(Meth)acrylamide compound, monomer composition, dental material composition and dental material

Abstract

A monomer composition for dental materials which includes a (meth)acrylamide compound (A) including a cyclic structure and a (meth)acrylamide group.

Description

[Technical Field]

[0001] The present disclosure relates to a (meth)acrylamide compound, a monomer composition, a dental material composition, and a dental material. [Background technology]

[0002] (Meth)acrylate compounds are widely used as monomers in curable compositions. For example, Patent Document 1 discloses (meth)acrylate (D) as a monomer capable of providing a cured product having both high toughness and rigidity. The (meth)acrylate (D) in this document is a reaction product of a thiol compound (A) having two or more mercapto groups, an iso(thio)cyanate compound (B) having two or more iso(thio)cyanate groups, and a hydroxy(meth)acrylate compound (C) having one or more polymerizable groups. The document also discloses a composition containing the (meth)acrylate (D).

[0003] Patent Document 1: International Publication No. 2019 / 107323 Summary of the Invention [Problem to be solved by the invention]

[0004] The (meth)acrylate compound may be used as a monomer contained in a monomer composition for dental materials, which may be used as a dental restorative agent such as a composite resin. Since dental monomer compositions are used in the oral cavity where humidity is high, the resulting cured products tend to absorb water. If the cured product has a high water absorption rate, the mechanical properties of the cured product may be reduced. Therefore, it is necessary to suppress the increase in water absorption of the cured product.

[0005] (Meth)acrylate compounds are known as polymerizable monomers, and are sometimes used as monomers contained in monomer compositions for dental materials. (Meth)acrylate compounds are monomers used in a variety of applications, and there is a demand for compounds having novel structures that have not been previously known.

[0006] The problem to be solved by embodiment A of the present disclosure is to provide a (meth)acrylamide compound capable of giving a cured product in which an increase in water absorption is suppressed, a monomer composition containing the (meth)acrylamide compound, a dental composition, and a dental material.

[0007] The problem to be solved by embodiment A-1 of the present disclosure is to provide a (meth)acrylamide compound having a novel structure, a monomer composition containing the (meth)acrylamide compound, a dental material composition, and a dental material. [Means for solving the problem]

[0008] The means for solving the above problems include the following aspects. The embodiment A of the present disclosure is as follows: <1> ~ <15> Among them, the following <6> ~ <15> is also included in the aspect of embodiment A-1 of the present disclosure. <1> A (meth)acrylamide compound (A) containing a cyclic structure and a (meth)acrylamide group. <2> The (meth)acrylamide compound (A) is a reaction product of a (meth)acrylic compound (X), which is at least one selected from the group consisting of (meth)acrylic acid and halides of (meth)acrylic acid, and a primary amine compound (Y), which contains two amino groups and a cyclic structure. <1> The (meth)acrylamide compound (A) described in 1. <3> The primary amine compound (Y) includes a compound represented by any one of the following formulas (1-1) to (1-7): <2> (Meth)acrylamide compound (A).

[0009] [ka]

[0010] <4> It is a compound represented by the following formula (1): <1> ~ <3> The (meth)acrylamide compound (A) according to any one of the above.

[0011] [ka]

[0012] In formula (1), R 1 and R 2 are each independently a hydrogen atom or a methyl group, and R 3 is a divalent group containing a cyclic structure. <5> The R in the formula (1) 3 is a group represented by the following formula (1a): <4> The (meth)acrylamide compound (A) described in 1.

[0013] [ka]

[0014] In formula (1a), X 1 and X 2 are each independently a single bond or a methylene group, Y is a divalent linking group having 6 to 13 carbon atoms and containing an alicyclic structure or an aromatic structure, and two * each represent a bonding position. <6> containing two (meth)acrylamide groups and a divalent alicyclic hydrocarbon group, the nitrogen atoms in the two (meth)acrylamide groups are both bonded to the divalent alicyclic hydrocarbon group via a methylene group; <1> The (meth)acrylamide compound (A) described in 1. <7> (X) a (meth)acrylic compound which is at least one selected from the group consisting of (meth)acrylic acid and halides of (meth)acrylic acid; and a primary amine compound (Y1) containing two amino groups and the divalent alicyclic hydrocarbon group, wherein the nitrogen atoms in the two amino groups are both bonded to the divalent alicyclic hydrocarbon group via a methylene group. <6> The (meth)acrylamide compound (A) described in 1. <8> The primary amine compound (Y1) includes a compound represented by the following formula (1-1) or (1-2): <7> The (meth)acrylamide compound (A) described in 1.

[0015] [ka]

[0016] <9> It is a compound represented by the following formula (1A): <6> ~ <8> The (meth)acrylamide compound (A) according to any one of the above.

[0017] [ka]

[0018] In formula (1A), R 1A and R 2A are each independently a hydrogen atom or a methyl group, and R 3A is a divalent group formed by linking a methylene group, a divalent alicyclic hydrocarbon group, and a methylene group in this order. <10> The R in the formula (1A) 3A is a group represented by the following formula (1Aa): <9> The (meth)acrylamide compound (A) described in 1.

[0019] [ka]

[0020] In formula (1Aa), X 1A and X 2A are each independently a methylene group, and Y A is a divalent alicyclic hydrocarbon group having 6 to 9 carbon atoms, and two * each represent a bonding position. <11> The molecular weight is 150 to 500. <1> ~ <10> The (meth)acrylamide compound (A) according to any one of the above. <12> <1> ~ <11> A monomer composition comprising the (meth)acrylamide compound (A) according to any one of the above. <13> For dental materials, <12> The monomer composition according to claim 1. <14> <12> or <13> 1. A dental composition comprising the monomer composition according to claim 1, and a polymerization initiator. <15> <14> A dental material comprising a cured product of the dental material composition described in 1. [Effects of the Invention]

[0021] According to embodiment A of the present disclosure, it is possible to provide a (meth)acrylamide compound capable of giving a cured product in which an increase in water absorption is suppressed, a monomer composition containing the (meth)acrylamide compound, a dental composition, and a dental material.

[0022] According to embodiment A-1 of the present disclosure, it is possible to provide a (meth)acrylamide compound having a novel structure, a monomer composition containing the (meth)acrylamide compound, a dental material composition, a cured product, and a dental material. DETAILED DESCRIPTION OF THE INVENTION

[0023] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present disclosure, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved. In the present disclosure, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, the term "light" is a concept that encompasses active energy rays such as ultraviolet light and visible light. In the present disclosure, "(meth)acrylic compound" means an acrylic compound or a methacrylic compound, "(meth)acryloyl group" means an acryloyl group or a methacryloyl group, "(meth)acrylate" means an acrylate or a methacrylate, and "(meth)acrylic acid" means acrylic acid or methacrylic acid. In this disclosure, "iso(thio)cyanate" means an isocyanate or an isothiocyanate.

[0024] The present disclosure includes, for example, embodiment A, and also includes embodiment A-1, which is a specific embodiment of embodiment A. Hereinafter, the embodiments A and A-1 will be described in detail.

[0025] [Embodiment A] <(Meth)acrylamide compound (A)> The (meth)acrylamide compound (A) contains a cyclic structure and a (meth)acrylamide group. The (meth)acrylamide compound (A) can be produced, for example, by reacting a (meth)acrylic compound (X), which is at least one selected from the group consisting of (meth)acrylic acid and halides of (meth)acrylic acid, with a primary amine compound (Y) containing two amino groups and a cyclic structure.

[0026] The (meth)acrylamide compound (A) is at least one (meth)acrylic compound selected from the group consisting of (meth)acrylic acid and halides of (meth)acrylic acid. Preferably, the compound (X) is a reaction product of a primary amine compound (Y) containing two amino groups and a cyclic structure.

[0027] In the primary amine compound (Y), the cyclic structure is not particularly limited. For example, the cyclic structure may be an alicyclic structure or an aromatic structure, but is preferably an alicyclic structure. The number of carbon atoms in the cyclic structure is preferably 4 to 15, and more preferably 6 to 13. When a hydrogen atom bonded to a carbon atom forming a ring is substituted with a carbon atom, the "number of carbon atoms in the cyclic structure" also includes the number of the substituted carbon atoms. An example of a case where a hydrogen atom bonded to a carbon atom forming a ring is replaced with a carbon atom is a case where a methyl group is bonded to a carbon atom forming a ring. The primary amine compound (Y) may contain only one cyclic structure, or may contain two or more cyclic structures. In the primary amine compound (Y), the cyclic structure and the two amino groups may be bonded directly or via a divalent linking group. Examples of the divalent linking group include a methylene group and an ethylene group, with a methylene group being preferred.

[0028] The primary amine compound (Y) preferably includes a compound represented by any one of the following formulas (1-1) to (1-7).

[0029] [ka]

[0030] The (meth)acrylamide compound (A) is preferably a compound represented by the following formula (1).

[0031] [ka]

[0032] In formula (1), R 1 and R 2 are each independently a hydrogen atom or a methyl group, and R 3 is a divalent group containing a cyclic structure.

[0033] The monomer composition for dental materials of embodiment A is a monomer composition represented by the formula (1) R 3 is preferably a group represented by the following formula (1a):

[0034] [ka]

[0035] In formula (1a), X 1 and X 2 are each independently a single bond or a methylene group, Y is a divalent linking group having 6 to 13 carbon atoms and containing an alicyclic structure or an aromatic structure, and two * each represent a bonding position.

[0036] In formula (1a), the divalent linking group for Y preferably has 6 to 10 carbon atoms, and more preferably 6 to 8 carbon atoms.

[0037] The (meth)acrylamide compound (A) preferably has a molecular weight of 150-500, more preferably 200-400, and even more preferably 200-350.

[0038] <Dental material monomer composition> The dental monomer composition of embodiment A contains a (meth)acrylamide compound (A) having a cyclic structure and a (meth)acrylamide group.

[0039] The dental monomer composition of embodiment A contains the (meth)acrylamide compound (A), and thus can provide a cured product with reduced increase in water absorption. As a result, a cured product can be obtained that maintains its mechanical properties even in the oral cavity, making it suitable for use as a dental material. The cured product of embodiment A has particularly excellent flexural strength, and therefore, for example, the elastic modulus and breaking strength of the cured product can be well maintained. In general, cured products obtained using a monomer composition for dental materials tend to have a high water absorption rate when the composition contains a monomer for improving adhesive strength, and the increased water absorption rate may result in a decrease in mechanical properties. In contrast, the dental monomer composition of embodiment A uses a (meth)acrylamide compound (A) containing a cyclic structure and a (meth)acrylamide group as a monomer, thereby increasing the adhesive strength of the resulting cured product to tooth tissue and suppressing an increase in water absorption. That is, the dental monomer composition of embodiment A can suppress an increase in water absorption and give a cured product with excellent adhesive strength to tooth structure.

