending on the purpose and application.

[0177] The glass transition temperature of the polymer can be calculated based on the FOX formula.

[0178] Such a composition can also be used as is.

[0179] In addition, the composition can be applied to an adherend (subject to be coated) (preferably a metal (copper plate, steel plate), the same applies below) and, if necessary, dried to form a coating film on the adherend (subject to be coated).

[0180] [Second embodiment] In a second embodiment, the composition comprises a polymerization component comprising compound (1), i.e., the composition comprises a monomer of compound (1).

[0181] The composition may also contain the polymerization initiator and molecular weight modifier exemplified in the first embodiment.

[0182] Such a composition can also be used as is.

[0183] Alternatively, the composition may be applied to an adherend (substrate) and then heated or irradiated with active energy rays (e.g., electron beams or ultraviolet rays), thereby forming a coating film containing a polymer of a polymerization component containing compound (1) on the adherend (substrate).

[0184] [Third embodiment] In a third embodiment, the composition comprises a polymer of a polymerization component comprising compound (1) and a polymerization component comprising compound (1).

[0185] Specific examples of such compositions include a mixture of a polymer (high molecular weight polymer) of the polymerization component and the polymerization component, and a mixture of an oligomer (low molecular weight polymer) of the polymerization component and the polymerization component.

[0186] The blending ratio of the polymerization component is, for example, 1 part by mass or more and, for example, 99 parts by mass or less, relative to 100 parts by mass of the total amount of the polymerization component and the polymer. The blending ratio of the polymer is, for example, 1 part by mass or more and, for example, 99 parts by mass or less.

[0187] The composition may also contain the polymerization initiator and molecular weight modifier exemplified in the first embodiment.

[0188] Such compositions are prepared by polymerizing some of the polymerizable components.

[0189] The composition can also be used as is.

[0190] The composition is then applied to an adherend (subject to be coated) and heated or irradiated with active energy rays (e.g., electron beams, ultraviolet rays), thereby forming a coating film containing a polymer of the polymerization component on the adherend (subject to be coated).

[0191] Furthermore, the compositions (first to third embodiments) may contain additives in appropriate proportions as needed. That is, the compositions contain additives as needed.

[0192] Examples of additives include other resin components (e.g., melamine resin, epoxy resin, alkyd resin, etc.), surfactants, emulsifiers, curing agents, crosslinking agents, film-forming aids, antifoaming agents, anti-cister agents, leveling agents, tackifiers, hardness-imparting agents, preservatives, thickeners, antifreeze agents, dispersants, inorganic pigments, and organic pigments.

[0193] The additives can be used alone or in combination of two or more kinds.

[0194] Furthermore, the above compositions (first to third embodiments) can also be diluted with a known organic solvent (for example, butyl acetate) if necessary.

[0195] In such cases, the concentration of the composition (solid content concentration) is not particularly limited, but is, for example, 10% by mass or more, preferably 20% by mass or more, and for example, 60% by mass or less, preferably 50% by mass or less.

[0196] <Rust inhibitor> The rust inhibitor contains the above composition, and therefore has excellent adhesion (to metals) and rust prevention properties.

[0197] <Adhesive> The adhesive contains the above composition and therefore has excellent adhesion (to metals) and rust prevention properties.

[0198] <Coating agent> The coating agent contains the above composition, and therefore has excellent adhesion (to metals) and rust prevention properties.

[0199] <Action and effect> Compound (1) can exhibit adhesion (to metals) and rust prevention properties due to its chemical structure.

[0200] Specifically, compound (1) has a hydroxyl group in its chemical structure, and the interaction between the hydroxyl group and metal allows the compound to exhibit adhesion to metal.

[0201] In addition, compound (1) has two catechol groups, which allows it to exhibit rust prevention properties.

[0202] The composition also contains a polymer of a polymerization component containing compound (1) and / or compound (1), and therefore has excellent adhesion (to metals) and rust prevention properties.

[0203] In particular, this composition has excellent adhesion to metals and can therefore be suitably used as a rust inhibitor, adhesive, and coating agent for metals.

[0204] Furthermore, as described above, the compounds represented by the formulas (12-1) to (12-5) can exhibit the same effects as those of the compound (1) (specifically, improved adhesion (adhesion to metals) and rust prevention) by carrying out a known deprotection operation after polymerization.

[0205] A polymer obtained by polymerizing a polymerization component containing the compound obtained by the above-mentioned deprotection operation can exhibit the same effects as a polymer obtained by polymerizing a polymerization component containing the above-mentioned compound (1) (specifically, improved adhesion (adhesion to metals) and rust prevention).

[0206] Furthermore, a polymer of a polymerization component containing the compound obtained by the above-mentioned deprotection operation, and / or a composition containing a polymerization component containing the compound obtained by the above-mentioned deprotection operation, can exhibit the same effects as the above-mentioned polymer of a polymerization component containing compound (1) and / or a composition containing a polymerization component containing compound (1) (specifically, improved adhesion (adhesion to metals) and rust prevention).

[0207] Furthermore, a polymer of a polymerization component containing the compound obtained by the above-mentioned deprotection operation, and / or a composition containing a polymerization component containing the compound obtained by the above-mentioned deprotection operation, are suitably used in rust inhibitors, adhesives, and coating agents. That is, rust inhibitors include the above-mentioned composition. Adhesives include the above-mentioned composition. Coating agents include the above-mentioned composition.

[0208] <Modification> Compound (10) can also be produced by reacting one of the hydroxyl groups of a trihydric alcohol represented by the following formula (10-1) with 3-chloropropionyl chloride represented by the following formula (10-2) to halogenate it, followed by an elimination reaction.1 , m and n are R in the above formula (1). 1 , m and n. [ka] [Example]

[0209] Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the following examples. Note that "parts" and "%" are by mass unless otherwise specified. Furthermore, specific numerical values ​​such as blending ratios (content ratios), physical property values, and parameters used in the following description can be substituted with the corresponding upper limit values ​​(numeric values ​​defined as "equal to or less than") or lower limit values ​​(numeric values ​​defined as "equal to or more than" or "exceeding") of the blending ratios (content ratios), physical property values, parameters, etc. described in the above "Form for Carrying Out the Invention."

