JP6629089B2 - Dental curable composition - Google Patents

Description

  The present invention relates to a curable dental composition containing a novel polymerizable monomer and a photopolymerization initiator useful for dental materials. In more detail, it is stable against environmental light, but the polymerization is completed in a very short time and rapidly by irradiation of light from an irradiator such as a halogen lamp or a xenon lamp, and a dental material with higher physical properties can be obtained. A curable composition is provided.

  (Meth) acrylate-based polymerizable monomers include a wide variety of dental materials such as dental curable compositions and dental adhesives, optical materials, printing plates, photoresist materials, paints, adhesives, inks, and optical molding resins. It can be used in the field (for example, Patent Documents 1 to 4). In particular, as a (meth) acrylate polymerizable monomer from which a cured product having excellent mechanical strength can be obtained, bisphenol A diglycidyl di (meth) acrylate (Bis-GMA) exemplified in Patent Documents 2 and 3 is represented. Polymerizable monomers having a bisphenol A skeleton, and polymerizable monomers having a biphenyl skeleton exemplified in Patent Documents 4 and 5 are known.

  In the restoration of a tooth having a defect caused by dental caries or the like, when the defect is small, the mainstream is a method of filling a composite resin for dental filling, giving a tooth shape, and then polymerizing and hardening. Here, the composite resin for dental filling is mainly composed of a (meth) acrylate-based polymerizable monomer (hereinafter, the polymerizable monomer is also referred to as a monomer) and an inorganic filler such as a metal oxide. It is a tooth restoration material comprising a paste-like polymerizable composition.

  In the field of dentistry, the method of polymerizing a dental restoration material is roughly classified into photopolymerization and chemical polymerization. In particular, in the case of a photopolymerization type restoration material using a photopolymerization initiator, if the light is blocked, the polymerization reaction hardly progresses. Therefore, all components should be manufactured and stored in a paste. Can be. Therefore, there is an advantage that mixing and kneading at the time of use, which is necessary for the chemical polymerization type, is not required, and the pot life is long. Therefore, in recent years, photopolymerization-type restoration materials have become mainstream.

  In the field of dental treatment, it is difficult to use a photopolymerization initiator having an activity in the ultraviolet region due to its harm to living organisms. Therefore, a photopolymerization initiator having an activity in the visible light region is mainly used. . Examples of the photopolymerization initiator include compounds that absorb light such as α-diketone and acylphosphine oxide and decompose themselves to generate polymerization active species, and further, suitable compounds such as tertiary amine compounds. Systems combining sensitizers are widely used.

In the above-mentioned method of treating a tooth, a light-curing type composite resin for filling is filled into a cavity of a tooth to be repaired and shaped into a tooth, and then the active light is irradiated using a special visible light irradiator. The restoration of teeth is performed by irradiation and polymerization and curing. Generally, if the photopolymerization initiator uses the α-diketone compound, such active light has a wavelength range of about 360 to 500 nm (which is a main absorption range of the α-diketone compound). The light is emitted from a distance of about 0 to 10 mm using a light source having an intensity of about 100 to 2000 mW / cm ² .

  After the filling composite resin is filled into the oral cavity of a patient, the resin is irradiated with active light and polymerized and cured. Therefore, if the light irradiation time for polymerization is long, not only the operation takes a long time but also there is a problem that a great burden is imposed on the patient, and a reduction in the light irradiation time (curing time) is demanded. . In recent years, good aesthetics have also been demanded. For example, a filling resin having a light color tone (white) that can respond to teeth after whitening has been demanded.

One of the techniques for shortening the curing time is to increase the amount of the photopolymerization initiator, particularly the amount of the α-diketone. However, when the blending amount of α-diketone is increased, the ambient light, that is, the operator visually recognizes the shape of the paste and the color tone of the cured product obtained by the polymerization of the paste, such as a dental light or a fluorescent lamp illuminating the oral cavity. White light from a room light or the like (adjusted to about 500 to 10000 lux in consideration of visibility, etc., and depending on the light source, ambient light at 360 to 500 nm which is the main absorption region of the α-diketone compound) The intensity is 1 mW / cm ² or less, and the sensitivity to less than several% of the actinic light is high, and the viscosity of the filling composite resin (paste) during the operations such as filling and building is increased. Has risen, making operation difficult.

  In order to solve such a problem, the curing time is shortened without increasing the amount of α-diketone or without using α-diketone, that is, excellent polymerization activity is exhibited even when the light irradiation time is short. As a photopolymerization initiator which can be suitably used as a photopolymerization initiator for a filling composite resin, a photopolymerization initiator comprising an α-diketone compound, an s-triazine compound substituted by a trihalomethyl group, and an amine compound has been proposed. (For example, see Patent Document 6).

  In addition, an appropriate sensitizer such as an acylphosphine oxide, which is a compound that absorbs light in the above-mentioned wavelength range and decomposes itself to generate a polymerization active species, and a tertiary amine compound and the like are further combined. Systems are also being considered.

JP 2008-534256 A JP 2007-126417 A JP-A-9-157124 JP-A-5-170705 JP-A-63-297344 JP 2005-089729 A

  On the other hand, from the viewpoint of facilitating the handling of the polymerizable monomer, it is advantageous that the polymerizable monomer is a low-viscosity liquid or liquid substance at room temperature. For example, in many cases, a polymerizable monomer is generally used as a mixed composition mixed with other components according to various uses, rather than used alone. In such a case, if the polymerizable monomer is a low-viscosity liquid or liquid substance, blending with other components is extremely easy.

  However, Bis-GMA exemplified in Patent Documents 2 and 3 has an extremely high viscosity in a room temperature environment, and the polymerizable monomer exemplified in Patent Document 4 is solid in a room temperature environment. Poor mechanical strength. Further, the polymerizable monomer exemplified in Patent Document 5 has relatively low viscosity, but also has poor mechanical strength.

  The present invention has been made in view of the above circumstances, and uses a polymerizable monomer that is excellent in mechanical strength of a cured product, has low viscosity even in a room temperature environment, and has excellent handleability. Is stable, but the polymerization is completed in an extremely short time and quickly by irradiation with light from an irradiator such as a halogen lamp or a xenon lamp, thereby providing a dental curable composition capable of obtaining higher cured physical properties. It is.

  The present inventors have conducted intensive studies to solve the above problems.

As a result, by using a specific polymerizable monomer, an α-diketone compound, an aromatic amine compound and a photoacid generator in combination, a dental curable composition using the same can be used with respect to environmental light. The inventors have found that the polymerization is stable and that the polymerization is completed in a remarkably short time, and thus completed the present invention.
That is, (A) a polymerizable monomer represented by the following general formula (1),

[In the general formula (1), X represents —O— , and Ar ¹ and Ar ² each represent an unsubstituted aromatic group having any valence selected from divalent to tetravalent. May be the same or different, and L ¹ and L ² each have a main chain atom number in the range of 2 to 60 and are selected from divalent to tetravalent And each may be the same or different, and R ¹ and R ² each represent hydrogen or a methyl group. Further, m1, m2, n1 and n2 are each an integer selected from the range of 1-3. ]
(B) A dental curable composition comprising a B1) α-diketone compound, B2) a photoacid generator, and B3) a photopolymerization initiator containing an aromatic amine compound. .

Another embodiment of the polymerizable monomer (A) in the dental curable composition of the present invention is as follows: "The number of atoms in the main chain is in the range of 2 to 60, and the divalent is selected from divalent to tetravalent. it is preferable that at least one of L ¹ and L ² 'is a hydrocarbon group having any one of the valency to be contain a hydroxyl group.

  Another embodiment of the polymerizable monomer (A) in the dental curable composition of the present invention is preferably represented by the following general formula (2).

[In the general formula (2), X, L ¹ , L ² , R ¹ and R ² are the same as those in the general formula (1). ]
Another embodiment of the polymerizable monomer (A) in the dental curable composition of the present invention is preferably represented by the following general formula (3).

[In the general formula (3), X is the same as that in the general formula (1), and Ar ¹ and Ar ² have the same general formula (1) except that the valence can take only two valences. And L ³ and L ⁴ each represent a divalent hydrocarbon group having a main chain atom number in the range of 1 to 8, and may be the same or different. Often, R ³ and R ⁴ each represent hydrogen or a methyl group. Also, j is 1 , k is 1, and j + k = 2. ]

The polymerizable monomer (A) in the dental curable composition of the present invention is, for example , at least through a reaction step of reacting a compound represented by the following general formula (4) with a compound represented by the following general formula (5). In this case, a polymerizable monomer containing two or more structural isomers selected from the group consisting of compounds represented by the following general formulas (6) to (8) is manufactured. it is Ru can.

[In the general formulas (4) to (8), X represents -O- , Ar ¹ and Ar ² each represent a divalent unsubstituted aromatic group, and even if they are the same, they may be different. L ⁵ represents a divalent hydrocarbon group having 1 to 7 atoms in the main chain. P is 0 or 1. ]

  According to the present invention, a polymerizable monomer having excellent mechanical strength of a cured product, low viscosity and excellent handleability even at room temperature is used, and furthermore, it is stable against environmental light, but a halogen lamp is used. Irradiation with an irradiator such as a xenon lamp or the like can provide a dental curable composition in which polymerization is completed quickly and in a remarkably short time and higher physical properties can be obtained.

Each component constituting the dental curable composition of the present invention will be described sequentially.
[(A) polymerizable monomer]
(A) The polymerizable monomer is represented by the following general formula (1).

Here, in the general formula (1), X represents a divalent group, Ar ¹ and Ar ² each represent an aromatic group having any valence selected from divalent to tetravalent, L ¹ and L ² may each be the same or different, and each of L ¹ and L ² is any one selected from divalent to tetravalent in which the number of atoms in the main chain is in the range of 2 to 60. Represents a hydrocarbon group having a valence, and may be the same or different, and R ¹ and R ² each represent a hydrogen or a methyl group. Further, m1, m2, n1 and n2 are each an integer selected from the range of 1-3. The polymerizable monomer represented by the general formula (1) may be a mixture of isomers containing two or more isomers.

(A) The polymerizable monomer has excellent mechanical strength of the cured product, and also has excellent handleability because it has a low viscosity even at room temperature. The reason why such an effect is obtained is not clear, but the present inventors presume as follows. First, it is considered that the reason why the cured product is excellent in mechanical strength is that the cured product has a structure (Ar ¹ -X-Ar ² ) containing an aromatic group with high rigidity at the center of the molecule.

In addition, the reason for exhibiting a low viscosity even in a room temperature environment is that the aromatic group Ar ¹ and the aromatic group Ar ² are directly linked via a σ bond, such as a biphenyl structure, at the center of the molecule. Instead of a bonded structure (Ar ¹ -Ar ² ), a structure (Ar ¹ -X-Ar ² ) in which an aromatic group Ar ¹ and an aromatic group Ar ² are bonded via a divalent group X was employed. It is mentioned. Although the structure (Ar ¹ -Ar ² ) has high symmetry in molecular structure and is easily crystallized, the structure (Ar ¹ -X-Ar ² ) in which a divalent group X is further introduced into such a structure has a molecular structure. It is considered that the flexibility of the polymer is increased and the symmetry is reduced, and as a result, the crystallinity is reduced and the viscosity is reduced. In addition, in the polymerizable monomer (A), it is considered that the ester bond connected to the aromatic groups Ar ¹ and Ar ² greatly contributes to the decrease in viscosity.

Further, as described above, the structure (Ar ¹ -X-Ar ² ) has a higher molecular flexibility than the structure (Ar ¹ -Ar ² ). For this reason, the polymerizable monomer (A) is less likely to become brittle and has excellent flexural strength as compared with a polymerizable monomer having a structure (Ar ¹ -Ar ² ) introduced at the molecular center.

Next, the polymerizable monomer represented by the general formula (1) will be described in more detail. First, in the general formula (1), Ar ¹ and Ar ² each represent an aromatic group having any valence selected from divalent to tetravalent, and may be the same or different. Good.

Specific examples of the aromatic groups Ar ¹ and Ar ² include divalent to tetravalent benzene represented by the following structural formulas Ar-a1 to Ar-a3, and divalent to tetravalent represented by the following structural formulas Ar-a4 to Ar-a6. Naphthalene, or divalent to tetravalent anthoselan represented by the following structural formulas Ar-a7 to Ar-a9. In these structural formulas, a bond is provided at an arbitrary carbon of a benzene ring constituting the aromatic groups Ar ¹ and Ar ² (excluding a carbon forming a condensed portion between the benzene ring and the benzene ring). Can be. For example, in the case of the structural formula Ar-a1 (divalent benzene), two bonds can be provided at any of the ortho, meta, and para positions.

The valence of the aromatic group Ar ¹ is determined according to the number of m1, and is represented by m1 + 1. Similarly, the valence of the aromatic group Ar ² is determined according to the number of m2, and is represented by m2 + 1.

The aromatic groups Ar ¹ and Ar ² may each have a substituent. In this case, hydrogen of the benzene ring constituting the aromatic groups Ar ¹ and Ar ² is replaced with another substituent. Can be. The substituent of the aromatic groups Ar ¹ and Ar ² is not particularly limited as long as it does not contain a reactive group (that is, an acryl group or a methacryl group) shown on the left side of the general formula (1) at its terminal. Those having a total number of atoms (number of atoms) constituting the substituent within the range of 1 to 60 can be appropriately selected. Specifically, mention may be made or a monovalent hydrocarbon group having 1 to 20 carbon atoms, -COOR ^3, -OR ^3, halogen group, an amino group, a nitro group, a carboxyl group or the like. Note that R ³ is the same as a monovalent hydrocarbon group having 1 to 20 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a linear or branched hydrocarbon group such as a methyl group and an ethyl group; an alicyclic hydrocarbon group such as a cyclohexyl group; a phenyl group; And a heterocyclic group such as furan.

