JP6615000B2 - Dental adhesive composition - Google Patents

Description

The present invention relates to a dental adhesive composition.

  In the case of a tooth cavity damaged by caries or the like, if it is a relatively small cavity in the first mid-stage, restoration by a composite resin is performed in terms of aesthetics, simplicity of operation, and rapidity. On the other hand, for repairing a relatively large cavity, a restoration using a prosthesis made of metal, ceramics, or dental resin is performed.

  Since these dental restorations such as composite resin and prosthesis do not have adhesiveness to the tooth, the dental adhesive is used for the composite resin to adhere to the tooth. For this, dental cement is used together. In general, these adhesives and cement materials are composed of a polymerizable monomer composition containing a methacrylate monomer as a main component.

  Therefore, the adhesive strength of the polymerizable monomer used for such an adhesive is not sufficient. Therefore, for example, for bonding to a composite resin, it often does not have an adhesive strength enough to overcome internal stress generated upon curing, that is, tensile stress generated at the interface between the tooth substance and the composite resin. . Furthermore, the adhesive strength is often not sufficient to withstand the force applied by occlusion. Therefore, in order to improve the adhesive strength of these adhesives, the following pretreatment is applied to the tooth surface and the application surface of the prosthesis in use.

  For teeth, (1) Apply an etching material to etch hard teeth (mainly enamel mainly composed of hydroxyapatite), and (2) Promote penetration into the teeth, called a primer. The pretreatment material is applied as an agent. In addition, a self-etching primer (hereinafter also referred to as a dental pretreatment material) having the functions (1) and (2) has been proposed. This dental pretreatment agent partially contains a polymerizable monomer having an acidic group such as phosphoric acid, carboxylic acid, or phosphonic acid. Due to the action of this acidic group, the aqueous acid solution can be removed by a single coating operation. An ash function and a primer penetration promoting function can be imparted.

  On the other hand, the dental prosthesis appropriate for various materials is applied to the prosthesis. For precious metal prostheses, a dental pretreatment compound containing a sulfur atom-containing polymerizable monomer is effective, and for ceramic prosthesis, a dental pretreatment compounded with a silane coupling agent An agent is effective (Patent Documents 1 to 3). Further, a dental pretreatment material containing an acidic group-containing polymerizable monomer is effective for ceramics and base metal adherends (Patent Documents 4 and 5).

  In addition, after the dental pretreatment material is applied, if the restoration is a composite resin, an adhesive is applied thereon and polymerized and cured (for example, refer to Patent Document 6). Dental cement is applied and polymerized and cured, and each is adhered to the tooth (see, for example, Patent Document 7). Since these are processed with the adhesive for composite resin or dental cement according to the restoration after the treatment with the dental pretreatment material, they are two-step type treatments.

  Under these circumstances, a dental one-component adhesive that exhibits high adhesiveness without using a dental pretreatment material in a dental adhesive for the purpose of reducing the operability of the pretreatment material as described above. (Hereinafter, also simply referred to as a dental adhesive) has been proposed. This dental adhesive partially contains a polymerizable monomer having an acidic group, and the action of this acidic group provides a deashing function of an acid aqueous solution and a primer penetration promoting function by a single coating operation. Furthermore, high adhesiveness is expressed by polymerizing and curing. Since this dental adhesive does not require a dental pretreatment material, it can be used as an adhesive excellent in operability (see, for example, Patent Documents 8 to 11).

  Furthermore, recently, for the purpose of reducing the complexity of further operations, a composite resin provided with the functions of the dental pretreatment material and the dental adhesive (hereinafter also simply referred to as a self-adhesive dental composite resin), A dental cement having a function of a pretreatment material (hereinafter, also simply referred to as a self-adhesive dental cement) has been proposed (see, for example, Patent Documents 12 to 14).

  However, in the self-adhesive dental composite resin and the self-adhesive dental cement, in exchange for the operability, the adhesiveness is still low and stronger adhesiveness is required. In addition, even when a two-step type or a one-part dental adhesive is used, the oral cavity is required to have water resistance, heat resistance and impact resistance (chewing resistance), although excellent adhesion can be obtained. However, after treatment, it is required to adhere stably over a long period of time, but it is not always sufficient, and more stable adhesiveness is required.

JP 2000-159621 A Japanese Patent Laid-Open No. 10-1409 JP 2000-248201 A International Publication No. 2010/016373 International Publication No. 2007/135742 Japanese Patent Laid-Open No. 7-82115 JP 2003-012430 A Japanese Patent Laid-Open No. 10-236912 JP-A-11-130465 JP 2007-137798 A International Publication No. 2007/139207 JP 2012-171885 A Special table 2008-510038 gazette JP 2008-260753 A

  A dental adhesive composition containing an acidic group-containing polymerizable monomer has high adhesive strength. However, as described above, since extremely strong adhesive strength is required between the tooth and the dental restoration, the adhesive strength is not yet sufficient, and further improvement is required.

  High adhesive strength can be achieved only by improving the performance of polymerizable monomers having adhesiveness to various adherends in the adhesive composition, that is, acidic group-containing polymerizable monomers and sulfur-containing polymerizable monomers. It is difficult to realize and it is necessary to improve the strength of the adhesive layer. In order to improve the strength of the adhesive layer, it is effective to add an inorganic filler or a polyfunctional monomer. On the other hand, if a large amount of these is added until the desired strength is obtained, the adhesive composition The viscosity of the adhesive increases rapidly, and the familiarity of the adhesive composition with the tooth and prosthesis decreases. For this reason, even if an adhesive composition containing a polymerizable monomer that has a high affinity with the tooth or prosthesis is used, the adhesive composition cannot be used with the tooth or the prosthesis, so that the performance cannot be achieved. Will fall.

  Furthermore, in order to obtain even higher adhesive strength in the pretreatment material, the two layers are fused and integrated at the laminated interface between the dental pretreatment material layer and the dental adhesive material layer or dental cement material layer. However, if the viscosity of the dental pretreatment material increases, not only will the familiarity with the tooth quality decrease, but the compatibility with adhesives and cement materials applied later will also decrease. However, it becomes impossible to bond with sufficient strength as desired. In the case of a dental adhesive, as well as the dental pretreatment material, not only does the familiarity with the tooth quality decrease, but the compatibility with the dental composite resin to be applied later decreases sufficiently. Adhesiveness cannot be obtained.

  From the above, it is a major challenge to increase the adhesive strength between the dental substance and the dental restoration by making both the strength of the dental adhesive composition and familiarity with the tooth and prosthesis and compatibility of various adhesive compositions compatible. Met.

  The inventors of the present invention have made extensive studies to overcome the above technical problems. As a result, it has been found that an adhesive composition containing a polymerizable monomer represented by the general formula (1) has excellent adhesiveness, and has completed the present invention.

  That is, the present invention comprises (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 represents an unsubstituted aromatic group having any valence selected from divalent to tetravalent. Each may be the same or different, and each of L ¹ and L ² has any number of main chain atoms within the range of 2 to 60 and is 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. Moreover, m1, m2, n1, and n2 are each an integer selected from the range of 1-3. ]
(B) A dental adhesive composition comprising an acidic group-containing polymerizable monomer.