[0210] <Synthesis of Compounds> Example 1 (Synthesis of 3-(methacryloyloxy)propane-1,2-diyl bis(3,4-dihydroxybenzoate) (compound represented by the above formula (6-1)) [1st step] As compound (10), glycerol monomethacrylate (a compound represented by the following formula (21) (hereinafter referred to as compound (21)), cas5919-74-4, product number 512-51862, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was prepared. [ka]

[0211] [Second process] Under a nitrogen atmosphere, 20 g (130 mmol) of 3,4-dihydroxybenzoic acid (compound (22)), 800 mg (4% by mass) of p-toluenesulfonic acid monohydrate, 32.7 g (221 mmol) of triethyl orthoformate, and 108 mL of toluene were placed in a 500 mL four-neck flask to form a suspension. The resulting suspension was stirred under reflux for 6 hours.

[0212] Next, the resulting mixture was allowed to cool to room temperature, and 60 mL of toluene was added. The suspension was filtered (using Kiriyama filter paper 5C), and a total of 180 mL of toluene was added in three portions for washing. This yielded 19.9 g of 2-ethoxybenzo-[d][1,3]-dioxole-5-carboxylic acid (a compound represented by the following formula (23) (hereinafter referred to as compound (23))) as a pale yellow solid (yield 73%).

[0213] The NMR analysis results of compound (23) are shown below. 1 H-NMR(400MHz,DMSO-d6)δ:12.8(1H,brd.s),7.60(1H,d,J=8.3Hz),7.45(1H,s), 7.22(1H,s),7.09(1H,d,J=8.3Hz),3.71(2H,q,J=7.1Hz),1.18(3H,t,J=7.1Hz). [ka]

[0214] Under a nitrogen atmosphere, a 500 mL four-neck flask was charged with 10.0 g (47.6 mmol) of compound (23), 13.7 g (52.3 mmol) of triphenylphosphine, and 7.3 mL (52.3 mmol) of triethylamine. 95 mL of dichloromethane was then added to dissolve the compounds. The mixture was then cooled to 0°C, and 10.1 mL (105 mmol) of carbon tetrachloride was added. The mixture was then stirred at room temperature for 2.5 hours. This resulted in the synthesis of a compound represented by the following formula (24) (hereinafter referred to as compound (24)). [ka]

[0215] [3rd step] The reaction solution containing compound (24) was cooled to 0°C under an air atmosphere. A mixture of 3.4 g (21.2 mmol) of glycerol monomethacrylate (compound (21)), 0.519 g (4.25 mmol) of 4-dimethylaminopyridine, and 3.4 mg (0.1% by mass) of 2,6-di-tert-butyl-p-cresol dissolved in 11 mL of dichloromethane was added dropwise and stirred at room temperature for 20 hours. After cooling to 0°C, 150 mL of saturated aqueous sodium bicarbonate solution was added and stirred for 10 minutes. The mixture was then extracted with dichloromethane (150 mL x 1). The combined extracts were dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was dissolved in 200 mL of ethyl acetate, cooled to 0°C, and stirred for 30 minutes to allow crystallization. Next, the obtained crystals were filtered, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (column: Biotage SfarD (Duo) 100 g, elution solvent: ethyl acetate-hexane gradient (ethyl acetate 7% to 42%)) to synthesize 5.2 g of 3-methacryloyloxypropane-1,2-dyl bis(2-ethoxybenzo-[d][1,3]-dioxole-5-carboxylate (a compound represented by the following formula (25) (hereinafter referred to as compound (25)))) as a colorless oil (yield 45%).

[0216] The NMR analysis results of compound (25) are shown below. 1 H-NMR(400MHz,DMSO-d6)δ:7.61(1H,d,J=8.0Hz),7.60(1H,d,J=8.0Hz),7.45(2H,s),7.24(2H,s),7.12(2H,d,J=8.0 Hz),6.02(1H,s),5.68(1H,s),5.60(1H,m),4.45-4.63(4H,m),3.70(4H,q,J=6.8Hz),1.84(3H,s),1.15-1.19(6H,m). [ka]

[0217] [4th step] A 200 mL four-neck flask was charged with 5.20 g (9.55 mmol) of 3-methacryloyloxypropane-1,2-diyl bis(2-ethoxybenzo-[d][1,3]-dioxole-5-carboxylate (compound (25))) and 1.04 g (20 mass%) of Dowex50wx2 (strongly acidic ion exchange resin, H type), and then 43 mL of methanol and 4.3 mL of water were added to dissolve the mixture. The resulting solution was stirred at 50° C. for 5.5 hours.

[0218] Next, this solution was allowed to cool to room temperature, filtered through Celite, and washed with 75 mL of ethyl acetate added in three portions. It was then dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (column: Biotage SfarD (Duo) 350 g, elution solvent: ethyl acetate-hexane gradient (ethyl acetate 16% to 100%)) to synthesize 3.96 g of 3-(methacryloyloxy)propane-1,2-diyl bis(3,4-dihydroxybenzoate) (compound represented by the following formula (6-1)) as a white solid (yield 96%).

[0219] The NMR analysis results of the compound represented by the following formula (6-1) are shown below. 1 H-NMR(400MHz,DMSO-d6)δ:9.61(3H,brs),7.34(2H,s),7.29-7.32(2H,m),6.82(1H,d,J=8.0Hz ),6.78(1H,d,J=8.0Hz),6.01(1H,s),5.68(1H,s),5.54(1H,m),4.39-4.55(4H,m),1.84(3H,s). [ka]

[0220] Example 2 (Synthesis of 3-(methacryloyloxy)propane-1,2-dyl bis(3,4,5-trihydroxybenzoate) (compound represented by the above formula (6-3)) [1st step] Glycerol monomethacrylate (compound (21) above, cas5919-74-4, product number 512-51862, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was prepared as compound (10).

[0221] [Second process] A 1000 mL four-neck flask was charged with 30.0 g (163 mmol) of methyl 3,4,5-trihydroxybenzoate (a compound represented by the following formula (26) (hereinafter referred to as compound (26))), 153.3 mL of N-ethyl-N,N-diisopropylamine, and 300 mL of methylene chloride, and the mixture was dissolved. Next, 52.3 mL of chloromethyl ethyl ether was added dropwise at room temperature, and the mixture was stirred at room temperature for 6 hours. The mixture was then transferred to a separatory funnel, and 250 mL of water and 230 mL of 2N aqueous hydrochloric acid were added. After shaking, the organic layer was separated. The organic layer was then washed with 100 mL of water and 100 mL of semi-saturated brine. The organic layer was then dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting oil was further desolvated using a vacuum pump, yielding 59.24 g of a crude compound represented by the following formula (27) (hereinafter referred to as compound (27)).