[0040] The dental monomer composition of embodiment A may contain components other than the (meth)acrylamide compound (A), but preferably does not substantially contain components other than the (meth)acrylamide compound (A). This allows the timing of initiation of polymerization to be adjusted. In other words, when the monomer composition for dental materials does not substantially contain any components other than the (meth)acrylamide compound (A), curing does not start, and polymerization can be initiated by adding a polymerization initiator at a desired time.

[0041] From the above viewpoint, for example, the content of the (meth)acrylamide compound (A) is preferably 90% by mass or more, more preferably 95% by mass or more, based on the total mass of the monomer composition for dental materials, and may be 99% by mass or less, based on the total mass of the monomer composition for dental materials.

[0042] <Dental material composition> The dental composition of embodiment A contains the dental monomer composition of embodiment A and a polymerization initiator.

[0043] The content of the monomer composition for dental materials is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total mass of the dental material composition, and is preferably 30% by mass or less, based on the total mass of the dental material composition.

[0044] <Polymerization initiator> The dental composition of embodiment A contains a polymerization initiator. When the dental composition of embodiment A contains a polymerization initiator, the polymerization initiator contained therein may be only one type, or two or more types. When the dental material composition of embodiment A contains a polymerization initiator, polymerization of the monomer (i.e., the (meth)acrylamide compound (A) and other monomers contained as needed; the same applies hereinafter) can be further promoted in the process of curing the dental material composition.

[0045] When room temperature polymerization is carried out as the polymerization of the monomer, a redox polymerization initiator in which an oxidizing agent and a reducing agent are combined is preferred. When a redox-based polymerization initiator is used, for example, an oxidizing agent and a reducing agent may be prepared in separately packaged forms and mixed together immediately before use.

[0046] The oxidizing agent is not particularly limited, and examples thereof include organic peroxides such as diacyl peroxides (benzoyl peroxide, etc.), peroxyesters (t-butyl peroxybenzoate, etc.), dialkyl peroxides (dicumyl peroxide, etc.), peroxyketals (1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, etc.), ketone peroxides (methyl ethyl ketone peroxide, etc.), and hydroperoxides (t-butyl hydroperoxide, etc.).

[0047] The reducing agent is not particularly limited, and a tertiary amine (N,N-dimethylaniline, etc.) is usually used.

[0048] In addition to these organic peroxide / amine systems, there are also cumene hydroperoxide / thiourea systems and ascorbic acid / Cu systems. 2+ Redox polymerization initiators such as salt-based and organic peroxide / amine / sulfinic acid (or its salt)-based initiators can be used. Furthermore, tributylborane, organic sulfinic acid, etc. are also preferably used as the polymerization initiator.

[0049] When thermal polymerization is carried out by heating to polymerize the monomer, the polymerization initiator is preferably a peroxide, an azo compound, or the like. The peroxide is not particularly limited, and examples thereof include benzoyl peroxide, t-butyl hydroperoxide, and cumene hydroperoxide. The azo compound is not particularly limited, and examples thereof include azobisisobutyronitrile.

[0050] When photopolymerization is performed by irradiation with visible light to polymerize a monomer, the polymerization initiator (hereinafter also referred to as "photopolymerization initiator") is preferably a redox initiator such as α-diketone / tertiary amine, α-diketone / aldehyde, or α-diketone / mercaptan. The photopolymerization initiator is not particularly limited, and examples thereof include α-diketone / reducing agent, ketal / reducing agent, and thioxanthone / reducing agent. Examples of α-diketones include camphorquinone. An example of the ketal is benzyl dimethyl ketal. Examples of thioxanthone include 2-chlorothioxanthone. Examples of reducing agents include tertiary amines (e.g., Michler's ketone), aldehydes (e.g., citronellal), and compounds having a thiol group (e.g., 2-mercaptobenzoxazole); Examples include: Furthermore, initiators of the type such as α-diketone / organic peroxide / reducing agent, in which an organic peroxide is added to these redox initiators, can also be suitably used.

[0051] When photopolymerization is carried out by irradiation with ultraviolet light, photopolymerization initiators such as benzoin alkyl ether, benzil dimethyl ketal, etc. are preferred. Photopolymerization initiators such as (bis)acylphosphine oxides are also preferably used.

[0052] Examples of the (bis)acylphosphine oxides include acylphosphine oxides (2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc.), and bisacylphosphine oxides (bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, etc.). These (bis)acylphosphine oxide photopolymerization initiators can be used alone or in combination with reducing agents such as various amines, aldehydes, mercaptans, and sulfinates. good. These (bis)acylphosphine oxide photopolymerization initiators may be used in combination with the above-mentioned visible light photopolymerization initiators.

[0053] In addition to these polymerization initiators, co-catalyst components such as amine compounds such as dimethylaminoethyl methacrylate, N,N-dimethyl-p-toluidine, ethyl p-dimethylaminobenzoate (also referred to as EDB), and 2-butoxyethyl 4-(dimethylamino)benzoate (also referred to as DMBE), aldehyde compounds such as citronellal and dimethylaminobenzaldehyde, and compounds having a thiol group such as 2-mercaptobenzoxazole and decanethiol may also be used in combination.

[0054] For example, a polymerization initiator may be used by referring to International Publication Nos. 2019 / 107323 and 2020 / 040141.

[0055] The content of the polymerization initiator is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 5% by mass, based on the total amount of monomers contained in the dental composition.

[0056] <Other Monomers> The dental material composition of embodiment A may contain other monomers in addition to the monomers (mainly the (meth)acrylamide compound (A)) contained in the dental material monomer composition. Examples of the other monomers include the following (meth)acrylate compounds (B).

[0057] <(Meth)acrylate Compound (B)> The dental composition of embodiment A preferably further contains a (meth)acrylate compound (B) other than the (meth)acrylamide compound (A).

[0058] The (meth)acrylate compound (B) can be any (meth)acrylate compound other than the (meth)acrylamide compound (A) without any particular limitation. Specifically, the (meth)acrylate compound (B) includes a (meth)acrylate compound containing two or more (meth)acryloyloxy groups, a (meth)acrylate compound containing one (meth)acryloyloxy group, and the like. Specific examples of the (meth)acrylate compound (B) will be described below.

[0059] ((Meth)acrylate compounds containing two or more (meth)acryloyloxy groups) The (meth)acrylate compound (B) may include a (meth)acrylate compound containing two or more (meth)acryloyloxy groups.

[0060] Examples of the (meth)acrylate compound containing two or more (meth)acryloyloxy groups include a difunctional (meth)acrylate compound and a tri- or higher functional (meth)acrylate compound. Examples of the bifunctional (meth)acrylate compound include aromatic compound-based bifunctional (meth)acrylate compounds, aliphatic compound-based bifunctional (meth)acrylate compounds, (meth)acrylate compounds containing two or more urethane bonds, and (meth)acrylate compounds containing two or more thiourethane bonds.

[0061] Examples of aromatic bifunctional (meth)acrylate compounds include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, and 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane. acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolypropoxyphenyl)propane, etc. Among these, at least one selected from the group consisting of 2,2-bis[4-(3-(methacryloyloxy)-2-hydroxypropoxyphenyl]propane (also referred to as Bis-GMA) and 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane is preferred.

[0062] Examples of the aliphatic compound-based bifunctional (meth)acrylate compound include an aliphatic compound-based bifunctional (meth)acrylate that does not contain a urethane bond or a thiourethane bond, a (meth)acrylate compound that contains two or more urethane bonds, and a (meth)acrylate compound that contains two or more thiourethane bonds.

[0063] Examples of aliphatic compound-based bifunctional (meth)acrylates that do not contain a urethane bond or a thiourethane bond include erythritol di(meth)acrylate, sorbitol di(meth)acrylate, mannitol di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate (also referred to as 3G), nonaethylene glycol ... Examples of the diol include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane. Among these, at least one selected from the group consisting of glycerol dimethacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate (also referred to as HexDMA), neopentyl glycol dimethacrylate (also referred to as NPG), and 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane is preferred.

[0064] A (meth)acrylate compound containing two or more urethane bonds can be produced, for example, as a reaction product of an iso(thio)cyanate compound containing two or more iso(thio)cyanate groups and a (meth)acrylate compound containing a hydroxy group described below. In a (meth)acrylate compound containing two or more urethane bonds, the number of urethane bonds is preferably two. The (meth)acrylate compound containing two or more urethane bonds is not particularly limited, and examples thereof include 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (also referred to as UDMA).

[0065] A (meth)acrylate compound containing two or more thiourethane bonds can be produced, for example, as a reaction product of a thiol compound containing two or more thiol groups (such as pentaerythritol tetrakis(3-mercaptopropionate)), an iso(thio)cyanate compound containing two or more iso(thio)cyanate groups, and a (meth)acrylate compound containing a hydroxy group.

[0066] In embodiment A, the "(meth)acrylate compound containing two or more urethane bonds" does not contain two or more thiourethane bonds. In embodiment A, the "(meth)acrylate compound containing two or more thiourethane bonds" may have two or more urethane bonds.

[0067] Examples of trifunctional or higher functional (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, and 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane.

[0068] (Iso(thio)cyanate compounds) Examples of isocyanate compounds containing two or more iso(thio)cyanate groups that can be used as raw materials for (meth)acrylate compounds containing two or more urethane bonds or thiourethane bonds include the following isocyanate compounds and isothiocyanate compounds.

[0069] Examples of the isocyanate compound include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, pentamethylene diisocyanate, m-xylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, isophorone diisocyanate, bis(isocyanatemethyl)cyclohexane, bis(isocyanatecyclohexyl)methane, 2,5-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, phenylene diisocyanate, and 4,4'-diphenylmethane diisocyanate. The isocyanate compound may be used alone or in combination of two or more.

[0070] Examples of the isothiocyanate compound include alicyclic polyisothiocyanate compounds such as hexamethylene diisothiocyanate; aromatic polyisothiocyanate compounds such as tolylene diisothiocyanate; and sulfur-containing heterocyclic polyisothiocyanate compounds such as 2,5-diisothiocyanate thiophene. The isothiocyanate compound may be used alone or in combination of two or more.

[0071] Among the above, it is preferable that the iso(thio)cyanate compound includes at least one selected from the group consisting of hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, pentamethylene diisocyanate, m-xylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, phenylene diisocyanate, and 4,4'-diphenylmethane diisocyanate.