X represents a divalent group, and specifically, the number of atoms in the main chain bridging the aromatic group Ar ¹ and the aromatic group Ar ² as exemplified in the following structural formulas X-1 to X-13 Is a divalent group of 1 to 3.

The number of atoms in the main chain of the divalent group X is more preferably 1 or 2, and most preferably 1. The divalent group X is an electron donating group capable of donating electrons to a benzoate structure (electron withdrawing group) composed of an aromatic group Ar ¹ (or Ar ² ) and an ester bond connected thereto. Is preferred. Examples of the divalent groups X of such _{electron-donating, -O -, - CH 2 -} , - CH (R 5) - or -S-. Among these -O- or -CH ₂ - Is more preferable, and -O- is particularly preferable. Here, R ⁵ is an alkyl group having 1 to 6 carbon atoms. The electron-donating divalent group X can have a resonance structure as exemplified by the following resonance structural formula, so that the polarity at the center of the molecule is relatively high. For this reason, the affinity with the hydrophilic material with high polarity can be further improved, and as a result, the compatibility with the hydrophilic material can be improved, and the affinity and adhesion to the hydrophilic surface can be improved. It becomes easier. Note that the following resonance structural formula shows that the divalent group X is —O— and the aromatic groups Ar ¹ and Ar ² are phenylene groups (provided that two bonds are provided at the para position). (A) shows the molecular center of the polymerizable monomer.

L ¹ and L ² each represent a hydrocarbon group in which the number of atoms in the main chain is in the range of 2 to 60, and which has any valence selected from divalent to tetravalent; Or different. The number of atoms in the main chain is preferably in the range of 2 to 12, more preferably in the range of 2 to 10, further preferably in the range of 2 to 6, and particularly preferably in the range of 2 to 3. In particular, when the number of atoms in the main chain is in the range of 2 to 3, it becomes easy to further increase the bending strength of the cured product.

  In addition, the atoms constituting the main chain are basically composed of carbon atoms, and all the atoms may be carbon atoms, but it is also possible to replace some of the carbon atoms constituting the main chain with hetero atoms. it can. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. When the main chain contains an oxygen atom as a hetero atom, an ether bond or an ester bond can be introduced into the main chain. The number of hetero atoms that can be introduced into the main chain is preferably about half or less of the number of atoms in the main chain. When the number of atoms in the main chain is 2, the number of hetero atoms that can be introduced into the main chain is one. .

Further, a substituent may be bonded to at least one of the atoms constituting the main chain (usually a carbon atom). Examples of such substituents include an alkyl group having 1 to 3 carbon atoms such as a methyl group, a hydroxyl group, a monovalent hydrocarbon group having a hydroxyl group, a halogen, -COOR ^4, and -OR ^4. Note that R ⁴ is the same as the alkyl group having 1 to 3 carbon atoms. Further, the monovalent hydrocarbon group having a hydroxyl group preferably has 1 to 3 carbon atoms, and more preferably 1 to 2 carbon atoms. Specific examples of the monovalent hydrocarbon group having a hydroxyl _{group, -CH 2 OH, -CH 2 CH} 2 OH, -CH (CH 3) OH and the like.

When it is desired to improve the compatibility with the hydrophilic material or the affinity for the hydrophilic surface, at least one of L ¹ and L ² contains a hydroxyl group. In other words, L ¹ and L ^{1 In} at least one of ² , the substituent is preferably a hydroxyl group and / or a monovalent hydrocarbon group having a hydroxyl group. In addition, the number of hydroxyl groups contained in each of L ¹ and L ² may be at least one or more, but is usually preferably one. Further, hydroxyl groups, it is more preferable that contains one to each of L ¹ and L ^2, in this case, will include two hydroxyl groups in the molecule, if m1, m @ 2 = 1.

In general, a compound having a plurality of hydroxyl groups in a molecule forms an intermolecular hydrogen bond, and as a result, the viscosity tends to increase. Therefore, even when the polymerizable monomer of this embodiment has a hydroxyl group in the molecule, the viscosity tends to increase. However, it is more preferable that a hydroxyl group is present in the vicinity of an ester bond directly bonded to the aromatic groups Ar ¹ and Ar ² , since the increase in viscosity can be relatively suppressed. Here, “when a hydroxyl group is present in the vicinity of the ester bond” specifically means that when one or both of L ¹ and L ² have a hydroxyl group, the main group of L ¹ or L ² having a hydroxyl group is The number of atoms in the chain means in the range of 2 to 10, and the number of atoms in the main chain is particularly preferably in the range of 2 to 3. Although the reason why the above-described effects can be obtained is not clear, the present inventors presume as follows.

When a hydroxyl group is present in the vicinity of an ester bond directly bonded to the aromatic groups Ar ¹ and Ar ² , the hydrogen of the hydroxyl group present in the divalent groups L ¹ and L ² is converted to an aromatic group as shown in the following structural formula. It is expected that an intramolecular hydrogen bond is likely to be formed between the ester group and the oxygen of the carbonyl group of the ester bond directly bonded to Ar ¹ and Ar ² . In addition, the structural formula exemplified below is represented by the following formula in general formula (1): Ar ¹ , Ar ² = phenylene group, X = —O—, L ¹ , L ² = —CH ₂ CH (OH) CH ₂ — , R ¹ , R ² = methyl group, m1, m2, n1 and n2 = 1.

  That is, when an intramolecular hydrogen bond is formed, the formation of an intermolecular hydrogen bond is suppressed. For this reason, in the polymerizable monomer (A), when a hydroxyl group is not contained in the molecule, the viscosity increases when the polymerizable monomer contains a hydroxyl group in the molecule. The increase in the viscosity is suppressed to the same level as the viscosity of the polymerizable monomer (such as Bis-GMA).

In addition, when the intramolecular hydrogen bond is formed, the benzene ring forming the aromatic groups Ar ¹ and Ar ² and the benzene ring directly forming the aromatic group are compared with the case where the intermolecular hydrogen bond is not formed. Distortion occurs in the benzoate structure composed of the ester bond to be bonded, and the symmetry of the molecular structure at the molecular center decreases. Therefore, it is considered that the crystallinity of the molecule is reduced and the remarkable increase in the viscosity is further suppressed. In addition, the formation of intramolecular hydrogen bonds weakens the intermolecular bonds, which may cause a decrease in the mechanical strength of the cured product. However, when (A) the polymerizable monomer has a hydroxyl group near an ester bond directly bonded to the aromatic groups Ar ¹ and Ar ² , the hydroxyl group is more precisely in the molecule than in the intermolecular hydrogen bond. It is considered that the degree of contribution to hydrogen bonding is relatively higher, and it is also considered that it contributes to the formation of a gentle hydrogen bonding network between molecules. Further, when a plurality of hydroxyl groups are contained in a molecule, such as when both L ¹ and L ² have a hydroxyl group, a high-density hydrogen bonding network is easily formed between the molecules. In this case, it is considered that the mechanical strength of the cured product can be higher than that of the polymerizable monomer (A) having no hydroxyl group in the molecule.

Specific examples of L ^{1, L 2,} in the case of ^{n1, n2 = 1 (L 1} , if ^{L 2} is a divalent hydrocarbon group), is the following structural formulas L-b1~L-b14 it can. Note that, of the two bonds shown in these structural formulas, the bond marked with * means a bond bonded to an oxygen atom of an ester bond constituting the benzoate structure at the center of the molecule. Here, in the following structural formulas L-b1 to L-b14, a represents an integer selected from the range of 1 to 11, b represents an integer selected from the range of 1 to 19, and c represents 0 to 11 Represents an integer selected from the range of, d represents an integer selected from the range of 0 to 5, e represents an integer selected from the range of 2 to 5, f is selected from the range of 1 to 6 Represents an integer. The values of a to f are preferably selected in the structural formulas L-b1 to L-b14 so that the number of atoms in the main chain is 12 or less.

On the other hand, when n1 and n2 = 2 (when L ¹ and L ² are trivalent hydrocarbon groups), in the structural formulas L-b1 to L-b14, among the carbon atoms constituting the main chain, * The carbon atom farthest from the carbon atom having the attached bond has two bonds. When n1 and n2 = 3 (when L ¹ and L ² are tetravalent hydrocarbon groups), the structural formulas L-b1 to L-b2, L-b6 to L-b8, and L-b10 to L In -b14, among the carbon atoms constituting the main chain, the carbon atom farthest from the carbon atom having the bond marked with * has three bonds.

The polymerizable monomer (A) represented by the general formula (1) is particularly preferably a polymerizable monomer represented by the following general formula (2). In general formula (2) are the compounds of formula (1), m1, m2, n1, n2 = 1, Ar 1, Ar 2 = -C 6 H 4 - ( structural formula Ar-a1) and to the case structure It is shown.

Further, the polymerizable monomer (A) is preferably a polymerizable monomer represented by the following general formula (3). Here, in the general formula (3), X is the same as that shown in the general formula (1), and Ar ¹ and Ar ² have the same general formula (1) except that the valence can take only two valences. And L ³ and L ⁴ each represent a divalent hydrocarbon group having a main chain atom number in the range of 1 to 8; R ³ and R ⁴ each represent hydrogen or a methyl group. Also, j is 0, 1, or 2, k is 0, 1, or 2, and j + k = 2. In general formula (3) are the compounds of formula ^{(1), m1, m2,} n1, n2 = 1, L 1 = -L 3 -CH (OH) CH 2 - or _-CH (CH 2 OH) -L ^{4 -, L 2 = -L 3} -CH (OH) CH 2 - or ^{_{-CH (CH 2 OH) -L 4}} -, R 1 corresponds to ^{R 3} or ^{R 4, R 2} is ^{R 3} or ^{R 4} (Bifunctional structure). Further, in the general formula (3), the groups shown in parentheses on both the left and right sides can be bonded to any of the two bonding hands of the group shown in the center; -Ar ¹ -X-Ar ^2- . That is, depending on the values of j and k, the group shown in the parenthesis on the left side in the general formula (3) may be bonded to both sides of the group shown in the center, or the group shown on the right side in the general formula (3). Groups shown in parentheses may be attached to both sides of the group shown in the center.

In L ³ and L ⁴ , the atoms constituting the main chain are basically composed of carbon atoms, and all the atoms may be carbon atoms, but a part of the carbon atoms constituting the main chain may be used. Can be replaced by a heteroatom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. When the main chain contains an oxygen atom as a hetero atom, an ether bond or an ester bond can be introduced into the main chain. The number of heteroatoms that can be introduced into the main chain is preferably one or two. However, when the number of atoms in the main chain is 2, the number of heteroatoms that can be introduced into the main chain is one.

In L ³ and L ⁴ , the number of atoms in the main chain may be 1 to 8, but is preferably 1 to 5, more preferably 1 to 3, and most preferably 1. Specific examples of L ³ and L ⁴ include an alkylene group having 1 to 8 carbon atoms in a main chain such as a methylene group, an ethylene group, an n-propylene group, and an n-butylene group, and a main chain of the alkylene group. A group in which a part or the whole is substituted by an ether bond or an ester bond (provided that the number of atoms in the main chain of the alkylene group is 2 or more);

  Examples of the combination (j, k) of the values j and k shown in the general formula (3) include (2, 0), (1, 1), and (0, 2). (1, 1) and (0, 2) are more preferable from the viewpoint that suppression of decomposition of body molecules can be expected. For this reason, the present inventors presume as follows.

Here, the formulas shown below are represented by (j, k) = (1, 1), X = —O—, Ar ¹ , Ar ² = —C ₆ H ₄ —, L ³ , L in the general formula (3). ^{FIG. 4} shows an example of a reaction mechanism in the presence of a water molecule in a polymerizable monomer molecule in which ⁴ = —CH ₂ —, R ³ , and R ⁴ = —CH ₃ . (A) The polymerizable monomer has a molecular structure in which an ester bond directly bonding to an aromatic group in the center of the molecule exists. One of the functions of the polymerizable monomer having such a molecular structure to be decomposed is expected to be a nucleophilic reaction (hydrolysis reaction) of a water molecule to an ester bond directly bonded to an aromatic group (see below). Route B). However, when a primary alcohol contained in the same molecule is present in the immediate vicinity of an ester bond directly bonded to an aromatic group, a cyclization reaction occurs between the primary alcohol and the ester bond in the molecule, thereby temporarily causing a cyclization reaction. A cyclic structure is formed (Route A below). Since this cyclization reaction is reversible, it easily returns to the original linear structure immediately, but this cyclization reaction inhibits the above-described nucleophilic reaction (hydrolysis reaction) and the like. For this reason, it is presumed that decomposition of the polymerizable monomer molecule is inhibited. In this case, since the degradation of the polymerizable monomer or the composition containing the same is suppressed (in other words, storage stability is improved), immediately after the production of the dental curable composition using the polymerizable monomer, Can be stably maintained over a long period of time (for example, the mechanical strength of a cured product).

  Further, (A) the polymerizable monomer has a combination (j, k) of values j and k shown in the general formula (3), which is determined from (2, 0), (1, 1) and (0, 2). Preferably, it contains any two or more structural isomers selected from the group consisting of: When the polymerizable monomer contains two or more types of structural isomers for the combination of (j, k) shown in the general formula (3), the mechanical strength of the cured product and the storage stability are well-balanced. It is easy to improve. In this case, the average value of the value k in all the polymerizable monomer molecules is in the range of 0.05 or more and less than 2.0 (in other words, the average value of the value j is more than 0 and 1.95 or less). Is preferred. Further, the lower limit of the average value k is preferably 0.1 or more, and the upper limit of the average value k is more preferably 1.7 or less, and further preferably 1.5 or less. , 0.4 or less. In addition, in order to improve the mechanical strength of the cured product and the storage stability in a well-balanced manner, the average value k is also 0.05 or more and 2. It is suitable similarly to the case where the range is less than 0. However, the mechanical strength in the initial state without a certain storage period is higher in the state containing two or more structural isomers than in the value k = 2 (in the state not containing structural isomers). be able to. In this regard, it is more advantageous that the average value of the value k is small as long as the average value of the value k is not less than 0.05.