[0222] The NMR analysis results of compound (27) are shown below. 1 H-NMR(400MHz,CDCl3)δ:7.54(2H,s), 5.28(4H, s),5.24(2H,s),3.89(3H,s),3.88(2H,q,J=7.1Hz),3.76(4H,q,J=7.1Hz),1.24(6H,t,J=7.1Hz),1.22(3H,t,J=7.1Hz). [ka]

[0223] Next, 52.94 g (81.4 mmol) of compound (27) was dissolved in 1,4-dioxane (390 mL). Then, 196 mL of 1N aqueous sodium hydroxide solution was added, and the mixture was stirred at 45°C for 6 hours. The mixture was then concentrated under reduced pressure to one-third of its original volume, followed by the addition of 200 mL of water and 100 mL of 2N hydrochloric acid. The resulting white suspension was transferred to a separatory funnel and extracted with ethyl acetate. The organic layer was washed with saturated brine. The organic layer was then dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting solid was further dried using a vacuum pump, synthesizing 56.1 g of methyl 3,4,5-tris(ethoxymethoxy)benzoic acid (a compound represented by the following formula (28) (hereinafter referred to as compound (28))) (yield: 99%).

[0224] The NMR analysis results of compound (28) are shown below. 1 H-NMR(400MHz,CDCl3)δ:7.61(2H,s),5.29(4H,s),5.28(2H,s),3.89(2H,q,J =7.1Hz),3.77(4H,q,J=7.1Hz),1.24(6H,t,J=7.1Hz),1.22(3H,t,J=7.1Hz). [ka]

[0225] Next, under a nitrogen atmosphere, a 500 mL four-neck flask was charged with 20.0 g (58.1 mmol) of methyl 3,4,5-tris(ethoxymethoxy)benzoic acid (compound (28)), 16.8 g (63.9 mmol) of triphenylphosphine, and 8.9 mL (63.9 mmol) of triethylamine. 116 mL of dichloromethane was then added to dissolve the components. The mixture was then cooled to 0°C, and 12.3 mL (128 mmol) of carbon tetrachloride was added. The mixture was then stirred at room temperature for 2.5 hours. This resulted in the synthesis of a compound represented by the following formula (29) (hereinafter referred to as compound (29)). [ka]

[0226] [3rd step] The reaction mixture containing compound (29) was cooled to 0°C under an air atmosphere. A mixture of 4.22 g (26.3 mmol) of glycerol monomethacrylate (compound (21)), 0.644 g (5.27 mmol) of 4-dimethylaminopyridine, and 4.2 mg (0.1% by mass) of 2,6-di-tert-butyl-p-cresol dissolved in 16 mL of dichloromethane was added dropwise and stirred at 40°C for 6.5 hours and at room temperature for 17.5 hours. After cooling to 0°C, 150 mL of saturated aqueous sodium bicarbonate solution was added and stirred for 10 minutes. The mixture was then extracted with dichloromethane (150 mL x 1). The combined extracts were dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was dissolved in 250 mL of ethyl acetate, cooled to 0°C, and stirred for 30 minutes to allow crystallization. Next, the obtained crystals were filtered, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (column: Biotage SfarD (Duo) 350 g, elution solvent: ethyl acetate-hexane gradient (ethyl acetate 8% to 63%)) to synthesize 14.8 g of a compound represented by the following formula (30) (hereinafter referred to as compound (30)) as a colorless oil (yield 69%).

[0227] The NMR analysis results of compound (30) are shown below. 1 H-NMR(400MHz,DMSO-d6)δ:7.53(4H,s),6.14(1H,s),5.67(1H,m),5.59(1H,s),5.24(12H,s),4.4 3-4.84(4H,m),3.87(4H,q,J=7.0Hz),3.74(8H,q,J=7.0Hz),1.94(3H,s),1.20(18H,t,J=7.0Hz). [ka] [4th step] A 300 mL four-neck flask was charged with 13.8 g (17.0 mmol) of compound (30), and 85 mL of methanol was added to dissolve the compound. The resulting solution was cooled to 0°C, and 22 mL (112 mmol) of 5.0 Maq. HCl was added dropwise, followed by stirring at room temperature for 42 hours.

[0228] Next, 100 mL of saturated aqueous sodium bicarbonate solution was added and stirred for 10 minutes. The mixture was then extracted with ethyl acetate (150 mL x 2). The combined extracts were washed with saturated brine (300 mL x 1), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (column: Biotage SfarD (Duo) 200 g, elution solvent: ethyl acetate-hexane gradient (ethyl acetate 16% to 100%)) to quantitatively obtain 8.24 g of 3-(methacryloyloxy)propane-1,2-diyl bis(3,4,5-trihydroxybenzoate) (compound represented by the following formula (6-3)) as a white solid.

[0229] The NMR analysis results of the compound represented by the following formula (6-3) are shown below. 1 H-NMR (400MHz, DMSO-d6) δ: 9.18 (5H, brs), 6.94 (4H, s), 6.01 (1H, s), 5.69 (1H, s), 5.52 (1H, m), 4.36-4.53 (4H, m), 1.85 (3H, s). [ka]

[0230] Example 3 (Synthesis of 6-(methacryloyloxy)hexane-1,2-diyl bis(3,4-dihydroxybenzoate) (compound represented by the above formula (8-1))

[0231] [1st step] Under a nitrogen atmosphere, 20.0 g (149 mmol) of 1,2,6-hexanetriol (a compound represented by the following formula (31) (hereinafter referred to as compound (31))) was placed in a 1000 mL four-neck flask, and 298 mL of tetrahydrofuran was added to dissolve the compound. To the resulting solution, 100 g of sodium sulfate, 298 mL (4.05 mol) of acetone, and 200 mg (1% by mass) of p-toluenesulfonic acid monohydrate were added. The resulting suspension was then stirred at room temperature for 24 hours to obtain a reaction solution.

[0232] The reaction mixture was then filtered through Celite, washed with saturated aqueous sodium bicarbonate (400 mL x 1) and water (400 mL x 2), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (column: Biotage SfarD (Duo) 350 g, elution solvent: ethyl acetate-hexane gradient (ethyl acetate 12% to 100%)) to obtain 19.0 g of 4-(2,2-dimethyl-1,3-dioxolan-4-yl)butan-1-ol (a compound represented by the following formula (32) (hereinafter referred to as compound (32))) as a colorless oil (yield: 73%).