[0072] ((Meth)acrylate compounds containing hydroxy groups) Examples of (meth)acrylate compounds containing a hydroxy group that can be used as a raw material for (meth)acrylate compounds containing two or more urethane bonds or thiourethane bonds include 2-hydroxyethyl (meth)acrylate (also known as HEMA), 2-hydroxypropyl ( hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Among the above, the (meth)acrylate compound containing a hydroxy group preferably includes at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

[0073] ((Meth)acrylate compound containing one (meth)acryloyloxy group) Examples of the (meth)acrylate compound containing one (meth)acryloyloxy group in the (meth)acrylate compound (B) of embodiment A include a (meth)acrylate compound containing a hydroxy group and a (meth)acrylate compound not containing a hydroxy group. Examples of the (meth)acrylate compound containing a hydroxy group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Among the above, the (meth)acrylate compound containing a hydroxy group preferably includes at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. Examples of (meth)acrylate compounds that do not contain a hydroxy group include alkyl (meth)acrylates such as dodecyl (meth)acrylate (DMA).

[0074] ((Meth)acrylate compound containing an acidic group) The (meth)acrylate compound (B) may include a (meth)acrylate compound containing an acidic group. The (meth)acrylate compound containing an acidic group has an affinity for the adherend and also has a demineralizing effect on the tooth structure.

[0075] Examples of the acidic group include a phosphate group, a pyrophosphate group, a thiophosphate group, a phosphonate group, a sulfonic acid group, and a carboxylic acid group. Among the above, the acidic group is preferably at least one selected from the group consisting of a phosphoric acid group and a carboxylic acid group, and more preferably a phosphoric acid group.

[0076] Examples of the (meth)acrylate compound containing a phosphate group include (meth)acryloyloxyalkyl dihydrogen phosphates such as 10-(phosphonooxy)decyl-(meth)acrylate (also referred to as MDP), bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogen phosphate, bis[9 ... [2-(meth)acryloyloxyethyl)phenyl]hydrogenphosphate, bis[10-(meth)acryloyloxydecyl]hydrogenphosphate, 1,3-di(meth)acryloyloxypropyl dihydrogenphosphate, 2-(meth)acryloyloxyethylphenylhydrogenphosphate, 2-(meth)acryloyloxyethyl-2-bromoethylhydrogenphosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl]hydrogenphosphate, and acid chlorides, alkali metal salts, and ammonium salts thereof. Examples of the (meth)acrylate compound containing a carboxylic acid group include 4-methacryloyloxyethyltrimellitic acid (also referred to as 4-MET) and its anhydride.

[0077] <Filler> The dental composition of embodiment A may contain a filler. The filler is a material used in the dental field. There are no particular limitations on the filler that can be used as long as it is a common filler that can be used. Fillers are generally broadly classified into organic fillers and inorganic fillers. Examples of the organic filler include fine powders of polymethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, and the like.

[0078] Examples of inorganic fillers include fine powders of various glasses (mainly composed of silicon dioxide and optionally containing oxides of heavy metals, boron, aluminum, etc.), various ceramics, diatomaceous earth, kaolin, clay minerals (montmorillonite, etc.), activated clay, synthetic zeolite, mica, calcium fluoride, ytterbium fluoride, calcium phosphate, barium sulfate, zirconium dioxide, titanium dioxide, hydroxyapatite, etc. Specific examples of such inorganic fillers include barium borosilicate glass (such as Schott 8235, Schott GM27884, and Schott G018-053), strontium boroaluminosilicate glass (such as Schott G018-163), lanthanum glass (such as Schott GM31684), fluoroaluminosilicate glass (such as Schott G018-117), and boroaluminosilicate glass containing zirconium, cesium, or the like (such as Schott G018-307).

[0079] These fillers may be used singly or in combination of two or more. The content of the filler may be appropriately determined in consideration of the workability (viscosity) of the dental material composition (e.g., composite resin composition), the bending strength of the cured product, etc., and is preferably 10 to 2,000 parts by mass, more preferably 50 to 1,000 parts by mass, and even more preferably 100 to 600 parts by mass, relative to 100 parts by mass of all components other than the filler contained in the dental material composition.

[0080] <Solvent> The dental composition of embodiment A preferably contains a solvent. Examples of the solvent include organic solvents and water. The dental composition of embodiment A preferably contains an organic solvent and water.

[0081] As the organic solvent, ethanol, isopropyl alcohol, acetone, etc. can be used. Examples of water include distilled water and ultrapure water.

[0082] <Dental materials> The dental material of embodiment A includes a hardened product of the dental material composition of embodiment A. The dental material composition of embodiment A can be used as a dental material. Dental materials include dental restorative materials, denture base resins, denture base lining materials, impression materials, bonding materials (resin cements, resin-added glass ionomer cements, etc.), dental adhesives (orthodontic adhesives, cavity application adhesives, etc.), fissure sealants, CAD / CAM resin blocks, temporary crowns, artificial tooth materials, etc. Examples of dental restorative materials include composite resins for crowns, composite resins for filling caries cavities, composite resins for core construction, and composite resins for filling and restoring.

[0083] Embodiment A of the present disclosure includes the following aspects. <1> A monomer composition for dental materials, comprising a (meth)acrylamide compound (A) having a cyclic structure and a (meth)acrylamide group. <2> The (meth)acrylamide compound (A) is a reaction product of a (meth)acrylic compound (X), which is at least one selected from the group consisting of (meth)acrylic acid and halides of the (meth)acrylic acid, and a primary amine compound (Y), which contains two amino groups and a cyclic structure. <1> The monomer composition for dental materials according to claim 1. <3> The primary amine compound (Y) includes a compound represented by any one of the following formulas (1-1) to (1-7): <2> The monomer composition for dental materials according to claim 1.

[0084] [ka]

[0085] <4> The (meth)acrylamide compound (A) is a compound represented by the following formula (1): <1> ~ <3> 10. The monomer composition for dental material according to claim 9, wherein the monomer composition for dental material is a hydroxybenzoate.

[0086] [ka]

[0087] In formula (1), R 1 and R 2 are each independently a hydrogen atom or a methyl group, and R 3 is a divalent group containing a cyclic structure. <5> The R in the formula (1) 3 is a group represented by the following formula (1a): <4> The monomer composition for dental materials according to claim 1.

[0088] [ka]

[0089] In formula (1a), X 1 and X 2 are each independently a single bond or a methylene group, Y is a divalent linking group having 6 to 13 carbon atoms and containing an alicyclic structure or an aromatic structure, and two * each represent a bonding position.

[0090] <6> The content of the (meth)acrylamide compound (A) is 90% by mass or more based on the total mass of the monomer composition for dental materials. <1> ~ <5> 10. The monomer composition for dental material according to claim 9, wherein the monomer composition for dental material is a hydroxybenzoate. <7> <1> ~ <6> 1. A dental composition comprising the monomer composition for dental material according to any one of 1 to 8 above and a polymerization initiator. <8> <7> A dental material comprising a cured product of the dental material composition described in 1.

[0091] [Embodiment A-1] (Meth)acrylamide compound (A) The (meth)acrylamide compound (A) of embodiment A-1 (also referred to as (meth)acrylamide compound (A-1) in the present disclosure) contains two (meth)acrylamide groups and a divalent alicyclic hydrocarbon group, and both nitrogen atoms in the two (meth)acrylamide groups are bonded to the divalent alicyclic hydrocarbon group via methylene groups.

[0092] The (meth)acrylamide compound (A-1) of embodiment A-1 has a novel structure. Furthermore, the cured product obtained by polymerizing the (meth)acrylamide compound (A-1) of embodiment A-1 has excellent adhesive strength to tooth tissue such as enamel. Furthermore, the cured product obtained by polymerizing the (meth)acrylamide compound (A-1) of embodiment A-1 exhibits suppressed increase in water absorption, and as a result, for example, the mechanical properties are maintained even in the oral cavity, making it suitable for use as a dental material. The cured product obtained by polymerizing the (meth)acrylamide compound (A-1) of embodiment A-1 has particularly excellent flexural strength, and therefore, for example, the elastic modulus and breaking strength of the cured product can be well maintained. In general, cured products obtained using a monomer composition for dental materials tend to have a high water absorption rate when the composition contains a monomer for improving adhesive strength, and the increased water absorption rate may result in a decrease in mechanical properties. In contrast, the dental monomer composition of embodiment A-1 not only provides a cured product with excellent adhesive strength to tooth structure, but also inhibits an increase in water absorption.

[0093] The (meth)acrylamide compound (A-1) of embodiment A-1 can be produced, for example, by reacting a (meth)acrylic compound (X) that is at least one selected from the group consisting of (meth)acrylic acid and halides of (meth)acrylic acid with a primary amine compound (Y1) that contains two amino groups and a divalent alicyclic hydrocarbon group, in which the nitrogen atoms in the two amino groups are both bonded to the divalent alicyclic hydrocarbon group via a methylene group.

[0094] The compound (X) is preferably a reaction product of at least one (meth)acrylic compound selected from the group consisting of (meth)acrylic acid and halides of (meth)acrylic acid, and a primary amine compound (Y1) containing two amino groups and a divalent alicyclic hydrocarbon group, in which nitrogen atoms in the two amino groups are both bonded to the divalent alicyclic hydrocarbon group via a methylene group.

[0095] In the primary amine compound (Y1), the alicyclic hydrocarbon group is not particularly limited. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 4 to 15, more preferably 6 to 13, even more preferably 6 to 10, and particularly preferably 6 to 8. When a hydrogen atom bonded to a carbon atom forming a ring is substituted with a carbon atom, the "number of carbon atoms in the alicyclic hydrocarbon group" also includes the number of the substituted carbon atoms. An example of a case where a hydrogen atom bonded to a carbon atom forming a ring is replaced with a carbon atom is a case where a methyl group is bonded to a carbon atom forming a ring. The primary amine compound (Y1) may contain only one alicyclic hydrocarbon group, or may contain two or more alicyclic hydrocarbon groups.

[0096] The primary amine compound (Y1) preferably includes a compound represented by the following formula (1-1) or (1-2).

[0097] [ka]

[0098] The (meth)acrylamide compound (A-1) is preferably a compound represented by the following formula (1A).

[0099] [ka]

[0100] In formula (1A), R 1A and R 2A are each independently a hydrogen atom or a methyl group, and R 3A is a divalent group formed by linking a methylene group, a divalent alicyclic hydrocarbon group, and a methylene group in this order.

[0101] The (meth)acrylamide compound (A-1) of embodiment A-1 is a compound represented by the formula (1A) R3A is preferably a group represented by the following formula (1Aa).