  When only the above-mentioned reaction mechanism is considered, it is expected that the storage stability will improve as the average value of the value k increases. However, the present inventors have studied that the average value of the value k is about 0.1 (the proportion of the primary alcohol present in the vicinity of the ester bond directly bonded to the aromatic group in the total polymerizable monomer is not large). It was confirmed that a remarkable effect of improving the storage stability was obtained even in the case of a small size. From these results, it is presumed that unexpected factors other than the above-described reaction mechanism exist in improving the storage stability.

  (A) The polymerizable monomer can be synthesized by appropriately combining known starting materials and known synthesis reaction methods, and the production method is not particularly limited. For example, when producing a polymerizable monomer represented by the general formula (3), a production method including at least a reaction step of reacting a compound represented by the following general formula (4) with a compound represented by the following general formula (5) May be used. In this case, a polymerizable monomer containing two or more structural isomers selected from the group consisting of compounds represented by the following general formulas (6) to (8) can be produced.

Here, in the general formulas (4) to (8), X, Ar ¹ and Ar ² are the same as those shown in the general formula (3), and L ⁵ is a main chain having 1 to 7 atoms. Represents a divalent hydrocarbon group. P is 0 or 1. Here, the average value of the value k, in other words, the abundance ratio of the structural isomers represented by the general formulas (6) to (8) can be easily adjusted by appropriately selecting the synthesis conditions. In addition, if necessary, by performing a purification treatment after the synthesis, the average value k (the abundance ratio of the structural isomers represented by the general formulas (6) to (8)) is adjusted so as to be closer to a desired value. You may.

In L ⁵ shown in the general formula (4) to (8), atoms composing the main chain is basically composed of carbon atoms, but all the atoms may be carbon atoms, constituting the main chain Some of the carbon atoms may be replaced by heteroatoms. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. When the main chain contains an oxygen atom as a hetero atom, an ether bond or an ester bond can be introduced into the main chain. The number of heteroatoms that can be introduced into the main chain is preferably one or two. However, when the number of atoms in the main chain is 2, the number of heteroatoms that can be introduced into the main chain is one.

The atomic number of the main chain in ^{L 5} represents, but may be a 1-7, preferably 1-4, 1-2 is more preferable. Specific examples of L ³ and L ⁴ include an alkylene group having 1 to 7 carbon atoms in the main chain such as a methylene group, an ethylene group, an n-propylene group, and an n-butylene group; A group in which a part or the whole is substituted by an ether bond or an ester bond (provided that the number of atoms in the main chain of the alkylene group is 2 or more);

In the general formula (6), each L ⁵ may be the same or different. This is the same in general formulas (7) and (8). In the case where it is assumed that different respective L ⁵ each other, as a compound represented by the general formula (5) used for the synthesis, can be used which L ⁵ different two or more compounds. Also, p is preferably 0.

  If necessary, a polymerizable monomer containing two or more structural isomers is obtained by the above-described production method, and then a polymerizable monomer substantially free of structural isomers (for example, a compound represented by the general formula: Only the polymerizable monomer shown in (6)) may be isolated and purified. However, the polymerizable monomer obtained by isolation and purification has a higher mechanical strength and storage stability than the polymerizable monomer containing two or more structural isomers before the isolation and purification treatment. It tends to be inferior in terms of compatibility with sex. In addition, the production and production of the polymerizable monomer requires an additional isolation and purification treatment, which is disadvantageous in terms of cost. Therefore, from these viewpoints, the isolation and purification treatment is preferably omitted.

Each of the substituents of L ¹ and L ² is a hydroxyl group and / or a monovalent hydrocarbon group having a hydroxyl group. (A) The polymerizable monomer and Bis-GMA have a) a hydroxyl group, b) The structure of the reactive group at the terminal of the molecule is the same (methacrylic group and methacrylic group) or substantially the same (acrylic group and methacrylic group); and c) the partial structure in which the central part of the molecule is mainly composed of an aromatic group There are similarities in the above three points. However, focusing on the molecular structure of the central portion of the molecule, the polymerizable monomer (A) has a benzoate structure having a higher polarity than the bisphenol A structure constituting the central skeleton of Bis-GMA. Therefore, each of the substituents of L ¹ and L ² is a hydroxyl group and / or a monovalent hydrocarbon group having a hydroxyl group (A) a polymerizable monomer (hereinafter referred to as “(A) polymerizable monomer having a hydroxyl group). ) May be more hydrophilic than Bis-GMA. Further, the polymerizable monomer shown in Patent Document 4 does not have a hydroxyl group. That is, the polymerizable monomer (A) having a hydroxyl group is hydrophilic, whereas the polymerizable monomer shown in Patent Document 4 is hydrophobic. In addition, the polymerizable monomers shown in Patent Documents 4 and 5 have a biphenyl structure in which the central portion of the molecule has a high symmetry and a low polarity, but a polymerizable monomer (A) having a hydroxyl group. Has a structure in which a divalent group X is introduced between two aromatic groups Ar ¹ and Ar ² , which tend to have higher polarity than the biphenyl structure. Therefore, when focusing only on the structure at the center of the molecule, particularly when the divalent group X is composed of an electron donating group, the polymerizable (A) polymer having a hydroxyl group more than the polymerizable monomer shown in Patent Documents 4 and 5 It is believed that the monomer is more hydrophilic.

  Considering these points, when compared with Bis-GMA and the polymerizable monomers shown in Patent Documents 4 and 5, the polymerizable monomer (A) having a hydroxyl group is required to have higher hydrophilicity. It can be said that it is preferable and advantageous to use it. Bis-GMA and patents can be used to prepare a mixed composition of a polymerizable monomer and a hydrophilic solid material such as an inorganic filler that is relatively hydrophilic even after surface treatment with a silane coupling agent. Compared with the polymerizable monomer shown in Reference 4, the polymerizable monomer (A) is easy to mix, and can also mix more hydrophilic solid materials. It is also easy to suppress the accompanying increase in the viscosity of the mixed composition.

  Compared with Bis-GMA and the polymerizable monomers disclosed in Patent Documents 4 and 5, pentaerythrium has low viscosity and excellent handleability and excellent adhesiveness to the surface of a hydrophilic member. A non-aromatic (meth) acrylate polymerizable monomer having a hydroxyl group such as stall dimethacrylate is also useful. However, a non-aromatic (meth) acrylate-based polymerizable monomer having a hydroxyl group does not have an aromatic skeleton in the molecule, and thus has poor mechanical strength of a cured product. In addition, the compound has a hydroxyl group in the molecule and thus has high hydrophilicity but poor water resistance, and thus is not suitable for long-term use in water or a high humidity environment such as the oral cavity. However, the polymerizable monomer of the present embodiment having a hydroxyl group also has a higher mechanical strength and water resistance than the non-aromatic (meth) acrylate polymerizable monomer having a hydroxyl group. Excellent characteristics can be demonstrated.

  The curable dental composition of the present invention may contain other polymerizable monomers as long as the effects of the present invention are not affected. As other polymerizable monomers, known polymerizable monomers can be used without limitation. However, in view of the fact that the polymerizable monomer (A) which is a component of the dental curable composition of the present invention has a low viscosity in a room temperature environment, other polymerizable monomers are considered. However, it is also preferable to have a relatively low viscosity that does not offset this feature. From such a viewpoint, the viscosity of the other polymerizable monomer is preferably 150 mPa · S or less at room temperature (25 ° C.). Furthermore, considering that the reactive groups provided at both ends of the molecule are the same or similar, it is easy to ensure compatibility, and the other polymerizable monomer is a bifunctional (meth) acrylate-based polymerizable monomer. Monomers are preferred.

  Examples of the bifunctional (meth) acrylate-based polymerizable monomer having the above-mentioned viscosity characteristics include polyalkylene glycol dimethacrylates such as triethylene glycol dimethacrylate (3G) (more specifically, the degree of polymerization of the alkylene glycol unit is Polyethylene glycol dimethacrylate having 1 to 14 or less, polypropylene glycol dimethacrylate having a degree of polymerization of alkylene glycol unit of 1 to 7 or less, polymethylene glycol dimethacrylate having 2 to 10 carbon atoms), neopentyl glycol dimethacrylate, tricyclodecanedi Examples thereof include methanol dimethacrylate (TCD) and 1.9-nonanediol dimethacrylate (ND). From the viewpoint of compatibility, the other polymerizable monomer preferably has a polyalkylene glycol chain, and more preferably has a polyethylene glycol chain. This is because the polyalkylene glycol chain has high affinity with the benzoate structure (that is, the non-hydrogen bonding polar group) constituting the molecular center of the polymerizable monomer (A). In consideration of the points described above, as the other polymerizable monomer, polyalkylene glycol dimethacrylate, tricyclodecane dimethanol dimethacrylate, 1.9-nonanediol dimethacrylate, and the like are preferable, and triethylene glycol dimethacrylate is preferable. Methacrylate is particularly preferred. When the polymerizable monomer (A) is mixed with another polymerizable monomer, the polymerizable monomer (A) accounts for 20% by mass or more of the total polymerizable monomer. Is more preferably 30% by mass or more, and particularly preferably 60% by mass or more.

[(B) Photopolymerization initiator]
B1) α-diketone compound,
As the B1) α-diketone compound used in the dental curable composition of the present invention, known compounds can be used without any limitation. Specific examples of the α-diketone compound include camphorquinones such as camphorquinone, camphorquinone carboxylic acid, and camphorquinone sulfonic acid; diacetyl, acetylbenzoyl, 2,3-pentadione, 2,3-octadione, 9,10 -Phenanthrenequinone, acenaphthenequinone and the like.

The α-diketone compound to be used may be appropriately selected and used depending on the wavelength and intensity of light used for polymerization, the time of light irradiation, or the type and amount of other components to be combined, and may be used alone or as a mixture of two or more. Although it can be used, camphorquinones are generally suitably used, and camphorquinone is particularly preferable. The amount of addition also varies depending on the other components to be combined and the type of the polymerizable monomer, but is usually 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, per 100 parts by weight of the polymerizable monomer. It is in the range of parts by weight. The larger the amount, the shorter the curing time by irradiation light, and the smaller the amount, the better the environmental light stability.

B2) Photoacid Generator The B2) photoacid generator used in the dental curable composition of the present invention is a compound capable of directly generating a Bronsted acid or a Lewis acid by irradiation with light such as ultraviolet rays, and is a known compound. Can be used without any limitation, and specific examples thereof include diaryliodonium salt compounds, sulfonium salt compounds, sulfonic acid ester compounds, and s-triazine compounds substituted with a halomethyl group. The halomethyl-substituted-s-triazine compound is preferably a compound in which the s-triazine compound has been substituted with a trihalomethyl group, from the viewpoint of high polymerization activity. In the present invention, the most preferable photoacid generator in view of particularly high polymerization activity is at least one selected from trihalomethyl group-substituted-s-triazine compounds and diaryliodonium salt compounds.

  As a typical trihalomethyl group-substituted -s-triazine compound, a known compound can be used without any limitation as long as it is an s-triazine compound having at least one trihalomethyl group such as a trichloromethyl group and a tribromomethyl group. Particularly preferred trihalomethyl group-substituted -s-triazine compounds are represented by the following general formula (9).

(In the formula, R ⁵ and R ⁶ are an alkyl group, an aryl group, an alkenyl group, or an alkoxy group, and X ² is a halogen atom.)
In the above general formula (9), as the halogen atom represented by X, each halogen atom of chlorine, bromine and iodine is preferably used, but a compound having a trichloromethyl group substituted by a chlorine atom is generally used. It is a target.

The alkyl group, the aryl group, the alkenyl group, and the alkoxy group represented by R ⁵ and R ⁶ are each an unsubstituted one, halogen, a different group among the groups listed in R ⁵ and R ⁶ , and the like. It may be replaced. Examples of the alkyl group include unsubstituted alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-hexyl group and n-octyl group; trichloromethyl group, tribromomethyl And an alkyl group substituted with a halogen such as an α, α, β-trichloroethyl group or the like having 1 to 10 carbon atoms. As the aryl group, a phenyl group, a p-alkoxyphenyl group (for example, p-methoxyphenyl), a p-alkyllthiophenyl group (for example, p-methylthiophenyl group), a p-halophenyl group (for example, p-chlorophenyl group) ), 4-biphenylyl group, naphthyl group, 4-alkoxy-1-naphthyl group (for example, 4-methoxy-1-naphthyl group), etc., having 6 to 14 carbon atoms. Those having 2 to 14 carbon atoms such as allyl group, isopropenyl group, butenyl group and 2-phenylethenyl group; and alkoxy groups such as methoxy group, ethoxy group, butoxy group, hexoxy group and octoxy group. Examples of the formulas 1 to 10 are exemplified.

  Hereinafter, specific examples of the triazine compound substituted by a trihalomethyl group include 2,4,6-tris (trichloromethyl) -s-triazine and 2,4,6-tris (tribromomethyl) -s-triazine. , 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl ) -S-Triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,6-bis ( (Chloromethyl) -s-triazine, 2- (p-bromophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s -Triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (p-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(O-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (p-butoxyphenyl) ethenyl] -4,6-bis (trichloromethyl ) -S-Triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4,5-trimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (1-naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-biphenylyl) -4 , 6-bis (trichloromethyl) -s-triazine and the like. The above triazine compounds may be used alone or in combination of two or more.

  As the photoacid generator suitably used in the present invention, known diaryliodonium salt compounds (hereinafter, also simply referred to as iodonium salt compounds) can be used without any limitation. Representative diaryliodonium salt-based compounds include compounds represented by the following general formula (10)

(In the above formula, R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, or a nitro group; M ^- is an anion).
Are shown.