  The intensity | strength of a dental adhesive composition improves the dental adhesive composition of this invention by mix | blending the polymerizable monomer shown to the said General formula (1). In addition, the polymerizable monomer represented by the general formula (1) is a Bis-GMA that is generally used to increase the strength of a cured product, despite the fact that the polymerizable monomer increases the strength. -Since an increase in viscosity is suppressed as compared with a dental adhesive composition containing GMA, a high adhesive strength can be obtained without reducing the affinity for a tooth or a prosthesis.

The reason why such an effect is obtained is not clear, but the present inventors presume as follows. First, the reason why the cured product is excellent in mechanical strength is considered to be because it has a structure (Ar ¹ -X-Ar ² ) containing an aromatic group having high rigidity at the center of the molecule.

The reason why the viscosity is low is that, as the structure of the center of the molecule, a structure in which an aromatic group Ar ¹ and an aromatic group Ar ² are directly bonded via a σ bond, such as a biphenyl structure (Ar ^1- Ar ² ) instead of the structure (Ar ¹ -X-Ar ² ) in which the aromatic group Ar ¹ and the aromatic group Ar ² are bonded via the divalent group X. The structure (Ar ¹ -Ar ² ) is easy to crystallize due to the high symmetry of the molecular structure, but in the structure (Ar ¹ -X-Ar ² ) in which a divalent group X is further introduced into such a structure, the molecular structure This increases the flexibility of the resin and lowers the symmetry. As a result, it is considered that the crystallinity is lowered and the viscosity is lowered. In addition to this, in the polymerizable monomer of the present embodiment, 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 ) is more flexible in molecular structure than the structure (Ar ¹ -Ar ² ). For this reason, the polymerizable monomer of the present embodiment is harder to be brittle and has excellent bending strength as compared with the polymerizable monomer having the structure (Ar ¹ -Ar ² ) introduced in the center of the molecule. .

  In addition, compared with Bis-GMA, non-aromatic (meta) having a hydroxyl group, such as pentaerythritol dimethacrylate, is low in viscosity and excellent in handleability and excellent in adhesion to the surface of a hydrophilic member. ) Acrylic polymerizable monomers are also useful. However, a non-aromatic (meth) acrylate polymerizable monomer having a hydroxyl group does not have an aromatic skeleton in the molecule, so that the mechanical strength of the cured product is inferior.

  In addition, since it has a hydroxyl group in the molecule, it has high hydrophilicity but is inferior in water resistance, so it is not suitable for long-term use in water or in a high humidity environment such as in the oral cavity. However, in the polymerizable monomer of this embodiment having a hydroxyl group, compared to a non-aromatic (meth) acrylate polymerizable monomer having a hydroxyl group, the mechanical strength and water resistance of the cured product are also improved. Excellent characteristics can be demonstrated.

  The dental adhesive composition of the present invention comprises (a) a polymerizable monomer represented by the general formula (1) and (b) an acidic group polymerizable monomer. It is an adhesive composition. Hereinafter, each component contained in the dental adhesive composition of the present invention will be described in detail sequentially.

  (A) The polymerizable monomer represented by the general formula (1) contained in the dental adhesive composition will be described. The polymerizable monomer of the present invention is represented by the general formula (1).

Here, in the general formula (1), X represents a divalent group, and Ar ¹ and Ar ² each represent an aromatic group having any valence selected from divalent to tetravalent. Each may be the same or different, and each of L ¹ and L ² has any number of main chain atoms within the range of 2 to 60 and is 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. Moreover, 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 an isomer mixture including two or more isomers.

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 4 represented by the following structural formulas Ar-a4 to Ar-a6. Valent naphthalene, or divalent to tetravalent anthelane represented by the following structural formulas Ar-a7 to Ar-a9. In these structural formulas, the bond is provided on any carbon of the benzene ring that constitutes the aromatic groups Ar ¹ and Ar ² (excluding the carbon that forms the condensed part of the benzene ring and the benzene ring). Can do. For example, in the case of the structural formula Ar-a1 (divalent benzene), two bonds can be provided at either the ortho position, the meta position, or the para position.

Note that 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.

In addition, the aromatic groups Ar ¹ and Ar ² may each have a substituent, and in this case, the hydrogen of the benzene ring constituting the aromatic groups Ar ¹ and Ar ² is replaced with another substituent. Can do. The substituents of the aromatic groups Ar ¹ and Ar ² are not particularly limited as long as they do 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 their ends. Those having a total number (number of atoms) of atoms constituting the substituent in the range of 1 to 60 can be appropriately selected. Specific examples include a monovalent hydrocarbon group having 1 to 20 carbon atoms, -COOR ³ , -OR ³ , a halogen group, an amino group, a nitro group, and a carboxyl group.

R ³ is the same as the 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 or an ethyl group, an alicyclic hydrocarbon group such as a cyclohexyl group, a phenyl group, and a monovalent group. And heterocyclic groups such as furan.

X represents a divalent group, and specifically, the number of atoms in the main chain that bridges the aromatic group Ar ¹ and the aromatic group Ar ² as exemplified by 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. It is preferable. Examples of such an electron-donating divalent group X include —O—, —CH ₂ —, —CH (R ⁵ ) —, and —S—, and 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 in the following resonance structural formula, so that the polarity at the center of the molecule is relatively high. For this reason, it is possible to further improve the affinity with a hydrophilic material having a high polarity. As a result, the compatibility with the hydrophilic material is improved, and the affinity / adhesion to the hydrophilic surface is improved. It becomes easy. In the resonance structural formula below, the divalent group X is —O— and the aromatic groups Ar ¹ and Ar ² are phenylene groups (however, two bonds are provided at the para position). It shows about the molecule | numerator center part of the polymerizable monomer of this embodiment.

L ¹ and L ² each represent a hydrocarbon group having a main chain number of 2 to 60 and a valence selected from divalent to tetravalent, each being the same 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, more 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.

  The atoms constituting the main chain are basically composed of carbon atoms, and all atoms may be carbon atoms, but some of the carbon atoms constituting the main chain may be replaced with heteroatoms. 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 heteroatoms 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 heteroatoms that can be introduced into the main chain is one. .

In addition, a substituent may be bonded to at least one of the atoms constituting the main chain (usually a carbon atom). Examples of such a substituent 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, halogen, —COOR ⁴ , and —OR ⁴ . R ⁴ is the same as the alkyl group having 1 to 3 carbon atoms. The monovalent hydrocarbon group having a hydroxyl group preferably has 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms. Specific examples of the monovalent hydrocarbon group having a hydroxyl group include —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 to improve 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 ^In at least one of ² , the substituent is preferably a hydroxyl group and / or a monovalent hydrocarbon group having a hydroxyl group. The number of hydroxyl groups contained in each of L ¹ and L ² may be at least one or more, but typically is preferably one. Further, it is more preferable that one hydroxyl group is contained in each of L ¹ and L ^{2. In} this case, if m 1 and m 2 = 1, two hydroxyl groups are contained in the molecule.

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, 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 the ester bond directly bonded to the aromatic groups Ar ¹ and Ar ² because the increase in viscosity is relatively suppressed. Here, “when a hydroxyl group is present in the vicinity of the ester bond” specifically refers to the main of L ¹ or L ² having a hydroxyl group when either or both of L ¹ and L ² have a hydroxyl group. The number of chain atoms means a range of 2 to 10, and the number of main chain atoms is particularly preferably a range of 2 to 3. Although the reason why the above-described effect can be obtained is not clear, the present inventors presume as follows.