[0102] [ka]

[0103] In formula (1Aa), X 1A and X 2A are each independently a methylene group, and Y A is a divalent alicyclic hydrocarbon group having 6 to 9 carbon atoms, and two * each represent a bonding position.

[0104] In formula (1Aa), Y A The divalent linking group in the formula (I) preferably has 6 to 10 carbon atoms, and more preferably 6 to 8 carbon atoms.

[0105] The (meth)acrylamide compound (A-1) preferably has a molecular weight of 150 to 500, more preferably 200 to 400, and even more preferably 200 to 350.

[0106] <Monomer composition> The monomer composition of embodiment A-1 contains the (meth)acrylamide compound (A-1) of embodiment A-1.

[0107] The monomer composition of embodiment A-1 may contain components other than the (meth)acrylamide compound (A-1), but preferably does not substantially contain components other than the (meth)acrylamide compound (A-1). This allows the timing of initiation of polymerization to be adjusted. In other words, when the monomer composition does not substantially contain any components other than the (meth)acrylamide compound (A-1), curing does not start, and polymerization can be initiated by adding a polymerization initiator at a desired time.

[0108] From the above viewpoint, for example, the content of the (meth)acrylamide compound (A-1) is preferably 90% by mass or more, more preferably 95% by mass or more, based on the total mass of the monomer composition, and may be 99% by mass or less, based on the total mass of the monomer composition.

[0109] The monomer composition of embodiment A-1 is preferably used as a dental material. The monomer composition of embodiment A-1 contains the (meth)acrylamide compound (A-1) of embodiment A-1, and thus can provide a cured product in which an increase in water absorption is suppressed, thereby providing a cured product with maintained mechanical properties. The cured product of embodiment A-1 particularly maintains good bending strength, and therefore, for example, the elastic modulus and breaking strength of the cured product can be maintained well. Furthermore, in general, when the adhesive strength of a cured product obtained using a monomer composition to tooth tissue such as enamel or dentin is increased, the water absorption rate increases, which may result in a decrease in mechanical properties. By using the (meth)acrylamide compound (A-1) of embodiment A-1 as a monomer, the adhesive strength of the resulting cured product to tooth structure can also be increased. That is, the monomer composition of embodiment A-1 can provide a cured product that suppresses an increase in water absorption and has excellent adhesive strength to tooth structure.

[0110] <Dental material composition> The dental composition of embodiment A-1 contains the monomer composition of embodiment A-1 and a polymerization initiator.

[0111] The content of the monomer composition is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total mass of the dental material composition, and is preferably 30% by mass or less, based on the total mass of the dental material composition.

[0112] <Polymerization initiator> The dental composition of embodiment A-1 contains a polymerization initiator. When the dental composition of embodiment A-1 contains a polymerization initiator, the polymerization initiator contained therein may be only one type, or two or more types. When the dental material composition of embodiment A-1 contains a polymerization initiator, the polymerization of the monomer (i.e., the (meth)acrylamide compound (A-1) and other monomers contained as needed; the same applies hereinafter) can be further promoted in the process of hardening the dental material composition.

[0113] When room temperature polymerization is carried out as the polymerization of the monomer, a redox polymerization initiator in which an oxidizing agent and a reducing agent are combined is preferred. When a redox-based polymerization initiator is used, for example, an oxidizing agent and a reducing agent may be prepared in separately packaged forms and mixed together immediately before use.

[0114] Details of the polymerization initiator, such as specific examples, preferred specific examples, preferred content, preferred aspects, and co-catalyst components, are the same as the details of the polymerization initiator, preferred specific examples, preferred content, preferred aspects, and co-catalyst components in embodiment A. <Other Monomers> The dental material composition of embodiment A-1 may contain other monomers in addition to the monomers contained in the dental material monomer composition (mainly the above-mentioned (meth)acrylamide compound (A-1)). Examples of the other monomers include the following (meth)acrylate compounds (B).

[0115] <(Meth)acrylate Compound (B)> The dental composition of embodiment A-1 preferably further contains a (meth)acrylate compound (B) other than the (meth)acrylamide compound (A-1).

[0116] The (meth)acrylate compound (B) can be any (meth)acrylate compound other than the (meth)acrylamide compound (A-1) without any particular limitation. Specifically, the (meth)acrylate compound (B) includes a (meth)acrylate compound containing two or more (meth)acryloyloxy groups, a (meth)acrylate compound containing one (meth)acryloyloxy group, and the like. Specific examples of the (meth)acrylate compound (B) will be described below. Details of specific examples, preferred specific examples, preferred aspects, etc. of the (meth)acrylate compound (B) are the same as the details of specific examples, preferred specific examples, preferred aspects, etc. of the (meth)acrylate compound (B) in embodiment A.

[0117] ((Meth)acrylate compounds containing two or more (meth)acryloyloxy groups) Details of specific examples, preferred specific examples, preferred aspects, etc. of the (meth)acrylate compound containing two or more (meth)acryloyloxy groups are the same as details of specific examples, preferred specific examples, preferred aspects, etc. of the (meth)acrylate compound containing two or more (meth)acryloyloxy groups in embodiment A.

[0118] ((Meth)acrylate compound containing one (meth)acryloyloxy group) Details of specific examples, preferred specific examples, preferred aspects, etc. of the (meth)acrylate compound containing one (meth)acryloyloxy group are the same as details of specific examples, preferred specific examples, preferred aspects, etc. of the (meth)acrylate compound containing one (meth)acryloyloxy group in embodiment A.

[0119] ((Meth)acrylate compound containing an acidic group) The (meth)acrylate compound (B) may include a (meth)acrylate compound containing an acidic group. Details of specific examples, preferred specific examples, preferred aspects, etc. of the (meth)acrylate compound containing an acidic group are the same as details of specific examples, preferred specific examples, preferred aspects, etc. of the (meth)acrylate compound containing an acidic group in embodiment A.

[0120] <Filler> The dental composition of embodiment A-1 may contain a filler. The filler is not particularly limited as long as it is a filler commonly used in the dental field. Fillers are generally broadly classified into organic fillers and inorganic fillers. Details of the filler, such as specific examples, preferred specific examples, and preferred aspects, are the same as those of the filler in embodiment A.

[0121] <Solvent> The dental composition of embodiment A-1 preferably contains a solvent. Examples of the solvent include organic solvents and water. The dental composition of embodiment A-1 preferably contains an organic solvent and water.

[0122] As the organic solvent, ethanol, isopropyl alcohol, acetone, etc. can be used. Examples of water include distilled water and ultrapure water.

[0123] ≪Cured product≫ The cured product of embodiment A-1 is a cured product of the dental composition of embodiment A-1. The cured product of embodiment A-1 has excellent adhesive strength to tooth tissue such as enamel. The cured product of embodiment A-1 is prevented from increasing in water absorption, and as a result, the bending strength is maintained. The cured product of embodiment A-1 maintains good bending strength, and therefore, for example, the elastic modulus and breaking strength of the cured product can be maintained well.

[0124] <Dental materials> The dental material of embodiment A-1 includes a cured product of the dental composition of embodiment A-1. The dental composition of embodiment A-1 can be used as a dental material. Dental materials include dental restorative materials, denture base resins, denture base lining materials, impression materials, and luting materials. Examples include materials (resin cement, resin-added glass ionomer cement, etc.), dental adhesives (orthodontic adhesives, cavity application adhesives, etc.), fissure sealants, CAD / CAM resin blocks, temporary crowns, and artificial tooth materials. Examples of dental restorative materials include composite resins for crowns, composite resins for filling caries cavities, composite resins for core construction, and composite resins for filling and restoring.

[0125] The means for solving the above problems include the following aspects. <1> A (meth)acrylamide compound comprising two (meth)acrylamide groups and a divalent alicyclic hydrocarbon group, wherein nitrogen atoms in the two (meth)acrylamide groups are both bonded to the divalent alicyclic hydrocarbon group via methylene groups. <2> The compound is a reaction product of a (meth)acrylic compound (X) which is at least one selected from the group consisting of (meth)acrylic acid and halides of (meth)acrylic acid, and a primary amine compound (Y1) which contains two amino groups and the divalent alicyclic hydrocarbon group, and in which nitrogen atoms in the two amino groups are both bonded to the divalent alicyclic hydrocarbon group via a methylene group. <1> The (meth)acrylamide compound according to any one of claims 1 to 4. <3> The primary amine compound (Y1) includes a compound represented by the following formula (1-1) or (1-2): <2> The (meth)acrylamide compound according to any one of claims 1 to 4.

[0126] [ka]

[0127] <4> It is a compound represented by the following formula (1A): <1> ~ <3> The (meth)acrylamide compound according to any one of the above items.

[0128] [ka]

[0129] In formula (1A), R 1A and R 2A are each independently a hydrogen atom or a methyl group, and R 3A is a divalent group formed by linking a methylene group, a divalent alicyclic hydrocarbon group, and a methylene group in this order. <5> The R in the formula (1A) 3A is a group represented by the following formula (1Aa): <4> The (meth)acrylamide compound according to any one of claims 1 to 4.

[0130] [ka]

[0131] In formula (1Aa), X 1A and X 2A are each independently a methylene group, and Y A is a divalent alicyclic hydrocarbon group having 6 to 9 carbon atoms, and two * each represent a bonding position.

[0132] <6> <1> ~ <5> A monomer composition comprising the (meth)acrylamide compound according to any one of the above items. <7> The content of the (meth)acrylamide compound is 90% by mass or more based on the total mass of the monomer composition. <6> The monomer composition according to claim 1. <8> For dental materials <6> or <7> The monomer composition according to claim 1. <9> <6> ~ <8> 1. A dental composition comprising the monomer composition according to any one of 1 to 8 above and a polymerization initiator. <10> <9> A cured product of the dental composition according to claim 1. <11> <10> A dental material comprising the cured product according to claim 1. [Example]

[0133] Hereinafter, embodiment A will be described in more detail with reference to examples, but embodiment A is not limited to the following examples. The abbreviations for the compounds used in the examples of embodiment A are shown below. EDC·HCl: 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride DCM: dichloromethane NBDA: bis(aminomethyl)norbornane H6XDA: 1,3-bis(aminomethyl)cyclohexane IPDA: Isophoronediamine XDA: m-xylylenediamine CHDA: 1,3-cyclohexanediamine H12MDA: 4,4'-methylenebis(cyclohexylamine) mPDA: m-phenylenediamine D-400: JEFFAMINE® D-400 D-2000: JEFFAMINE® D-2000 DODA: 1,2-bis(2-aminoethoxy)ethane UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate HEMA: 2-hydroxyethyl methacrylate MDP: 10-(phosphonooxy)decyl methacrylate 3G: Triethylene glycol dimethacrylate CQ: Camphorquinone DMBE: 2-butoxyethyl 4-(dimethylamino)benzoate EtOH: ethanol DW: Distilled water

[0134] The structural formulae of the above-mentioned NBDA, H6XDA, IPDA, XDA, CHDA, H12MDA, mPDA, D-400, D-2000, and DODA are as follows:

[0135] [ka]

[0136] [ka]

[0137] [HPLC measurement method] The HPLC chart spectrum of the (meth)acrylamide compound obtained in each of the Examples and Comparative Examples was measured using an HPLC apparatus: LC-20AT manufactured by Shimadzu Corporation. The (meth)acrylamide compounds obtained in each Example or Comparative Example were dissolved in CH3CN, and then the (meth)acrylamide compounds were measured using an eluent of CH3CN / H2O=90 / 10.

