Vinyl compounds and their cured products

Abstract

The present invention provides a vinyl compound that can be obtained from biomass, has good performance in various aspects, and can be rapidly cured by radical reactions. [Solution] A vinyl compound represented by the following formula (I). JPEG2026165481000026.jpg3142 In equation (I), at least one of R1 to R4 is a group represented by the following equation (II). JPEG2026165481000027.jpg2468 In formula (II), R5 and R6 are either or both hydrogen atoms, R8 is a specific bond or a single bond, and R8 is bonded to the cyclobutane ring of formula (I).

Description

[Technical Field]

[0001] This invention relates to vinyl compounds and cured products thereof. [Background technology]

[0002] Because petroleum is a finite resource and contributes to global environmental problems such as carbon dioxide emissions, the use of alternative resources has been increasingly sought in recent years. Biomass is attracting attention as an alternative to petroleum. Polylactic acid and polyhydroxybutyric acid are commercially available resins made from biomass, and production is increasing, particularly in response to growing demand in the EU.

[0003] In recent years, the production of valuable substances using microorganisms has also been explored. For example, it is known that compounds with a hydroxycinnamic acid structure, such as p-coumaric acid, can be synthesized from biomass-derived compounds such as L-tyrosine using microorganisms. Generally, microbial reactions are highly efficient and can be carried out in mild environments.

[0004] Compounds that can be synthesized by microorganisms are also being considered for use in resin production. For example, Patent Document 1 discloses that an epoxy resin is synthesized by reacting p-hydroxycinnamic acid with epichlorohydrin, and that the resulting epoxy resin has a high glass transition temperature and excellent mechanical strength when cured with a curing agent together with glycidyl furfuryl ether. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] China Public Gazette No. 112409298 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, compounds obtained from biomass generally have inferior performance compared to polymers derived from petrochemicals, often exhibiting insufficient heat resistance and strength. Furthermore, while the epoxy resin described in Patent Document 1 is disclosed to have excellent heat resistance and strength in its cured form, it requires prolonged heating with a curing agent to cure. Therefore, there is a need for a biomass-derived resin that offers high heat resistance and strength while also being able to cure rapidly.

[0007] Therefore, the object of the present invention is to provide a vinyl compound that can be obtained from biomass, yet has good performance in various aspects such as heat resistance, strength, and adhesive strength, and can be rapidly cured by radical reaction. [Means for solving the problem]

[0008] As a result of diligent research, the inventors have found that the above problems can be solved by a vinyl compound having a cyclobutane structure obtained by dimerizing a cinnamic acid structure, for example, that can be obtained from biomass, and a specific carbon-carbon double bond structure, and have completed the present invention. The present invention provides the following [1] to

[14] . [1] A vinyl compound represented by the following formula (I). [ka] (In formula (I), R1 to R4 are each organic groups having 1 to 30 carbon atoms, which may each independently contain a hydrogen atom or a heteroatom, and at least one of R1 to R4 is the group shown in formula (II) below. However, if one of R1 to R4 is the group shown in formula (II), the remaining three are not simultaneously COOH groups.) [ka] (In formula (II), R5 and R6 may each independently contain a hydrogen atom, a halogen atom, or a heteroatom, and the bond position is not an aromatic ring; one or both of R5 and R6 are hydrogen atoms.) R7 is a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 10 carbon atoms which may contain a heteroatom, R8 is -O-, -S-, -OCO-, or -NR9- (R9 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms which may contain a heteroatom), or a single bond, and is bonded to the group represented by formula (III) or bonded to the cyclobutane ring of formula (I).)

Chemical Formula

[10] The vinyl compound according to any of [1] to [9] above, wherein R2 and R4 in formula (I) are the group shown in formula (II) which is bonded to the group shown in formula (III) and R8 is -O-.

[11] The vinyl compound according to any of [1] to

[10] above, wherein R1 and R3 in formula (I) are the group represented by formula (II) in which R8 is -OCO- and bonded to a cyclobutane ring.

[12] R1 and R3 in equation (I) are -COOR A It is a group represented by R A A vinyl compound according to any one of the above [1] to

[11] , wherein is a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a heteroatom.

[13] The vinyl compound according to any of [1] to

[12] above, wherein at least one of R1 to R4 is a group represented by formula (II) and R8 is a group bonded to formula (III), and the other groups either do not contain a cyclic structure or contain only one cyclic structure.

[14] A cured body obtained by curing any of the vinyl compounds described in [1] to

[13] above. [Effects of the Invention]

[0009] The present invention provides a vinyl compound that can be obtained from biomass, yet exhibits good performance in terms of heat resistance, strength, and adhesive strength, and is capable of rapid curing by radical reaction. [Brief explanation of the drawing]

[0010] [Figure 1] The 1H-NMR spectrum of the epoxy resin from Production Example 1, which is a reaction intermediate in Example 1, is shown. [Figure 2] The 1H-NMR spectrum of the vinyl compound (epoxy acrylate) produced in Example 1 is shown. [Figure 3] The GPC chromatograms of the vinyl compound produced in Example 1 and the epoxy resin of Production Example 1, which is a reaction intermediate in Example 1, are shown. [Figure 4] The 1H-NMR spectrum of the epoxy resin, which is a reaction intermediate in Example 3, is shown. [Figure 5] The 1H-NMR spectrum of the vinyl compound (epoxy acrylate) produced in Example 3 is shown. [Figure 6] The GPC chromatograms of the vinyl compound produced in Example 3 and the epoxy resin, which is a reaction intermediate in Example 3, are shown. [Modes for carrying out the invention]

[0011] <Vinyl compounds> The present invention will be described in more detail below using embodiments. The vinyl compound of the present invention is represented by the following formula (I). The vinyl compound represented by the following formula (I) is a compound that can be obtained from biomass, yet it has good performance in terms of heat resistance, strength, adhesive strength, etc., and can be rapidly cured by radical reaction.

[0012] [ka] (In formula (I), R1 to R4 are each organic groups having 1 to 30 carbon atoms, which may each independently contain a hydrogen atom or a heteroatom, and at least one of R1 to R4 is the group shown in formula (II) below. However, if one of R1 to R4 is the group shown in formula (II), the remaining three are not simultaneously COOH groups.)

[0013] [ka] (In formula (II), R5 and R6 may each independently contain a hydrogen atom, a halogen atom, or a heteroatom, and the bond position is not an aromatic ring; one or both of R5 and R6 are hydrogen atoms.) R7 is a monovalent organic group having 1 to 10 carbon atoms, which may contain a hydrogen atom, a halogen atom, or a heteroatom. R8 is -O-, -S-, -OCO-, or -NR9- (where R9 represents an organic group having 1 to 10 carbon atoms, which may contain a hydrogen atom or a heteroatom), or a single bond, which is bonded to the group shown in formula (III) or to the cyclobutane ring of formula (I).

[0014] [ka] (In formula (III), R 10 ~R 14 Each of these is independently a single bond attached to the cyclobutane ring of formula (I), or a group consisting of a hydrogen atom, a halogen atom, a heteroatom and hydrogen, or an organic group having 1 to 20 carbon atoms which may contain a heteroatom, and * indicates a bond to R8 in formula (II), and R 10 ~R 14 One of these is bonded to the cyclobutane ring of formula (I).

[0015] In formula (II) above, R5 and R6 are monovalent organic groups having 1 to 10 carbon atoms, each independently containing a hydrogen atom, a halogen atom, or a heteroatom. Here, a monovalent organic group having 1 to 10 carbon atoms is one in which the bonded position is not an aromatic ring. That is, R5 and R6 do not have an aromatic ring at a position directly bonded to the carbon atom constituting the carbon-carbon double bond shown in formula (II). By not having an aromatic ring at the bonded position, R5 and R6 can prevent the formation of a conjugated structure with the carbon-carbon double bond in formula (II). Furthermore, either or both of R5 and R6 are hydrogen atoms. The vinyl compound of the present invention can be rapidly cured by radical polymerization because formula (II) has the above structure.

[0016] In formula (II) above, R7 is a monovalent organic group having 1 to 10 carbon atoms, which may contain a hydrogen atom, a halogen atom, or a heteroatom, and R8 is -O-, -S-, -OCO-, -NR9-, or a single bond, which is bonded to the group shown in formula (III) or to the cyclobutane ring of formula (I). In -NR9-, R9 represents an organic group having 1 to 10 carbon atoms, which may contain a hydrogen atom or a heteroatom.

[0017] R 5、 Examples of halogen atoms in R6 and R7 include fluorine, chlorine, bromine, and iodine. R 5、 Examples of monovalent C1-C10 organic groups that may contain heteroatoms in R6, R7, and R9 include hydrocarbon groups that may have heteroatoms. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group having an aromatic ring. The aliphatic hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of heteroatoms include nitrogen atoms, sulfur atoms, oxygen atoms, halogen atoms, and phosphorus atoms. There are no particular limitations on heteroatoms, but examples include oxygen atoms that constitute ether bonds, ester bonds, keto groups, alkoxy groups, nitro groups, carboxyl groups, etc., sulfur atoms that constitute sulfonyl groups, thiol bonds, etc., nitrogen atoms that constitute nitro groups, cyano groups, etc., and halogen atoms that substitute for hydrogen atoms in hydrocarbon groups. The heteroatom may be in the middle of the hydrocarbon chain or at the end. R 5、 If R6, R7, and R9 have heteroatoms, they are preferably saturated hydrocarbon groups having an oxygen atom, such as ether bonds, ester bonds, keto groups, alkoxy groups, or carboxyl groups. R 5、 When R6, R7, and R9 are organic groups, the number of carbon atoms in each of them is preferably 1 to 6, more preferably 1 to 3, even more preferably 1 to 2, and even more preferably 1.