Here, the halogen atom of R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ includes a fluoro group, a chloro group, a bromo group, an iodo group, and the like. Examples of the alkyl group include those having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a pentyl group, an isopentyl group, a hexyl group, and an n-octyl group. preferable. The aryl group preferably has 6 to 14 carbon atoms, such as a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, and a naphthyl group. The alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms such as a vinyl group, an allyl group, an isopropenyl group and a butenyl group. The alkoxy group is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group having 1 to 6 carbon atoms. Further, as the aryloxy group, phenoxy and the like are preferable.

  Specific examples of the above diaryliodonium salts include diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium, p-isopropylphenyl-p-methylphenyliodonium, and bis ( cations such as m-nitrophenyl) iodonium, p-tert-butylphenylphenyliodonium, p-methoxyphenylphenyliodonium, bis (p-methoxyphenyl) iodonium, p-octyloxyphenylphenyliodonium and chloride, bromide, p- Toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakispentafluorophenylborate, tetrakispentafluorophenylgallate, Kisa fluorophosphate, can be mentioned hexafluoroarsenate, diphenyliodonium salt comprising anions such as hexafluoroantimonate.

  Among these diaryliodonium salt compounds, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakispentafluorophenylborate, tetrakispentafluorophenylgallate, hexafluorophospho, etc. Fate, hexafluoroarsenate and hexafluoroantimonate salts are preferred, and from the viewpoint of storage stability, tetrakispentafluorophenylborate, tetrakispentafluorophenylgallate and hexafluoroantimonate salts are particularly preferred. These diaryliodonium salt compounds may be used alone or in combination of two or more.

  Further, specific examples of other photoacid generators suitably used in the photopolymerizable composition of the present invention include sulfonium salt-based compounds, such as dimethylphenacylsulfonium, dimethylbenzylsulfonium, and dimethyl-4-. Hydroxyphenylsulfonium, dimethyl-4-hydroxynaphthylsulfonium, dimethyl-4,7-dihydroxynaphthylsulfonium, dimethyl-4,8-dihydroxynaphthylsulfonium, triphenylsulfonium, p-tolyldiphenylsulfonium, p-tert-butylphenyldiphenylsulfonium , Chlorides such as diphenyl-4-phenylthiophenylsulfonium, bromide, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakispentafluorophenyl Examples include ruborate, tetrakispentafluorophenylgallate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate salts.

  Specific examples of the sulfonic acid ester compound include benzoin tosylate, α-methylol benzoin tosylate, o-nitrobenzyl p-toluenesulfonate, p-nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate and the like. Can be mentioned.

  One or more of these photoacid generators may be used in combination.

Further, the general amount is 0.005 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, based on 100 parts by weight of the radical polymerizable monomer (A).
[B3) Aromatic amine compound]
The B3) aromatic amine compound used in the dental curable composition of the present invention may be any amine compound in which at least one of the organic groups bonded to the nitrogen atom is an aromatic group, and known compounds are particularly limited. It can be used without any problems, but one aromatic group and two aliphatic groups are bonded to the tertiary nitrogen atom in terms of higher polymerization activity, lower volatility, less odor, and easy availability. (Hereinafter, also referred to as “tertiary aromatic amine compound”). Representative tertiary aromatic amine compounds include those represented by the following general formula (11).

(In the formula, R ¹¹ and R ¹² are each independently an alkyl group, and R ¹³ is a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, or an alkyloxycarbonyl group.)
The alkyl group represented by R ¹¹ and R ¹² , or the alkyl group, aryl group, alkenyl group, alkoxy group and alkyloxycarbonyl group represented by R ¹³ are each an unsubstituted one, and the above R ⁵ and R ⁶ And those substituted with a substituent or a hydroxyl group as described in the above group. Examples of the alkyl group include unsubstituted alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-hexyl group and n-octyl group; chloromethyl group, An alkyl group substituted with a halogen such as a chloroethyl group; and an alkyl group substituted with a hydroxyl group such as a 2-hydroxyethyl group having 1 to 10 carbon atoms. Examples of the aryl group which may have a substituent include a phenyl group, a p-alkoxyphenyl (for example, p-methoxyphenyl), a p-alkyllthiophenyl group (for example, p-methylthiophenyl group), and a p-halophenyl group Examples thereof include those having 6 to 12 carbon atoms such as a (p-chlorophenyl group) and 4-biphenylyl group. Examples of the alkenyl group include 2 to 12 carbon atoms such as a vinyl group, an allyl group and a 2-phenylethenyl group. Examples of the alkoxy group include those having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a butoxy group, a hexoxy group, and an octoxy group. Examples of the alkyloxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. Group, butoxycarbonyl group, amyloxycarbonyl group, alkyl such as isoamyloxycarbonyl group The number of carbon atoms of the alkoxy moiety is exemplified has 1 to 10.

R ¹¹ and R ¹² are preferably an alkyl group which may have a substituent having 1 to 6 carbon atoms, and more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms. Specific examples of such an alkyl group again include a methyl group, an ethyl group, and an n-propyl group.

Further, as for R ¹³ , the bonding position is more preferably a para position, and further preferably an alkyloxycarbonyl group. By using such an amine compound having an aromatic group substituted by an alkyloxycarbonyl group, more excellent storage stability can be obtained when combined with the component (B4) described below.

Specific examples of such an aromatic amine compound in which R ¹³ is an alkyloxycarbonyl group bonded to the para-position include methyl p-N, N-dimethylaminobenzoate, p-N, N-dimethylaminobenzoic acid Ethyl, propyl p-N, N-dimethylaminobenzoate, amyl p-N, N-dimethylaminobenzoate, isoamyl p-N, N-dimethylaminobenzoate, ethyl p-N, N-diethylaminobenzoate, p -N, N-diethylaminopropyl benzoate and the like are exemplified.

  Specific examples of other aromatic amine compounds represented by the general formula (11) include N, N-dimethylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N-diethyl-p-toluidine, N, N-di (β-hydroxyethyl) -p-toluidine and the like can be mentioned.

These aromatic amine compounds may be used alone or in combination of two or more. Further, the general amount is 0.01 to 5 parts by weight, more preferably 0.02 to 3 parts by weight, based on 100 parts by weight of the polymerizable monomer.
[B4) Tertiary aliphatic amine compound]
The photopolymerization initiator in the dental curable composition of the present invention may be a photopolymerization initiator composed of the above-mentioned α-diketone, photoacid generator, and aromatic amine compound. When an amine compound is used in combination, the polymerization activity can be further improved.

  The tertiary aliphatic amine compound is B4) a tertiary amine compound having three saturated aliphatic groups attached to a nitrogen atom, and at least two of the saturated aliphatic groups have an electron-withdrawing group. It is necessary to be an aliphatic amine compound which is a saturated aliphatic group substituted by By using an amine compound having a saturated aliphatic group substituted by an electron-withdrawing group, high polymerization activity can be obtained, and further excellent storage stability can be obtained.

  The electron-withdrawing group in the aliphatic amine compound is a group having an inducing effect of attracting an electron from a carbon atom of the saturated aliphatic group to which the group is bonded, and may be any known electron-withdrawing group. Considering chemical stability, a hydroxyl group; an aryl group such as a phenyl group and a naphthyl group; an unsaturated aliphatic group such as an ethenyl group (vinyl group), a 1-propenyl group and an ethynyl group; a fluorine atom; A carbonyl group; a carbonyloxy group or a cyano group is preferred. Among these, an aryl group, an unsaturated aliphatic group or a hydroxyl group is particularly excellent in stability of the compound, easy to synthesize, and excellent in solubility in a radical polymerizable monomer. Preferably, a hydroxyl group is particularly preferred.

  The saturated aliphatic group substituted by such an electron-withdrawing group is not particularly limited, and may be linear, branched, or cyclic. It is preferably a chain or branched saturated aliphatic group having 1 to 6 carbon atoms. Further, the position and the number of substitution (bonding) of the electron-withdrawing group are not particularly limited, but the substitution on a carbon atom close to the nitrogen atom of the amine is more excellent in storage stability. Preferably, substitution is performed on the carbon atom bonded to the nitrogen atom (1st position of the saturated aliphatic group) or on the adjacent carbon atom (2nd position).

  Specific examples of the saturated aliphatic group substituted by such an electron-withdrawing group include a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 2-hydroxybutyl group, and a 2,3-dihydroxypropyl group. Substituted with a hydroxyl group; substituted with an unsaturated aliphatic group such as an allyl group (ethenylmethyl group), 2-propynyl group (ethynylmethyl group) or 2-butenyl group; substituted with an aryl group such as a benzyl group And the like.

  As the B4) component in the photopolymerization initiator in the photopolymerizable composition of the present invention, at least two of the three saturated aliphatic groups bonded to the nitrogen atom are substituted by such an electron-withdrawing group. Need to be a saturated aliphatic group.

  The saturated aliphatic group which is not substituted by the electron-withdrawing group is not particularly limited, but may be a linear or branched alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group. Are preferred.

  Specific examples of such tertiary aliphatic amine compounds having at least two saturated aliphatic groups substituted by electron-withdrawing groups include N-methyldiethanolamine, N-ethyldiethanolamine, and N-propyl. Compounds having two saturated aliphatic groups substituted by electron-withdrawing groups such as diethanolamine, N-ethyldiallylamine, and N-ethyldibenzylamine; triethanolamine, tri (isopropanol) amine, tri (2-hydroxy (Butyl) amine, triallylamine, tribenzylamine and the like, and compounds having three saturated aliphatic groups substituted by electron-withdrawing groups.

  These tertiary aliphatic amine compounds of component B4) may be used alone or in combination of two or more. The general amount is 0.005 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, per 100 parts by weight of the radical polymerizable monomer (A).

  Further, in the photopolymerization initiator of the dental curable composition of the present invention, the aromatic amine compound as the component B3) and the tertiary aliphatic amine compound as the component B4) are polymerizable in total. It is preferable to mix in a range of 0.015 to 10 parts by mass with respect to 100 parts by mass of the monomer, more preferably 0.03 to 6 parts by mass, and the mass ratio thereof is B3) component: B4). It is preferable that the component is in the range of 3:97 to 97: 3.

  Particularly preferably, the amount of the photopolymerization initiator, that is, the total amount of all components blended as a component of the photopolymerization initiator, 0.03 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, Is in the range of 0.05 to 10 parts by mass, particularly preferably 0.1 to 3 parts by mass.

Further, a pigment, a fluorescent pigment, a dye, an ultraviolet absorber may be added to prevent discoloration to ultraviolet light in order to match the color tone of the tooth, and other known additives as components of the dental curable composition. It may be blended within a range that does not affect the effects of the present invention.

  It is also preferable to add a filler to the dental curable composition of the present invention. By using a filler, the effect of suppressing polymerization shrinkage can be further increased. By using a filler, the operability of the composition before curing or the curable composition can be improved, or the mechanical properties after curing can be improved. As the filler, a known inorganic filler as a filler for the tooth restoration material is used without any limitation.

  The material of the inorganic filler is not particularly limited, and any material used as a filler in a conventional tooth restoration material can be used. Specifically, a simple substance of a metal selected from Group I, II, III, IV, and transition metals; oxides and composite oxides of these metals; fluorides, carbonates, sulfates, and silicates of these metals Metal salts composed of salts, hydroxides, chlorides, sulfites, phosphates and the like; composites of these metal salts and the like. Preferably, metal oxides such as amorphous silica, quartz, alumina, titania, zirconia, barium oxide, yttrium oxide, lanthanum oxide, ytterbium oxide; silica-zirconia, silica-titania, silica-titania-barium oxide, silica Glasses such as silica-based composite oxides such as -titania-zirconia, borosilicate glass, aluminosilicate glass, and fluoroaluminosilicate glass; metals such as barium fluoride, strontium fluoride, yttrium fluoride, lanthanum fluoride, and ytterbium fluoride Fluoride; inorganic carbonates such as calcium carbonate, magnesium carbonate, strontium carbonate and barium carbonate; and metal sulfates such as magnesium sulfate and barium sulfate are used.

  Particles such as silica-zirconia, silica-titania, silica-titania-barium oxide, and silica-titania-zirconia exemplified above are preferable because they have strong X-ray contrast properties. Further, a silica-zirconia particle is most preferable since a cured product having more excellent wear resistance can be obtained.

  The particle size of these fillers is not particularly limited, and fillers having an average particle size of 0.01 μm to 100 μm (particularly preferably 0.01 to 5 μm) generally used as a tooth restoration material may be used depending on the purpose. Can be used as appropriate. Also, the refractive index of the filler is not particularly limited, and those having a range of 1.4 to 1.7 of a general inorganic filler for dental use can be used without limitation, and may be appropriately set according to the purpose. Good. A plurality of inorganic fillers having different particle diameter ranges or different refractive indices may be used in combination.

  Furthermore, when a spherical inorganic filler is used among the above-mentioned fillers, the surface lubricity of the obtained cured product is increased, and an excellent tooth restoration material can be obtained.

  It is desirable to treat the above-mentioned inorganic filler with a surface treating agent represented by a silane coupling agent in order to improve the compatibility with the polymerizable monomer and to improve the mechanical strength and the water resistance. The method of the surface treatment may be performed by a known method, and as the silane coupling agent, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, Vinyl tris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, hexamethyldisilazane and the like are preferably used.

  The proportion of these fillers may be appropriately determined depending on the purpose of use, in consideration of the viscosity (operability) when mixed with the polymerizable monomer and the mechanical properties of the cured product. Is used in an amount of 50 to 1500 parts by weight, preferably 70 to 1000 parts by weight, based on 100 parts by weight of the polymerizable monomer.

Further, a pigment, a fluorescent pigment, a dye, an ultraviolet absorber may be added to prevent discoloration to ultraviolet light in order to match the color tone of the tooth, and other known additives as components of the dental curable composition. It may be blended within a range that does not affect the effects of the present invention.