[0138] [Adhesion strength test method] The adhesive strength test method for the examples and comparative examples of embodiment A is shown below.

[0139] (Preparation of test pieces for adhesive strength test) Extracted and frozen bovine mandibular anterior teeth were thawed under running water, and the roots were amputated and the pulp removed. They were placed in a 25mm diameter, 25mm deep plastic cylindrical container and embedded in acrylic resin. The surface was wet polished with #120 and #400 emery paper, and the enamel was scraped off parallel to the labial surface to prepare enamel specimens. Next, the flat surface was dried by blowing compressed air onto it for approximately 1 second, and then the adhesive strength test composition prepared was applied to the flat surface of the enamel and gently blown with compressed air. This surface was then irradiated with visible light for 20 seconds using a Translux 2Wave (Heraeus-Kulzer). A 2.38 mm diameter plastic mold (ULTRADENT) was then placed on top of the mold, and dental composite resin (Venus Diamond, Heraeus-Kulzer) was filled in and cured by irradiating with visible light for 20 seconds using a visible light irradiator. The mold was then removed, and an enamel adhesive sample was prepared. Dentin was used instead of enamel to prepare a dentin adherend, which was then used to prepare a dentin adhesive specimen.

[0140] (Method for measuring adhesive strength test) The samples were stored in 37°C warm water for 24 hours, and then a shear load was applied to each adhesive sample parallel to and in contact with the surface at a crosshead speed of 1.0 mm / min using a general-purpose testing machine (Precision Universal Material Testing Machine 210X, manufactured by INTESCO Corporation). The shear adhesive strength was determined from the shear load at which the columnar composition formed on the surface of the sample separated from the surface.

[0141] [Bending strength test method] The bending strength test method for the examples and comparative examples of embodiment A is shown below.

[0142] (Preparation of test specimens for bending strength test) The bending strength test composition was placed in a 2x2x25mm stainless steel mold and irradiated with light for 3 minutes on each side for a total of 6 minutes on both sides using a visible light irradiation device (Alpha Light V, manufactured by Morita Corporation). The test specimen was then removed from the mold and heat-treated in an oven at 130°C for 2 hours. After removing the test specimen from the oven and cooling it to room temperature, it was immersed in distilled water in a sealable sample bottle and kept at 37°C for 24 hours to be used as the test specimen (test specimen for bending strength test).

[0143] (Bending strength test) The test pieces prepared by the above method were subjected to a three-point bending test using a testing machine (Shimadzu Autograph EZ-S) at a support distance of 20 mm and a crosshead speed of 1 mm / min to measure the elastic modulus and breaking strength.

[0144] [Water absorption test method] The method for the water absorption test in the examples and comparative examples of embodiment A is shown below.

[0145] (Preparation of test specimens for water absorption test) The composition for the water absorption test is strengthThe composition was the same as the test composition and was prepared in accordance with JIS T 6514:2015 and ISO 4049:2009. A visible light irradiation device (Alpha Light V manufactured by Morita Corporation) was used for curing.

[0146] (Water absorption test) The water absorption test was carried out using the test pieces prepared by the above method in accordance with JIS T 6514:2015 and ISO4049:2009 (N=5). Calculations were made using the measured values ​​of each test piece.

[0147] [IR spectrum measurement method] The IR spectrum of the (meth)acrylamide compound obtained in each production example was measured using a Fourier transform infrared spectrometer, Spectrum Two / UATR (Universal Attenuated Total Reflectance), manufactured by PerkinElmer Japan Co., Ltd. The obtained (meth)acrylamide compound was allowed to stand at 20°C for 24 hours, and then the infrared absorption spectrum of the (meth)acrylamide compound was measured at 20°C.

[0148] [Production Example 1: Production of NBDA + methacrylic acid condensate] A 300 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 17.22 parts by mass of methacrylic acid and 100 parts by mass of DCM and dissolved. The solution was then cooled to 10°C, and 38.34 parts by mass of EDC·HCl was added in portions so that the internal temperature did not exceed 10°C. After dissolving to form a homogeneous solution, the reaction was allowed to proceed at 10°C for 0.5 hours. 15.43 parts by mass of NBDA was added dropwise to the solution over 0.5 hours. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 30°C. After the entire amount was added dropwise, the reaction temperature was maintained at 30°C and the reaction was continued for 6 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. 50 parts by mass of 5% citric acid aqueous solution was added to the flask and stirred for 10 minutes, after which the aqueous layer was discarded. The same procedure was repeated with distilled water, 5% sodium carbonate aqueous solution, and distilled water, in that order. The remaining DCM layer was distilled off using an evaporator to obtain 21.0 g of methacrylamide (1) as a white solid. The IR spectrum of methacrylamide (1) was measured and found to be 3200 cm -1 ~3500cm -1 The decrease in the peak intensity of the amino group was confirmed. The structure of methacrylamide (1) was confirmed to be the following structure.

[0149] [ka]

[0150] [Production Example 2: Production of H6XDA + methacrylic acid condensate] A 300 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 17.22 parts by mass of methacrylic acid and 100 parts by mass of DCM and dissolved. The solution was then cooled to 10°C, and 38.34 parts by mass of EDC·HCl was added in portions so that the internal temperature did not exceed 10°C. After dissolving to form a homogeneous solution, the reaction was allowed to proceed at 10°C for 0.5 hours. 14.23 parts by mass of H6XDA was added dropwise to the solution over 0.5 hours. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 30°C. After the entire amount was added dropwise, the reaction temperature was maintained at 30°C and the reaction was continued for 5.5 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. 50 parts by mass of 5% aqueous citric acid solution was added to the flask, stirred for 10 minutes, and then the aqueous layer was discarded. The same procedure was repeated with distilled water, 5% aqueous sodium carbonate, and distilled water in that order. The remaining DCM layer was evaporated using an evaporator to obtain 21.8 g of methacrylamide (2) as a white solid. The IR spectrum of methacrylamide (2) was measured and found to be 3200 cm -1 ~3500cm -1 The decrease in the peak intensity of the amino group was confirmed. The structure of methacrylamide (2) was confirmed to be as follows:

[0151] [ka]

[0152] [Production Example 3: Production of IPDA + methacrylic acid condensate] A 300 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 17.22 parts by mass of methacrylic acid and 100 parts by mass of DCM and dissolved. The solution was then cooled to 10°C, and 38.34 parts by mass of EDC·HCl was added in portions so that the internal temperature did not exceed 10°C. After dissolving to form a homogeneous solution, the reaction was allowed to proceed at 10°C for 0.5 hours. 17.03 parts by mass of IPDA was added dropwise to the solution over 0.5 hours. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 30°C. After the entire amount was added dropwise, the reaction temperature was maintained at 30°C and the reaction was continued for 6.5 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. 50 parts by mass of 5% citric acid aqueous solution was added to the flask and stirred for 10 minutes, after which the aqueous layer was discarded. The same procedure was repeated with distilled water, 5% sodium carbonate aqueous solution, and distilled water, in that order. The remaining DCM layer was distilled off using an evaporator to obtain 21.9 g of methacrylamide (3) as a white solid. The IR spectrum of methacrylamide (3) was measured and the -1 ~3500cm -1 The decrease in the peak intensity of the amino group was confirmed. The structure of methacrylamide (3) was confirmed to be the following structure.

[0153] [ka]

[0154] [Production Example 4: Production of XDA + methacrylic acid condensate] A 300 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 17.22 parts by mass of methacrylic acid and 100 parts by mass of DCM and dissolved. The solution was then cooled to 10°C, and 38.34 parts by mass of EDC·HCl was added in portions so that the internal temperature did not exceed 10°C. After dissolving to form a homogeneous solution, the reaction was allowed to proceed at 10°C for 0.5 hours. 13.62 parts by mass of XDA was added dropwise to the solution over 0.5 hours. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 30°C. After the entire amount was added dropwise, the reaction temperature was maintained at 30°C and the reaction was continued for 5 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. 50 parts by mass of 5% citric acid solution was added to the flask and stirred for 10 minutes, after which the aqueous layer was discarded. The same procedure was repeated with distilled water, 5% sodium carbonate solution, and distilled water, in that order. The remaining DCM layer was distilled off using an evaporator to obtain 21.1 g of methacrylamide (4) as a white solid. The IR spectrum of methacrylamide (4) was measured and found to be at 3200 cm -1 ~3500cm -1 The decrease in the peak intensity of the amino group was confirmed. The structure of methacrylamide (4) was confirmed to be the following structure.

[0155] [ka]

[0156] [Production Example 5: Production of CHDA + methacrylic acid condensate] A 300 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 17.22 parts by mass of methacrylic acid and 100 parts by mass of DCM and dissolved. The solution was then cooled to 10°C, and 38.34 parts by mass of EDC·HCl was added in portions so that the internal temperature did not exceed 10°C. After dissolving to form a homogeneous solution, the reaction was allowed to proceed at 10°C for 0.5 hours. 11.42 parts by mass of CHDA was added dropwise to the solution over 0.5 hours. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 30°C. After the entire amount was added dropwise, the reaction temperature was maintained at 30°C and the reaction was continued for 6.5 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. 50 parts by mass of 5% citric acid aqueous solution was added to the flask and stirred for 10 minutes, after which the aqueous layer was discarded. The same procedure was repeated with distilled water, 5% sodium carbonate aqueous solution, and distilled water, in that order. The remaining DCM layer was distilled off using an evaporator to obtain 18.4 g of methacrylamide (5) as a white solid. The IR spectrum of methacrylamide (5) was measured and the -1 ~3500cm -1 The decrease in the peak intensity of the amino group was confirmed. The structure of methacrylamide (5) was confirmed to be as follows:

[0157] [ka]

[0158] [Production Example 6: Production of H12MDA + methacrylic acid condensate] A 300 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 17.22 parts by mass of methacrylic acid and 100 parts by mass of DCM and dissolved. The solution was then cooled to 10°C, and 38.34 parts by mass of EDC·HCl was added in portions so that the internal temperature did not exceed 10°C. After dissolving to form a homogeneous solution, the reaction was carried out at 10°C for 0.5 hours. 21.03 parts by mass of H12MDA was added dropwise to the above solution over 0.5 hours. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 30°C. After the entire amount was added dropwise, the reaction temperature was maintained at 30°C and the reaction was carried out for 7 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. 50 parts by mass of 5% citric acid aqueous solution was added to the flask and stirred for 10 minutes, after which the aqueous layer was discharged. The same procedure was repeated with distilled water, 5% sodium carbonate aqueous solution, and distilled water, in that order. The remaining DCM layer was distilled off using an evaporator to obtain 24.8 g of methacrylamide (6) as a white solid. The IR spectrum of methacrylamide (6) was measured and found to be at 3200 cm -1 ~3500cm -1 The decrease in the peak intensity of the amino group was confirmed. The structure of methacrylamide (6) was confirmed to be the following structure.