[0018] R 5、R6 and R7 are preferably, among the above, independently a hydrogen atom or an alkyl group. The alkyl group may be linear, branched, or cyclic. Specific alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups. "Various" refers to various isomers including linear (n-), sec-, tert-, iso-, etc., and the same applies hereafter. In addition, alkyl groups may also have cyclic structures such as cyclohexyl groups. R 5、 Among the above, R6 is more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and even more preferably a hydrogen atom or a methyl group (-CH3 group). From the viewpoint of improving curability, it is even more preferable that both R5 and R6 are hydrogen atoms. Furthermore, among the above, R7 is more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and even more preferably a hydrogen atom or a methyl group (-CH3 group). In particular, it is especially preferable that both R5 and R6 are hydrogen atoms, and R7 is either a hydrogen atom or a methyl group. Similarly, R9 is preferably a hydrogen atom or an alkyl group, and for details, see R 5、 As stated in R6 and R7.

[0019] Furthermore, among the above, R8 is preferably -O- or -OCO-. In the case of -O-, it is preferably bonded to the group shown in formula (III), and in the case of -OCO-, it is preferably bonded to the cyclobutane ring of formula (I). That is, in formula (I), it is preferable that at least one of R1 to R4 is the group shown in formula (II) which is bonded to the group shown in formula (III) when R8 is -O-. Also, in formula (I), it is preferable that at least one of R1 to R4 is the group which is bonded to the cyclobutane ring of formula (I) when R8 is -OCO-. When -OCO- is bonded to the cyclobutane ring of formula (I), it is preferable that the C (carbon atom) of -OCO- is bonded to the cyclobutane ring and the O (oxygen atom) is bonded to the group shown in formula (II), and the same applies to the -OCO- in R8 described below. When cinnamic acids are dimerized to obtain a cyclobutane structure, the cyclobutane structure readily has carboxyl groups at the R1 and R3 positions in formula (I), making it easy to introduce -OCO- groups to the cyclobutane ring. Furthermore, since many cinnamic acids have a structure in which a hydroxyl group is bonded to a benzene ring, it is easy to introduce oxygen atoms (-O-) to the group shown in formula (III).

[0020] R in equation (III) 10 ~R 14 Examples of halogen atoms in R include fluorine, chlorine, bromine, and iodine. 10 ~R 14 Examples of groups consisting of a heteroatom and hydrogen include hydroxyl groups (-OH), thiol groups (-SH), and amino groups (-NH2), and among these, hydroxyl groups are preferred. R 10 ~R 14 The C1-C20 organic groups that may have heteroatoms in the above are specifically hydrocarbon groups that may have heteroatoms. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group having an aromatic ring. The aliphatic hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further details of the heteroatoms are described in the above-mentioned R 5、As explained in R6, R7, and R9. R 10 ~R 14 The C1-C20 organic group in which a heteroatom may be present may be the group shown in formula (II) above. That is, the benzene ring shown in formula (III) may have two or more substituents shown in formula (II). However, the benzene ring shown in formula (III) preferably has one to three substituents shown in formula (II), more preferably one to two, and even more preferably one substituent shown in formula (II). R other than the group shown in formula (II) 10 ~R 14 The number of carbon atoms in each organic group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3, independently of each other.

[0021] R other than the single bond attached to the cyclobutane ring in formula (I) 10 ~R 14 Each of these is preferably independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, a hydrocarbon group, or a group shown in formula (II). Furthermore, an alkyl group is preferred as the hydrocarbon group. Examples of alkoxy groups include alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy groups. Among these, the methoxy group is preferred. Furthermore, alkyl groups are preferred as hydrocarbon groups. Details of alkyl groups are shown in R 5、 As explained in R6 and R7. 10 ~R 14 The alkyl group is preferably one to ten carbon atoms, more preferably one to six carbon atoms, even more preferably one to three carbon atoms, and most preferably a methyl group.

[0022] R other than the single bond attached to the cyclobutane ring in formula (I) 10 ~R 14Each of these is more preferably a hydrogen atom, a hydroxyl group, an alkoxy group, or an alkyl group, with a hydrogen atom or an alkoxy group being even more preferred, and a hydrogen atom or a methoxy group (-OCH3 group) being even more preferred. On the other hand, in formula (III), the single bond attached to the cyclobutane ring of formula (I) is R of formula (III). 10 ~R 14 Either is acceptable, but it is preferable that the bond to R8 is at the para or meta position (*), and more preferably at the para position. That is, in formula (III), the single bond attached to the cyclobutane ring of formula (I) is R 11 ~R 13 It is preferable that it be one of the following, R 12 It is preferable that it be so.

[0023] On the other hand, R 10 ~R 14 The alkoxy group in this compound is preferably in the para or meta position relative to the single bond attached to the cyclobutane ring, and more preferably in the meta position. Therefore, the group shown in equation (III) is R 11 ~R 13 Either (preferably R) 12 ) is a single bond that connects to the cyclobutane ring, and R is located adjacent to the single bond that connects to the cyclobutane ring. 10 ~R 14 These are all hydrogen atoms, and the other R 10 ~R 14 However, it is more preferable that it be either a hydrogen atom or an alkoxy group.

[0024] R other than the group bonded to the cyclobutane ring shown in formula (I) 10 ~R 14 Preferably, 0 to 2 of these are alkoxy groups, more preferably 0 to 1 are alkoxy groups, and even more preferably 0 are alkoxy groups. Furthermore, R other than the group that binds to the cyclobutane ring shown in formula (I) 10 ~R 14It is preferable that 1 to 4 of them are hydrogen atoms, and more preferably that 2 to 4 are hydrogen atoms. In this case, R 12 It is a single bond attached to the cyclobutane ring, and R in formula (III) 11 and R 13 It is preferable that all of them are hydrogen atoms. Also, R other than the group bonded to the cyclobutane ring shown in formula (I) 10 ~R 14 It is even more preferable that 3 to 4 of them are hydrogen atoms, R 10 ~R 14 It is even more preferable that all the groups other than the group bonded to the cyclobutane ring shown in formula (I) are hydrogen atoms. Therefore, as described above, R 12 It is a single bond attached to the cyclobutane ring, and R in formula (III) 10 , R 11 , R 13 , R 14 It is particularly preferable that all of them are hydrogen atoms.

[0025] The C1 to C30 organic groups in R1 to R4 of formula (I), which may have heteroatoms, may each be independently a group represented by formula (II) or an organic group other than the group represented by formula (II). Specifically, an organic group other than the group represented by formula (II) is a hydrocarbon group which may have heteroatoms. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group which has an aromatic ring. The aliphatic hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Furthermore, details of the heteroatoms are as described above in R 5、 As explained in R6, R7, and R9.

[0026] The organic groups in R1 to R4, other than the group represented by formula (II), preferably have 1 to 10 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3 carbon atoms. In R1 to R4, the organic groups other than the group shown in formula (II) are each independently -COOR AThe group is preferably represented by , a carboxyl group (-COOH), or a monovalent hydrocarbon group. Here, the monovalent hydrocarbon group is preferably an aromatic hydrocarbon group. When the organic group other than the group represented by formula (II) in R1 to R4 is an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably the group represented by the following formula (I-1). When cinnamic acids are dimerized to obtain a cyclobutane structure, phenyl groups are introduced at the positions of R2 and R4 in formula (I), so vinyl compounds having the group represented by the following formula (I-1) can be easily produced from biomass.

[0027] [ka] (In formula (I-1), R 15 ~R 19 Each of these is independently a hydrogen atom, a halogen atom, a group consisting of a heteroatom and hydrogen, or an organic group having 1 to 20 carbon atoms that may contain a heteroatom, and * indicates a bond to the cyclobutane ring.

[0028] In equation (I-1), R 15 ~R 19 Examples of halogen atoms in R include fluorine, chlorine, bromine, and iodine. 15 ~R 19 The groups consisting of a heteroatom and hydrogen in this context include hydroxyl groups, thiol groups (-SH), and amino groups (-NH2), with the hydroxyl group being preferred among these. R 15 ~R 19 The C1-C20 organic groups that may have heteroatoms include hydrocarbon groups that may have heteroatoms. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group having an aromatic ring. The aliphatic hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further details of the heteroatoms are described in R above. 5、 As explained in R6, R7, and R9. R 15 ~R 19The number of carbon atoms of the aforementioned organic group in is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 3, and most preferably 1. R 15 to R 19 Preferable specific examples of the organic group in are an alkoxy group or a hydrocarbon group.

[0029] Among those described above, R 15 to R 19 each independently is preferably any one of a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, a -OCOR B group (R B is a hydrocarbon group) or a hydrocarbon group. Further, R 15 to R 19 As for the hydrocarbon group in and R in the -OCOR B group, each independently is preferably an alkyl group. Here, the details of the alkoxy group and the alkyl group are as described for R B to R 10 to R 14 , and the preferred examples thereof are also the same. R 15 to R 19 each independently is more preferably any one of a hydrogen atom, a hydroxyl group, a -OCOR B group, an alkoxy group, or an alkyl group, among them a hydrogen atom or an alkoxy group is still more preferable, and a hydrogen atom or a methoxy group is even more preferable. Note that OCO in the -OCOR B group is preferably such that the carbon atom is bonded to R B and the oxygen atom is bonded to the benzene ring represented by formula (I-1).