  The dental curable composition of the present invention may contain other known polymerization initiators as long as the effects of the present invention are not impaired. Examples of the other polymerization initiator components include organic peroxides such as benzoyl peroxide and cumene hydroperoxide; and + IV valence or + V such as vanadium (IV) oxide acetylacetonate and bis (maltolate) oxovanadium (IV). Divalent vanadium compounds such as sodium tetraphenylboron, tetraphenylboron triethanolamine salt, tetraphenylboron dimethyl-p-toluidine salt, sodium tetrakis (p-fluorophenyl) boron, sodium butyltri (p-fluorophenyl) boron Aryl borate compounds; Coumarin dyes such as 3,3'-carbonylbis (7-diethylamino) coumarin and 7-hydroxy-4-methyl-coumarin; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide , Bi Acylphosphine oxides such as (2,6-dimethoxybensoyl) -2,4,4-trimethylpentylphosphine oxide; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin propyl ether; Thioxanthone derivatives such as diethoxythioxanthone, 2-chlorothioxanthone and methylthioxanthone; benzophenone derivatives such as benzophenone, p, p'-bis (dimethylamino) benzophenone and p, p'-dimethoxybenzophenone; Can be However, in order to obtain high ambient light stability, it is better to use the aryl borate compounds and the organic peroxide as small as possible. In addition, when the pigments such as coumarin-based pigments are added in such an amount as to act as a polymerization initiator, they greatly affect the color tone of the photopolymerizable composition, and are used in dental composite resins which require high aesthetics. Tend to have a different color from the teeth.

  In addition, water, an organic solvent, a thickener, and the like can be added to the dental curable composition of the present invention as long as the performance is not reduced according to the purpose. Examples of the organic solvent include hexane, heptane, octane, toluene, dichloromethane, methanol, ethanol, and ethyl acetate.Examples of the thickener include polyvinylpyrrolidone, carboxymethylcellulose, and high-dispersion silica such as polyvinyl alcohol. Is exemplified.

  When curing the dental curable composition of the present invention, the same known light source as used for curing the α-diketone-based photopolymerization initiator may be used. On the other hand, it is relatively stable, and on the other hand, in order to take advantage of the characteristics of the photopolymerization initiator of the present invention that it is rapidly cured by irradiation with light of a certain intensity or higher, a carbon arc, a xenon lamp, a metal halide lamp, a tungsten lamp, A visible light source such as an LED, a halogen lamp, a helium cadmium laser, and an argon laser is used without any limitation. The irradiation time varies depending on the wavelength and intensity of the light source, the shape and the material of the cured body, and may be determined in advance by a preliminary experiment.

  EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, the abbreviations and abbreviations of the substances and the structural formulas or names of the substances used for preparing the samples of the respective examples and comparative examples, the preparation methods of various samples, and various evaluation methods will be described.

(1) Abbreviations / abbreviations and their structural formulas or substance names (A) Polymerizable monomers

  In addition, in the above structural formula, the number of repetitions r and s of the unit structure can take an integer value of 0 or more in each molecule, and the above structural formula has different combinations of integer values (r, s). It is a mixture of two or more kinds of polymerizable monomer molecules.

In addition, 4-DPEGMA is obtained as a mixture of the following compounds (a), (b) and (c), and the ratio is 65: 30: 5 in molar ratio. The values g and h shown together with the above structural formulas are average values of the mixture of the compounds (a), (b) and (c). The values g and h shown together with the above structural formulas and the structural formulas shown below mean average values. In each molecule, the values of g and h can take an integer of 0, 1, or 2. . Except when the average of the values g and h is 0 or 2, the structural formula indicating the average of the values g and h has two or three different combinations of integer values (g, h). It means a mixture of structural isomers. Further, in the general formula (3), when Ar ¹ = Ar ² = phenylene group, the value g is a value corresponding to the value j shown in the general formula (3), and the value h is the general formula (3) ) Is a value corresponding to the value k shown in parentheses.

[(A) Polymerizable monomer (polymerizable monomer having a molecular structure other than general formula (1)]]

3G: triethylene glycol dimethacrylate

(B) Photopolymerization initiator B1)
CQ: Camphor quinone B2)
TCT: 2,4,6-tris (trichloromethyl) -s-triazine IP: diphenyliodonium hexafluorophosphate IB: 4-isopropyl-4′methyldiphenyliodonium tetrakis (pentafluorophenyl) borate B3)
DMBE: ethyl pN, N-dimethylaminobenzoate DMBI: isoamyl pN, N-dimethylaminobenzoate DMPT: N, N-dimethyl-p-toluidine B4)
TEOA: triethanolamine MDEOA: N-methyldiethanolamine [polymerization inhibitor]
HQME: Hydroquinone monomethyl ether [inorganic filler]
F1: Spherical silica zirconia filler; average particle diameter of primary particles = 0.4 μm, γ-methacryloyloxypropyltrimethoxysilane surface treatment F2: Spherical silica zirconia filler; average particle diameter of primary particles = 0.07 μm, γ-methacryloyl Oxypropyltrimethoxysilane surface treatment

(2) Viscosity measurement The viscosity of the polymerizable monomer was measured using a CS rheometer. As a measuring device, a viscoelasticity measuring device CS rheometer “CVO120HR” (manufactured by Bolin Corporation) equipped with a cone / plate geometry of 4 cm / 2 ° and a temperature control system was used. Then, three measurements were performed under the measurement conditions of a measurement temperature (plate temperature) of 25 ° C. and a shear rate of 1 rps, and the average of the three measured values was defined as the viscosity.

(3) Preparation method of dental curable composition A predetermined amount of a photopolymerization initiator, an inorganic filler, and other components are added to a polymerizable monomer, and the mixture is stirred under red light until uniform. Defoamed and adjusted.

(4) Bending strength In a state where the curable composition is filled in a stainless steel mold frame and pressed with polypropylene, visible light is irradiated from one side for 10 seconds x 3 times while changing the place so that light is applied to the whole. Light irradiation was performed by bringing the irradiation port of a vessel “TOKUSO POWER LIGHT” manufactured by Tokuyama Corporation into close contact with polypropylene. Then, light irradiation was performed for 10 seconds × 3 times in the same manner as described above from the opposite surface, and a cured product was obtained. The cured product was prepared into a 2 × 2 × 25 mm prism using water-resistant abrasive paper of # 800, and this sample was mounted on a tester (Autograph AG5000D, manufactured by Shimadzu Corporation). The three-point bending strength was measured at 1 mm / min.

(5) Environmental light stability test The distance between the light source and the sample was set so that the surface of the paste-like curable composition sample had a surface of 10,000 lux. Dental light (light source: halogen light, manufactured by Takara Labelmont Co., Ltd.) was used as the light source, and the distance was adjusted so that the illuminance measured by the illuminometer became the above illuminance. The prepared dental curable composition paste was weighed in an amount of 0.03 g on a polypropylene film, irradiated with the light for a predetermined time, crushed, and the time when the inside of the sample began to solidify was measured. The irradiation time was set at intervals of 5 seconds. The longer this time is, the more excellent the ambient light stability is, so that a good operation allowance time can be obtained. The illuminance meter used was Digital Looks Meter FLX-1330, manufactured by Tokyo Glass Instruments Co., Ltd. Note that this illuminometer has sensitivity at 400 to 700 nm.

(6) Procedure for synthesizing polymerizable monomer Those that correspond to the polymerizable monomer represented by the general formula (1) used for preparing the matrix monomer sample were synthesized by the following procedure.

<Synthesis of acid chloride (A)>
A first mixture of 2,5.3 g (0.096 mol) of 4,4'-diphenyletherdicarboxylic acid, 0.85 g (0.012 mol) of dimethylformamide and 80 ml of toluene was prepared. To the stirred first mixture, a second mixture consisting of 58.4 g (0.46 mol) of thionyl chloride and 20 ml of toluene was gradually added dropwise at room temperature. After completion of the dropwise addition, the obtained liquid was heated to 95 ° C. and refluxed for 3 hours. Then, by allowing the yellow transparent liquid obtained after heating and reflux to cool, the 4,4′-diphenyl ether dicarboxylic acid chloride having the molecular structure shown below (hereinafter sometimes referred to as “acid chloride (A)”) Was obtained. Further, this toluene solution was applied to a rotary evaporator to remove toluene, thionyl chloride and hydrogen chloride at 40 ° C., to obtain 26.9 g (0.091 mol, yield 95%) of 4,4′-diphenyletherdicarboxylic acid chloride solid. Was.

<Synthesis of 4-DPEHE>
120 ml of methylene chloride was added to 15.3 g (0.052 mol) of the acid chloride (A) to obtain a dispersion containing the acid chloride (A). A mixed solution obtained by mixing 16.9 g (0.13 mol) of 2-hydroxyethyl methacrylate, 7.7 g (0.13 mol) of triethylamine, 0.16 g (0.0013 mol) of 4-dimethylaminopyridine, 0.002 g of BHT, and 10 ml of methylene chloride. Was gradually added dropwise at −78 ° C. to the dispersion of the acid chloride (A) using a dropping funnel, and the mixture was further stirred for 5 hours. Water was added to the liquid obtained after the dropwise addition and stirring, and the solvent was removed using a rotary evaporator. The residue obtained after removing the solvent was dissolved in 100 ml of toluene, washed with a 0.5 N hydrochloric acid solution, washed with a saturated saline solution, dried over magnesium sulfate, and filtered. After concentrating the obtained filtrate with a rotary evaporator, the concentrate was further dried under vacuum to obtain 4-DPEHE (19.0 g, yield 76%, HPLC purity 97%). The ¹ H NMR spectrum data of the obtained 4-DPEHE was as follows.
¹ H NMR δ 1.93 (s, 6H), 4.58 (t, 4H), 4.63 (t, 4H), 5.59 (s, 2H), 6.14 (s, 2H), 7. 06 (d, 4H), 7.96 (d, 4H)

<Synthesis of 2-DPEHE>
Except that 25.3 g (0.096 mol) of 2,2'-diphenyletherdicarboxylic acid was used instead of 25.3 g of 4,4'-diphenyletherdicarboxylic acid, a method similar to that for synthesizing the acid chloride (A) was used. There was obtained 27.8 g (0.094 mol, 98% yield) of 2,2'-diphenyletherdicarboxylic acid chloride.

A method similar to that for synthesizing 4-DPEHE except that 15.3 g (0.052 mol) of 2,2′-diphenyletherdicarboxylic acid chloride was used instead of 15.3 g (0.052 mol) of acid chloride (A). Thus, 2-DPEHE (19.5 g, yield 78%, HPLC purity 97%) was obtained. The ¹ H NMR spectrum data of the obtained 2-DPEHE was as follows.
¹ H NMR δ 1.93 (s, 6H), 4.54 (t, 4H), 4.62 (t, 4H), 5.58 (s, 2H), 6.16 (s, 2H), 7. 06 (d, 4H), 7.45 (d, 2H), 7.96 (d, 2H).

<Synthesis of 4-DPEHP>
8.6 g (0.1 mol) of methacrylic acid, 15.2 g (0.2 mol) of 1,3-propanediol, 0.86 g (0.005 mol) of p-toluenesulfonic acid, and 0.1 g of BHT as a polymerization inhibitor Place in a glass container, heat to 85 ° C. and stir. The pressure in the reaction system in the heated and stirred state was reduced, and stirring was continued for 5 hours while removing water from the reaction system. Thereafter, the obtained liquid was cooled, purified using silica gel column chromatography, and concentrated to obtain 6.3 g (yield 44%) of 3-hydroxypropyl methacrylate.

Next, a solution containing 3.0 g (0.01 mol) of the acid chloride (A), 70 ml of methylene chloride, and 0.001 g of di-tertbutylmethylphenol was added to another glass container while stirring the solution. A solution prepared by dissolving 3.2 g (0.022 mol) of the above-mentioned 3-hydroxypropyl methacrylate, 2.0 g (0.02 mol) of triethylamine and 0.025 g (0.0002 mol) of 4-dimethylaminopyridine in 10 ml of methylene chloride was used. The solution was slowly dropped over 1 hour. After the solution obtained after completion of the dropwise addition was stirred at room temperature for 1 hour, water was added, and the solvent was removed using a rotary evaporator. The residue obtained after removing the solvent was dissolved in 100 ml of toluene, washed with a 0.5 N hydrochloric acid solution, washed with a saturated saline solution, dried over magnesium sulfate, and filtered. The obtained filtrate was again concentrated by a rotary evaporator, and the concentrated solution was further dried in vacuo to obtain 4-DPEHP (4.1 g, yield 76%, HPLC purity 97%). The ¹ H NMR spectrum data of the obtained 4-DPEHB was as follows.
¹ H NMR δ 1.93 (s, 6H), 2.10 (m, 4H), 4.18 (t, 4H), 4.27 (t, 4H), 5.59 (s, 2H), 6. 13 (s, 2H), 7.05 (d, 4H), 7.93 (d, 4H).

<Synthesis of 4-DPEHB>
-Process 1-
8.6 g (0.1 mol) of methacrylic acid, 18.0 g (0.2 mol) of 1,4-butanediol, 0.86 g (0.005 mol) of p-toluenesulfonic acid, and 0.1 g of BHT as a polymerization inhibitor The mixture was placed in a glass container and heated to 85 ° C. and stirred. Next, the pressure in the reaction system in the heated and stirred state was reduced, and stirring was continued for 5 hours while removing water from the reaction system. Thereafter, the obtained liquid was cooled, purified using silica gel column chromatography, and concentrated to obtain 6.7 g (yield 42%) of 4-hydroxybutyl methacrylate.
-Process 2-
Next, a solution containing 3.0 g (0.01 mol) of the acid chloride (A), 70 ml of methylene chloride, and 0.001 g of di-tertbutylmethylphenol was added to another glass container while stirring the solution. A solution prepared by dissolving 3.5 g (0.022 mol) of the above 4-hydroxybutyl methacrylate, 2.0 g (0.02 mol) of triethylamine, and 0.025 g (0.0002 mol) of 4-dimethylaminopyridine in 10 ml of methylene chloride was used. The solution was slowly dropped over 1 hour. After the solution obtained after completion of the dropwise addition was stirred at room temperature for 1 hour, water was added, and the solvent was removed using a rotary evaporator. The residue obtained after removing the solvent was dissolved in 100 ml of toluene, washed with a 0.5 N hydrochloric acid solution, washed with a saturated saline solution, dried over magnesium sulfate, and filtered. The obtained filtrate was again concentrated by a rotary evaporator, and the concentrated solution was further dried in vacuo to obtain 4-DPEHB (yield 4.1 g, yield 76%, HPLC purity 97%). The ¹ H NMR spectrum data of the obtained 4-DPEHB was as follows.
¹ H NMR δ 1.52-1.63 (m, 8H), 1.93 (s, 6H), 4.14 (t, 4H), 4.27 (t, 4H), 5.59 (s, 2H) ), 6.13 (s, 2H), 7.05 (d, 4H), 7.93 (d, 4H).