When a hydroxyl group is present in the vicinity of the 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 aromatic as shown in the structural formula shown below. It is expected that an intramolecular hydrogen bond is easily formed between the oxygen of the carbonyl group of the ester bond directly bonded to the group Ar ¹ and Ar ² . In the general formula (1), the structural formulas exemplified below are 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, formation of an intermolecular hydrogen bond is suppressed. For this reason, in the polymerizable monomer of the present embodiment, when the hydroxyl group is not contained in the molecule, the viscosity increases when the hydroxyl group is contained in the molecule, but the conventional molecule has a hydroxyl group. It is suppressed that the viscosity is remarkably increased to the same level as that of a polymerizable monomer having a viscosity (such as Bis-GMA).

In addition to this, when the intramolecular hydrogen bond is formed, compared to the case where the intermolecular hydrogen bond is not formed as a reference, the benzene rings constituting the aromatic groups Ar ¹ and Ar ² and Distortion occurs in the benzoate structure consisting of the ester bond to be bonded, and the symmetry of the molecular structure at the center of the molecule is lowered. Therefore, it is considered that the crystallinity of the molecule is lowered and the significant increase in viscosity is further suppressed. In addition, since formation of an intramolecular hydrogen bond weakens the bond between molecule | numerators, there exists a possibility of causing the fall of the mechanical strength of hardened | cured material.

However, when the polymerizable monomer of the present embodiment has a hydroxyl group in the vicinity of the ester bond directly bonded to the aromatic groups Ar ¹ and Ar ² , the hydroxyl group is more precisely the molecule than the intermolecular hydrogen bond. The degree of contribution to the internal hydrogen bond is considered to be relatively higher, and it is also considered that it contributes to the formation of a slow hydrogen bond network between molecules. Further, when a plurality of hydroxyl groups are contained in the molecule as in the case where both L ¹ and L ² have a hydroxyl group, a hydrogen bond network having a high density between the molecules is easily formed. In this case, it is considered that the mechanical strength of the cured product can be further increased as compared with the polymerizable monomer of the present embodiment having no hydroxyl group in the molecule.

Specific examples of L ¹ and L ² include the following structural formulas Lb1 to Lb14 when n1 and n2 = 1 (when L ¹ and L ² are divalent hydrocarbon groups). it can. 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 Lb1 to Lb14, 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 0, d represents an integer selected from the range of 0 to 5, e represents an integer selected from the range of 2 to 5, and f is selected from the range of 1 to 6 Represents an integer. Note that the values of a to f are preferably selected in the range where the number of atoms of the main chain is 12 or less in the structural formulas Lb1 to Lb14.

On the other hand, when n1 and n2 = 2 (when L ¹ and L ² are trivalent hydrocarbon groups), in structural formulas Lb1 to Lb14, among the carbon atoms constituting the main chain, * The carbon atom farthest from the carbon atom having the attached bond has two bonds. Further, when n1 and n2 = 3 (when L ¹ and L ² are tetravalent hydrocarbon groups), structural formulas Lb1 to Lb2, Lb6 to Lb8, Lbb10 to L In -b14, among the carbon atoms constituting the main chain, the carbon atom located farthest from the carbon atom having a bond marked with * has three bonds.

In addition, it is especially preferable that the polymerizable monomer of this embodiment represented by the general formula (1) is a polymerizable monomer represented by the following general formula (2). Note that the general formula (2) has a structure in which m1, m2, n1, n2 = 1, Ar ¹ , Ar ² = —C ₆ H ₄ — (structural formula Ar-a1) in the general formula (1). Is shown.

Moreover, it is preferable that the polymerizable monomer of this embodiment is a polymerizable monomer shown by 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 general formula (1) except that the valence can take only two valences. And L ³ and L ⁴ each represents a divalent hydrocarbon group having 1 to 8 atoms in the main chain, and each may be the same or different. R ³ and R ⁴ each represent hydrogen or a methyl group. Further, 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} The structure (bifunctional structure) in the case of corresponding to is shown. In the general formula (3), the groups shown in parentheses on the left and right sides can be bonded to any of the two bonds 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 left parenthesis in the general formula (3) may be bonded to both sides of the group shown in the center, or the right side in the general formula (3) In some cases, groups shown in parentheses are bonded 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 atoms may be carbon atoms, but some of the carbon atoms constituting the main chain 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, more preferably 1 to 5, still 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 the 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. Examples thereof include a group in which a part or all of them are substituted with 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). Among these, the polymerizable monomer (1, 1) and (0, 2) are more preferable from the viewpoint that suppression of decomposition of body molecules can be expected. As the reason for this, the present inventors speculate as follows.

Here, the formula shown below is (j, k) = (1, 1), X = —O—, Ar ¹ , Ar ² = —C ₆ H ₄ —, L ³ , L in the general formula (3). ⁴ shows an example of a reaction mechanism in the presence of water molecules in a polymerizable monomer molecule in which ⁴ = —CH ₂ —, R ³ , and R ⁴ = —CH ₃ . The polymerizable monomer of this embodiment has a molecular structure in which an ester bond that is directly bonded to the aromatic group at the center of the molecule exists. One of the reaction functions that the polymerizable monomer having such a molecular structure decomposes is expected to be a nucleophilic reaction (hydrolysis reaction) of water molecules 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 the ester bond directly bonded to the aromatic group, the primary alcohol and the ester bond cause a cyclization reaction in the molecule. To form a cyclic structure (Route A below). Since this cyclization reaction is reversible, it easily returns to the original linear structure, but this cyclization reaction inhibits the nucleophilic reaction (hydrolysis reaction) described above. For this reason, it is estimated that decomposition | disassembly of a polymerizable monomer molecule | numerator is inhibited. In this case, the degradation performance of the polymerizable monomer or the composition containing the same is suppressed (in other words, the storage stability is improved), so that the initial performance immediately after production of various compositions using the polymerizable monomer. Can be maintained stably over a long period of time. For example, in dental compositions that use polymerizable monomers (dental filling restoration materials, dental adhesives, etc.), the adhesive strength immediately after production and the mechanical strength of the cured product are maintained even after long-term storage. Easy to do.

  Further, in the polymerizable monomer of the present embodiment, the combination (j, k) of the values j and k shown in the general formula (3) is (2, 0), (1, 1) and (0, 2). It is preferable that any two or more structural isomers selected from the group consisting of: When the polymerizable monomer contains two or more kinds of structural isomers with respect to 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 becomes easy to improve. In this case, the average value k of all 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 greater than 0 and less than or equal to 1.95). Is preferred. Further, the lower limit of the average value of the value k is preferably 0.1 or more, the upper limit of the average value of the value k is more preferably 1.7 or less, and further preferably 1.5 or less. , 0.4 or less is particularly preferable. In order to improve the mechanical strength and the storage stability of the cured product in a well-balanced manner, the average value k is 0.05 or more even when the value k = 2 (state not including the structural isomer). It is suitable as in 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 kinds of structural isomers than in the value k = 2 (state not containing the structural isomer). be able to. In this respect, it is more advantageous that the average value of the values k is smaller as long as the average value of the values k is not less than 0.05.

  The polymerizable monomer of this embodiment can be synthesized by appropriately combining known starting materials and known synthetic reaction methods, and the production method thereof 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 types of 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 has 1 to 7 atoms in the main chain. Represents a divalent hydrocarbon group. P is 0 or 1. Here, the average value of the values 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, by performing purification after synthesis as necessary, the average value of the values k (the abundance ratio of the structural isomers represented by the general formulas (6) to (8)) is adjusted so as to be closer to the desired value. May be.