[0233] The NMR analysis results of compound (32) are shown below. 1 H-NMR(400MHz,CDCl3)δ:4.10(1H,m),4.04(1H,t,J=6.7Hz),3.67(1H,d,J=6.7Hz),3.6 4(1H,d,J=6.7Hz),3.52(1H,t,J=6.7Hz),1.46-1.71(6H,m),1.41(3H,s),1.36(3H,s). [ka]

[0234] Next, 1.0 g (5.74 mmol) of 4-(2,2-dimethyl-1,3-dioxolan-4-yl)butan-1-ol (compound (32)) was placed in a 100 mL three-neck flask, and 29 mL of dichloromethane was added to dissolve the solution. The resulting solution was cooled to 0 °C, and 7.0 mg (0.057 mmol) of dimethylaminopyridine, 0.88 mL (6.31 mmol) of triethylamine, and 1.0 mL (6.89 mmol) of methacrylic anhydride (compound represented by the following formula (33)) were added. The solution was then stirred at room temperature for 22 hours to obtain a reaction solution.

[0235] Next, 6.3 mL of 1 M hydrochloric acid and 20 mL of water were added to the reaction mixture and stirred for 10 minutes to obtain a mixture. The mixture in the flask was extracted with dichloromethane (30 mL x 2). The combined extracts were washed with 90 mL of saturated brine, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The resulting residues were combined and purified by silica gel column chromatography (column: Biotage SfarD (Duo) 50 g, elution solvent: ethyl acetate-hexane gradient (ethyl acetate 5% to 40%)) to obtain 1.35 g of 4-(2,2-dimethyl-1,3-dioxolan-4-yl)butyl methacrylate (a compound represented by the following formula (34) (hereinafter referred to as compound (34))) as a colorless oil (yield: 97%).

[0236] The NMR analysis results of compound (34) are shown below. 1 H-NMR(400MHz,CDCl3)δ:6.10(1H,dq,J=0.89,1.8Hz),5.55(1H,dq,J=1.6,1 .8Hz),4.16(2H,t,J=6.6Hz),4.08(1H,m),4.04(1H,dd,J=5.9,7.8Hz),3.51 (1H,dd,J=7.2,7.8Hz),1.94(3H,dd,J=0.89,1.6Hz),1.61-1.76(3H,m),1.4 7-1.60(2H,m),1.41(1H,m),1.41(3H,d,J=0.73Hz),1.36(3H,d,J=0.73Hz). [ka]

[0237] Next, 0.17 g (0.702 mmol) of 4-(2,2-dimethyl-1,3-dioxolan-4-yl)butyl methacrylate (compound (34)) was placed in a 30 mL three-neck flask, and 7.0 mL of methanol and dichloromethane were added to dissolve the mixture. The resulting solution was cooled to 0°C, and 1.5 mL (1.54 mmol) of 1 M hydrochloric acid was added. The solution was then stirred at room temperature for 3.5 hours to obtain a reaction solution.

[0238] Next, 3.0 mL of saturated aqueous sodium bicarbonate solution and 10 mL of water were added to the reaction mixture and stirred for 10 minutes to obtain a mixture. The mixture in the flask was extracted with ethyl acetate (20 mL x 3). The combined extracts were washed with 60 mL of saturated brine, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The resulting residues were combined and purified by silica gel column chromatography (column: Biotage SfarD (Duo) 25 g, elution solvent: ethyl acetate-hexane gradient (ethyl acetate 16% to 100%)) to obtain 0.143 g (yield quant.) of 5,6-dihydroxyhexyl methacrylate (a compound represented by the following formula (35) (hereinafter referred to as compound (35))) as a colorless oil.

[0239] The NMR analysis results of compound (35) are shown below. 1 H-NMR(400MHz,CDCl3)δ:6.10(1H,dq,J=0.98,1.9Hz),5.56(1H,dq,J=1.6,1.9Hz),4.16(2H,t,J=6.6Hz),3.71(1H,m),3.65(1H,dd, J=3.0,11.2Hz),3.44(1H,dd,J=7.6,11.2Hz),2.70(2H,brd.s),1.94(3H,dd,J=0.98,1.6Hz),1.67-1.76(2H,m),1.40-1.60(4H,m). [ka]

[0240] [Second process] Compound (24) was synthesized in the same manner as in the second step of Example 1.

[0241] [3rd step] The same procedure as in the third step of Example 1 was carried out, except that glycerol monomethacrylate (compound (21)) in the third step of Example 1 was changed to 5,6-dihydroxyhexyl methacrylate (compound (35)). As a result, 16.7 g of 6-(methacryloyloxy)hexane-1,2-diyl bis(2-ethoxybenzo-[d][1,3]-dioxole-5-carboxylate (a compound represented by the following formula (36) (hereinafter referred to as compound (36)))) was synthesized as a colorless oil (yield: 52%).

[0242] The NMR analysis results of compound (36) are shown below. 1 H-NMR(400MHz,CDCl3)δ:7.69(1H,dd,J=1.7,8.2Hz),7.65(1H,dd,J=1.7,8.2Hz),7.52(1H,d,J=1.7Hz),7.48(1H,d,J=1.7H z),6.94(1H,s),6.92(1H,s),6.89(1H,d,J=8.2Hz),6.87(1H,d,J=8.2Hz),6.06(1H,m),5.52(1H,dq,J=1.5,1.7Hz),5.45(1 H,m),4.50(1H,dd,J=2.7,11.9Hz),4.41(1H,ddd,J=1.6,6.6,11.9Hz),4.15(2H,t,J=6.7Hz),3.74(2H,dt,J=2.0,7.2Hz),3 .71(2H,dt,J=2.0,7.2Hz),1.91(3H,m),1.70-1.88(4H,m),1.52-1.60(2H,m),1.27(2H,t,J=7.1Hz),1.27(2H,t,J=7.1Hz). [ka]

[0243] [4th step] Into a 500 mL four-neck flask, 15.6 g (27.2 mmol) of 6-(methacryloyloxy)hexane-1,2-diyl bis(2-ethoxybenzo-[d][1,3]-dioxole-5-carboxylate (compound (36))) and 136 mL of methanol were added and dissolved. The mixture was then cooled to 0°C, and 41 mL (82.0 mmol) of 2 M hydrochloric acid was added dropwise, followed by stirring at room temperature for 22.5 hours.