<Synthesis of 4-DPEHH>
According to the synthesis method shown in Process 1 of <Synthesis of 4-DPEHB>, 19.7 g of 6-hydroxyhexyl methacrylate was used except that 23.6 g of 1,6-hexanediol was used instead of 18.0 g of 1,4-butanediol. 16.0 g (yield 43%) was obtained (yield 53%).

Then, according to the synthesis method shown in Process 2 of <Synthesis of 4-DPEHB>, 6-hydroxyhexyl methacrylate and acid chloride (A) were used, except that 4.1 g of 6-hydroxyhexyl methacrylate was used instead of 4-hydroxybutyl methacrylate. ) To give 4-DPEHH (4.6 g, 78%, 98% HPLC purity). The ¹ H NMR spectrum data of the obtained 4-DPEHH was as follows.
¹ H NMR δ 1.29 (m, 8H), 1.57 (t, 4H), 1.77 (t, 4H), 1.93 (s, 6H), 4.16 (t, 4H), 4. 22 (t, 4H), 5.58 (s, 2H), 6.14 (s, 2H), 7.04 (d, 4H), 7.96 (d, 4H).

<4-DPEHIP>
Except that 18.7 g (0.13 mol) of 2-hydroxypropyl methacrylate was used instead of 16.9 g of 2-hydroxyethyl methacrylate, 4-DPEHP was obtained in the same manner as in the synthesis method of 4-DPEHE (yield: 19.9 g). 9 g, yield 75%, HPLC purity 97%). The ¹ H NMR spectrum data of the obtained 4-DPEHP was as follows.
¹ H NMR δ 1.40 (d, 6H), 1.93 (s, 6H), 4.61 (d, 4H), 4.74 (t, 2H), 5.56 (s, 2H), 6. 13 (s, 2H), 7.01 (d, 4H), 7.92 (d, 4H).

<4-DPEPE>
Instead of 16.9 g of 2-hydroxyethyl methacrylate, 22.6 g (0.13 mol) of polyethylene glycol monomethacrylate (average number of repetitions n of ethylene glycol chains (—CH ₂ CH ₂ O—) n ≒ 2) was used. Except for the above, 4-DPEPE (22.5 g, 78% yield, HPLC purity 97%) was synthesized in the same manner as the synthesis method of 4-DPEHE. The ¹ H NMR spectrum data of the obtained 4-DPEPE was as follows.
^{1 H NMR δ1.93 (s, 6H} ), 3.64-3.82 (m, 8H), 4.36-4.42 (m, 8H), 5.58 (s, 2H), 6.17 (S, 2H), 7.04 (d, 4H), 7.99 (d, 4H).

<Synthesis of 4-DPEGAM>
Except for using 29.6 g (0.13 mol) of glycerol dimethacrylate instead of 16.9 g of 2-hydroxyethyl methacrylate, 4-DPEGAM (yield 25.7 g, yield 73%, HPLC purity 92%). The ¹ H NMR spectrum data of the obtained 4-DPEGAM was as follows.
¹ H NMR δ 1.93 (s, 12H), 4.58 (d, 8H), 5.20 (m, 2H), 5.52 (s, 4H), 6.10 (s, 4H), 7. 01 (d, 4H), 7.92 (d, 4H).

<Synthesis of 4-DPEU>
While stirring a solution obtained by dissolving 50.0 g (0.8 mol) of ethylene glycol, 40.5 g (0.4 mol) of triethylamine, and 0.49 g (4 mol) of N, N-dimethylaminopyridine in 100 ml of methylene chloride, And cooled to 0 ° C. Next, a solution of 44.8 g (0.2 mol) of the acid chloride (A) dissolved in methylene chloride (200 ml) was slowly added dropwise to the solution over 2 hours. After the solution obtained after the dropwise addition was stirred for another 1 hour, water was added, and the solvent was removed using a rotary evaporator. The residue obtained after removing the solvent was dissolved in 100 ml of toluene, washed with a 0.5 N hydrochloric acid solution, washed with a saturated saline solution, dried over magnesium sulfate, and filtered. The obtained filtrate was again concentrated by a rotary evaporator, and the concentrated solution was purified by silica gel column chromatography to obtain 41.6 g of 4,4'-bis (2-hydroxyethoxycarbonyl) diphenyl ether (yield: 60%). .

In a solution obtained by dissolving 34.6 g (0.1 mol) of the obtained 4,4′-bis (2-hydroxyethoxycarbonyl) diphenyl ether and 3.2 g (5 mmol) of dibutyltin dilaurate in 100 ml of anhydrous dimethylformamide. And 31.0 g (0.2 mol) of 2-methacryloyloxyethyl isocyanate were further added, and the mixture was stirred at room temperature for 3 hours. 100 ml of methylene chloride was added to the solution after stirring, and the mixture was washed three times with distilled water using a separating funnel, and the methylene chloride layer was dried using magnesium sulfate. After drying, magnesium sulfate was filtered off, the filtrate was concentrated by a rotary evaporator, and the concentrate was further dried in vacuo to obtain 4-DPEU (yield 63.7 g, 97%, HPLC purity 94%). . The ¹ H NMR spectrum data of the obtained 4-DPEU was as follows.
¹ H NMR δ 1.93 (s, 6H), 3.30 (t, 4H), 4.40-4.56 (m, 12H), 5.60 (s, 2H), 6.17 (s, 2H) ), 7.06 (d, 4H), 7.98 (d, 4H), 8.03 (s, 2H).

<Synthesis of 4-DPEUE>
Except that 39.8 g (0.2 mol) of 2- (2-methacryloyloxyethyloxy) ethyl isocyanate was used instead of 31.0 g of 2-methacryloyloxyethyl isocyanate, a method similar to the method of synthesizing 4-DPEU was used. 4-DPEUE (yield 70.3 g, yield 95%, HPLC purity 96%) was obtained. The ¹ H NMR spectrum data of the obtained 4-DPEUE was as follows.
¹ H NMR δ 1.93 (s, 6H), 3.10 (m, 4H), 3.66 (m, 8H), 4.33 (t, 4H), 4.54 (m, 8H), 5. 58 (s, 2H), 6.14 (s, 2H), 7.06 (d, 4H), 7.96 (d, 4H), 8.02 (s, 2H).

<Synthesis of 4-DPSHE>
After dissolving 48.4 g (0.2 mol) of 4,4-diformyldiphenyl sulfide synthesized by the synthesis method described in JP-A-2005-154379 in 200 ml of t-butanol and 50 ml of water, phosphoric acid is added. A reaction solution was prepared by adding 50 ml of an aqueous sodium hydrogen solution and 140 g (2 mol) of 2-methyl-2-butene, and further adding 36 g (0.4 mol) of sodium chlorite. Next, after stirring the reaction solution for 5 hours, the reaction solution was acidified using a 1N hydrochloric acid solution to precipitate a solid. Subsequently, the reaction solution in which the solid was precipitated was subjected to suction filtration, and the precipitated solid was washed with water. The solid (compound) obtained after the washing was vacuum dried to obtain 4,4′-dicarboxydiphenyl sulfide (45.5 g, 83% yield).

  Next, acid chloride (A) was used except that 26.4 g (0.096 mol) of 4,4′-dicarboxydiphenyl sulfide was used instead of 25.3 g (0.096 mol) of 4,4′-diphenyl ether dicarboxylic acid. 28.4 g (0.091 mol) of 4,4′-diphenylsulfidedicarboxylic acid chloride was synthesized in the same manner as in the synthesis method of (2).

Next, a method similar to that for synthesizing 4-DPEHE was used, except that 16.1 g (0.052 mol) of 4,4′-diphenylsulfidedicarboxylic acid chloride was used instead of 15.3 g of the acid chloride (A). -DPSHE (18.9 g, 73% yield, 91% HPLC purity) was obtained. The ¹ H NMR spectrum data of the obtained 4-DPSHE was as follows.
¹ H NMR δ 1.93 (s, 6H), 4.52 (t, 4H), 4.63 (t, 4H), 5.58 (s, 2H), 6.11 (s, 2H), 7. 30 (d, 4H), 7.81 (d, 4H).

<Synthesis of 4-DPSOHE>
Synthesis of acid chloride (A) except that 29.4 g (0.096 mol) of 4,4'-dicarboxydiphenyl sulfone was used instead of 25.3 g (0.096 mol) of 4,4'-diphenyl ether dicarboxylic acid In the same manner as in the above method, 31.6 g (0.092 mol) of 4,4′-diphenylsulfonedicarboxylic acid chloride was synthesized.

Then, the same method as the synthesis method of 4-DPEHE was used except that 17.8 g (0.052 mol) of 4,4′-diphenylsulfone dicarboxylic acid chloride was used instead of 15.3 g of the acid chloride (A). -DPSOHE (20.4 g, 74% yield, 92% HPLC purity) was obtained. The ¹ H NMR spectrum data of the obtained 4-DPSOHE was as follows.
¹ H NMR δ 1.93 (s, 6H), 4.58 (t, 4H), 4.63 (t, 4H), 5.59 (s, 2H), 6.14 (s, 2H), 8. 06 (d, 4H), 8.20 (d, 4H).

<Synthesis of 4-DPFHE>
After dissolving 44.8 g (0.2 mol) of 4,4'-diformyldiphenylmethane synthesized by the synthesis method described in JP-A-2005-154379 in 200 ml of t-butanol and 50 ml of water, the phosphorous is dissolved. A reaction solution was obtained by adding 50 ml of an aqueous sodium hydrogen oxyoxide solution and 140 g (2 mol) of 2-methyl-2-butene, and further adding 36 g (0.4 mol) of sodium chlorite. Next, after stirring the reaction solution for 5 hours, the reaction solution was acidified using a 1N hydrochloric acid solution to precipitate a solid. Subsequently, the reaction solution in which the solid was precipitated was subjected to suction filtration, and the precipitated solid was washed with water. The resulting solid (compound) was dried under vacuum to obtain 39.8 g (yield 83%) of 4,4′-dicarboxydiphenylmethane.

  Next, acid chloride (A) was used except that 23.0 g (0.096 mol) of 4,4′-dicarboxydiphenylmethane was used instead of 25.3 g (0.096 mol) of 4,4′-diphenyletherdicarboxylic acid. Was synthesized in the same manner as in the above method to synthesize 4,4′-diphenylmethanedicarboxylic acid chloride (25.2 g, 0.091 mol).

Next, 4-DPEHE was synthesized in the same manner as in the synthesis method of 4-DPEHE except that 14.4 g (0.052 mol) of 4,4′-diphenylmethanedicarboxylic acid chloride was used instead of 15.3 g of the acid chloride (A). DPFHE (18.7 g, 75% yield, 94% HPLC purity) was obtained. The ¹ H NMR spectrum data of the obtained 4-DPFHE was as follows.
¹ H NMR δ 1.93 (s, 6H), 3.85 (s, 2H), 4.52-4.63 (m, 8H), 5.58 (s, 2H), 6.12 (s, 2H) ), 7.15 (d, 4H), 7.86 (d, 4H).

<Synthesis of 4-DPAHE>
Except for using 27.2 g (0.096 mol) of 2,2-bis (4-carboxyphenyl) propane synthesized by a synthesis method described in British Patent GB 753384 instead of 25.3 g of 4,4′-diphenyl ether dicarboxylic acid. In the same manner as in the method for synthesizing the acid chloride (A), 29.6 g (96% yield) of 2,2-bis (4-chlorocarbonylphenyl) propane was obtained.

Next, the same method as in the synthesis method of 4-DPEHE except that 16.7 g (0.052 mol) of 2,2′-bis (4-chlorocarbonylphenyl) propane was used instead of 15.3 g of the acid chloride (A). By the method, 4-DPAHE (19.3 g, 73% yield, 92% HPLC purity) was obtained. The data of the obtained ¹ H NMR spectrum of 4-DPAHE was as follows.
¹ H NMR δ 1.64 (s, 6H), 1.93 (s, 6H), 4.53-4.64 (m, 8H), 5.59 (s, 2H), 6.12 (s, 2H) ), 7.22 (d, 4H), 7.90 (d, 4H).

<Synthesis of 4-DPBHE>
After dissolving 50.8 g (0.2 mol) of 4-formylphenyl-4′-formylbenzoate synthesized by the synthesis method described in JP-A-2007-106779 in 200 ml of t-butanol and 50 ml of water. , 50 ml of an aqueous solution of sodium hydrogen phosphate and 140 g (2 mol) of 2-methyl-2-butene, and further, 36 g (0.4 mol) of sodium chlorite were added to obtain a reaction solution. Next, after stirring the reaction solution for 5 hours, the reaction solution was acidified using a 1N hydrochloric acid solution to precipitate a solid. Subsequently, the reaction solution in which the solid was precipitated was subjected to suction filtration, and the precipitated solid was washed with water. The obtained solid (compound) was dried under vacuum to obtain 45.4 g of 4-carboxyphenyl-4′-carboxybenzoate (yield 84%).