In L ⁵ represented by the general formulas (4) to (8), the atoms constituting the main chain are basically composed of carbon atoms, and all the atoms may be carbon atoms, but the main chain is composed. It is also possible to replace some of the carbon atoms to be replaced with hetero atoms. 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.

Further, the number of atoms in the main chain in L ⁵ may be 1 to 7, but 1 to 4 is preferable, and 1 to 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, and a main chain of the alkylene group. Examples thereof include a group in which a part or all of them are substituted with 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. The same applies to the 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. Further, p is preferably 0.

  If necessary, after obtaining a polymerizable monomer containing two or more kinds of structural isomers by the above-described production method, a polymerizable monomer substantially free of structural isomers (for example, a general formula Only the polymerizable monomer shown in (6) may be isolated and purified. However, the polymerizable monomer obtained by isolation and purification is compared with the polymerizable monomer containing two or more types of structural isomers before the isolation and purification treatment, and the mechanical strength and the storage stability of the cured product. It tends to be inferior in terms of compatibility with sex. In addition, when the polymerizable monomer is produced, further isolation and purification treatment is required, which tends to be disadvantageous in terms of cost. Therefore, it is preferable to omit the isolation and purification treatment from these viewpoints.

  Next, the (b) acidic group-containing polymerizable monomer contained in the dental adhesive composition will be described. By containing an acidic group polymerizable monomer, adhesion to the tooth can be imparted. Furthermore, adhesion to base metals such as cobalt, chromium and titanium and metal oxide ceramics such as alumina and zirconia is also improved.

  The acidic group-containing polymerizable monomer is not particularly limited as long as it is a polymerizable monomer having at least one radical polymerizable unsaturated group and at least one acidic group in one molecule. Compounds can be used. Here, the radical polymerizable unsaturated group is a (meth) acryloyl group and a (meth) acryloyl group derivative group such as a (meth) acryloyloxy group, a (meth) acryloylamino group, a (meth) acryloylthio group; Examples include vinyl group; aryl group; styryl group and (meth) acrylamide group.

Moreover, in this specification, an acidic group is a phosphinico group {= P (= O) OH}, a phosphono group {—P (═O) (OH) ₂ }, a carboxyl group {—C (═O) OH}, Not only a free acid group having —OH such as a sulfo group (—SO ₃ H), but also an acid anhydride structure (for example, —C (═O ) —O—C (═O) —) or an acid halide group in which —OH of the acidic group having —OH exemplified above is substituted with a halogen (eg, —C (═O) Cl) In this way, an aqueous solution or aqueous suspension of a polymerizable monomer having the group exhibits acidity. The acidic group preferably has a pKa of less than 5.

  Specific examples of acidic group-containing polymerizable monomers include 2- (meth) acryloyloxyethyl dihydrogen phosphate, bis (2- (meth) acryloyloxyethyl) hydrogen phosphate, 2- (meth) acryloyl. Oxyethyl phenyl hydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, bis (6- (meth) acryloyloxyhexyl) hydrogen phosphate Acid group-containing polymerizable monomer having a phosphinicooxy group or a phosphonooxy group in the molecule such as feto, 2- (meth) acryloyloxyethyl 2-bromoethyl hydrogen phosphate (hereinafter referred to as “polymerizable acid”). , And these acid anhydrides and acid halides.

  (Meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloylaspartic acid, N- (meth) acryloyl-5-aminosalicylic acid, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxyethyl hydrogen maleate, 6- (meth) acryloyloxyethyl naphthalene-1,2,6-tricarboxylic acid, O- (meth) acryloyl tyrosine N- (meth) acryloyltyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-O-aminobenzoic acid, p-vinylbenzoic acid, 2 -(Meth) acryloyloxy Molecules such as benzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid Examples thereof include an acidic group-containing polymerizable monomer having one carboxyl group therein, and acid anhydrides and acid halides thereof.

  Also, 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 10- (meth) acryloyloxydecane-1,1-dicarboxylic acid, 12- (meth) acryloyl oxide decane-1,1-dicarboxylic acid, 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid, 2- (meth) acryloyloxyethyl-3′-methacryloyloxy-2 ′-(3,4-dicarboxybenzoyloxy) propyl succinate, 1, 4-bis (2- (meth) acryloyloxyethyl) pyromellitate, N, o-di (meth) acryloyl tyrosine, 4- (2- (meth) acryloyloxyethyl) trimellitate, 4- (meth) acryloyloxyethyl trimellitate Tate, 4- (meth) acryloyloxybutyl trimellitate, -(Meth) acryloyloxyhexyl trimellitate, 4- (meth) acryloyloxydecyl trimellitate, 4-acryloyloxybutyl trimellitate, 6- (meth) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid Anhydride, 6- (meth) acryloyloxyethylnaphthalene-2,3,6-tricarboxylic anhydride, 4- (meth) acryloyloxyethylcarbonylpropionyl-1,8-naphthalic anhydride, 4- (meth ) An acidic group-containing polymerizable monomer having a plurality of carboxyl groups or acid anhydride groups in the molecule such as acryloyloxyethylnaphthalene-1,8-tricarboxylic acid anhydride, and these acid anhydrides and acids Halides are mentioned.

  Moreover, the acidic group containing polymeric monomer which has a phosphono group in a molecule | numerator, such as vinylphosphonic acid and p-vinylbenzenephosphonic acid, is mentioned.

  Moreover, acidic group-containing polymerizable monomers having a sulfo group in the molecule such as 2- (meth) acrylamide-2-methylpropanesulfonic acid, p-vinylbenzenesulfonic acid, vinylsulfonic acid and the like can be mentioned.

  In addition to those exemplified above, JP-A No. 54-11149, JP-A No. 58-140046, JP-A No. 59-15468, JP-A No. 58-173175, JP-A No. 61- Dentistry disclosed in Japanese Patent No. 293951, Japanese Patent Laid-Open No. 7-179401, Japanese Patent Laid-Open No. 8-208760, Japanese Patent Laid-Open No. 8-319209, Japanese Patent Laid-Open No. 10-236912, Japanese Patent Laid-Open No. 10-245525, etc. An acidic group-containing polymerizable monomer described as a component of the adhesive for use can be suitably used.

These acidic group-containing polymerizable monomers may be used alone or in combination of a plurality of types. In particular, among the acidic group-containing polymerizable monomers, the acidic group is preferably a phosphoric acid group from the viewpoint of excellent adhesion to tooth. As such an acidic group-containing polymerizable monomer having a phosphate group, in particular, a dihydrogen phosphate monoester group {—O—P (═O) (OH) ₂ } or a hydrogen phosphate diester group {(—O _-) a polymerizable acidic phosphoric acid ester having 2 P (= O) OH} are preferable. Furthermore, when the dental adhesive composition of the present invention is cured by light irradiation, the polymerizable unsaturated group constituting the acidic group-containing polymerizable monomer is preferable in terms of good polymerizability during light irradiation. Is preferably a derivative group of a (meth) acryloyl group.