[0244] Next, 100 mL of saturated aqueous sodium bicarbonate solution was added and stirred for 10 minutes. The mixture was then extracted with ethyl acetate (200 mL x 2). The combined extracts were washed with saturated brine (400 mL x 1), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (column: Biotage SfarD (Duo) 100 g, elution solvent: ethyl acetate-hexane gradient (ethyl acetate 16% to 100%)) to obtain 12.9 g of 6-(methacryloyloxy)hexane-1,2-diyl bis(3,4-dihydroxybenzoate) (compound represented by the following formula (8-1)) as a yellow solid (96% yield).

[0245] The NMR analysis results of the compound represented by the following formula (8-1) are shown below. 1 H-NMR(400MHz,DMSO-d6)δ:9.57(4H,brd.s),7.34(2H,dd,J=2.2,12.6Hz),7.30 (1H,dd,J=2.2,8.3Hz),7.27(1H,dd,J=2.2,8.3Hz),6.79(2H,dd,J=5.9,8.3Hz), 5.96(1H,m),5.60(1H,dq,J=1.5,1.6Hz),5.29(1H,m),4.44(1H,dd,J=3.3,11.9Hz),4.33(1H,dd,J=6.6,11.9Hz) ,4.10(2H,t,J=6.5Hz),1.83(3H,dd,J=0.98,1.5Hz),1.77(2H,q,J=7.4Hz),1.60-1.71(2H,m),1.38-1.52(2H,m) [ka]

[0246] Example 4 (Synthesis of 2-((acryloyloxy)methyl)-2-ethylpropane-1,3-dyl bis(3,4-dihydroxybenzoate) (compound represented by the above formula (9-14))

[0247] [1st step] Under a nitrogen atmosphere, 3.0 g (22.4 mmol) of 2-ethyl-2-(hydroxymethyl)propane-1,3-diol (compound (37)) was placed in a 300 mL four-neck flask, and 112 mL of tetrahydrofuran was added to dissolve the solution. The resulting solution was cooled to 0 °C, and 2.2 mL (22.4 mmol) of 3-chloropropionyl chloride (compound (38)) was added. The solution was then stirred at room temperature for 43 hours to obtain a reaction solution.

[0248] Next, the reaction solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (column: Biotage SfarD (Duo) 100 g, elution solvent: ethyl acetate-hexane gradient (ethyl acetate 16% to 100%)) to obtain 3.0 g of 2,2-bis(hydroxymethyl)butyl 3-chloropropanoate (a compound represented by the following formula (39) (hereinafter referred to as compound (39))) as a colorless oil (yield 60%).

[0249] The NMR analysis results of compound (39) are shown below. 1 H-NMR(400MHz,CDCl3)δ:4.26(2H,s),3.78(2H,t,J=6.5Hz),3.60(4H,d,J=2.7Hz),2 .85(2H,t,J=6.5Hz),2.70(2H,brd.s),1.32(2H,q,J=7.7Hz),0.88(3H,t,J=7.7Hz). [ka]

[0250] Next, under a nitrogen atmosphere, 14.3 g (63.6 mmol) of 2,2-bis(hydroxymethyl)butyl 3-chloropropanoate (compound (39)) was placed in a 1000 mL four-neck flask, and 218 mL of dichloromethane was added to dissolve the mixture. The resulting solution was cooled to 0 °C, and 31 mL (223 mmol) of triethylamine was added. The solution was then stirred at room temperature for 24 hours to obtain a reaction solution.

[0251] Next, 230 mL of 1 M hydrochloric acid and 100 mL of water were added to the reaction mixture and stirred for 10 minutes to obtain a mixture. The mixture in the flask was extracted with dichloromethane (300 mL x 1) and ethyl acetate (300 mL x 2). The extracts were washed with 300 mL and 600 mL of saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residues were combined and purified by silica gel column chromatography (column: Biotage SfarD (Duo) 200 g, elution solvent: ethyl acetate-hexane gradient (ethyl acetate 16% to 100%)) to obtain 11.8 g of 2,2-bis(hydroxymethyl)butyl acrylate (a compound represented by the following formula (40) (hereinafter referred to as compound (40))) as a colorless oil (yield: 98%).

[0252] The NMR analysis results of compound (40) are shown below. 1 H-NMR(400MHz,CDCl3)δ:6.45(1H,dd,J=1.4,17.3Hz),6.15(1H,dd,J=10.2,17.3Hz),5.89(1H,dd,J=1.4,10.2Hz),4.3 0(2H,s),3.62(2H,d,J=11.2Hz),3.57(2H,d,J=11.2Hz),2.81(2H,br.s),1.33(2H,q,J=7.6Hz),0.89(3H,t,J=7.6Hz). [ka]

[0253] [Second process] Compound (24) was synthesized in the same manner as in the second step of Example 1.

[0254] [3rd step] Glycerol monomethacrylate (compound (21)) in the third step of Example 1 was converted into 2,2-bis(hydroxymethyl)butyl acrylate (the following formula (40) The same procedure as in the third step of Example 1 was carried out, except that the above-mentioned procedure was changed to the following: As a result, 15.6 g of 2-((acryloyloxy)methyl)-2-ethylpropane-1,3-dyl bis(2-ethoxybenzo-[d][1,3]-dioxole-5-carboxylate) (a compound represented by the following formula (41) (hereinafter referred to as compound 41)) was synthesized as a colorless oil (yield: 51%).

[0255] The NMR analysis results of compound (41) are shown below. 1 H-NMR(400MHz,CDCl3)δ:7.66(2H,dd,J=1.4,8.3Hz),7.48(2H,d,J=1.4Hz),6. 94(2H,s),6.88(2H,d,J=8.3Hz),6.40(1H,dd,J=1.3,12.3Hz),6.11(1H,dd,J= 10.5,12.3Hz),5.84(1H,dd,J=1.3,10.5Hz),4.37(4H,s),4.30(2H,s),3.70-3 .79(4H,m),1.68(2H,q,J=7.7Hz),1.27(6H,t,J=7.1Hz),1.01(3H,t,J=7.7Hz) [ka]

[0256] [4th step] The same procedure as in the third step of Example 3 was carried out, except that 6-(methacryloyloxy)hexane-1,2-dyl bis(2-ethoxybenzo-[d][1,3]-dioxole-5-carboxylate (compound (36)) in the fourth step of Example 3 was changed to 2-((acryloyloxy)methyl)-2-ethylpropane-1,3-dyl bis(2-ethoxybenzo-[d][1,3]-dioxole-5-carboxylate) (compound (41)). As a result, 11.8 g of 2-((acryloyloxy)methyl)-2-ethylpropane-1,3-dyl bis(3,4-dihydroxybenzoate) (compound represented by the following formula (9-14)) was synthesized as a pale yellow solid (yield 95%).