  Next, except that 25.9 g (0.096 mol) of the above 4-carboxyphenyl-4'-carboxybenzoate was used instead of 25.3 g of 4,4'-diphenyletherdicarboxylic acid, the acid chloride (A) 29.8 g (96% yield) of 4-chlorocarbonylphenyl-4′-chlorocarbonylphenylbenzoate was obtained in the same manner as in the synthesis method.

Next, the same method as the synthesis method of 4-DPEHE except that 16.8 g (0.052 mol) of 4-chlorocarbonylphenyl-4′-chlorocarbonylphenylbenzoate was used instead of 15.3 g of the acid chloride (A). Thus, 4-DPBHE (yield 20.2 g, yield 76%, HPLC purity 94%) was obtained. The ¹ H NMR spectrum data of the obtained 4-DPBHE was as follows.
¹ H NMR δ 1.93 (d, 6H), 4.51 (m, 4H), 4.61 (t, 4H), 5.58 (d, 2H), 6.13 (d, 2H), 7. 25 (d, 2H), 8.02 (d, 2H), 8.12 (d, 2H), 8.272 (d, 2H).

<Synthesis of 4-DPALHE>
After dissolving 58.4 g (0.2 mol) of 1,1-bis (4-formylphenyl) cyclohexane synthesized by the synthesis method described in Japanese Patent No. 3076603 in 200 ml of t-butanol and 50 ml of water, A reaction solution was obtained by adding 50 ml of an aqueous solution of sodium hydrogen phosphate and 140 g (2 mol) of 2-methyl-2-butene, and further adding 36 g (0.4 mol) of sodium chlorite. Next, after stirring the reaction solution for 5 hours, the reaction solution was acidified using a 1N hydrochloric acid solution to precipitate a solid. Subsequently, the reaction solution in which the solid was precipitated was subjected to suction filtration, and the precipitated solid was washed with water. The obtained solid (compound) was dried under vacuum to obtain 54.4 g (yield 84%) of 1,1-bis (4-carboxylphenyl) cyclohexane.

  Next, acid chloride (A) was used except that 31.1 g (0.096 mol) of 1,1-bis (4-carboxylphenyl) cyclohexane was used instead of 25.3 g of 4,4′-diphenyletherdicarboxylic acid. 33.3 g (96% yield) of 1,1-bis (4-chlorocarbonylphenyl) cyclohexane was obtained in the same manner as in the above synthesis method.

Next, a method similar to the method for synthesizing 4-DPEHE, except that 18.8 g (0.052 mol) of 1,1-bis (4-chlorocarbonylphenyl) cyclohexane was used instead of 15.3 g of the acid chloride (A). To give 4-DPALHE (yield 24.3 g, 85%, HPLC purity 92%). The ¹ H NMR spectrum data of the obtained 4-DPALHE was as follows.
¹ H NMR δ 1.45 (m, 6H), 1.93 (s, 6H), 2.01 (m, 4H), 4.53-4.64 (m, 4H), 5.58 (s, 2H) ), 6.13 (s, 2H), 7.23 (d, 4H), 7.90 (d, 4H).

<Synthesis of 4-DPEGMA>
To 12.8 g of glycidyl methacrylate (0.09 mol), 12.9 g (0.05 mol) of 4,4'-diphenyletherdicarboxylic acid, 0.02 g (0.00009 mol) of benzyltriethylammonium chloride, 0.02 g of BHT ( 0.00009 mol) and 20 g of dimethylformamide were reacted at 100 ° C. for 4 hours. 40 ml of ethyl acetate was added to the liquid obtained by the reaction to form a uniform solution. Next, this solution was transferred to a separating funnel, washed three times with 40 ml of a 10 wt% aqueous solution of potassium carbonate, and further three times with distilled water, and then an ethyl acetate layer was recovered. Thereafter, magnesium sulfate was added to the collected ethyl acetate layer to remove water contained in the ethyl acetate layer. Subsequently, magnesium sulfate was filtered off from the ethyl acetate layer, and the filtrate was concentrated with a rotary evaporator to obtain a concentrate. The concentrate was further dried in vacuo to give 4-DPEGMA (22.8 g, 84% yield, 95% HPLC purity). The ¹ H NMR spectrum data of the obtained 4-DPEGMA was as follows.
^{1 H NMR δ1.93 (s, 6H} ), 3.90 (d, 0.8H), 4.30~4.70 (m, 9.2H), 5.59 (s, 2H), 6.16 (S, 2H), 7.07 (d, 4H), 8.07 (d, 4H).

<Synthesis of 4-DPEGMAI>
A methylene chloride solution was prepared by dissolving 15.3 g (0.052 mol) of the solid acid chloride (A) in 30 ml of methylene chloride.

Separately, a solution was prepared by mixing 33.3 g (0.208 mol) of glycerol-1-yl monomethacrylate, 12.1 g (0.104 mol) of tetramethylethylenediamine, 0.002 g of BHT, and 20 ml of methylene chloride. This solution was gradually added dropwise at −78 ° C. to a methylene chloride solution in which the acid chloride A was dissolved, and the mixture was further stirred for 5 hours. The liquid obtained after the dropping and stirring was washed three times with 60 ml of 0.4 mol / L hydrochloric acid aqueous solution, then three times with 60 ml of a 10 wt% aqueous potassium carbonate solution, and further three times with distilled water, and then washed with methylene chloride. The layers were collected. Thereafter, magnesium sulfate was added to the collected methylene chloride layer to remove water contained in the methylene chloride layer. Next, magnesium sulfate was filtered off from the methylene chloride layer, and the filtrate was concentrated with a rotary evaporator to obtain a concentrate. The concentrate was purified by silica gel column chromatography to give 4-DPEGMAI (25.9 g, 92% yield, 97% HPLC purity). The ¹ H NMR spectrum data of the obtained 4-DPEGMAI was as follows.
^{1 H NMR δ1.93 (s, 6H} ), 3.90 (d, 0.2H), 4.30~4.70 (m, 9.8H), 5.59 (s, 2H), 6.16 (S, 2H), 7.07 (d, 4H), 8.07 (d, 4H).

<Synthesis of 4-DPEGMAII>
To 12.8 g of glycidyl methacrylate (0.09 mol), 12.9 g (0.05 mol) of 4,4′-diphenyletherdicarboxylic acid, 0.02 g (0.00009 mol) of tetrabutylammonium bromide, 0.02 g of BHT ( 0.00009 mol), and a mixed solution containing 20 g of dimethylacetamide was reacted at 100 ° C. for 4 hours. 40 ml of ethyl acetate was added to the liquid obtained by the reaction to form a uniform solution. Next, this solution was transferred to a separating funnel, washed three times with 40 ml of a 10 wt% aqueous solution of potassium carbonate, and further three times with distilled water, and then an ethyl acetate layer was recovered. Thereafter, magnesium sulfate was added to the collected ethyl acetate layer to remove water contained in the ethyl acetate layer. Subsequently, magnesium sulfate was filtered off from the ethyl acetate layer, and the filtrate was concentrated with a rotary evaporator to obtain a concentrate. The concentrate was further dried under vacuum to obtain 4-DPEGMAII (yield 25.3 g, 90%, HPLC purity 95%). The ¹ H NMR spectrum data of the obtained 4-DPEGMAII was as follows.
^{1 H NMR δ1.93 (s, 6H} ), 3.90 (d, 0.4H), 4.30~4.70 (m, 9.6H), 5.62 (s, 2H), 6.16 (S, 2H), 7.07 (d, 4H), 8.07 (d, 4H).

<Synthesis of 4-DPEGMAIII>
After synthesizing 4-DPEGMAII by the above method, purification is performed by silica gel column chromatography (filler: SiO ₂ , developing solvent: ethyl acetate / hexane = 3/1 to 2/1) to obtain 4-DPEGMAIII (yield). 18.7 g, yield 69%, HPLC purity 99%). The ¹ H NMR spectrum data of the obtained 4-DPEGMAIII was as follows.
¹ H NMR δ 1.93 (s, 6H), 4.30 to 4.41 (m, 10H), 5.62 (s, 2H), 6.16 (s, 2H), 7.07 (d, 4H) ), 8.07 (d, 4H).

<Synthesis of 4-DPEGMIV>
After synthesizing 4-DPEGMA by the above method, purification is performed by silica gel column chromatography (filler: SiO ₂ , developing solvent: ethyl acetate / hexane = 3/1 to 2/1) to obtain 4-DPEGMAIV (yield). 2.2 g, yield 8%, HPLC purity 99%). The ¹ H NMR spectrum data of the obtained 4-DPEGMAIV was as follows.
^{1 H NMR δ1.93 (s, 6H} ), 3.90 (d, 3.2H), 4.30~4.70 (m, 7.8H), 5.62 (s, 2H), 6.16 (S, 2H), 7.07 (d, 4H), 8.07 (d, 4H).

<Synthesis of 4-DPEGA>
Except that 11.5 g (0.09 mol) of glycidyl acrylate was used instead of 12.8 g (0.09 mol) of glycidyl methacrylate, 4-DPEGA (yield 21.50 g) was obtained in the same manner as the synthesis method of 4-DPEGMA. 8 g, yield 85%, HPLC purity 96%). In addition, the ¹ H NMR spectrum data of the obtained 4-DPEGA was as follows.
¹ H NMR δ 1.93 (s, 6H), 3.84 (d, 2H), 4.00 to 4.65 (m, 8H), 5.83 (t, 2H), 6.12 (d, 2H) ), 6.43 (d, 2H), 7.09 (d, 4H), 7.99 (d, 4H).

<Synthesis of 2-DPEGMA>
A method similar to that for synthesizing 4-DPEGMA, except that 12.9 g (0.05 mol) of 2,2′-diphenyl ether dicarboxylic acid was used instead of 12.9 g (0.05 mol) of 4,4′-diphenyl ether dicarboxylic acid. By the method, 2-DPEGMA (yield 23.0 g, yield 85%, HPLC purity 95%) was obtained. The ¹ H NMR spectrum data of the obtained 2-DPEGMA was as follows.
^{1 H NMR δ1.93 (s, 6H} ), 3.80 (d, 1.8H), 4.00~4.65 (m, 8.2H), 5.59 (s, 2H), 6.16 (S, 2H), 7.07 (d, 2H), 7.42 (d, 4H), 8.17 (d, 2H).

<Synthesis of 4-DPEHGMA>
After dissolving 5-hexen-1-ol (30.1 g, 0.3 mol) in 100 ml of methylene chloride, 33.4 g (0.33 mol) of triethylamine and 1.8 g (0.015 mol) of N, N-dimethylaminopyridine are added. The added solution was adjusted, and the solution was cooled with ice. Next, a methylene chloride solution in which 31.4 g (0.3 mol) of methacrylic acid chloride was dissolved in methylene chloride (50 ml) was added dropwise to the ice-cooled solution. After the solution obtained after the completion of the dropwise addition was stirred at room temperature for 3 hours, 100 ml of distilled water was added thereto, and the mixture was further extracted with methylene chloride three times. The residue was obtained by removing the solvent from the methylene chloride layer obtained by the extraction using a rotary evaporator. Further, the obtained residue was dissolved in 100 ml of toluene. The obtained toluene solution was washed three times with a 0.5 N hydrochloric acid solution, then three times with a saturated saline solution, and dried with a magnesium sulfate solution. After drying, the magnesium sulfate solution was filtered off, the filtrate was concentrated by a rotary evaporator, and the concentrate was further dried under vacuum to obtain 46.4 g of 5-hexen-1-yl methacrylate (yield 92%).

  After dissolving 45.4 g (0.27 mol) of the obtained 5-hexen-1-yl methacrylate in 100 ml of methylene chloride, 196 g (equivalent to 0.675 mol) of a 60% by mass methchloroperbenzoic acid / water mixture was added, and the mixture was added at room temperature. Stirred for 10 hours. After stirring, the by-product metachlorobenzoic acid was filtered off, and the filtrate was subjected to a reduction treatment with 150 ml of a 15% by mass aqueous solution of sodium sulfite. The methylene chloride layer separated from the filtrate after the reduction treatment was washed twice with a 5% by mass aqueous solution of potassium carbonate, dried over magnesium sulfate, and concentrated by a rotary evaporator to obtain a concentrate. The concentrate was further dried under vacuum to obtain 44.8 g (yield 90%) of 5,6-epoxyhexan-1-yl methacrylate.

The obtained 5,6-epoxyhexane-1-yl methacrylate (23.0 g, 0.125 mol), 4,4′-diphenyletherdicarboxylic acid (12.9 g, 0.05 mol), and benzyltriethylammonium chloride 0.045 g. (0.2 mmol) and 0.03 g of p-methoxyphenol were stirred at 90 ° C. for 4 hours. The mixture after heating and stirring was allowed to cool to room temperature, 50 ml of water was added, and the mixture was extracted with methylene chloride. The obtained methylene chloride layer was dried over magnesium sulfate, and then concentrated by a rotary evaporator to obtain a concentrate. Further, the concentrate was dried in vacuo to obtain 4-DPEHGMA (yield 29.0 g, 0.046 mol, yield 93%, HPLC purity 95%). The ¹ H NMR spectrum data of the obtained 4-DPEHGMA was as follows.
^{1 H NMR δ1.29 (t, 4H} ), 1.44 (m, 4H), 1.57 (t, 4H), 1.93 (s, 6H), 3.85 (d, 1.9H), 4.15 to 4.70 (m, 8.1H), 5.59 (s, 2H), 6.16 (s, 2H), 7.05 (d, 4H), 7.95 (d, 4H) .