[0030] R 15 to R 19 preferably are all hydrogen atoms, or at least one is an alkoxy group. When at least one is an alkoxy group, it is more preferable that 1 to 3 of R 15 to R 19 are alkoxy groups, it is still more preferable that 1 to 3 of R 16 to R 18 are alkoxy groups, and it is further preferable that 1 to 3 of R 16 to R 18It is even more preferable that one of them is an alkoxy group. Also, if at least one is an alkoxy group, then at least R 17 It is preferable that the group is an alkoxy group.

[0031] -COOR in R1~R4 A In R A This is a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may contain heteroatoms. The hydrocarbon group which may contain heteroatoms may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group having an aromatic ring. The aliphatic hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. For details on the heteroatoms, see R above. 5、 As explained in R6, R7, and R9. R A The number of carbon atoms in the hydrocarbon group which may have heteroatoms is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, and most preferably 1. Hydrocarbon groups that may have heteroatoms are preferably aromatic hydrocarbon groups and saturated hydrocarbon groups, more preferably aryl groups such as phenyl groups, alkyl-substituted aryl groups such as methylphenyl groups and ethylphenyl groups, aralkyl groups such as benzyl groups and phenethyl groups, and alkyl groups, and even more preferably alkyl groups. Details of alkyl groups are shown in R 10 ~R 14 As explained in [the relevant section], and similarly, a suitable example is also provided. Therefore, R A The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms, and most preferably a methyl group.

[0032] Furthermore, in the vinyl compound of the present invention, if at least one of R1 to R4 is a group represented by formula (II) and R8 is a group bonded to formula (III), it is preferable that the groups other than the group represented by formula (II) and the group R8 is bonded to formula (III) either do not contain a cyclic structure or contain only one cyclic structure.

[0033] In the vinyl compound of the present invention, it is preferable that at least two of R1 to R4 in formula (I) are groups represented by formula (II). In the vinyl compound of the present invention, having at least two of R1 to R4 as groups represented by formula (II) allows for the formation of a crosslinked structure during curing, which makes it easier to improve the strength, adhesion, heat resistance, etc. of the cured product. When at least two of R1 to R4 are groups represented by formula (II), it is good if 2 to 4 of R1 to R4 are groups represented by formula (II), and from the viewpoint of further increasing strength, adhesion, and heat resistance, it is more preferable that all of R1 to R4 are groups represented by formula (II).

[0034] In formula (I), if at least two of R1 to R4 are groups represented by formula (II), it is preferable that at least two of R1 to R4 (particularly preferably R1 and R3) are groups represented by formula (II) in which R8 is bonded to a cyclobutane ring, and more preferably that R8 is a group represented by formula (II) that is -OCO- and bonded to a cyclobutane ring. Furthermore, if at least two of R1 to R4 are groups represented by formula (II), it is preferable that at least two of R1 to R4 (particularly R2 and R4) are groups represented by formula (II) to which R8 is bonded to a group represented by formula (III), and it is more preferable that R8 is -O- and a group represented by formula (II) to which is bonded to a group represented by formula (III). In particular, it is even more preferable that in formula (I), R1 and R3 are groups represented by formula (II) in which R8 is bonded to a cyclobutane ring, and R2 and R4 are groups represented by formula (II) in which R8 is bonded to a group represented by formula (III). In particular, it is preferable that R1 and R3 are groups represented by formula (II) in which R8 is -OCO- and bonded to a cyclobutane ring, and R2 and R4 are groups represented by formula (II) in which R8 is -O- and bonded to a group represented by formula (III). The vinyl compound shown in formula (I) above is readily synthesizable from biomass and is therefore suitable.

[0035] In another embodiment, R1 and R3 are each independently -COORA It is also preferable that the group or hydrogen atom is represented by -COOR, and in particular, both R1 and R3 are -COOR A It is more preferable that the group is represented by . In this case, from the viewpoint of improving the strength, adhesion, heat resistance, etc. of the cured product, it is preferable that both R2 and R4 are groups represented by formula (II), and in particular from the viewpoint of being easily synthesized from biomass, it is more preferable that both R2 and R4 are groups represented by formula (II) in which R8 is bonded to a group represented by formula (III), and it is even more preferable that R8 is -O- and is bonded to a group represented by formula (II).

[0036] Preferred specific examples of vinyl compounds include the compound shown in the following formula (1a), and among these, the compound shown in the following formula (1a-1) is more preferred. [ka]

[0037] In the group represented by X above (hereinafter referred to as the "X group"), R is a hydrogen atom or a methyl group, and * indicates the bond position. In one embodiment of formula (1a), R 30 ~R 32 One of them is an X group, and the rest are independently a hydrogen atom or an alkoxy group, and R 33 ~R 35 One of them is an X group, and the rest are independently a hydrogen atom or an alkoxy group. However, R 30 ~R 32 All of the rest and R 33 ~R 35 The remaining atoms are preferably all hydrogen atoms. Furthermore, the alkoxy group is preferably a methoxy group. In another embodiment of equation (1a), R 30 ~R 35 Each of these is independently a hydrogen atom or an alkoxy group, but among them R 30 ~R 35 It is more preferable that all of them are hydrogen atoms. In another embodiment, it is preferable that the alkoxy group is a methoxy group.

[0038] [ka] In equation (1a-1), X is as described above, and R 30 , R 32 Each is independently a hydrogen atom or an alkoxy group, and R 33 , R 35 Each is independently a hydrogen atom or an alkoxy group, but in this case, R 32 and R 35 They are identical and R 30 and R 33 It is preferable that they are the same. Also, R 30 , R 32 , R 33 , R 35 It is more preferable that all of them are hydrogen atoms. In formula (1a-1), the alkoxy group is preferably a methoxy group.

[0039] Another preferred example of a vinyl compound is the compound shown in formula (1b) below, and among these, the compound shown in formula (1b-1) below is preferred. [ka] In equation (1b), R A As stated above. Also, R 30 ~R 32 One of them is an X group, and the rest are independently a hydrogen atom or an alkoxy group, and R 33 ~R 35 One of them is an X group, and the rest are independently a hydrogen atom or an alkoxy group. However, R 30 ~R 32 All of the rest and R 33 ~R 35 The remaining atoms are preferably all hydrogen atoms. Furthermore, the alkoxy group is preferably a methoxy group.

[0040] [ka] In equation (1b-1), X and R A As stated above, R 30 , R 32 Each is independently a hydrogen atom or an alkoxy group, and R 33 , R 35 Each of these is independently a hydrogen atom or an alkoxy group. In this case, R 32 and R 35 They are identical, R 30 and R 33 It is preferable that they are the same. Also, R 30 , R 32 , R 33 , R 35 It is more preferable that all of them are hydrogen atoms. In formula (1b-1), the alkoxy group is preferably a methoxy group.

[0041] Another specific example of a vinyl compound is the compound shown in formula (1c) below, and among these, the compound shown in formula (1c-1) below is preferred. [ka] In equation (1c), R 30 ~R 32 One of them is an X group, and the rest are independently a hydrogen atom or an alkoxy group, and R 33 ~R 35 One of them is an X group, and the rest are independently a hydrogen atom or an alkoxy group. However, R 30 ~R 32 All of the rest and R 33 ~R 35 The remaining atoms are preferably all hydrogen atoms. Furthermore, the alkoxy group is preferably a methoxy group.

[0042] [ka] In equation (1c-1), X is as described above, and R 30 , R 32 Each is independently a hydrogen atom or an alkoxy group, and R 33 , R 35Each of these is independently a hydrogen atom or an alkoxy group. In this case, R 32 and R 35 They are identical, R 30 and R 33 It is preferable that they are the same. Also, R 30 , R 32 , R 33 , R 35 It is more preferable that all of them are hydrogen atoms. In formula (1c-1), the alkoxy group is preferably a methoxy group.

[0043] <Method for producing vinyl compounds> The present invention provides a method for producing vinyl compounds by reacting a compound having a cyclobutane ring (cyclobutane compound) with a compound containing an epoxy group (epoxy group-containing compound) to obtain a reaction intermediate having an epoxy group and a cyclobutane ring. This intermediate is then reacted with a polymerizable double bond-containing compound, as described later, to synthesize the compound. By utilizing the above reaction, the group shown in formula (II) can be easily introduced, simplifying the synthesis of the vinyl compound shown in formula (I).

[0044] (Cyclobutane compounds) The above cyclobutane compound is not particularly limited as long as it is a compound that can be used as a raw material for the vinyl compound shown in formula (I), but dimerized cinnamic acids are preferred. By using dimerized cinnamic acids as the cyclobutane compound, R1 and R3 can be easily made into carboxylic acids or structures derived from carboxylic acids, and R2 and R4 can be made into groups having the group shown in formula (III) or formula (I-1). Preferably, the cyclobutane compound has the structure of formula (V) below. [ka]

[0045] (In equation (V), R 20 ~R 29Each of these is independently a hydrogen atom, a halogen atom, a group consisting of a heteroatom and hydrogen, or an organic group having 1 to 20 carbon atoms which may contain a heteroatom, and R 30 and R 31 Each is independently a hydrogen atom, a carboxyl group, or -COOR A (R A R is a group represented as above. In equation (V), 20 and R 25 It is preferable that they are the same. 21 and R 26 , R 22 and R 27 , R 23 and R 28 , R 24 and R 29 It is preferable that each of them be identical to the others.