  In the dental adhesive composition of the present invention, the blending amount of (a) the polymerizable monomer represented by the general formula (1) and (b) the acidic group-containing polymerizable monomer is not particularly limited, and is arbitrary. It can be used by mixing at a ratio of In order to obtain better adhesive strength, for example, when the adherend is a tooth, it is preferable to contain 5 parts by weight or more in the total polymerizable monomer component, and 5 to 80 parts by weight. It is more preferable to make it contain, and it is most preferred to make it contain 10-60 weight part. If the blending amount of the acidic group-containing polymerizable monomer is small, the adhesive strength to enamel tends to decrease, and conversely if it is large, the adhesive strength to dentin tends to decrease. In addition, when the adherend is a metal such as a cobalt chromium alloy or a titanium alloy, or a ceramic such as silica, zirconia, or alumina, it is preferable to contain 0.1 part by weight or more in the total polymerizable monomer component. Yes, it is more preferable to contain 0.1 to 80 parts by weight, and most preferable to contain 0.5 to 60 parts by weight. When there are too few compounding quantities of an acidic group containing polymeric monomer, the polymerizable monomer which acts on a to-be-adhered body will decrease, and adhesiveness will fall. On the other hand, when there are too many compounding quantities, the intensity | strength of a contact bonding layer will fall and there exists a tendency for adhesiveness to fall.

  In addition, for the purpose of adjusting the permeability of the adhesive to the tooth substance and improving the hardness of the cured body, (a) a polymerizable monomer represented by the general formula (1), and (b) an acid Other polymerizable monomers may be contained in addition to the group-containing polymerizable monomer.

  The other polymerizable monomer refers to a compound that contains at least one polymerizable unsaturated group in the molecule and can form a polymer by a polymerization reaction, and can be appropriately selected from known compounds. Examples of the polymerizable unsaturated group include groups such as acrylate group, methacrylate group, acrylamide group, methacrylamide group, vinyl group, allyl group, ethynyl group, and styryl group. Of these, acrylate groups, methacrylate groups, acrylamide groups, methacrylamide groups, and the like are preferable, and acrylate groups and methacrylate groups are particularly preferable because of the high curing rate.

Specific examples of other polymerizable monomers containing an acrylate group and a methacrylate group, which are preferred embodiments, include those shown in the following (1) to (4).
(1) Monofunctional polymerizable monomer Examples of the monofunctional polymerizable monomer include ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate, n- Stearyl (meth) acrylate cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, tetrahydrofur Alkyl ester of (meth) acrylic acid such as furyl (meth) acrylate or glycidyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl methacrylate, 1H, 1H, 5H-octafluoropen Fluorine-containing (meth) acrylates such as til methacrylate, 1H, 1H, 6H-decafluorohexyl methacrylate or 1H, 1H, 7H-dodecafluoroheptyl methacrylate, or the following formulas (i) to (v), (vi) to (vii) ) And the like.

In the above formulas, R ^a is a hydrogen atom or a methyl group. R ^b or R ^c in the above formulas is an independent alkylene group. R ^d in the above formulas is an alkyl group. S in the above formulas is 0 or an integer of 1 to 10, and t is an integer of 1 to 10 (provided that m + n is an integer of 2 to 10).

(2) Bifunctional polymerizable monomer Examples of the bifunctional polymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene glycol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6- Xanthdiol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2,2-bis ((meth) acryloxyphenyl) propane, 2,2 -Bis [4- (3- (meth) acryloxyethoxy) 2-hydroxypropoxyphenyl] propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxydipropoxyphenylpropane) 2- (4-Methacryloxyethoxyphenyl) -2- (4- (meth) acryloxydiethoxyphenyl) propane, 2- (4- (meth) acryloxydiethoxyphenyl) -2- (4- (meta ) Acryloxytriethoxyphenyl) propane, 2- (4- (meth) acryloxydipropoxyphenyl-2- ( 4- (meth) acryloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane, or 2,2-bis (4- (meth) acryloxyisopropoxyphenyl) propane Etc.

(3) Trifunctional polymerizable monomer Examples of the trifunctional polymerizable monomer include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate or Examples include trimethylol methane tri (meth) acrylate.

(4) Tetrafunctional polymerizable monomer Examples of the tetrafunctional polymerizable monomer include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and pentaerythritol hexa (meth) acrylate. It is done.

  In the present invention, other polymerizable monomers may be used alone, or two or more other polymerizable monomers may be combined. Further, a plurality of other polymerizable monomers having different functional groups may be combined. In addition, a) When the polymerizable monomer represented by the general formula (1) is combined with (b) an acidic group-containing polymerizable monomer and another polymerizable monomer, the content of the other polymerizable monomer Is not particularly limited, but in order to further exhibit adhesiveness, it is preferable that the blending amount of the acidic group polymerizable monomer is set to the blending amount described above.

  Further, the dental adhesive composition of the present invention includes a sulfur atom-containing polymerizable monomer that is a polymerizable monomer having a functional group that binds to a noble metal for the purpose of imparting adhesion to the noble metal, ceramics, and the like. It is also possible to add a coupling agent having a functional group that binds to ceramics for the purpose of imparting adhesion to the ceramic.

  Such a sulfur atom-containing polymerizable monomer is not particularly limited as long as it contains at least one polymerizable group and a sulfur atom in the molecule, and a known compound can be used. Specific examples include polymerizable monomers described in JP-A-10-1409, JP-A-10-1473, JP-A-8-113763, and the like. Preferably, a compound represented by the following general formula can be used.

  That is, a polymerizable compound capable of generating a mercapto group by tautomerism represented by the following general formulas A1 to A5; a disulfide compound represented by the following general formulas A6 to A9; a chain or cyclic structure represented by the following general formulas A10 to A11 Examples include thioether compounds.

{In the formula, R ^e represents a hydrogen atom or a methyl group; R ^f represents a divalent saturated hydrocarbon group having 1 to 12 carbon atoms, a —CH ₂ —C ₆ H ₄ —CH ₂ — group, — (CH _{2 ) o -Si (CH 3) 2} OSi (CH 3) 2 - (CH 2) p -. group (provided that, o and p are an integer from 1 to 5, respectively), or -CH ₂ CH ₂ OCH ₂ CH ₂ is a group, and X is an —OC (═O) — group, —OCH ₂ — group, or —OCH ₂ —C ₆ H ₄ — group (provided that the rightmost carbon atom in any of these groups X) Is bonded to an unsaturated carbon, and the oxygen atom at the left end is bonded to the group R ^f ), X ′ is a —OC (═O) — group (where the carbon atom at the right end is bonded to the unsaturated carbon, The oxygen atom at the left end is bonded to the group R ^f ), a —C ₆ H ₄ — group, or a bond (where the group X ′ is a bond) the group R ^f and the unsaturated carbon And W is -S-, -O-, or -N (R ')-(where R' is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). ). }
If these compounds A are specifically illustrated, as a polymeric compound which can produce a mercapto group by the tautomerism shown by the said general formula A1-A5, the compound shown next is mentioned.

  Examples of the disulfide compound represented by the general formulas A6 to A9 include the following compounds.

  Further, examples of the chain or cyclic thioether compound represented by the general formulas A10 to A11 include the following compounds.

  These sulfur atom-containing polymerizable monomers can be used alone or in combination of two or more.

  Among these, as the sulfur atom-containing polymerizable monomer, from the viewpoint of storage stability, a polymerizable compound or a disulfide compound capable of generating a mercapto group by tautomerism is preferably used, and further, a viewpoint of adhesive strength. Most preferred is a polymerizable compound capable of generating a mercapto group by tautomerism.