[0159] [ka]

[0160] [Production Example 7: Production of mPDA + methacrylic acid condensate] A 300 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 17.22 parts by mass of methacrylic acid and 100 parts by mass of DCM and dissolved. The solution was then cooled to 10°C, and 38.34 parts by mass of EDC·HCl was added in portions so that the internal temperature did not exceed 10°C. After dissolving to form a homogeneous solution, the reaction was carried out at 10°C for 0.5 hours. 10.81 parts by mass of mPDA was added dropwise to the above solution over 0.5 hours. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 30°C. After the entire amount was added dropwise, the reaction temperature was maintained at 30°C and the reaction was carried out for 5.5 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. 50 parts by mass of 5% citric acid aqueous solution was added to the flask and stirred for 10 minutes, after which the aqueous layer was discarded. The same procedure was repeated with distilled water, 5% sodium carbonate aqueous solution, and distilled water, in that order. The remaining DCM layer was distilled off using an evaporator to obtain 19.3 g of methacrylamide (7) as a white solid. The IR spectrum of methacrylamide (7) was measured and found to be at 3200 cm -1 ~3500cm -1 The decrease in the peak intensity of the amino group was confirmed. The structure of methacrylamide (7) was confirmed to be the following structure.

[0161] [ka]

[0162] [Production Example 8: Production of D-400 + methacrylic acid condensate] A 300 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 8.61 parts by mass of methacrylic acid and 100 parts by mass of DCM and dissolved. The solution was then cooled to 10°C, and 19.17 parts by mass of EDC·HCl was added in portions so that the internal temperature did not exceed 10°C. After dissolving to form a homogeneous solution, the reaction was allowed to proceed at 10°C for 0.5 hours. 20.00 parts by mass of D-400 was added dropwise to the solution over 0.5 hours. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 30°C. After the entire amount was added dropwise, the reaction temperature was maintained at 30°C and the reaction was continued for 6 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. 50 parts by mass of 5% citric acid aqueous solution was added to the flask and stirred for 10 minutes, after which the aqueous layer was discarded. The same procedure was repeated with distilled water, 5% sodium carbonate aqueous solution, and distilled water, in that order. The remaining DCM layer was distilled off using an evaporator to obtain 18.6 g of methacrylamide (8) as a colorless liquid. The IR spectrum of methacrylamide (8) was measured and the peak was observed at 3200 cm -1 ~3500cm -1 The decrease in the peak intensity of the amino group was confirmed. The structure of methacrylamide (8) was confirmed to be the following structure.

[0163] [ka]

[0164] [Production Example 9: Production of D-2000 + methacrylic acid condensate] A 300 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 1.72 parts by mass of methacrylic acid and 100 parts by mass of DCM and dissolved. The solution was then cooled to 10°C, and 3.83 parts by mass of EDC·HCl was added in portions so that the internal temperature did not exceed 10°C. After dissolving to form a homogeneous solution, the reaction was allowed to proceed at 10°C for 0.5 hours. 20.00 parts by mass of D-2000 was added dropwise to the solution over 0.5 hours. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 30°C. After the entire amount was added dropwise, the reaction temperature was maintained at 30°C and the reaction was continued for 5.5 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. 50 parts by mass of 5% aqueous citric acid solution was added to the flask, stirred for 10 minutes, and then the aqueous layer was discarded. The same procedure was repeated with distilled water, 5% aqueous sodium carbonate, and distilled water in that order. The remaining DCM layer was evaporated using an evaporator to obtain 13.7 g of methacrylamide (9) as a brown liquid. The IR spectrum of methacrylamide (9) was measured and the peak was observed at 3200 cm -1 ~3500cm -1 The decrease in the peak intensity of the amino group was confirmed. The structure of methacrylamide (9) was confirmed to be the following structure.

[0165] [ka]

[0166] [Production Example 10: Production of DODA + methacrylic acid condensate] A 300 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 17.22 parts by mass of methacrylic acid and 100 parts by mass of DCM and dissolved. The solution was then cooled to 10°C, and 38.34 parts by mass of EDC·HCl was added in portions so that the internal temperature did not exceed 10°C. After dissolving to form a homogeneous solution, the reaction was allowed to proceed at 10°C for 0.5 hours. 14.82 parts by mass of DODA was added dropwise to the solution over 0.5 hours. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 30°C. After the entire amount was added dropwise, the reaction temperature was maintained at 30°C and the reaction was continued for 6 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. 50 parts by mass of 5% citric acid aqueous solution was added to the flask and stirred for 10 minutes, after which the aqueous layer was discarded. The same procedure was repeated with distilled water, 5% sodium carbonate aqueous solution, and distilled water, in that order. The remaining DCM layer was removed by distillation using an evaporator to obtain 17.8 g of methacrylamide (10) as a pale yellow liquid. The IR spectrum of methacrylamide (10) was measured at 3200 cm -1 ~3500cm -1 The decrease in the peak intensity of the amino group was confirmed. The structure of methacrylamide (10) was confirmed to be the following structure.

[0167] [ka]

[0168] [Example 1] 0.79 parts by mass of methacrylamide (1) obtained in Production Example 1, 2.38 parts by mass of UDMA, 0.79 parts by mass of 3G, 0.02 parts by mass of CQ, and 0.02 parts by mass of DMBE were placed in a container and stirred at 50°C until a uniform mixture of 1 was obtained. Next, 6 parts by mass of silica glass (Fuselex-X (Tatsumori Co., Ltd.)) was added, and the mixture was stirred in a mortar until a uniform mixture of 1 was obtained, followed by degassing to prepare a composition for a bending strength test. A water absorption test was conducted using the resulting bending strength test composition according to the methods described in the sections (Preparation of test pieces for water absorption test) and (Water absorption test). The results are shown in Table 1.

[0169] [Examples 2 to 7, Comparative Examples 1 to 3] The compositions shown in Table 1 were prepared in the same manner as in Example 1, and bending strength tests and water absorption tests were carried out. The results are also shown in Table 1.

[0170] [Reference example 1] UDMA 3.17 parts by mass, 3G 0.79 parts by mass, CQ 0.02 parts by mass, DMBE 0.02 parts by mass of the mixture was placed in a container and stirred at 50°C until the mixture was uniformly mixed to 1. Next, 6 parts by mass of silica glass (Fuselex-X (Tatsumori Co., Ltd.)) was added, and the mixture was stirred in a mortar until the mixture was uniformly mixed to 1. After that, the mixture was degassed to prepare a composition for a bending strength test. A water absorption test was carried out using the obtained composition for a bending strength test according to the methods described in the sections (Preparation of test pieces for water absorption test) and (Water absorption test). The results are shown in Table 1.

[0171] [Table 1]

[0172] As shown in Table 1, in the examples using a monomer composition for dental materials containing a (meth)acrylamide compound (A) having a cyclic structure and a (meth)acrylamide group, the increase in water absorption was suppressed and the bending strength was well maintained. On the other hand, in Comparative Examples 1 to 3, which used a (meth)acrylamide compound not containing a cyclic structure, the increase in water absorption could not be suppressed, resulting in a decrease in bending strength. Furthermore, in the Examples, the increase in water absorption was suppressed to a similar extent as in Reference Example 1, and the bending strength was well maintained.

[0173] [Example 8] 0.50 parts by mass of methacrylamide (1) obtained in Production Example 1, 2.97 parts by mass of UDMA, 0.99 parts by mass of HEMA, 0.50 parts by mass of MDP, 0.02 parts by mass of CQ, and 0.02 parts by mass of DMBE were placed in a container and stirred at 50°C until homogenous. Next, 5 g of an aqueous solution adjusted to EtOH:DW = 3:2 was added and stirred at room temperature until homogenous to obtain a composition for adhesive strength testing. From the obtained composition for adhesive strength testing (preparation of test pieces for adhesive strength testing), and (contact Wear strength test Measurement method The adhesive strength test was carried out according to the method described in the previous section. The results are shown in Table 2.

[0174] [Examples 9 to 14, Comparative Example 4] The compositions shown in Table 2 were prepared in the same manner as in Example 8, and adhesive strength tests were carried out. The results are also shown in Table 2.

[0175] [Reference example 2] 3.47 parts by mass of UDMA, 0.99 parts by mass of HEMA, 0.50 parts by mass of MDP, 0.02 parts by mass of CQ, and 0.02 parts by mass of DMBE were placed in a container and stirred at 50°C until homogenous. Next, 5 g of an aqueous solution adjusted to EtOH:DW = 3:2 was added and stirred at room temperature until homogenous to obtain a composition for adhesive strength testing. From the obtained composition for adhesive strength testing, (preparation of test pieces for adhesive strength testing) and (contact Wear strength test Measurement method The adhesive strength test was carried out according to the method described in the previous section. The results are shown in Table 2.

[0176] [Table 2]

[0177] As shown in Table 2, the examples using the monomer composition for dental materials containing the (meth)acrylamide compound (A) having a cyclic structure and a (meth)acrylamide group had excellent adhesive strength to enamel and dentin when compared with Reference Example 2. On the other hand, Comparative Example 4, which used a (meth)acrylamide compound not containing a cyclic structure, was inferior in adhesive strength to enamel and dentin when Reference Example 2 was used as the standard.