[0046] In equation (V), R 20 ~R 29 Examples of halogen atoms in R include fluorine, chlorine, bromine, and iodine. 20 ~R 29 The groups consisting of a heteroatom and hydrogen in this context include hydroxyl groups, thiol groups (-SH), and amino groups (-NH2), with the hydroxyl group being preferred among these. 20 ~R 29 The C1-C20 organic groups that may have heteroatoms include hydrocarbon groups that may have heteroatoms. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group having an aromatic ring. The aliphatic hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further details of the heteroatoms are described in R above. 5、 As explained in R6, R7, and R9. 20 ~R 29 In this process, by using hydroxyl groups, thiol groups (-SH), amino groups (-NH2), etc., -O-, -S-, -NR9-, etc. can be introduced into R8 through reaction with epoxy group-containing compounds such as epihalohydrins, which will be described later. R 20 ~R 29The number of carbon atoms in the above organic group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 3, and most preferably 1. 20 ~R 29 Preferred examples of the organic group in this context are alkoxy groups or hydrocarbon groups, and more preferably alkoxy groups. The hydrocarbon group is preferably an alkyl group.

[0047] Among the above, R 20 ~R 29 These are, independently, a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, an alkoxy group, and an -OCOR group. B Group (R B It is preferable that the group is either (as described above) or a hydrocarbon group (such as an alkyl group). Here, the details of the alkoxy group and alkyl group are R 10 ~R 14 As explained above, the preferred groups are also as described above. 20 ~R 29 These are, independently, a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group, and an -OCOR group. B It is more preferable that the group be either a group or an alkyl group, and among these, a hydrogen atom, a hydroxyl group, or an alkoxy group is even more preferable, a hydrogen atom, a hydroxyl group, or a methoxy group is even more preferable, and it is even more preferable that the group be either a hydrogen atom or a hydroxyl group.

[0048] R 20 ~R 24 Preferably, at least one of them is a hydroxyl group, R 20 ~R 24 The number of hydroxyl groups in is more preferably 1 to 3, even more preferably 1 or 2, and most preferably 1. 25 ~R 29 The same applies to the latter. Also, R 20 ~R 24 This is at least R 22 It is more preferable that there is a hydroxyl group, R 20 ~R 24 R 22 It is even more preferable that only R has a hydroxyl group. Similarly, 25~R 29 This is at least R 27 It is more preferable that there is a hydroxyl group, R 25 ~R 29 R 27 It is even more preferable that only the hydroxyl group is present.

[0049] In particular, from the perspective of being easily obtainable from biomass-derived raw materials, R 20 , R 24 , R 25 , R 29 is a hydrogen atom, and R 21 ~R 23 One of them is a hydroxyl group, and the rest are independently a hydrogen atom or an alkoxy group, and R 26 ~R 28 Preferably, one of them is a hydroxyl group and the rest are independently hydrogen atoms or alkoxy groups. 20 , R 24 , R 25 , and R 29 Both are hydrogen atoms, R 22 and R 27 is a hydroxyl group, R 21 , R 23 , R 26 and R 28 It is more preferable that each of them is independently a hydrogen atom or an alkoxy group, 22 and R 27 is a hydroxyl group, R 20 , R 21 , R 23 ~R 26 , R 28 , and R 29 It is even more preferable that it be a hydrogen atom.

[0050] R 30 and R 31 Each of these independently consists of a hydrogen atom, a carboxyl group, or a -COOR group. A However, R 30 and R 31 Both are hydrogen atoms, carboxyl groups, or -COOR A It is preferable that R 30 and R 31 It is more preferable that both are carboxyl groups. However, R 30 and R 31 Both are hydrogen atoms, or R 30 and R 31 Both are -COOR A If so, R 20 ~R 29 At least one of them is a group consisting of a heteroatom and hydrogen. Among them, R 20 ~R 24 At least one of the following, and R 25 ~R 29 Preferably, at least one of these groups is a group consisting of a heteroatom and hydrogen, and more preferably a hydroxyl group. The compounds shown in formula (V) may be used individually or in combination of two or more.

[0051] The above cyclobutane compounds can be synthesized by dimerizing cinnamic acids. Cinnamic acids are cinnamic acid or its derivatives, and include compounds having the structure shown in the following formula (VI). [ka] (In equation (VI), R 20 ~R 24 , and R 30 (This is the same as above.)

[0052] Specific examples of cinnamic acids include o-coumaric acid, m-coumaric acid, p-coumaric acid, ferulic acid, sinapic acid, caffeic acid, isoferulic acid, umbellic acid, 3,4,5-trihydroxycinnamic acid, 2,4,5-trihydroxycinnamic acid, cinnamic acid, 4-vinylphenol, and 4-aminocinnamic acid, in which some or all of the hydroxyl groups of these compounds are alkoxylated or esterified (i.e., -OCOR). B (Formed from) or by esterifying some or all of the carboxyl groups of each of these compounds (i.e., -COOR ACompounds such as those derived from (or modified) are also examples. Among these, p-coumaric acid is particularly preferred. These compounds, especially p-coumaric acid, are preferred because biomass-derived compounds are readily available. The compound represented by formula (VI) may be used alone or in combination of two or more.

[0053] The method for dimerizing cinnamic acids is not particularly limited, but one method is dimerization by light irradiation such as ultraviolet irradiation. When cinnamic acids are irradiated with UV light, the double bond at the beta position of the compound shown in formula (VI) is cleaved, and the molecules recombine to dimerize, yielding a cyclobutane compound having the structure shown in formula (V). Furthermore, the alkoxylation or esterification of the hydroxyl group and the esterification of the carboxyl group described above may be performed after dimerization.

[0054] (Epoxy group-containing compound) Epoxy group-containing compounds used in the synthesis of vinyl compounds include epoxy groups and, in the above-mentioned cyclobutane compounds, carboxyl groups or R 20 ~R 29 It is preferable that the compound has a functional group that can react with a reactive group such as a group consisting of a heteroatom and hydrogen (preferably an amino group or a hydroxyl group, more preferably a hydroxyl group). Here, examples of functional groups include groups that can react with a carboxyl group or a group consisting of a heteroatom and hydrogen to form -O-, -S-, -OCO-, -NR9-, or a single bond. Specifically, examples include halogeno groups, tosyl groups, mesyl groups, etc., with halogeno groups being preferred. Examples of halogeno groups include fluoro groups, chloro groups, bromo groups, and iodine groups, with chloro groups being preferred among these. The halogeno group is preferably a group that bonds to a carbon atom.

[0055] A suitable example of an epoxy group-containing compound is an epihalohydrin. Examples of epihalohydrins include epifluorohydrin, epichlorohydrin, epibromohydrin, and epiiodohydrin, among which epichlorohydrin is preferred in terms of reactivity and cost-effectiveness. Furthermore, when using an epihalohydrin, it is preferable that the cyclobutane compound has at least one of a carboxyl group or a hydroxyl group.

[0056] In this manufacturing method, it is preferable to obtain the reaction intermediate by reacting a cyclobutane compound with an epihalohydrin, as described above. In particular, it is preferable to obtain the reaction intermediate by reacting a cyclobutane compound shown in formula (V) and having at least one of a carboxyl group and a hydroxyl group with an epihalohydrin. An example of the reaction formula is as follows. [ka] (Note that in the above reaction equation, Z is a halogeno group, and R 20 , R 21 , R 23 ~R 26 , R 28 , and R 29 (As stated above.)

[0057] When reacting a cyclobutane compound with an epihalohydrin, the amount of epihalohydrin added relative to the cyclobutane compound in the reaction system is not particularly limited, but it is preferable to add at least one equivalent. By adding at least one equivalent of epihalohydrin, epoxy groups can be appropriately introduced into the cyclobutane compound. Furthermore, by introducing epoxy groups into all of the reactive groups of the cyclobutane compound, a reaction intermediate with a desired structure can be synthesized in high yield. Note that equivalent refers to the molar equivalent relative to the reactive groups of the cyclobutane compound (preferably at least one of a hydroxyl group and a carboxyl group, more preferably a hydroxyl group and a carboxyl group), and the same applies hereinafter.

[0058] From the viewpoint of synthesizing a reaction intermediate with a desired structure in higher yield, it is preferable to add a large excess of the epihalohydrin. Specifically, it is preferable to add 2 equivalents or more, more preferably 5 equivalents or more, and even more preferably 8 equivalents or more. Furthermore, from the viewpoint of making it easier to remove unreacted epihalohydrin after the reaction and increasing production efficiency, the amount of epihalohydrin added is preferably 50 equivalents or less, more preferably 30 equivalents or less, even more preferably 20 equivalents or less, and even more preferably 15 equivalents or less. However, the amount of epihalohydrin added may be less than one equivalent, and by using less than one equivalent, a reaction intermediate containing unreacted reactive groups (e.g., hydroxyl groups or carboxyl groups) can be obtained.

[0059] The reaction between cyclobutane compounds and epihalohydrins is preferably carried out in the presence of a catalyst. Examples of catalysts include quaternary ammonium salts such as benzyltriethylammonium chloride, benzyltriethylammonium bromide, tetrabutylammonium fluoride, and tetrabutylammonium bromide. The catalyst may be used alone or in combination of two or more. The amount of catalyst added is preferably 0.01 to 2 moles, more preferably 0.03 to 1 mole, and even more preferably 0.05 to 0.5 moles per mole of cyclobutane compound.

[0060] The above reaction may be carried out in the presence of a solvent or in the absence of a solvent. By using a large excess of epihalohydrin as described above, the cyclobutane compound is appropriately diluted by the epihalohydrin, allowing the reaction to proceed appropriately even in the absence of a solvent or with only a small amount of solvent. Suitable reaction solvents include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ester solvents, and ether solvents. The reaction in the presence of the catalyst is carried out, for example, at 40 to 150°C, preferably 60 to 120°C, for 30 minutes to 24 hours, preferably 2 to 12 hours.