[0257] The NMR analysis results of the compound represented by the following formula (9-14) are shown below. 1 H-NMR(400MHz,DMSO-d6)δ:9.54(4H,brd.s),7.37(2H,d,J=2.2Hz),7.33(2H,dd,J=2.2,8.3Hz),6.80(2H,d,J=8.3Hz),6.32(1H,dd,J=1.5, 17.3Hz),6.15(1H,dd,J=10.5,17.3Hz),5.93(1H,dd,J=1.5,10.5Hz),4.26(4H,s),4.24(2H,s),1.61(2H,q,J=7.6Hz),0.94(3H,t,J=7.6Hz) [ka]

[0258] Example 5 (Synthesis of 2-((acryloyloxy)methyl)-2-methylpropane-1,3-dyl bis(3,4,5-trihydroxybenzoate) (compound represented by the above formula (9-12)))

[0259] [1st step] Under a nitrogen atmosphere, 6.0 g (44.9 mmol) of 2-(hydroxymethyl)-2-methylpropane-1,3-diol (compound (42)) was placed in a 500 mL four-neck flask, and 250 mL of tetrahydrofuran was added to dissolve the mixture. The resulting solution was cooled to 0 °C, and 4.8 mL (49.9 mmol) of 3-chloropropionyl chloride (compound (38)) was added. The solution was then stirred at room temperature for 24 hours to obtain a reaction solution.

[0260] Next, the reaction solution was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (column: Biotage SfarD (Duo) 200 g, elution solvent: ethyl acetate-hexane gradient (ethyl acetate 16% to 100%)) to obtain 5.96 g of 3-hydroxy-2-(hydroxymethyl)-2-methylpropyl 3-chloropropanoate (a compound represented by the following formula (43) (hereinafter referred to as compound (43))) as a colorless oil (yield 57%).

[0261] The NMR analysis results of compound (43) are shown below. 1 H-NMR(400MHz,DMSO-d6)δ:4.47(2H,t,J=5.4Hz),3.93(2H,s),3.80(2H,t,J=6.3Hz),3.26(4H,dd,J=2.9,5.4Hz),2.81(2H,t,J=6.3Hz),0.79(3H,s). [ka]

[0262] Next, under a nitrogen atmosphere, 13.1 g (62.1 mmol) of 3-hydroxy-2-(hydroxymethyl)-2-methylpropyl 3-chloropropanoate (compound (43)) was placed in a 1000 mL four-neck flask, and 310 mL of dichloromethane was added to dissolve the mixture. The resulting solution was cooled to 0 °C, and 30 mL (217 mmol) of triethylamine was added. The solution was then stirred at room temperature for 41 hours to obtain a reaction solution.

[0263] Next, 220 mL of 1 M hydrochloric acid and 100 mL of water were added to the reaction mixture and stirred for 10 minutes to obtain a mixture. The mixture in the flask was extracted with dichloromethane (300 mL x 2). The combined extracts were washed with 600 mL of saturated brine, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The resulting residues were combined and purified by silica gel column chromatography (column: Biotage SfarD (Duo) 200 g, elution solvent: ethyl acetate-hexane gradient (ethyl acetate 16% to 100%)) to obtain 6.73 g of 3-hydroxy-2-(hydroxymethyl)-2-methylpropyl acrylate (a compound represented by the following formula (44) (hereinafter referred to as compound (44))) as a colorless oil (yield: 62%). [ka]

[0264] The NMR analysis results of compound (44) are shown below. 1 H-NMR(400MHz,CDCl3)δ:6.45(1H,dd,J=1.3,17.3Hz),6.16(1H,dd,J=10.5,17.3Hz),5.90(1H,dd,J=1. 3,10.5Hz),4.27(2H,s),3.60(2H,d,J=11.2Hz),3.55(2H,d,J=11.2Hz),2.98(2H,brd.s),0.87(3H,s).

[0265] [Second process] Compound (29) was synthesized in the same manner as in the second step of Example 2.

[0266] [3rd step] The same procedure as in the third step of Example 2 was carried out, except that glycerol monomethacrylate (compound (21)) in the third step of Example 2 was changed to 3-hydroxy-2-(hydroxymethyl)-2-methylpropyl acrylate (the following formula (44)). As a result, 1.32 g of 2-((acryloyloxy)methyl)-2-methylpropane-1,3-dyl bis(3,4,5-tris(ethoxymethoxy)benzoate) (a compound represented by the following formula (45) (hereinafter referred to as compound (45))) was synthesized as a colorless oil (yield: 34%).

[0267] The NMR analysis results of compound (45) are shown below. 1 H-NMR(400MHz,CDCl3)δ:7.57(4H,s),6.40(1H,dd,J=1.5,17.3Hz),6.13(1H,dd,J=10.5,17.3Hz),5.84(1H,dd,J=1.5,10.5Hz),5.27(8H,s),5 .24(4H,s),4.34(2H,s),4.34(2H,s),4.26(2H,s),3.87(4H,q,J=7.1Hz ),3.75(8H,q,J=7.1Hz),1.22(12H,t,J=7.1Hz),1.21(6H,t,J=7.1Hz). [ka]

[0268] [4th step] The same procedure as in the third step of Example 3 was carried out, except that 6-(methacryloyloxy)hexane-1,2-dyl bis(2-ethoxybenzo-[d][1,3]-dioxole-5-carboxylate (compound (36)) in the fourth step of Example 3 was changed to 2-((acryloyloxy)methyl)-2-methylpropane-1,3-dyl bis(3,4,5-tris(ethoxymethoxy)benzoate) (compound (45)). As a result, 0.548 g of 2-((acryloyloxy)methyl)-2-methylpropane-1,3-dyl bis(3,4,5-trihydroxybenzoate) (compound represented by the following formula (9-12)) was synthesized as a white solid (yield 72%).