[0178] Hereinafter, embodiment A-1 will be described in more detail with reference to examples, but embodiment A-1 is not limited to the following examples. The abbreviations for the compounds used in the examples of embodiment A-1 are shown below. EDC·HCl: 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride DCM: dichloromethane NBDA: bis(aminomethyl)norbornane H6XDA: 1,3-bis(aminomethyl)cyclohexane IPDA: Isophoronediamine XDA: m-xylylenediamine D-400: JEFFAMINE® D-400 D-2000: JEFFAMINE® D-2000 DODA: 1,2-bis(2-aminoethoxy)ethane UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate HEMA: 2-hydroxyethyl methacrylate MDP: 10-(phosphonooxy)decyl methacrylate 3G: Triethylene glycol dimethacrylate CQ: Camphorquinone DMBE: 2-butoxyethyl 4-(dimethylamino)benzoate EtOH: ethanol DW: Distilled water

[0179] The structural formulae of the above-mentioned NBDA, H6XDA, IPDA, XDA, D-400, D-2000, and DODA are as follows:

[0180] [ka]

[0181] [ka]

[0182] [HPLC measurement method] In the examples of embodiment A-1, the HPLC measurement method is the same as the method described in [HPLC measurement method] in the examples of embodiment A.

[0183] [Adhesion strength test method] The adhesive strength test method for the examples and comparative examples of embodiment A-1 is shown below.

[0184] (Preparation of test pieces for adhesive strength test) In the examples of embodiment A-1, test pieces for adhesive strength tests are prepared by the same method as that described in (Preparation of test pieces for adhesive strength tests) in the examples of embodiment A.

[0185] (Method for measuring adhesive strength test) In the examples of embodiment A-1, the measurement method for the adhesive strength test was the same as the method described in (Method for measuring adhesive strength test) in the examples of embodiment A.

[0186] [Bending strength test method] The bending strength test method for the examples and comparative examples of embodiment A-1 is shown below.

[0187] (Preparation of test specimens for bending strength test) In the examples of embodiment A-1, the test piece for the bending strength test is prepared by the same method as that described in (Preparation of test piece for bending strength test) in the examples of embodiment A.

[0188] (Bending strength test) In the examples of embodiment A-1, the bending strength test is carried out by the same method as that described in the (Bending Strength Test) in the examples of embodiment A.

[0189] [Water absorption test method] The method of the water absorption test in the examples and comparative examples of embodiment A-1 is shown below.

[0190] (Preparation of test specimens for water absorption test) In the examples of embodiment A-1, the test piece for the water absorption test is prepared by the same method as that described in (Preparation of test piece for water absorption test) in the examples of embodiment A.

[0191] (Water absorption test) In the examples of embodiment A-1, the water absorption test is carried out by the same method as that described in (Water absorption test) in the examples of embodiment A.

[0192] [IR spectrum measurement method] In the examples of embodiment A-1, the method for measuring IR spectrum is the same as the method described in [Method for measuring IR spectrum] in the examples of embodiment A.

[0193] [Production Example 1A: Production of NBDA + methacrylic acid condensate] A 300 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 17.22 parts by mass of methacrylic acid and 100 parts by mass of DCM and dissolved. The solution was then cooled to 10°C, and 38.34 parts by mass of EDC·HCl was added in portions so that the internal temperature did not exceed 10°C. After dissolving to form a homogeneous solution, the reaction was carried out at 10°C for 0.5 hours. 15.43 parts by mass of NBDA was added dropwise to the solution over 0.5 hours. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 30°C. After the entire amount was added dropwise, the reaction temperature was maintained at 30°C and the reaction was carried out for 6 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. 50 parts by mass of 5% citric acid aqueous solution was added to the flask and stirred for 10 minutes, after which the aqueous layer was discharged. The same procedure was repeated with distilled water, 5% sodium carbonate aqueous solution, and distilled water, in that order. The remaining DCM layer was distilled off using an evaporator to obtain 21.0 g of methacrylamide (1) as a white solid. The IR spectrum of methacrylamide (1) was measured and found to be 3200 cm -1 ~3500cm -1 The decrease in the peak intensity of the amino group was confirmed. The structure of methacrylamide (1) was confirmed to be the following structure.

[0194] [ka]

[0195] [Production Example 2A: Production of H6XDA + methacrylic acid condensate] A 300 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 17.22 parts by mass of methacrylic acid and 100 parts by mass of DCM and dissolved. The solution was then cooled to 10°C, and 38.34 parts by mass of EDC·HCl was added in portions so that the internal temperature did not exceed 10°C. After dissolving to form a homogeneous solution, the reaction was allowed to proceed at 10°C for 0.5 hours. 14.23 parts by mass of H6XDA was added dropwise to the solution over 0.5 hours. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 30°C. After the entire amount was added dropwise, the reaction temperature was maintained at 30°C and the reaction was continued for 5.5 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. 50 parts by mass of 5% aqueous citric acid solution was added to the flask, stirred for 10 minutes, and then the aqueous layer was discarded. The same procedure was repeated with distilled water, 5% aqueous sodium carbonate, and distilled water in that order. The remaining DCM layer was evaporated using an evaporator to obtain 21.8 g of methacrylamide (2) as a white solid. The IR spectrum of methacrylamide (2) was measured and found to be 3200 cm -1 ~3500cm -1 The decrease in the peak intensity of the amino group was confirmed. The structure of methacrylamide (2) was confirmed to be as follows:

[0196] [ka]

[0197] [Production Example 3A: Production of IPDA + methacrylic acid condensate] A 300 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 17.22 parts by mass of methacrylic acid and 100 parts by mass of DCM and dissolved. The solution was then cooled to 10°C, and 38.34 parts by mass of EDC·HCl was added in portions so that the internal temperature did not exceed 10°C. After dissolving to form a homogeneous solution, the reaction was allowed to proceed at 10°C for 0.5 hours. 17.03 parts by mass of IPDA was then added dropwise to the solution over 0.5 hours. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 30°C. After the entire amount was added dropwise, the reaction temperature was maintained at 30°C and the reaction was continued for 6.5 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. 50 parts by mass of 5% citric acid aqueous solution was added to the flask and stirred for 10 minutes, after which the aqueous layer was discarded. The same procedure was repeated with distilled water, 5% sodium carbonate aqueous solution, and distilled water, in that order. The remaining DCM layer was distilled off using an evaporator to obtain 21.9 g of methacrylamide (3) as a white solid. The IR spectrum of methacrylamide (3) was measured and the -1 ~3500cm -1 The decrease in the peak intensity of the amino group was confirmed. The structure of methacrylamide (3) was confirmed to be the following structure.

[0198] [ka]

[0199] [Production Example 4A: Production of XDA + methacrylic acid condensate] A 300 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 17.22 parts by mass of methacrylic acid and 100 parts by mass of DCM and dissolved. The solution was then cooled to 10°C, and 38.34 parts by mass of EDC·HCl was added in portions so that the internal temperature did not exceed 10°C. After dissolving to form a homogeneous solution, the reaction was allowed to proceed at 10°C for 0.5 hours. 13.62 parts by mass of XDA was then added dropwise to the solution over 0.5 hours. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 30°C. After the entire amount was added dropwise, the reaction temperature was maintained at 30°C and the reaction was continued for 5 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. 50 parts by mass of 5% citric acid aqueous solution was added to the flask and stirred for 10 minutes, after which the aqueous layer was discarded. The same procedure was repeated with distilled water, 5% sodium carbonate aqueous solution, and distilled water, in that order. The remaining DCM layer was distilled off using an evaporator to obtain 21.1 g of methacrylamide (4) as a white solid. The IR spectrum of methacrylamide (4) was measured and found to be at 3200 cm -1 ~3500cm -1 The decrease in the peak intensity of the amino group was confirmed. The structure of methacrylamide (4) was confirmed to be the following structure.

[0200] [ka]

[0201] [Production Example 5A: Production of D-400 + methacrylic acid condensate] A 300 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 8.61 parts by mass of methacrylic acid and 100 parts by mass of DCM and dissolved. The solution was then cooled to 10°C, and 19.17 parts by mass of EDC·HCl was added in portions so that the internal temperature did not exceed 10°C. After dissolving to form a homogeneous solution, the reaction was allowed to proceed at 10°C for 0.5 hours. 20.00 parts by mass of D-400 was added dropwise to the solution over 0.5 hours. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 30°C. After the entire amount was added dropwise, the reaction temperature was maintained at 30°C and the reaction was continued for 6 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. 50 parts by mass of 5% citric acid aqueous solution was added to the flask and stirred for 10 minutes, after which the aqueous layer was discarded. The same procedure was repeated with distilled water, 5% sodium carbonate aqueous solution, and distilled water, in that order. The remaining DCM layer was distilled off using an evaporator to obtain 18.6 g of methacrylamide (5) as a colorless liquid. The IR spectrum of methacrylamide (5) was measured and the -1 ~3500cm -1 The decrease in the peak intensity of the amino group was confirmed. The structure of methacrylamide (5) was confirmed to be as follows:

[0202] [ka]

[0203] [Production Example 6A: Production of D-2000 + methacrylic acid condensate] A 300 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 1.72 parts by mass of methacrylic acid and 100 parts by mass of DCM and dissolved. The solution was then cooled to 10°C, and 3.83 parts by mass of EDC·HCl was added in portions so that the internal temperature did not exceed 10°C. After dissolving to form a homogeneous solution, the reaction was allowed to proceed at 10°C for 0.5 hours. 20.00 parts by mass of D-2000 were added dropwise to the solution over 0.5 hours. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 30°C. After the entire amount was added dropwise, the reaction temperature was maintained at 30°C and the reaction was continued for 5.5 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. 50 parts by mass of 5% aqueous citric acid solution was added to the flask, stirred for 10 minutes, and then the aqueous layer was discarded. The same procedure was repeated with distilled water, 5% aqueous sodium carbonate, and distilled water in that order. The remaining DCM layer was evaporated using an evaporator to obtain 13.7 g of methacrylamide (6) as a brown liquid. The IR spectrum of methacrylamide (6) was measured and found to be at 3200 cm -1 ~3500cm -1 The decrease in the peak intensity of the amino group was confirmed. The structure of methacrylamide (6) was confirmed to be the following structure.