[0061] Furthermore, in this manufacturing method, it is preferable to add a basic compound to the reaction system in addition to the catalyst. Adding a basic compound facilitates the dehalogenation process, making it possible to improve the yield of the target epoxy resin. It is preferable to react the basic compound in the presence of the catalyst for a certain period of time as described above, then add it to the reaction system and allow it to react for a further period of time. The reaction after adding the basic compound is carried out at, for example, 0 to 90°C, preferably 40 to 80°C, for, for example, 10 minutes to 24 hours, preferably 30 minutes to 12 hours.

[0062] The basic compound used is not particularly limited as long as it is a compound that acts as a base. Specifically, examples of metallic bases include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, lithium hydride, sodium hydride, potassium hydride, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, lithium alkoxide, sodium alkoxide, and potassium alkoxide. Among these, it is preferable to use at least one of sodium hydroxide and potassium hydroxide due to economic and availability. The basic compound is not particularly limited, but may be added to the reaction system, for example, as an aqueous solution or an alcohol solution. The amount of the basic compound added is, for example, 0.5 to 10 equivalents, preferably 0.8 to 4 equivalents, relative to the reactive groups of the cyclobutane compound.

[0063] In this manufacturing method, the reaction intermediate may be purified as appropriate. Purification of the reaction intermediate can be carried out by general unit operations such as distillation off the epihalohydrin, distillation off the reaction solvent used as needed, separation of the target reaction intermediate and water-soluble compounds by extraction using water and a hydrophobic solvent, distillation off the extraction solvent, distillation, or a combination of these as appropriate. Furthermore, the reaction intermediate may be recrystallized using known and conventional methods as needed. By improving the purity through recrystallization, unintended side reactions can be suppressed.

[0064] Furthermore, the method for obtaining a reaction intermediate having an epoxy group and a cyclobutane ring is not limited to the above. For example, R 20 ~R 29 At least one of the (preferably R 22 and R 27 A cyclobutane compound having the structure of formula (V), in which R8 is an allyl group, may be used as a starting material. The allyl group of this cyclobutane compound may be oxidized to epoxidize it to obtain a reaction intermediate having an epoxy group and a cyclobutane ring. According to this method, a single bond can also be introduced at R8. In this case, the cyclobutane compound can be synthesized, for example, by dimerizing cinnamic acid, which has an allyl group bonded at the 4-position.

[0065] (Polymerizable double bond-containing compound) The resulting reaction intermediate may be further reacted with a polymerizable double bond-containing compound to obtain the target product, the compound shown in formula (I). Examples of polymerizable double bond-containing compounds include the compound shown in formula (VII) below, or its derivatives. [ka] (In equation (VII), R 5、 R6 and R7 are the same as described above.)

[0066] Examples of compounds represented by formula (VII) include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, 2-ethylacrylic acid, 2-ethylmethacrylic acid, itaconic acid, fumaric acid, maleic acid, and metaconic acid. Among these, acrylic acid and methacrylic acid are preferred from the viewpoint of versatility and the curability of the resulting product. Furthermore, derivatives of the compound shown in formula (VII) include those in which the carboxyl group of the compound shown in formula (VII) has been appropriately modified, such as carboxylate salts or esterified compounds. In addition, if the compound shown in formula (VII) has two carboxyl groups in one molecule, the two carboxyl groups may be anhydrous.

[0067] When reacting a reaction intermediate with a polymerizable double bond-containing compound, the amount of polymerizable double bond-containing compound added to the reaction intermediate in the reaction system is not particularly limited, and may be, for example, about 1 to 10 equivalents, preferably about 1 to 5 equivalents. The reaction between the reaction intermediate and the polymerizable double bond-containing compound is not particularly limited, but it is preferable to carry it out in the presence of a catalyst. Examples of catalysts include known catalysts that promote the reaction between epoxy groups and carboxylic acids or their derivatives. Specifically, examples include quaternary ammonium salts, tertiary amines, and imidazole catalysts, among which quaternary ammonium salts are preferred. Quaternary ammonium salts are as described above. The amount of catalyst added is preferably 0.01 to 2 moles, more preferably 0.05 to 1 mole, and even more preferably 0.1 to 0.5 moles per mole of reaction intermediate. Furthermore, the reaction system may contain a polymerization inhibitor in addition to the catalyst. Examples of polymerization inhibitors include hydroquinones such as hydroquinone monomethyl ether.

[0068] The reaction between the reaction intermediate and the polymerizable double bond-containing compound is preferably carried out in the presence of a solvent. Suitable reaction solvents include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ester solvents, and ether solvents. The reaction is preferably carried out at a temperature of 40 to 150°C, preferably 70 to 120°C, for 30 minutes to 24 hours, preferably 2 to 12 hours, but may also be carried out under reflux.

[0069] The target product (vinyl compound) obtained by the above reaction may be purified as appropriate. Purification of the target product can be carried out by general unit operations such as distillation of the reaction solvent, separation of the target product and water-soluble compounds by extraction using water and a hydrophobic solvent, distillation of the extraction solvent, distillation, or a combination of these as appropriate. Furthermore, the target product may be recrystallized using known and conventional methods as needed. By improving the purity through recrystallization, the quality of the cured product can be improved.

[0070] The method for producing the vinyl compound of the present invention is not limited to the above, and can be produced by various methods. For example, a starting compound having a carbon-carbon double bond and an epoxy group, and a cyclobutane compound having a cyclobutane ring may be prepared, and the vinyl compound may be synthesized by reacting the epoxy group of the starting compound with the reactive group of the cyclobutane compound. The starting compound is preferably a (meth)acrylic acid ester having an epoxy group. Specifically, glycidyl (meth)acrylate is an example.

[0071] In the vinyl compounds of the present invention, instead of the group represented by formula (II) above, the group represented by formula (IV) below may be generated during the manufacturing process. Therefore, in the vinyl compounds of the present invention, some of R1 to R4 may be the group represented by formula (IV) below. That is, in the vinyl compounds of the present invention, at least one of R1 to R4 may be the group represented by formula (II), and at least one of R1 to R4 may be the group represented by formula (IV). Furthermore, if the vinyl compounds of the present invention contain the group represented by formula (IV) below, it is preferable that in each structure of the vinyl compounds described above, some of the group represented by formula (II) be replaced with the group represented by formula (IV).

[0072] [ka] (Note that in equation (IV), R5, R6, R7, and R8 are the same as above.)

[0073] <Cured body> The cured product of the present invention (hereinafter also referred to as the "vinyl cured product") is obtained by curing the vinyl compound described above. The vinyl compound of the present invention can be cured by a radical reaction. Specifically, it is preferable that the carbon-carbon double bond in formula (II) is cleaved, and the vinyl compound is polymerized by bonding with other vinyl compounds, thereby curing. Alternatively, curing may occur when the carbon-carbon double bond represented by formula (II) is cleaved and bonded with a compound other than the vinyl compound of the present invention (hereinafter also referred to as "other polymerizable compounds"). Other polymerizable compounds include, but are not limited to, compounds having polymerizable carbon-carbon double bonds such as vinyl groups, methacryloyl groups, and acryloyl groups. Therefore, the vinyl cured product of the present invention may be obtained by curing a vinyl composition containing the vinyl compound of the present invention, but the vinyl composition may be obtained by curing a vinyl composition containing the vinyl compound of the present invention and other polymerizable compounds. In this specification, "vinyl composition" may refer not only to a composition containing a vinyl compound and components other than a vinyl compound, but also to a composition consisting solely of a vinyl compound.

[0074] The vinyl-based composition of the present invention may be cured in any manner, for example, by irradiation with active energy rays capable of generating radical active species. Examples of active energy rays include ionizing radiation such as ultraviolet rays, electron beams, X-rays, alpha rays, beta rays, and gamma rays. The vinyl-based composition of the present invention may also be cured by heating. Depending on the type of energy ray used for curing, the vinyl composition of the present invention may contain a polymerization initiator as appropriate. For example, if curing is performed by ultraviolet irradiation, a photopolymerization initiator may be included. Examples of photopolymerization initiators include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, benzyl ketal compounds, and thioxanthone compounds. Furthermore, when curing by heat, known radical polymerization initiators may be used. Examples of radical polymerization initiators include peroxides and azo compounds.

[0075] The vinyl-based composition in this invention may be diluted by adding a solvent or the like, and may contain other components as appropriate. When diluted with a solvent, the solvent may be removed by heating during curing, or by heating as appropriate before irradiation with active energy rays, and drying as appropriate.

[0076] The vinyl compounds and cured products of the present invention can be used in a variety of fields, and are not particularly limited, but can be used in any field, such as the electrical, transportation, civil engineering, construction, mechanical, and medical fields. The vinyl compounds and cured products of the present invention can be used in various forms, such as various molded articles, adhesives, paints, fillers, films, powders, composites, and foams. More specifically, it can be used in a variety of applications, including adhesives for dissimilar materials, rubber-resin adhesives, wellbond applications, bonding substrates to semiconductor elements such as die attach, bonding films for flexible substrates, various adhesives for construction and civil engineering applications, various coating applications such as anti-fogging paints, electrodeposition coatings, corrosion-resistant paints, floor coatings, and other coatings for construction and civil engineering applications, sealing materials such as for insulated wires, fiber scrubbers, fiber reinforcement materials such as for prepregs, electrical insulating materials and protective materials for electronic components, photosensitive resins, lens applications, dental materials, and more, but is not limited to these applications.