[0269] The NMR analysis results of the compound represented by the following formula (9-12) are shown below. 1 H-NMR(400MHz,DMSO-d6)δ:9.19(6H,brd.s),6.97(4H,s),6.35(1H,dd,J=1.5,17.3Hz),6.17( 1H,dd,J=10.3,17.3Hz),5.94(1H,dd,J=1.5,10.3Hz),4.22(4H,s),4.20(2H,s),2.08(3H,s). [ka]

[0270] <Manufacturing of rust inhibitors> Example 6 A 500 mL four-neck flask equipped with a Dimroth condenser, a thermometer, and a stirring blade was purged with nitrogen, and then butyl acetate (42.8 g) was added and the temperature was raised to 95°C.

[0271] Next, a mixture of methyl methacrylate (45.95 g, 0.49 mol), styrene (42.2 g, 0.40 mol), butyl acrylate (26.7 g, 0.21 mol), and 3-(methacryloyloxy)propane-1,2-diyl bis(3,4-dihydroxybenzoate) (0.02 mol) obtained in Example 1, butyl acetate (1.02 g) as a solvent, and azobisisobutyronitrile (hereinafter referred to as AIBN, 0.97 g, 5.9 mmol) as a polymerization initiator was added to the flask in 20 mL portions every 30 minutes. After the entire mixture was added, the mixture was heated for 1 hour and then cooled to 90°C.

[0272] Then, AIBN (0.185 g, 1.1 mmol) was added, and the temperature was then raised to 95°C, heated for 1 hour, and then cooled to 90°C.

[0273] Next, AIBN (0.165 g, 1.0 mmol) was added again, and then the temperature was raised to 105°C, heated for 1 hour, and then cooled to 90°C.

[0274] Next, AIBN (0.165 g, 1.0 mmol) was added again, and then the temperature was raised to 115°C, heated for 1 hour, and then cooled to 77°C.

[0275] Thereafter, a mixed solvent of ethyl acetate (42.2 g) and butyl acetate (4.45 g) was added as a solvent, and the mixture was stirred uniformly and then cooled to 50° C. or less.

[0276] As a result, a (meth)acrylic resin containing the 3-(methacryloyloxy)propane-1,2-dyl bis(3,4-dihydroxybenzoate) obtained in Example 1 as a polymer unit was obtained.

[0277] The obtained (meth)acrylic resin was diluted with butyl acetate to obtain a resin solution with a solid content concentration of 40% by mass.

[0278] This resin solution was used as a rust inhibitor.

[0279] Example 7 A (meth)acrylic resin was obtained in the same manner as in Example 6, except that 3-(methacryloyloxy)propane-1,2-dyl bis(3,4,5-trihydroxybenzoate) (0.013 mol) obtained in Example 2 was used instead of 3-(methacryloyloxy)propane-1,2-dyl bis(3,4-dihydroxybenzoate) (0.02 mol) obtained in Example 1. A rust inhibitor was prepared using the obtained (meth)acrylic resin.

[0280] Example 8 A (meth)acrylic resin was obtained in the same manner as in Example 6, except that 6-(methacryloyloxy)hexane-1,2-diyl bis(3,4-dihydroxybenzoate) (0.02 mol) obtained in Example 3 was used instead of 3-(methacryloyloxy)propane-1,2-diyl bis(3,4-dihydroxybenzoate) (0.02 mol) obtained in Example 1. A rust inhibitor was prepared using the obtained (meth)acrylic resin.

[0281] Example 9 A (meth)acrylic resin was obtained in the same manner as in Example 6, except that 2-((acryloyloxy)methyl)-2-ethylpropane-1,3-dyl bis(3,4-dihydroxybenzoate) (0.02 mol) obtained in Example 4 was used instead of 3-(methacryloyloxy)propane-1,2-dyl bis(3,4-dihydroxybenzoate) (0.02 mol) obtained in Example 1. A rust inhibitor was also prepared using the obtained (meth)acrylic resin.

[0282] Comparative Example 1 A (meth)acrylic resin was obtained in the same manner as in Example 6, except that 2-hydroxyethyl methacrylate (HEMA) (0.04 mol) was used instead of the 3-(methacryloyloxy)propane-1,2-dyl bis(3,4-dihydroxybenzoate) (0.02 mol) obtained in Synthesis Example 1. A rust inhibitor was also prepared using the obtained (meth)acrylic resin.

[0283] Comparative Example 2 Instead of the 3-(methacryloyloxy)propane-1,2-dyl bis(3,4-dihydroxybenzoate) (0.02 mol) obtained in Synthesis Example 1, 10-(methacryloyloxy)decyl 3,4-dihydroxybenzoate (0.04 mol) (compound represented by the following formula (46)) synthesized according to Synthesis Example 2 described in JP 2021-155537 A was used, except that a (meth)acrylic resin was obtained in the same manner as in Example 6. In addition, a rust inhibitor was prepared using the obtained (meth)acrylic resin. [ka]

[0284] Comparative Example 3 Instead of the 3-(methacryloyloxy)propane-1,2-dyl bis(3,4-dihydroxybenzoate) (0.02 mol) obtained in Synthesis Example 1, 10-(methacryloyloxy)decyl 3,4,5-trihydroxybenzoate (0.04 mol) (compound represented by the following formula (47)) synthesized according to Synthesis Example 1 described in JP 2021-155537 A was used, except that a (meth)acrylic resin was obtained in the same manner as in Example 6. In addition, a rust inhibitor was prepared using the obtained (meth)acrylic resin. [ka]

[0285] <Evaluation> (1) Preparation of test specimens The rust inhibitors (solid content concentration: 40% by mass) obtained in each Example and Comparative Example were applied to steel plates and copper plates using a bar coater No. 14. The resulting coating films were then left to stand at room temperature for 20 minutes, and then further left to stand at 120°C for 20 minutes. This yielded test pieces with dried coating films of the rust inhibitor.

[0286] (2) Water resistance The test pieces were left to stand in water at 40°C for 24 hours, and the appearance was observed. The water resistance was evaluated based on the following criteria. The results are shown in Table 1. {standard} ◎: No change in the appearance of the coating film. ○: Partial whitening was observed in the appearance of the coating film. The whitened area was less than 50%. △: Whitening was observed over the entire surface of the coating film, with the whitened area being 50% or more. ×: A change in appearance not corresponding to any of the above was observed.