<Synthesis of 4-DPEEGMA>
After dissolving 30.6 g (0.3 mol) of allyloxyethanol in 100 ml of methylene chloride, 33.4 g (0.33 mol) of triethylamine and 1.8 g (0.015 mol) of N, N-dimethylaminopyridine were further added. A solution was prepared. Next, the obtained solution was ice-cooled, and a solution prepared by dissolving 31.4 g (0.3 mol) of methacrylic acid chloride in 50 ml of methylene chloride was added dropwise to this solution. After the solution obtained after the completion of the dropwise addition was stirred at room temperature for 3 hours, 100 ml of distilled water was added, and the mixture was extracted three times with methylene chloride. Next, the residue obtained by removing the solvent from the obtained methylene chloride layer using a rotary evaporator was dissolved in 100 ml of toluene to obtain a toluene solution. The toluene solution was washed three times with a 0.5N hydrochloric acid solution, then three times with a saturated saline solution, and dried with a magnesium sulfate solution. After drying, the magnesium sulfate solution was filtered off, and the filtrate was concentrated with a rotary evaporator to obtain a concentrate. Further, this concentrate was dried under vacuum to obtain 46.0 g (90% yield) of allyloxyethyl methacrylate.

  A solution prepared by dissolving 46.0 g (0.27 mol) of the obtained allyloxyethyl methacrylate in 100 ml of methylene chloride and further adding 196 g (corresponding to 0.675 mol) of a 60% by mass metachloroperbenzoic acid / water mixture. And stirred at room temperature for 10 hours. The by-product metachlorobenzoic acid was filtered off from the solution after stirring, and the filtrate was subjected to a reduction treatment with 150 ml of a 15% by mass aqueous sodium sulfite solution. Subsequently, the methylene chloride layer separated from the filtrate subjected to the reduction treatment was washed twice with a 5% by mass aqueous solution of potassium carbonate, dried over magnesium sulfate, and then concentrated by a rotary evaporator to obtain a concentrate. Further, this concentrate was dried in vacuo to obtain 47.3 g (94% yield) of glycidyloxyethyl methacrylate.

23.3 g (0.125 mol) of the obtained glycidyloxyethyl methacrylate, 12.9 g (0.05 mol) of 4,4′-diphenyletherdicarboxylic acid, 0.045 g (0.2 mmol) of benzyltriethylammonium chloride, And a mixture of 0.03 g of p-methoxyphenol was stirred at 90 ° C. for 4 hours. The mixture after heating and stirring was allowed to cool to room temperature, 50 ml of water was added, and the mixture was extracted with methylene chloride. The obtained methylene chloride layer was dried over magnesium sulfate and concentrated by a rotary evaporator to obtain a concentrate. Finally, the concentrate was dried in vacuo to give 4-DPEEGMA (29.0 g, 92% yield, 94% HPLC purity). The ¹ H NMR spectrum data of the obtained 4-DPEHGMA was as follows.
¹ H NMR δ 1.93 (s, 6H), 3.50 to 4.50 (m, 18H), 4.15 to 4.70 (m, 8.1H), 5.59 (s, 2H), 6 .16 (s, 2H), 7.02 (d, 4H), 8.02 (d, 4H).

<Synthesis of 4-DPSGMA>
After dissolving 48.4 g (0.2 mol) of 4,4-diformyldiphenyl sulfide synthesized by the synthesis method described in JP-A-2005-154379 in 200 ml of t-butanol and 50 ml of water, phosphorus is added. A reaction solution was prepared by adding 50 ml of an aqueous solution of sodium hydrogen oxyate, 140 g (2 mol) of 2-methyl-2-butene, and 36 g (0.4 mol) of sodium chlorite. Next, after stirring the reaction solution for 5 hours, the reaction solution was acidified using a 1N hydrochloric acid solution to precipitate a solid. Subsequently, the reaction solution in which the solid was precipitated was subjected to suction filtration, and the precipitated solid was washed with water. The solid (compound) obtained after the washing was vacuum-dried to obtain 45.5 g of 4,4'-dicarboxydiphenyl sulfide (83% yield).

Next, in the same manner as in the synthesis method of 4-DPEGMA, except that 13.7 g (0.05 mol) of the above 4,4'-dicarboxydiphenyl sulfide was used instead of 12.9 g of 4,4'-diphenyl ether dicarboxylic acid. To obtain 4-DPSGMA (22.3 g, 80% yield, 95% HPLC purity). The ¹ H NMR spectrum data of the obtained 4-DPSGMA was as follows.
¹ H NMR δ 1.93 (s, 6H), 3.62 (d, 2H), 3.90 to 4.70 (m, 8H), 5.58 (s, 2H), 6.14 (s, 2H) ), 7.33 (d, 4H), 7.78 (d, 4H).

<Synthesis of 4-DPSOGMA>
Except for using 15.3 g of 4,4'-dicarboxydiphenylsulfone instead of 12.9 g of 4,4'-diphenyletherdicarboxylic acid, a method similar to that for synthesizing 4-DPEGMA was used. -DPSOGMA (yield 24.5 g, yield 83%, HPLC purity 97%) was obtained. The ¹ H NMR spectrum data of the obtained 4-DPSOGMA was as follows.
¹ H NMR δ 1.93 (s, 6H), 3.70 (d, 2H), 3.90 to 4.70 (m, 8H), 5.58 (s, 2H), 6.14 (s, 2H) ), 8.04 (d, 4H), 8.20 (d, 4H).

<Synthesis of 4-DPFGMA>
After dissolving 44.8 g (0.2 mol) of 4,4′-diformyldiphenylmethane synthesized by the synthesis method described in JP-A-2005-154379 in 200 ml of t-butanol and 50 ml of water, the phosphorous is dissolved. A reaction solution was prepared by adding 50 ml of an aqueous solution of sodium hydrogen oxyate, 140 g (2 mol) of 2-methyl-2-butene, and 36 g (0.4 mol) of sodium chlorite. Next, after stirring the reaction solution for 5 hours, the reaction solution was acidified using a 1N hydrochloric acid solution to precipitate a solid. Subsequently, the reaction solution in which the solid was precipitated was subjected to suction filtration, and the precipitated solid was washed with water. The solid (compound) obtained after the washing was vacuum dried to obtain 39.8 g (yield 78%) of 4,4'-dicarboxydiphenylmethane.

Next, the method for synthesizing 4-DPEGMA was performed except that 12.8 g (0.05 mol) of 4,4′-dicarboxydiphenylmethane obtained above was used instead of 12.9 g of 4,4′-diphenyletherdicarboxylic acid. In the same manner, 4-DPFGMA (22.1 g, yield 82%, HPLC purity 94%) was obtained. The ¹ H NMR spectrum data of the obtained 4-DPFGMA was as follows.
¹ H NMR δ 1.93 (s, 6H), 3.78 (s, 2H), 3.90 (d, 2H), 4.00 to 4.70 (m, 8H), 5.58 (s, 2H) ), 6.14 (s, 2H), 7.20 (d, 4H), 7.87 (d, 4H).

<Synthesis of 4-DPAGMA>
Except that instead of 12.9 g of 4,4'-diphenyletherdicarboxylic acid, 14.2 (0.05 mol) of 2,2-bis (4-carboxyphenyl) propane 14.2 (0.05 mol) synthesized by a synthesis method described in British Patent GB 753384 was used. Gave 4-DPAGMA (22.7 g, 80% yield, 93% HPLC purity) in the same manner as in the synthesis of 4-DPEGMA. The ¹ H NMR spectrum data of the obtained 4-DPAGMA was as follows.
¹ H NMR δ 1.65 (s, 6H), 1.93 (s, 6H), 3.85 (d, 2H), 3.90 to 4.65 (m, 8H), 5.57 (s, 2H) ), 6.12 (s, 2H), 7.23 (d, 4H), 7.90 (d, 4H).

<Synthesis of 4-DPBGMA>
After dissolving 50.8 g (0.2 mol) of 4-formylphenyl-4′-formylbenzoate synthesized by the synthesis method described in JP-A-2007-106779 in 200 ml of t-butanol and 50 ml of water. , 50 ml of an aqueous solution of sodium hydrogen phosphate, 140 g (2 mol) of 2-methyl-2-butene, and 36 g (0.4 mol) of sodium chlorite were further added to prepare a reaction solution. Next, after stirring the reaction solution for 5 hours, the reaction solution was acidified using a 1N hydrochloric acid solution to precipitate a solid. Subsequently, the reaction solution in which the solid was precipitated was subjected to suction filtration, and the precipitated solid was washed with water. The solid (compound) obtained after the washing was vacuum-dried to obtain 45.4 g (yield 79%) of 4-carboxyphenyl-4′-carboxybenzoate.

Next, a method for synthesizing 4-DPEGMA, except that 14.3 g (0.05 mol) of 4-carboxyphenyl-4′-carboxybenzoate described above was used instead of 12.9 g of 4,4′-diphenyletherdicarboxylic acid. In the same manner, 4-DPBGMA (22.8 g, 80% yield, 94% HPLC purity) was obtained. The ¹ H NMR spectrum data of the obtained 4-DPBGMA was as follows.
¹ H NMR δ 1.93 (s, 6H), 3.87 (d, 2H), 3.90 to 4.65 (m, 8H), 5.60 (s, 2H), 6.14 (s, 2H) ), 7.25 (d, 2H), 8.10 (d, 2H), 8.15 (d, 2H), 8.27 (d, 2H).

<Synthesis of 4-DPALGMA>
After dissolving 1,1-bis (4-formylphenyl) cyclohexane (58.4 g, 0.2 mol) synthesized by the synthesis method described in Patent No. 3076603 in 200 ml of t-butanol and 50 ml of water. A reaction solution was prepared by adding 50 ml of an aqueous solution of sodium hydrogen phosphate, 140 g (2 mol) of 2-methyl-2-butene, and 36 g (0.4 mol) of sodium chlorite. Next, after stirring the reaction solution for 5 hours, the reaction solution was acidified using a 1N hydrochloric acid solution to precipitate a solid. Subsequently, the reaction solution in which the solid was precipitated was subjected to suction filtration, and the precipitated solid was washed with water. The solid (compound) obtained after the washing was vacuum-dried to obtain 54.4 g (yield 84%) of 1,1-bis (4-carboxylphenyl) cyclohexane.

Next, a method for synthesizing 4-DPEGMA was performed except that 16.2 g (0.05 mol) of 1,1-bis (4-carboxylphenyl) cyclohexane was used instead of 12.9 g of 4,4′-diphenyletherdicarboxylic acid. In a similar manner, 4-DPALGMA (yield 23.7 g, yield 78%, HPLC purity 92%) was obtained. The ¹ H NMR spectrum data of the obtained 4-DPALGMA was as follows.
¹ H NMR δ 1.42 (t, 6H), 1.93 (s, 6H), 2.10 (t, 4H), 3.77 (d, 2H), 3.85 to 4.60 (m, 8H) ), 5.61 (s, 2H), 6.15 (s, 2H), 7.24 (d, 4H), 7.90 (d, 4H).

<Example 1>
A dental curable composition comprising 4-DPEHE (60 parts by mass), 3G (40 parts by mass), 0.15 parts by mass of HQME as a polymerization inhibitor, a photopolymerization initiator shown in Table 1, and a filler was used in a dark place. A paste-like composition was prepared by stirring and mixing using an agate mortar. For the above paste, the bending strength and the ambient light stability were measured according to the above-described methods for evaluating the bending strength and the ambient light stability. The results are shown in Table 1.

<Examples 2 to 50>
A paste was prepared in the same manner as in Example 1, except that the composition of the polymerizable monomer and the photopolymerization initiator were changed to those shown in Table 2, and the obtained paste was measured for bending strength and ambient light stability. The results are shown in Tables 1 and 2.

<Comparative Examples 1 to 7>
A paste was prepared in the same manner as in Example 1, except that the polymerizable monomer and the photopolymerization initiator were changed to the compositions shown in Table 3, and the obtained paste was measured for bending strength and ambient light stability. The results are shown in Table 3.

  As understood from the results shown in Examples 1 to 50, Examples 1 to 50 satisfying the constitution of the dental curable composition of the present invention have (A) a polymerizable monomer having a low viscosity. Therefore, mixing was easy, and the resulting dental curable composition had high bending strength and was stable to ambient light. On the other hand, as can be understood from the results shown in Comparative Examples 1 to 8, the polymerizable monomers other than the polymerizable monomer (A) of the present invention were difficult to mix due to high viscosity. The resulting dental curable composition has a low bending strength as shown in Comparative Examples 1 to 4, but is stable to ambient light. As shown in Comparative Examples 5 to 7, It was a composition having low stability to, and was not compatible with both bending strength and ambient light stability. In Comparative Example 8, both bending strength and environmental light stability were compatible, but the polymerizable monomer used was difficult to mix due to its high viscosity.

Claims (5)

(A) a polymerizable monomer represented by the following general formula (1),

[In the general formula (1), X represents —O— , and Ar ¹ and Ar ² each represent an unsubstituted aromatic group having any valence selected from divalent to tetravalent. May be the same or different, and L ¹ and L ² each have a main chain atom number in the range of 2 to 60 and are selected from divalent to tetravalent And each may be the same or different, and R ¹ and R ² each represent hydrogen or a methyl group. Further, m1, m2, n1 and n2 are each an integer selected from the range of 1-3. ]
A curable dental composition comprising (B) B1) an α-diketone compound, B2) a photoacid generator, and B3) a photopolymerization initiator containing an aromatic amine compound. The dental curable composition according to claim 1 wherein at least one of L ¹ and L ² in the general formula (1) comprises a hydroxyl group. The polymerizable monomer (A) is represented by the following general formula (2)

[In the general formula (2), X, L ¹ , L ² , R ¹ and R ² are the same as those in the general formula (1). ]
In a polymerizable monomer represented, dental curable composition according to claim 1 or 2. (B) B2 in the photopolymerization initiator) photoacid generator, s- triazine compounds substituted by a trihalomethyl group, and any one of claims 1 to 3 is at least one selected from diaryl iodonium salt compound 3. The dental curable composition according to item 1. (B) As a photopolymerization initiator, further B4) a tertiary amino group in which three saturated aliphatic groups are bonded to a nitrogen atom, and at least two of the saturated aliphatic groups are The dental curable composition according to any one of claims 1 to 4 , comprising a tertiary aliphatic amine compound having an electron-withdrawing group as a substituent.