[0077] A vinyl composition containing the vinyl compound of the present invention can be blended with various components depending on the application. Such components include, in addition to the polymerization initiator and other polymerizable compounds mentioned above, resins or resin precursors other than the vinyl compound of the present invention and other polymerizable compounds, latex, fillers, pigments, silane coupling agents, surfactants, ultraviolet absorbers, antioxidants, stabilizers, plasticizers, leveling agents, defoamers, antistatic agents, flame retardants, lubricants, dispersants, and the like. The following describes in more detail the compositions containing the vinyl compounds of the present invention used for each application (vinyl compositions). However, each of the following compositions may, if necessary, contain components other than those specifically described below.

[0078] (For adhesive use) For example, when used as an adhesive, the vinyl composition may contain the vinyl compound of the present invention, or optionally further contain at least one of a polymerization initiator and other polymerizable compounds. Furthermore, when the vinyl composition is used as an adhesive, in addition to these, the vinyl composition may also contain polymer fine particles as a filler component, for example, from the viewpoint of improving the adhesive strength and imparting impact properties to the adhesive. When polymer fine particles are included, the adhesive is preferably used for dissimilar material adhesive applications in fields such as automobiles, or for wellbond applications. Examples of dissimilar materials in dissimilar adhesive applications include combinations of two materials selected from various materials such as various steels, aluminum, aluminum alloys, fiber-reinforced plastic (FRP) sheets and carbon fiber reinforced plastic (CFRP) sheets made from carbon fiber or glass fiber.

[0079] The polymer microparticles are preferably polymer microparticles having a core-shell structure. Polymer microparticles having a core-shell structure refer to polymer particles in which the molecular structure differs between the central part (core) and the outer part (shell). Examples of components constituting the core portion of polymer microparticles having a core-shell structure include butadiene rubber (BR), acrylic rubber (ACM), silicone rubber (Si), butyl rubber (IIR), nitrile rubber (NBR), styrene-butadiene rubber (SBR), isoprene rubber (IR), and ethylene propylene rubber (EPR). Among these, butadiene rubber is preferred. The components constituting the shell portion of polymer microparticles having a core-shell structure are graft polymerized onto the core portion and are preferably covalently bonded to the polymer constituting the core component. Examples of components constituting the shell portion include acrylic acid ester monomers, methacrylic acid ester monomers, and aromatic vinyl monomers. The polymer fine particles are contained in the vinyl composition in an amount of, for example, 1 to 100 parts by mass, preferably 2 to 80 parts by mass, and more preferably 4 to 60 parts by mass, per 100 parts by mass of the vinyl compound contained in the vinyl composition. The polymer fine particles having a core-shell structure may be used alone or in combination of two or more types.

[0080] Furthermore, when the above adhesive is used for Wellbond, the vinyl composition preferably contains blocked urethane. Blocked urethane refers to an elastomer type compound containing urethane groups and / or urea groups, and having isocyanate groups at its terminals, wherein all or part of the terminal isocyanate groups are capped with various blocking agents having active hydrogen groups. Compounds in which all of the terminal isocyanate groups are capped with blocking agents are particularly preferred. Specific examples of blocked urethane include the compounds described in International Publication No. 2016 / 163491. The content of blocked urethane in the vinyl composition is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, and even more preferably 5 to 30 parts by mass, per 100 parts by mass of the vinyl compound.

[0081] Furthermore, the vinyl-based composition may be used as a rubber-resin adhesive in tires and the like. An example of a rubber-resin adhesive is a curable composition containing the vinyl-based compound of the present invention, and optionally at least one of a polymerization initiator and other polymerizable compounds, as well as synthetic rubber latex. The synthetic rubber latex is not particularly limited, but examples include those containing an unsaturated diene, such as styrene-butadiene copolymer rubber latex, vinylpyridine-styrene-butadiene copolymer rubber latex, carboxyl group-modified styrene-butadiene copolymer rubber latex, nitrile rubber latex, and chloroprene rubber latex. These may be used individually or in combination of two or more. In a vinyl-based composition used as a rubber-resin adhesive, the content of the synthetic rubber latex is not particularly limited, but is, for example, 25 to 80% by mass, preferably 35 to 75% by mass, and more preferably 55 to 75% by mass, based on solid content.

[0082] Furthermore, vinyl compositions containing synthetic rubber latex preferably further contain water-soluble carbodiimide. Water-soluble carbodiimide means carbodiimide that is soluble in water, and includes carbodiimide that is aqueous and partially water-soluble. The water-soluble carbodiimide is a compound having a carbodiimide (chemical formula: -N=C=N-) and a hydrophilic segment in its molecule. Water-soluble carbodiimide can be used as a dehydration condensation agent capable of forming ester or amide bonds between the COOH group and the OH group or amino group of a compound contained in an aqueous solution. For example, 1-ethyl-3-(3-(dimethylaminopropyl)carbodiimide (WSC) is known to activate carboxyl groups, and its activated intermediate reacts with amino and hydroxyl groups to form amides and esters.

[0083] It is presumed that water-soluble carbodiimide can crosslink and coat the surface of synthetic rubber latex having an unsaturated diene, and that when combined with the vinyl compound of the present invention, it can bond the resin of the adherend to the rubber. The water-soluble carbodiimide is preferably a water-soluble salt such as a hydrochloride or sulfate. More specifically, examples of water-soluble carbodiimides include 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC); water-soluble salts of 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide such as 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide-metho-p-toluenesulfate; triazine-based condensing agents such as 4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-4-methylmorpholinium chloride (DMT-MM); and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) is preferably used. In vinyl compositions used as rubber-resin adhesives, the content of water-soluble carbodiimide is not particularly limited, but is preferably 0.1 to 15% by mass, more preferably 0.3 to 10% by mass, even more preferably 0.5 to 7% by mass, and still more preferably 0.5 to 5% by mass, based on solid content.

[0084] Furthermore, the vinyl compound of the present invention used in rubber-resin adhesives may contain two or more groups shown in formula (II) per molecule, but preferably contains three or four groups shown in formula (II) per molecule. In a vinyl-based composition of a rubber-resin adhesive, the content of the vinyl compound is not particularly limited, but is preferably 0.1 to 40% by mass, more preferably 0.4 to 40% by mass, and particularly preferably 1.0 to 30% by mass, based on solid content. The vinyl-based composition for rubber-resin adhesives is not particularly limited, but it is preferable that each component be dispersed or dissolved in water and used as a dispersion.

[0085] In adhesive applications, it may be used in electronic equipment applications, for example, in applications where it is used to bond a substrate to a semiconductor element. More specifically, it may be used in die-attach applications, and may also be used as a silver paste material by incorporating silver particles, for example. When used as a silver paste material, the vinyl composition may contain silver particles and the vinyl compound of the present invention, and may optionally further contain at least one polymerization initiator and other polymerizable compounds. Furthermore, the composition may be used diluted with a solvent. In the vinyl-based composition, the content of silver particles is, for example, 70 to 98% by mass, preferably 75 to 95% by mass or less, based on solid content. The content of the vinyl compound is, for example, 1 to 20% by mass, preferably 2 to 15% by mass, based on solid content. The content of the curing agent is, for example, 0.1 to 1.5% by mass, preferably 0.2 to 1.0% by mass.

[0086] When used as an adhesive, it may be used for flexible substrates. As an adhesive for flexible substrates, for example, it may be used to bond copper foil to the polyimide film that makes up the substrate, and may be used as a bonding film. The vinyl-based composition for flexible substrates may contain resins other than the vinyl-based compound of the present invention and other polymerizable compounds. Examples of such resins include polyester polymers such as polyester polyurethane resin. The polyester polyurethane resin is preferably a resin obtained by reacting at least a polyester polyol, a polyisocyanate, and a chain extender such as a diol compound other than polyester polyol as raw materials. Furthermore, in addition to the polyester polyurethane resin, the composition may also contain a resin having a carboxyl group or a carboxylic acid anhydride structure. Furthermore, the vinyl-based compositions for flexible substrates described above may also contain organic fillers, metal fillers, inorganic fillers other than metal fillers, and the like. In the vinyl-based composition used for the flexible substrate described above, the content of the vinyl compound is preferably 1 to 60% by mass, more preferably 2 to 40% by mass, and even more preferably 3 to 20% by mass, based on the total amount of components other than the filler mentioned above.

[0087] (Paint application) The vinyl compound of the present invention may be used in paint applications or as a binder resin for paints. Specifically, for example, when used as an anti-fogging paint, it may be used in a paint composition containing the vinyl compound of the present invention and silica particles. The paint composition may further contain at least one polymerization initiator and other polymerizable compounds as needed. The paint composition may also optionally contain a silane coupling agent or the like. When used as an anti-fogging paint, it is preferable that the paint composition be used as a dispersion by dispersing or dissolving each component in a liquid medium such as water. Furthermore, the binder resin may include resins other than the vinyl compound of the present invention or other polymerizable compounds. As the silica particles mentioned above, water-dispersible silica is preferred, and colloidal silica is also preferred. As the liquid medium, water and organic solvents are examples, and water or a mixed solvent of water and an organic solvent is preferred. In the case of a mixed solvent, the organic solvent can be any solvent that can disperse silica, for example, ethylene glycol monobutyl ether is preferred. In the above paint composition, the content of the vinyl compound may be 0.1 to 1000 parts by mass, 0.5 to 500 parts by mass, or 1 to 100 parts by mass per 100 parts by mass of silica particles.

[0088] (Anti-corrosion paint) The paint composition used in paint applications may be other than those described above. For example, it may contain the vinyl compound of the present invention, and optionally at least one polymerization initiator and other polymerizable compounds, as well as a pigment and a pigment dispersant. It may also contain a silane coupling agent to improve adhesion. It may also be used diluted with an organic solvent. The paint composition is preferably used for corrosion protection, and more preferably for corrosion protection of ships. In the paint composition, the content of the vinyl compound is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, based on solid content.