  Moreover, a well-known thing can be used without a restriction | limiting as a coupling agent which has a functional group couple | bonded with ceramics. Specifically, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, Vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-fluoro Silicate coupling agents such as nyl-γ-aminopropyltrimethoxysilane, hexamethyldisilazane, 11-methacryloxyundecyltrimethoxysilane, 11-methacryloxyundecylmethyldimethoxysilane, isopropyl triisostearoyl titanate, isopropyl Titanate coupling agents such as trioctanoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tricumylphenyl titanate, aluminum systems such as acetoalkoxyaluminum diisopropylate Coupling agents, allyltrimethoxyzirconium, allyltriacetoxyzirconium Γ- (meth) acryloyloxypropyltrimethoxyzirconium, γ- (meth) acryloyloxypropyltris (β-methoxyethoxy) zirconium, ω- (meth) acryloyloxydecyltrimethoxyzirconium, vinyltrimethoxyzirconium, vinyltris ( Zirconium-based coupling agents such as (β-methoxyethoxy) zirconium.

  In addition, from the viewpoint of adhesiveness and handleability, a coupling material having a polymerizable group is also preferably used. For example, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri (trimethylsiloxy) silane, ω-methacryloxydecyltrimethoxysilane, γ-methacryloxypropylpentamethyldisiloxane, γ- (meth) acryloyloxypropyl Examples include trimethoxyzirconium and γ- (meth) acryloyloxypropyltris (β-methoxyethoxy) zirconium.

  In the dental adhesive composition of the present invention, these sulfur atom-containing polymerizable monomers and coupling agents are contained in combination of two or more kinds, and can be freely applied to two or more kinds of adherends. You may make it. Further, in order to obtain better adhesive strength, if the sulfur atom-containing polymerizable monomer in the dental adhesive composition of the present invention, 0.1 to 100 parts by weight of the total polymerizable monomer. 60 parts by weight is preferably contained, more preferably 0.5 to 40 parts by weight. Furthermore, if it is a coupling agent, it is preferable to contain 0.1-70 weight part in 100 weight part of all the polymerizable monomers, and it is more preferable to contain 1-50 weight part.

  The dental adhesive composition of the present invention is preferably used as a dental pretreatment material, dental adhesive, dental cement, or dental composite resin in dental applications. In particular, when used as a dental adhesive, dental cement, or dental composite resin, (c) an effective amount of a polymerization initiator is blended. Further, in the dental pretreatment material, an effective amount of a polymerization initiator may be blended for the purpose of further improving the adhesiveness. The polymerization initiator is classified into a chemical polymerization type and a photopolymerization type, and may be appropriately selected according to the purpose. It is also possible to use a dual cure type in which a photopolymerization initiator and a chemical polymerization initiator are used in combination, and polymerization can be initiated by either photopolymerization or chemical polymerization.

  Representative photopolymerization initiators include diacetyl, acetylbenzoyl, benzyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, 4,4′-oxybenzyl, camphorquinone, 9, Α-diketones such as 10-phenanthrenequinone and acenaphthenequinone, benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin propyl ether, 2,4-diethoxythioxanthone and 2-chlorothioxan Thioxanthone derivatives such as Son, Methylthioxanthone, benzophenone, benzophenone derivatives such as p, p′-dimethylaminobenzophenone, p, p′-methoxybenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2, -Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, acylphosphine oxide derivatives such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and aryl borate compounds / dyes / photoacid generators A system consisting of Among these, an α-diketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, and a photopolymerization initiator composed of a combination of an aryl borate compound / dye / photoacid generator are particularly preferable. is there.

  As the α-diketone, camphorquinone and benzyl are preferable. As the acylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4- Trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide are preferable. Although these α-diketones and acyl phosphine oxides exhibit photopolymerization activity alone, they are used in combination with amine compounds such as ethyl 4-dimethylaminobenzoate, lauryl 4-dimethylaminobenzoate, and dimethylaminoethyl (meth) acrylate. It is preferable to obtain higher polymerization activity. In addition, as a photopolymerization initiator of an aryl borate compound / dye / photoacid generator system, an aryl borate compound such as tetraphenyl boron sodium salt is used as a dye, and 3,3′-carbonylbis (7-diethylamino) coumarin is used as a dye. Substitution of halomethyl group such as 2,4,6-tris (trichloromethyl) -s-triazine, using a coumarin dye such as 3,3'-carbonylbis (4-cyano-7-diethylaminocoumarin) as a photoacid generator Those using s-triazine derivatives or diphenyliodonium salt compounds can be particularly preferably used.

  On the other hand, representative chemical polymerization initiators include combinations of organic peroxides and amines, organic peroxides, combinations of amines and sulfinates, combinations of acidic compounds and aryl borates, barbituric acid, Examples thereof include chemical polymerization initiators such as alkylborane.

  Examples of compounds suitable for use in the chemical polymerization initiator are as follows. Examples of the organic peroxides include t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, Examples include acetyl peroxide, lauroyl peroxide, benzoyl peroxide and the like. These can be used alone or in combination of two or more.

  As the amines, secondary or tertiary amines are preferable, and specific examples thereof include N-methylaniline, N-methyl-p-toluidine and the like as secondary amines. N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl -P-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p -Dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylan Ranilic acid methyl ester, N, N-dihydroxyethylaniline, N, N-dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol, p-dimethylaminostilbene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N dimethylhexyl Amine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 2,2 ′-(n-butylimino Diethanol, and the like.

  Any aryl borate can be used as long as it has at least one boron-aryl bond in one molecule, but it has high storage stability, ease of handling, and availability. From the viewpoint of ease of use, aryl borates having four boron-aryl bonds in one molecule are most preferable. Specific examples of aryl borates having four boron-aryl bonds in one molecule include tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl). ) Phenyl boron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis ( m-nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis (p-octyl) Oxyphenyl) boron, tetrakis ( - it can be mentioned salts of boron compounds such as octyloxy phenyl) boron. As a cation forming a salt with a boron compound, a metal ion, a tertiary or quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion, or a quaternary phosphonium ion may be used. it can.

  Among the above chemical polymerization initiators, a chemical polymerization initiator obtained by using a combination of an acidic compound and an aryl borate in combination with a + IV and / or + V vanadium compound is particularly suitable because of its high polymerization activity. Furthermore, the combined use of the above organic peroxide is most preferable because the polymerization activity can be further enhanced.

  Specific examples of the vanadium compound include divanadium tetraoxide (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl-1,3-butanedionate) vanadium (IV), bis (Maltrate) oxo vanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), ammonium metavanadate (V) and the like can be mentioned.

  These polymerization initiators can be blended not only alone but also in combination of a plurality of types as required. These blending amounts are preferably in the range of 0.01 to 10 parts by weight when the total polymerizable monomer is 100 parts by weight. If the amount is less than 0.01 part by weight, the curability of the adhesive tends to be reduced. Conversely, if the amount exceeds 10 parts by weight, the strength of the cured product of the adhesive tends to be reduced. The blending amount of the polymerization initiator is more preferably in the range of 0.1 to 8 parts by weight.

  Furthermore, you may make the dental composition of this invention contain a filler as needed. Here, as the filler, any conventionally known silica-based inorganic filler, organic filler, or organic-inorganic composite filler can be used without any limitation.

  Moreover, a silica type inorganic filler means the complex oxide particle | grains which have a silica or the periodic table 2-14 group metal oxide which can be combined with a silica, and a silica as a main component. In the case of the composite oxide particles, the silica component is preferably contained at least 10 mol% or more, preferably 50 mol% or more.