[0204] [ka]

[0205] [Production Example 7A: Production of DODA + methacrylic acid condensate] A 300 mL four-neck flask equipped with a thoroughly dried stirring blade and thermometer was charged with 17.22 parts by mass of methacrylic acid and 100 parts by mass of DCM and dissolved. The solution was then cooled to 10°C, and 38.34 parts by mass of EDC·HCl was added in portions so that the internal temperature did not exceed 10°C. After dissolving to form a homogeneous solution, the reaction was allowed to proceed at 10°C for 0.5 hours. 14.82 parts by mass of DODA was added dropwise to the solution over 0.5 hours. During the addition, the internal temperature rose due to the heat of reaction, so the amount added was controlled to keep the temperature below 30°C. After the entire amount was added dropwise, the reaction temperature was maintained at 30°C and the reaction was continued for 6 hours. The reaction progress was monitored by HPLC analysis to confirm the end point. 50 parts by mass of 5% citric acid aqueous solution was added to the flask and stirred for 10 minutes, after which the aqueous layer was discarded. The same procedure was repeated with distilled water, 5% sodium carbonate aqueous solution, and distilled water, in that order. The remaining DCM layer was removed by distillation using an evaporator to obtain 17.8 g of methacrylamide (7) as a pale yellow liquid. The IR spectrum of methacrylamide (7) was measured and found to be at 3200 cm -1 ~3500cm -1 The decrease in the peak intensity of the amino group was confirmed. The structure of methacrylamide (7) was confirmed to be the following structure.

[0206] [ka]

[0207] Example 1A 0.50 parts by mass of methacrylamide (1) obtained in Production Example 1A, 2.97 parts by mass of UDMA, 0.99 parts by mass of HEMA, 0.50 parts by mass of MDP, 0.02 parts by mass of CQ, and 0.02 parts by mass of DMBE were placed in a container and stirred at 50°C until homogenous. Next, 5 g of an aqueous solution adjusted to EtOH:DW = 3:2 was added and stirred at room temperature until homogenous to obtain a composition for adhesive strength testing. From the obtained composition for adhesive strength testing (preparation of test pieces for adhesive strength testing), and (contact Wear strength test Measurement method The adhesive strength test was carried out according to the method described in the previous section. The results are shown in Table 3.

[0208] [Examples 2A to 4A, Comparative Example 1A] The compositions shown in Table 3 were prepared in the same manner as in Example 1A, and adhesive strength tests were carried out. The results are also shown in Table 3.

[0209] [Reference Example 1A] 3.47 parts by mass of UDMA, 0.99 parts by mass of HEMA, 0.50 parts by mass of MDP, 0.02 parts by mass of CQ, and 0.02 parts by mass of DMBE were placed in a container and stirred at 50°C until homogenous. Next, 5 g of an aqueous solution adjusted to EtOH:DW = 3:2 was added and stirred at room temperature until homogenous to obtain a composition for adhesive strength testing. From the obtained composition for adhesive strength testing, (preparation of test pieces for adhesive strength testing) and (contact Wear strength test Measurement method The adhesive strength test was carried out according to the method described in the previous section. The results are shown in Table 3.

[0210] [Table 3]

[0211] As shown in Table 3, Examples 1A and 2A, which used a (meth)acrylamide compound (A-1) containing two (meth)acrylamide groups and a divalent alicyclic hydrocarbon group, in which the nitrogen atoms in the two (meth)acrylamide groups are both bonded to the divalent alicyclic hydrocarbon group via a methylene group, had superior adhesive strength to enamel and dentin compared to Examples 3A to 4A and Comparative Example 1A.

[0212] Example 5A 0.79 parts by weight of methacrylamide (1) obtained in Production Example 1A, 2.38 parts by weight of UDMA, 0.79 parts by weight of 3G, 0.02 parts by weight of CQ, and 0.02 parts by weight of DMBE were placed in a container and stirred at 50 °C until uniform. Next, 6 parts by weight of silica glass (Fuselex-X (Tatsumori Co., Ltd.)) was added, and the mixture was stirred in a mortar until uniform, followed by degassing to prepare a flexural strength test composition (1). A water absorption test was conducted using the resulting flexural strength test composition according to the methods described in the sections "Preparation of test pieces for water absorption test" and "Water absorption test." The results are shown in Table 4.

[0213] [Examples 6A to 8A, Comparative Examples 2A to 4A] The compositions shown in Table 4 were prepared in the same manner as in Example 5A, and bending strength tests and water absorption tests were carried out. The results are also shown in Table 4.

[0214] [Reference example 2A] UDMA 3.17 parts by mass, 3G 0.79 parts by mass, CQ 0.02 parts by mass, DMBE 0.02 parts by mass of the composition was placed in a container and stirred at 50°C until uniform. Next, 6 parts by mass of silica glass (Fuselex-X (Tatsumori Co., Ltd.)) was added, and the mixture was stirred in a mortar until uniform, followed by degassing to prepare a composition for flexural strength testing. A water absorption test was carried out using the obtained composition for flexural strength testing according to the methods described in the sections (Preparation of test pieces for water absorption test) and (Water absorption test). The results are shown in Table 4.

[0215] [Table 4]

[0216] As shown in Table 4, in Examples 5A to 8A, cured products were obtained in which the increase in water absorption was suppressed. Among them, as shown in Table 4, in Examples 5A and 6A, which used a (meth)acrylamide compound (A-1) containing two (meth)acrylamide groups and a divalent alicyclic hydrocarbon group, in which the nitrogen atoms in the two (meth)acrylamide groups are both bonded to the divalent alicyclic hydrocarbon group via a methylene group, the increase in water absorption was suppressed and bending strength was well maintained, compared to Reference Example 2. Furthermore, in Examples 5A and 6A, the increase in water absorption was suppressed to the same extent or greater and bending strength was well maintained compared to Example 7A, which used a (meth)acrylamide compound in which one of the nitrogen atoms in the two (meth)acrylamide groups was not bonded to a divalent alicyclic hydrocarbon group via a methylene group, and Example 8A, which used a (meth)acrylamide compound that did not contain an alicyclic hydrocarbon group, and Comparative Examples 2A to 4A.

[0217] The disclosures of Japanese Patent Application No. 2021-152359, filed on September 17, 2021, and Japanese Patent Application No. 2021-152360, filed on September 17, 2021, are incorporated by reference in their entirety into this specification. All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. a (meth)acrylamide compound (A) containing a cyclic structure and a (meth)acrylamide group, The (meth)acrylamide compound (A) is a reaction product of (meth)acrylic compound (X), which is at least one selected from the group consisting of (meth)acrylic acid and halides of (meth)acrylic acid, and primary amine compound (Y), which has two amino groups and a cyclic structure; The primary amine compound (Y) is a (meth)acrylamide compound (A) containing a compound represented by any one of the following formulas (1-1) to (1-7): 【Chemistry 1】

2. A monomer composition for use as a dental material, comprising the (meth)acrylamide compound (A) according to claim 1, which is a compound represented by the following formula (1): 【Chemistry 2】 In formula (1), R １ and R ２ are each independently a hydrogen atom or a methyl group, and R ３ is a divalent group containing a cyclic structure.

3. The R in the formula (1) ３ A monomer composition for use as a dental material, comprising the (meth)acrylamide compound (A) according to claim 2, wherein is a group represented by the following formula (1a): 【Transformation 3】 In formula (1a), X １ and X ２ are each independently a single bond or a methylene group, Y is a divalent linking group having 6 to 13 carbon atoms and containing an alicyclic structure or an aromatic structure, and two * symbols each represent a bonding position.

4. containing two (meth)acrylamide groups and a divalent alicyclic hydrocarbon group, 2. A monomer composition for use as a dental material, comprising the (meth)acrylamide compound (A) according to claim 1, wherein nitrogen atoms in the two (meth)acrylamide groups are both bonded to the divalent alicyclic hydrocarbon group via a methylene group.

5. (X) a (meth)acrylic compound which is at least one selected from the group consisting of (meth)acrylic acid and halides of (meth)acrylic acid; and a primary amine compound (Y1) which contains two amino groups and the divalent alicyclic hydrocarbon group, in which nitrogen atoms in the two amino groups are both bonded to the divalent alicyclic hydrocarbon group via a methylene group.

6. a (meth)acrylamide compound (A) containing a cyclic structure and a (meth)acrylamide group, The (meth)acrylamide compound (A) is a reaction product of (meth)acrylic compound (X), which is at least one selected from the group consisting of (meth)acrylic acid and halides of (meth)acrylic acid, and primary amine compound (Y), which has two amino groups and a cyclic structure; containing two (meth)acrylamide groups and a divalent alicyclic hydrocarbon group, each nitrogen atom in the two (meth)acrylamide groups is bonded to the divalent alicyclic hydrocarbon group via a methylene group; (X) a (meth)acrylic compound which is at least one selected from the group consisting of (meth)acrylic acid and halides of (meth)acrylic acid; a primary amine compound (Y1) containing two amino groups and the divalent alicyclic hydrocarbon group, wherein nitrogen atoms in the two amino groups are both bonded to the divalent alicyclic hydrocarbon group via a methylene group; A monomer composition for use as a dental material, comprising a (meth)acrylamide compound (A), in which the primary amine compound (Y1) comprises a compound represented by the following formula (1-1) or (1-2): 【Chemistry 4】

7. The (meth)acrylamide compound according to claim 4, which is a compound represented by the following formula (1A): A monomer composition for use as a dental material, comprising the substance (A). 【Transformation 5】 In formula (1A), R １Ａ and R ２Ａ are each independently a hydrogen atom or a methyl group, and R ３Ａ is a divalent group formed by linking a methylene group, a divalent alicyclic hydrocarbon group, and a methylene group in this order.

8. a (meth)acrylamide compound (A) containing a cyclic structure and a (meth)acrylamide group, The (meth)acrylamide compound (A) is a reaction product of (meth)acrylic compound (X), which is at least one selected from the group consisting of (meth)acrylic acid and halides of (meth)acrylic acid, and primary amine compound (Y), which has two amino groups and a cyclic structure; containing two (meth)acrylamide groups and a divalent alicyclic hydrocarbon group, each nitrogen atom in the two (meth)acrylamide groups is bonded to the divalent alicyclic hydrocarbon group via a methylene group; A compound represented by the following formula (1A): The R 3A in the formula (1A) is a group represented by the following formula (1Aa): A monomer composition for use as a dental material, comprising a (meth)acrylamide compound (A). 【Transformation 6】 In formula (1A), R 1A and R 2A each independently represent a hydrogen atom or a methyl group, and R 3A represents a divalent group formed by linking a methylene group, a divalent alicyclic hydrocarbon group, and a methylene group in this order. 【Transformation 7】 In formula (1Aa), X 1A and X 2A each independently represent a methylene group, Y A represents a divalent alicyclic hydrocarbon group having 6 to 9 carbon atoms, and two *'s each represent a bonding position.

9. A monomer composition for use as a dental material, comprising the (meth)acrylamide compound (A) according to claim 1, which has a molecular weight of 150 to 500.

10. A dental composition comprising the monomer composition according to claim 1 and a polymerization initiator.

11. A dental material comprising a cured product of the dental composition according to claim 10.

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