[0089] (Floor coating agent) The vinyl compounds of the present invention may be used in building and civil engineering applications, for example, as floor coatings. When used as floor coatings, vinyl compositions may contain the vinyl compounds of the present invention, but it is preferable that they also contain inorganic fillers. As inorganic fillers, known inorganic fillers used in floor coatings such as carbon nanotubes, silica, silica sand, barite, calcium carbonate, and talc may be used. In addition to these inorganic fillers, pigments used as colorants may also be appropriately blended. Vinyl compositions for floor coatings may also contain, if necessary, at least one of a polymerization initiator and other polymerizable compounds. In a vinyl-based composition for floor coatings, the content of inorganic filler is, for example, about 1 to 1000 parts by mass, preferably 10 to 200 parts by mass, and more preferably 20 to 100 parts by mass, per 100 parts by mass of the vinyl compound. Of course, vinyl compositions may be used in building and civil engineering applications other than as floor coatings, and may be used as tank paints, pipe interior paints, exterior paints, etc. They may also be used as adhesives in building and civil engineering applications, for example, to bond various structures.

[0090] (For encapsulant use) The vinyl compounds of the present invention may be used for sealing applications, preferably for sealing insulated wires. In this case, the vinyl composition may also contain, if necessary, at least one of a polymerization initiator and other polymerizable compounds in addition to the vinyl compound. Furthermore, vinyl compositions used for sealing applications may preferably contain a silane coupling agent or the like.

[0091] (Fiber scrubber) When the vinyl compound of the present invention is used as a fiber sizing agent, it is preferable to use it in combination with a polyester resin having a sulfonic acid base. As the polyester resin having a sulfonic acid base, aromatic polyester resins and aliphatic polyester resins can be used, but it is preferable to use an aromatic polyester resin. As the aromatic polyester resin, it is preferable to have structural units derived from aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid. Furthermore, the vinyl composition for fiber sizing agents preferably contains a surfactant in addition to the vinyl compound and the polyester resin having a sulfonic acid base as described above, and an aromatic nonionic surfactant is preferred as the surfactant. Examples of aromatic nonionic surfactants include polyoxyalkylene alkylphenyl ethers, polyoxyalkylene styrene phenyl ethers, polyoxyalkylene benzylphenyl ethers, polyoxyalkylene cumylphenyl ethers, polyoxyalkylene naphthylphenyl ethers, and polyoxyalkylene styrene (alkylphenyl ethers), among which polyoxyalkylene styrene styrene phenyl ethers such as polyoxyethylene styrene phenyl ethers are preferred. The vinyl composition may also optionally contain a polymerization initiator and at least one of other polymerizable compounds. The vinyl-based composition for fiber sizing agents is preferably used as an aqueous composition, for example, as an aqueous dispersant. In a vinyl-based composition for fiber sizing agents, the content of the vinyl-based compound of the present invention is, for example, 75 to 95% by mass on a solid content basis, but preferably 80 to 95% by mass.

[0092] (For prepreg use) The vinyl compounds of the present invention may be used in prepreg applications, and are particularly suitable for use as matrix resins impregnated into fibrous materials such as reinforcing fibers used in prepreg applications. When used as a matrix resin, the vinyl composition may be any curable composition and may contain the vinyl compound of the present invention, and may optionally contain at least one of a polymerization initiator and other polymerizable compounds (e.g., other vinyl group-containing compounds, polyfunctional (meth)acrylate compounds, etc.). Furthermore, the vinyl composition may also contain, in addition to the vinyl compound of the present invention and other polymerizable compounds, cyanate ester resins containing two or more cyanate groups. It is also preferable that the vinyl composition contains a thermoplastic resin. Additionally, vinyl compositions used for prepreg applications may contain a flame retardant. Examples of flame retardants include phosphorus-containing compounds such as phosphate esters, nitrogen-containing compounds such as red phosphorus, melamine, melamine cyanurate, and melamine isocyanurate, metal hydroxides, and metal oxides. In vinyl compositions used for prepreg applications, the content of the vinyl compound of the present invention is preferably about 20 to 99% by mass, and more preferably about 50 to 80% by mass. The content of the curing agent is preferably 1 to 25% by mass, and more preferably 2 to 20% by mass.

[0093] (Electrical insulating materials and protective materials) The vinyl-based compound of the present invention may be used in electronic substrates and the like, and more specifically, it may be used as a protective material or an electrical insulating material for forming an electrical insulating layer. When used as an electrical insulating material or protective material, the curable resin composition may contain a filler in addition to the vinyl compound of the present invention, and optionally a polymerization initiator and other polymerizable compounds. The filler is preferably insulating. Examples of such fillers include silica, alumina, aluminum nitride, boron nitride, silicon carbide, and silicon nitride. In addition, a filler other than the inorganic filler described above may be used, and an organic filler may also be used. In the curable resin composition, the filler content is, for example, 50 to 90% by mass, preferably 65 to 85% by mass, based on the solid content.

[0094] Curable resin compositions used for electrical insulating materials and protective materials may contain resins other than the vinyl compounds of the present invention, for example, rubbery polymer compounds such as conjugated diene rubber. The content of the rubbery polymer compound is, for example, 30 to 70% by mass, preferably 40 to 60% by mass, based on the solid content of the total amount of components other than fillers. In curable resin compositions used for electrical insulating materials and protective materials, the content of the vinyl compound of the present invention is, for example, 20 to 70% by mass, preferably 25 to 40% by mass, based on the solid content of the total amount of components other than fillers.

[0095] (Photosensitive resin) When used as an electrical insulating material or protective material for electronic circuit boards, the vinyl-based composition may also be used as a photosensitive resin composition. In such cases, the vinyl-based compound is preferably used as a photosensitive resin, and the vinyl-based composition preferably contains the photopolymerization initiator of the present invention. In addition, the vinyl-based composition may also contain other photosensitive resins other than vinyl-based compounds, such as carboxyl group-containing photosensitive resins, a photopolymerization initiator, a reactive diluent, a photosensitive monomer, a filler, and the like. Furthermore, when used as a photosensitive resin composition, it may be used for applications other than the protective materials and electrical insulating materials for electronic substrates described above. Furthermore, as mentioned above, the applications of the photosensitive resin composition are not particularly limited, but include dental applications, and more specifically, filling and restorative materials used to repair damaged teeth, denture base relining materials, hybrid ceramics for crown restorations, and lens applications. The uses and specific formulations described above are merely examples, and the materials may be used for purposes other than those described above, and the formulations of each composition for each use may differ from those described above. [Examples]

[0096] The present invention will be described below with reference to examples, but the present invention is not limited in any way by these examples. The measurement conditions in the following examples are as follows.

[0097] <Measurement conditions> [ 1 [H-NMR spectral measurement] Measurements were taken at 23°C using the JEOL Ltd. NMR analyzer "ECX-400". [Glass transition temperature (DSC measurement)] A differential scanning calorimeter (product name "DSC7020") manufactured by Hitachi High-Tech Science Corporation was used to measure the temperature under a nitrogen atmosphere with a heating rate of 10°C / min. The midpoint of the baseline displacement was defined as the glass transition temperature. In this case, the glass transition temperature (Tg) was measured when the temperature was raised to 200°C at a rate of 10°C / min, then cooled to -20°C, and then heated again at a rate of 10°C / min. [GPC] The GPC measurement method is as follows: Measurements were taken using a GPC system manufactured by Shimadzu Corporation. The conditions were as follows: Columns: Two SHODEX "KF803L" columns manufactured by Showa Denko (exclusion limit molecular weight 70,000) are used in series. Column temperature: 40°C, Flow rate: 1.0 ml / min, Eluent: Tetrahydrofuran Detectors: RI, UV (PDA)

[0098] [Manufacturing Example 1] (Synthesis of vinyl compounds by glycidylation of toluxyl acid) In a three-necked flask equipped with a condenser, thermometer, and nitrogen inlet tube, 15.0 g (0.046 mol) of 4,4'-dihydroxythruxylic acid obtained by photodimerization of p-coumaric acid, 169 g (1.83 mol) of epichlorohydrin, and 1.18 g (0.004 mol) of tetrabutylammonium bromide (TBAB) were mixed and stirred at room temperature for several minutes under nitrogen purging. The solution was then heated to 90°C and reacted for 4 hours. After the reaction was complete, the mixture was allowed to cool to room temperature, and a solution of 10.3 g (0.184 mol) of potassium hydroxide dissolved in 130 ml of isopropanol was added dropwise over 50 minutes. A white precipitate began to form immediately after the start of the dropwise addition. After the dropwise addition was complete, the solution containing a large amount of white precipitate was heated to 60°C and stirred for 4 hours to allow it to mature. The matured solution was allowed to cool to room temperature, and 150 ml of deionized water was added to dissolve the precipitate and separate the aqueous phase. The solution was then washed twice with 100 ml of 1% NaH2PO4 aqueous solution and twice with 100 ml of deionized water. The resulting solution was dehydrated with anhydrous magnesium sulfate, and the solvent was removed using an evaporator to obtain 24.8 g (solid) of the target epoxy resin (reaction intermediate) (yield 98%). This epoxy resin was further recrystallized from ethyl acetate to obtain 13.2 g of the recrystallized product. The structure is in CDCl3. 1 This was confirmed by 1H-NMR measurement. The reaction equation for Production Example 1 is shown below. 1 The 1H-NMR spectral data is shown in Figure 1. [ka]