  Specific examples of the silica-based inorganic filler include quartz, silica, silica-alumina, silica-titania, silica-zirconia, lanthanum glass, barium glass, and strontium glass. The silica may be wet silica, but is preferably dry silica called fumed silica. Moreover, a polyvalent metal ion-eluting filler such as fluoroaluminosilicate glass can also be suitably used. Among them, silica-zirconia, barium glass, etc. having X-ray contrast properties can be preferably used.

  The particle diameter and shape of these silica-based inorganic fillers are not particularly limited, and spherical or irregular particles having an average particle diameter of 0.01 μm to 100 μm, which are generally used as dental materials, are appropriately selected depending on the purpose. Use it. The method for producing the silica-based inorganic filler is not limited at all, and a spraying method, a sol-gel method, a flame melting method, and the like can be used. When applying the dental adhesive composition of this invention to a dental adhesive, the filler by a flame melting method is preferable. Moreover, when applying the dental adhesive composition of this invention to a dental adhesive composite resin, the filler by a sol gel method is preferable and a spherical filler is more preferable.

  As such a silica-based inorganic filler, those subjected to silane coupling treatment can be suitably used. Specific examples of silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane , Vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropyl Methyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, N- phenyl--γ- aminopropyltrimethoxysilane, hexamethyldisilazane, 11-methacryloxy undecyl trimethoxysilane, 11-methacryloxy-undecyl methyl dimethoxy silane.

  Examples of the organic filler include polyalkyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polyalkyl methacrylate, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-butadiene- Examples thereof include particles made of an organic polymer such as a styrene copolymer. Particularly, particles made of polyalkyl methacrylate are preferably used. Examples of the organic-inorganic composite filler include granular organic-inorganic composite fillers obtained by mixing these inorganic particles and a polymerizable monomer in advance, forming a paste, polymerizing, and pulverizing.

  The blending amount of these fillers when used for a dental adhesive and a dental pretreatment material is in the range of 2 to 100 parts by weight, more preferably 5 to 50 parts by weight with respect to 100 parts by weight of all polymerizable monomers. Part. If the amount is less than 2 parts by mass, the strength cannot be sufficiently improved, and if the amount exceeds 100 parts by weight, the viscosity increases excessively, the penetration into the tooth is inhibited, and the effect of improving the adhesive strength of the tooth cannot be obtained sufficiently. .

  Moreover, the filler compounding amount when the adhesive composition of the present invention is used as a dental resin cement or a dental composite resin is in the range of 100 to 2000 parts by weight with respect to 100 parts by weight of all polymerizable monomers. is there. If the amount is less than 100 parts by weight, sufficient strength of the cured product cannot be obtained, and if it exceeds 2000 parts by weight, the paste becomes hard and the operability is deteriorated.

  Moreover, you may mix | blend a polyvalent metal ion with the dental adhesive composition of this invention. By blending the polyvalent metal ion, high adhesive strength can be obtained by ionic crosslinking formed by ionic bonding between the acidic group of the acidic group-containing polymerizable monomer and the polyvalent metal ion at the time of polymerization and curing. There is no restriction | limiting in particular as such a polyvalent metal ion, The metal element of the 2nd-13th group of a periodic table is mentioned. For example, beryllium (II), magnesium (II), calcium (II), strontium (II), barium (II), aluminum (III), iron (III), ruthenium (III), cobalt (III), lanthanum (III ), Ytterbium (III), titanium (IV), zirconium (IV), hafnium (IV), yttrium (IV), cerium (IV), samarium (IV) and the like. Among the polyvalent metal ions, titanium (IV), zirconium (IV), and hafnium (IV), which are Group 4 element ions, are preferable. Among these, titanium ions are particularly preferable because they are excellent in the effect of improving adhesive strength. These polyvalent metal ions may be used alone or in combination of two or more.

  Here, the content of the polyvalent metal ion is not particularly limited and can be appropriately selected according to the purpose. However, the number of moles of acidic groups in the (b) acidic group-containing polymerizable monomer is as follows. A range that is larger than the total valence of the polyvalent metal ions is preferred. Here, the total valence of the polyvalent metal ion is obtained by multiplying the number of moles of the polyvalent metal ion contained in the dental adhesive composition of the present invention by the valence of the polyvalent metal ion. . If the total valence of polyvalent metal ions is greater than the number of moles of acidic groups in the acidic group polymerizable monomer, all of the acidic groups will be neutralized with polyvalent metal ions, resulting in decalcification of the tooth. Therefore, it becomes difficult to obtain a stable adhesive strength.

  Within the above range, the ratio of the number of moles of acidic groups of the (b) acidic group-containing polymerizable monomer to the total number of polyvalent metal ions (of the acidic group-containing polymerizable monomer) The number of moles of acidic groups / total number of polyvalent metal ions) is preferably 0.3 to 2.5, more preferably 0.75 to 2.0, and 1.0 to 1. Particularly preferred is 75. The kind and content of the polyvalent metal can be measured using an inductively coupled plasma (ICP) emission spectrometer.

  In the dental adhesive composition of the present invention, the method for allowing polyvalent metal ions to be present in the composition is not particularly limited, and when preparing the adhesive composition, the polymerizable monomer component is used. A substance that serves as an ion source for the polyvalent metal ions may be blended or brought into contact to elute the polyvalent metal ions into the composition. Examples of the polyvalent metal ion source include an ionic element simple substance, an ion-eluting filler, and an ionic element compound.

  Here, as the ionic element compound, a metal salt, a metal halide, or a metal alkoxide can be used. Metal salts include 1,3-diketone enol, citrate, tartrate, fluoride, malonate, glycolate, lactate, phthalate, isophthalate, terephthalate, acetate, Examples of metal halides include magnesium fluoride, strontium fluoride, strontium chloride, aluminum fluoride, aluminum chloride, lanthanum fluoride, titanium fluoride, titanium chloride, zirconium fluoride, hafnium fluoride, etc. Is mentioned. Metal alkoxides include magnesium diethoxide, calcium diisopropoxide, barium diisopropoxide, aluminum triethoxide, aluminum triisopropoxide, gallium triethoxide, scandium triisopropoxide, lanthanum triisopropoxy. Ytterbium triisopropoxide, yttrium tetraisopropoxide, cerium tetraisopropoxide, samarium tetraisopropoxide, titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, zirconium tetramethoxy , Zirconium tetraethoxide, zirconium tetrapropoxide, zirconium tetraisopropoxide, etc. Tetra methoxide, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, etc. is particularly preferred. Among these ionic element compounds, lower alkoxides having 4 or less carbon atoms, more preferably 3 or less carbon ions are eluted quickly and the by-product is alcohol, so that the adhesive strength is not affected and easy to remove. Further, it is more preferable from the viewpoint of easy handling.

  On the other hand, the polyvalent metal ion-eluting filler can elute polyvalent metal ions in the dental adhesive composition. Usually, it is easy to elute when the dental adhesive composition is acidic. As the polyvalent metal ion-eluting filler, known fillers can be used without limitation, but glass having a chain, layered, or network-like skeleton, in which the polyvalent metal ions are held in the gaps of the skeleton is preferable. Used for. Specifically, examples of the glass having a chain-like, layer-like, or network-like skeleton include oxide glass and fluoride glass. Examples of the oxide glass include those made of titania silicate glass, borosilicate glass, soda lime glass, and the like, and examples of the fluoride glass include those made of fluoroaluminosilicate glass, titanium fluoride glass, and the like. In addition, the polyvalent metal ion-eluting filler made of these glasses is at least after the polyvalent metal ions are eluted, by filtering out the aggregated particles or those having a large particle diameter, for example, A part may be removed, but if it is left as it is in the dental adhesive composition as porous particles, it can contribute to the improvement of strength of the cured product as a filler.