[0287] (3) Adhesion Adhesion was evaluated by the cross-cut method in accordance with JIS K 5600-5-6 (1999) "General test methods for paints - Part 5: Mechanical properties of coating films - Section 6: Adhesion (cross-cut method)."

[0288] Specifically, the coating film of the above test specimen was cross-cut into a 1 x 1 mm grid (100 squares) using a utility knife. Next, 24 mm wide adhesive tape (manufactured by Nichiban) was attached to the grid and pressed so that the dried coating film was visible through the grid. The adhesive tape was then peeled off at an angle of 60° to the coating film in 0.5 seconds, and the number of remaining squares was counted to evaluate adhesion. Adhesion was evaluated based on the following criteria. The results are shown in Table 1. {standard} ⊚: The edges of the cuts were completely smooth, and no peeling of the coating was observed on any of the grid holes. ○: Peeling of the coating was observed along the edges of the cuts and / or at the intersections. The percentage of cross-cut areas where peeling was observed was less than 15% of the total. Δ: Peeling of the coating was observed along the edges of the cuts and / or at the intersections. The percentage of cross-cut areas where peeling was observed was 15% or more but less than 35% of the total. ×: Peeling that does not fall into any of the above categories was observed.

[0289] (4) Rust prevention The test pieces were left to stand in water at 40°C for 168 hours. After that, the degree of rust formation was evaluated by visual observation. The rust prevention properties were evaluated based on the following criteria. The results are shown in Table 1. {standard} 5: No rust occurred on the coating. 4: Rust was partially formed on the edge of the cut. The proportion of the cut edge on which rust was formed was less than 40%. 3: Rust was partially formed on the edge of the cut. The percentage of the edge of the cut where rust was formed was 40% or more but less than 80%. 2: Rust has partially occurred on the edges of the cuts and the grid. 1: Rust has occurred all over the cut edges and grid.

[0290] (5) Weight average molecular weight <Weight average molecular weight and weight average molecular weight / number average molecular weight> The (meth)acrylic resins of each Example and Comparative Example were measured for weight average molecular weight (Mw) and weight average molecular weight / number average molecular weight (Mw / Mn) in terms of standard polystyrene by GPC under the following measurement conditions. The results are shown in Table 1. Detector: RI-71S Column: GPC-101 manufactured by Showa Denko K.K. Mobile phase: THF (tetrahydrofuran) Column temperature: 40℃ Flow rate: 1.0ml / min Sample concentration: 50mg / 10mL Injection volume: 450μL

[0291] [Table 1]

[0292] The above invention is provided as an exemplary embodiment of the present invention, but it is merely an example and should not be interpreted as being limiting. Modifications of the present invention that are obvious to those skilled in the art are intended to be included in the scope of the following claims. [Industrial Applicability]

[0293] The compound of the present invention is preferably used, for example, as a rust inhibitor, and is preferably used in adhesives and coating agents.

Claims

1. A compound represented by the following formula (1): 【Chemical 1】 (In the above formula (1), R １ represents a hydrogen atom, a methyl group, an ethyl group, a methacryloyloxymethyl group, or an acryloyloxymethyl group. ２ represents a hydrogen atom or a methyl group. ３ represents a hydrogen atom or a hydroxyl group. n represents 0 or 1. m represents an integer of 0 or more and 4 or less, except when both m and n are 0.

2. R １ The compound according to claim 1 , wherein represents a hydrogen atom, a methyl group, or an ethyl group.

3. n represents 0 and m represents 1, or n represents 0 and m represents 4, or 2. The compound according to claim 1, wherein n is 1 and m is 1.

4. R １ represents a hydrogen atom, and R ２ represents a methyl group, and R ３ The compound according to claim 1 , wherein represents a hydrogen atom, n represents 0, and m represents 1.

5. R １ represents a hydrogen atom, and R ２ represents a methyl group, and R ３ The compound according to claim 1 , wherein represents a hydroxyl group, n represents 0, and m represents 1.

6. R １ represents a hydrogen atom, and R ２ represents a methyl group, and R ３ The compound according to claim 1 , wherein represents a hydrogen atom, n represents 0, and m represents 4.

7. R １ represents a methyl group, and R ２ represents a hydrogen atom, and R ３ The compound according to claim 1 , wherein: represents a hydroxyl group; n represents 1; and m represents 1.

8. R １ represents an ethyl group, and R ２ represents a hydrogen atom, and R ３ The compound according to claim 1 , wherein represents a hydrogen atom, n represents 1, and m represents 1.

9. A polymer obtained by polymerizing a polymerization component containing the compound according to any one of claims 1 to 8.

10. A polymer of a polymerization component comprising the compound according to any one of claims 1 to 8, and / or a composition comprising said polymerization component.

11. A rust inhibitor comprising the composition of claim 10.

12. An adhesive comprising the composition of claim 10.

13. A coating agent comprising the composition of claim 10.

14. A compound represented by the following formula (2): 【Chemistry 2】 (In the above formula (2), R 1 represents a hydrogen atom, a methyl group, an ethyl group, a methacryloyloxymethyl group, or an acryloyloxymethyl group. R 2 represents a hydrogen atom or a methyl group. n represents 0 or 1. m represents an integer of 0 or more and 4 or less, except when both m and n are 0. R ４ and R ５ represents a protecting group for a hydroxyl group. ４ and R ５ are taken together to form a 5-membered ring, and the ring may be substituted with alkyl having 1 to 6 carbon atoms or alkoxy having 1 to 6 carbon atoms. ８ represents a protecting group for a hydrogen atom or a hydroxyl group.)

15. R １ The compound according to claim 14, wherein represents a hydrogen atom, a methyl group, or an ethyl group.

16. n represents 0 and m represents 1, or n represents 0 and m represents 4, or 15. The compound of claim 14, wherein n represents 1 and m represents 1.

17. The compound according to claim 14, represented by the following formula (2-1): 【Chemistry 3】

18. The compound according to claim 14, represented by the following formula (2-2): 【Chemistry 4】

19. The compound according to claim 14, represented by the following formula (2-3): 【Chemistry 5】

20. The compound according to claim 14, represented by the following formula (2-4): 【Chemistry 6】

21. The compound according to claim 14, represented by the following formula (2-5): 【Chemistry 7】

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