[0099] [Example 1] (Synthesis of vinyl compounds (epoxyacrylates)) In a three-necked flask equipped with a condenser and thermometer, 3.00 g (0.005 mol) of the recrystallized epoxy resin (reaction intermediate) obtained in Preparation Example 1, 3.15 g (0.044 mol) of acrylic acid, and 30 ml of cyclopentyl methyl ether as a solvent were mixed. To this mixture, 0.35 g (0.001 mol) of tetrabutylammonium bromide (TBAB) and 0.005 g of hydroquinone monomethyl ether were added, and the mixture was heated and reacted under reflux conditions for 8 hours. The solution temperature at this time was 106-108°C. After the reaction was complete, the mixture was allowed to cool to room temperature, diluted with solvent, and washed three times with 50 ml of 5% sodium bicarbonate aqueous solution. Then, it was washed once with 50 ml of 1% by mass NaH2PO4 aqueous solution and twice with 50 ml of deionized water. The resulting solution was dehydrated with anhydrous magnesium sulfate, and the solvent was removed using an evaporator to obtain an 80% concentrated solution. A portion of this concentrated solution was taken and dried in a vacuum oven at 100°C to calculate the yield, which was 91%. Since the dried product at 100°C was insoluble, a portion of the concentrated solution was further desolvated at 60°C, and the resulting sample was dissolved in CDCl3. 1 The 1H-NMR spectrum was measured to confirm the disappearance of the glycidyl group and the formation of the acrylic group.1 The H-NMR spectrum is shown in Figure 2. Furthermore, GPC measurement of the concentrated solution confirmed that the peak was shifted to the high molecular weight side (Figure 3), thus confirming that the vinyl compound of Example 1 was obtained. In Figure 3, peak A is the peak of the manufactured vinyl compound, and peak B is the peak of the epoxy resin (reaction intermediate). The reaction equation in Example 1 is as follows.

[0100] [ka]

[0101] [Example 2] (Preparation and evaluation of hardened bodies) 1.0 g of the 80% by mass vinyl compound obtained in Example 1 was diluted with 0.5 g of tetrahydrofuran, and 24 mg of 2,2-dimethoxy-2-phenylacetophenone as a photopolymerization initiator, 32 mg of epoxy silane coupling agent (KBM403, Shin-Etsu Chemical Co., Ltd.), and a small amount of aqueous acetic acid were added and mixed uniformly. The mixture was then coated onto glass. After drying in a vacuum oven at 60°C to remove the solvent, it was laminated with a release-treated PET film and then subjected to 1700 mJ / cm² of LED-UV irradiation (365 nm). 2 The coating was exposed to light and cured. After curing, the PET film was peeled off and a pencil hardness test was performed. The hardness of the coating was 2H, indicating excellent hardness. Furthermore, a portion of the cured material was crushed and DSC measurement was performed. The glass transition temperature (Tg) was not observed below 200°C, indicating excellent heat resistance.

[0102] [Example 3] (Synthesis of vinyl compounds (epoxyacrylates)) In a three-necked flask equipped with a condenser, 3.16 g (6.02 mmol) of epoxy resin shown in the following reaction formula, obtained by glycidylating 4,4'-dihydroxytoluxylate diisopropyl ester in the same manner as in Preparation Example 1, 1.54 g (21.37 mmol) of acrylic acid, and 30 ml of 4-methyltetrahydropyran (4MTHP) as a solvent were mixed. Then, 0.50 g (1.55 mmol) of tetrabutylammonium bromide (TBAB) was added, and the mixture was heated and reacted under reflux conditions for 5 hours. After the reaction was complete, the mixture was allowed to cool to room temperature, diluted with 4MTHP (30 ml), washed twice with 50 ml of 5% sodium bicarbonate aqueous solution, then washed once with 50 ml of 1% H2SO4 aqueous solution and twice with 50 ml of deionized water. The resulting solution was dehydrated with anhydrous magnesium sulfate, and the solvent was removed by evaporation to obtain 3.83 g of crude product (colorless oily) (yield 95%). This solution was diluted with CDCl3. 1 ¹H-NMR spectra were measured, and as shown in Figures 4 and 5, the disappearance of the glycidyl group and the formation of the acrylic group were confirmed. Furthermore, as shown in Figure 6, the GPC measurement showed a shift in the peak toward the higher molecular weight side, confirming that the target vinyl compound was obtained. In Figure 6, peak A is the peak of the manufactured vinyl compound, and peak B is the peak of the epoxy resin (reaction intermediate). The reaction equation in Example 3 is as follows.

[0103] [ka]

[0104] [Example 4] (Synthesis of vinyl compounds (epoxyacrylates)) In a three-necked flask equipped with a condenser, 3.23 g (6.89 mmol) of recrystallized epoxy resin, shown in the following reaction formula, obtained by glycidylating dimethyl 4,4'-dihydroxytoluxylate in the same manner as in Preparation Example 1, 1.65 g (22.90 mmol) of acrylic acid, and 30 mL of 4-methyltetrahydropyran (4MTHP) as a solvent were mixed. Then, 0.48 g of tetrabutylammonium bromide (TBAB) was added, and the mixture was heated and reacted under reflux conditions for 5 hours. After the reaction was complete, the mixture was allowed to cool to room temperature, diluted with 60 mL of 4MTHP, washed twice with 30 mL of 5% sodium bicarbonate aqueous solution, and then washed twice again with 50 mL of deionized water. The resulting solution was dehydrated with anhydrous magnesium sulfate, and the solvent was removed by evaporation to obtain 3.67 g of crude product (white crystals) (yield 87%). This crude product was diluted with CDCl3. 1 The 1H-NMR spectrum was measured to confirm the disappearance of the glycidyl group and the formation of the acrylic group. Furthermore, GPC measurement showed a shift in the peak toward the higher molecular weight side, confirming that the target vinyl compound was obtained. The reaction equation for Example 4 is as follows.

[0105] [ka]

Claims

1. A vinyl compound represented by the following formula (I). 【Chemistry 1】 (In formula (I), R １ ~R ４ Each of these is an organic group having 1 to 30 carbon atoms, which may independently have a hydrogen atom or a heteroatom, and R １ ~R ４ At least one of them is a group represented by the following formula (II), where R １ ~R ４ If one of them is the group represented by formula (II), then the remaining three are not simultaneously COOH groups. 【Chemistry 2】 (In formula (II), R ５ and R ６ are each independently a hydrogen atom, a halogen atom, or a monovalent C1-C10 organic group that may contain a heteroatom and whose bonding position is not an aromatic ring, and R ５ and R ６ either or both are hydrogen atoms, R ７ This is a monovalent organic group having 1 to 10 carbon atoms, which may contain a hydrogen atom, a halogen atom, or a heteroatom. R ８ is -O-, -S-, -OCO-, or -NR ９ - (R ９ ) represents an organic group having 1 to 10 carbon atoms, which may contain a hydrogen atom or a heteroatom. ) or a single bond, which is bonded to the group shown in formula (III) or to the cyclobutane ring of formula (I). ) 【Transformation 3】 (In formula (III), R １０ ~R １４ Each of these is independently a single bond attached to the cyclobutane ring of formula (I), or a group consisting of a hydrogen atom, a halogen atom, a heteroatom and hydrogen, or an organic group having 1 to 20 carbon atoms which may contain a heteroatom, and * is R of formula (II). ８ It shows binding to R １０ ~R １４ One of these is bonded to the cyclobutane ring of formula (I).

2. In equation (I), R １ ~R ４ The vinyl compound according to claim 1, wherein at least two of the groups are represented by formula (II).

3. In equation (I), R in equation (II) ５ and R ６ Both are hydrogen atoms, R ７ is a hydrogen atom or -CH ３ A vinyl compound according to claim 1 or 2, wherein the compound is any of the groups.

4. In equation (I), R １ ~R ４ At least one of them is R ８ The vinyl compound according to claim 1 or 2, wherein is -O- and is a group represented by formula (II) that is bonded to a group represented by formula (III).

5. R in equation (III) １０ ~R １４ In formula (I), each group other than the single bond attached to the cyclobutane ring is independently either a hydrogen atom or -OCH ３ The vinyl compound according to claim 4, which is any of the groups.

6. R in equation (III) １０ ~R １４ Of these, R １2 The vinyl compound according to claim 5, wherein the bond is a single bond attached to the cyclobutane ring of formula (I).

7. R in equation (III) １１ and R １３ The vinyl compound according to claim 6, wherein all of them are hydrogen atoms.

8. R in equation (III) １０ and R １４ The vinyl compound according to claim 7, wherein all of them are hydrogen atoms.

9. R in equation (I) １ ~R ４ At least one of them is R ８ The vinyl compound according to claim 1 or 2, wherein is a group represented by formula (II) that is -OCO- and bonded to a cyclobutane ring.

10. R in equation (I) ２ and R ４ R ８ The vinyl compound according to claim 1, wherein is -O- and is a group represented by formula (II) that is bonded to a group represented by formula (III).

11. R in equation (I) １ and R ３ R ８ The vinyl compound according to claim 1 or 10, wherein is a group represented by formula (II) that is -OCO- and bonded to a cyclobutane ring.

12. R in equation (I) １ and R ３ However, -COOR Ａ It is a group represented by R Ａ The vinyl compound according to claim 1 or 10, wherein is a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may have a heteroatom.

13. R １ ~R ４ at least one of which is a group represented by formula (II) and R ８ The vinyl compound according to claim 1 or 2, wherein if is a group bonded to formula (III), the other groups either do not contain a cyclic structure or contain only one cyclic structure.

14. A cured body obtained by curing the vinyl compound described in claim 1 or 2.

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