  Moreover, the dental adhesive composition of this invention may be mix | blended with the organic solvent which has fluidity | liquidity as needed. In particular, when used as a dental pretreatment material or dental adhesive, an organic solvent is used to further improve the permeability, operability, and tooth decalcification of the dental pretreatment material and dental adhesive. It is suitable to be blended. Such an organic solvent is generally removed by air blowing when the dental adhesive composition of the present invention is applied to an adherend and before the adhesive composition is cured. As the organic solvent, any known organic solvent can be used without any limitation as long as it exhibits fluidity. For example, acetone, ethanol or isopropyl alcohol, tertiary butanol and the like can be mentioned. In particular, an organic solvent that is hydrophilic, highly volatile, and low in toxicity, such as acetone, ethanol, or isopropyl alcohol, is preferably used because it can be easily dried by air blowing. A plurality of these organic solvents can be mixed and used as necessary. In the case of a dental pretreatment material or a dental adhesive, the amount of the organic solvent is usually 2 to 400 parts by weight, preferably 50 to 250 parts by weight, based on 100 parts by weight of the polymerizable monomer. Is preferred. On the other hand, in the case of a dental composite resin or a dental cement material, it is preferable that substantially no organic solvent is contained in order to obtain better cured body strength, but in order to improve the familiarity to the tooth, To the extent that the strength does not decrease, specifically, it may contain 5 parts by weight or less of an organic solvent with respect to 100 parts by weight of the polymerizable monomer.

  Furthermore, the dental adhesive composition of the present invention may be blended with water to further improve decalcification as necessary. The water is preferably substantially free of impurities that reduce the storage stability, biocompatibility and adhesiveness of the dental adhesive composition, and it is preferable to use deionized water, distilled water, or the like. Such water is generally removed by air blowing before the adhesive composition is cured when the dental adhesive composition of the present invention is applied to an adherend in the same manner as the organic solvent. In the case of a dental pretreatment material or a dental adhesive, the amount of water is usually 0.01 to 50 parts by weight, preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polymerizable monomer. It is. If the amount of water added is less than 0.01 parts by mass, the decalcification of the tooth will be insufficient. On the other hand, when the amount is more than 50 parts by mass, the above-described drying by air blow is insufficient, and a large amount of water remains on the treated surface, so that a sufficient adhesive force cannot be obtained. On the other hand, in the case of a dental composite resin or dental cement material, it is preferable to contain substantially no water in order to obtain a better cured body strength. However, in order to improve the decalcification of the tooth, In particular, it may contain 5 parts by weight or less of water with respect to 100 parts by weight of the polymerizable monomer.

  Furthermore, the dental adhesive composition of the present invention includes an organic thickener, a polymerization inhibitor, a polymerization preparation agent, an ultraviolet absorber, and a dye as long as the performance is not deteriorated as required regardless of the application. It is possible to add various additives such as antistatic agents, pigments, and fragrances.

  Below, a preferable composition is shown according to the use of a dental adhesive composition. Here, the polymerizable monomer component shown below means (a) a polymerizable monomer represented by the general formula (1), (b) an acidic group-containing polymerizable monomer, and a sulfur atom-containing polymerizable monomer. A component containing a polymer group such as a monomer or a silane coupling agent is shown. However, regarding the silane coupling agent, a compound not containing a polymerization group is also included, but in that case, it is handled as a polymerizable monomer component.

  In the case of a dental pretreatment material for dental use, it contains (a) a polymerizable monomer component represented by the general formula (1), (b) an acidic group-containing polymerizable monomer component, water, and an organic solvent. Become a composition. The blending ratio of the polymerizable monomer component is (B) 95 to 20 parts by weight of the polymerizable monomer component represented by the general formula (1) in 100 parts by weight of the total polymerizable monomer component. It is preferable that the acidic group-containing polymerizable monomer component is 5 to 80 parts by weight. Moreover, the compounding quantity of water and the organic solvent is 0.01-50 weight part of water with respect to 100 weight part of all the polymerizable monomers, and it is suitable that it is 2-400 weight part of organic solvent.

  When the dental adhesive composition is used as a dental pretreatment material of base metal (cobalt, chromium, titanium, nickel, etc.) or metal oxide ceramics (zirconia, alumina, titania, etc.), the preferred composition is (i) The composition contains a polymerizable monomer component represented by the general formula (1), (b) an acidic group-containing polymerizable monomer component, and an organic solvent. The blending ratio of the polymerizable monomer component is 99.9 to 20 parts by weight of the polymerizable monomer component shown in the general formula (1) in 100 parts by weight of the total polymerizable monomer component, (B) It is preferred that the acidic group-containing polymerizable monomer component is 0.1 to 80 parts by weight. Moreover, it is suitable that the compounding quantity of an organic solvent is 2-400 weight part of organic solvents with respect to 100 weight part of all the polymerizable monomers.

  When the dental adhesive composition is used for a dental pretreatment material of silica-based ceramics (leucite, lithium disilicate glass, etc.), the preferred composition is (a) a polymerizable monomer represented by the general formula (1). The composition contains a body component, (b) an acidic group-containing polymerizable monomer component, a silane coupling agent, and an organic solvent. The blending ratio of the polymerizable monomer is (9) 99.8 to 20 parts by weight of the polymerizable monomer component represented by the general formula (1) in 100 parts by weight of the total polymerizable monomer component. B) 0.1 to 75 parts by weight of the acidic group-containing polymerizable monomer component, and preferably 0.1 to 70 parts by weight of the silane coupling agent. Moreover, it is suitable that the compounding quantity of an organic solvent is 2-400 weight part of organic solvents with respect to 100 weight part of all the polymerizable monomers.

  When the dental adhesive composition is used for a dental pretreatment material of a noble metal (gold, platinum, silver, etc.), the preferred composition is (a) a polymerizable monomer component represented by the general formula (1), ( B) A composition containing an acidic group-containing polymerizable monomer component, a sulfur atom-containing polymerizable monomer, and an organic solvent. The blending ratio of the polymerizable monomer is (9) 99.8 to 20 parts by weight of the polymerizable monomer component represented by the general formula (1) in 100 parts by weight of the total polymerizable monomer component. (B) 0.1 to 75 parts by weight of the acidic group-containing polymerizable monomer component, and preferably 0.1 to 60 parts by weight of the sulfur atom-containing polymerizable monomer. Moreover, it is suitable that the compounding quantity of an organic solvent is 2-400 weight part of organic solvents with respect to 100 weight part of all the polymerizable monomers.

  When the use of the dental adhesive composition is a self-etching type dental adhesive, preferred compositions are (a) a polymerizable monomer component represented by the general formula (1), and (b) an acidic group-containing polymerizability. The composition contains a monomer component, (c) a polymerization initiator, water, an organic solvent, and a filler. The blending ratio of the polymerizable monomer is (B) 95 to 20 parts by weight of the polymerizable monomer component represented by the general formula (1) in 100 parts by weight of the total polymerizable monomer component. The acidic group-containing polymerizable monomer component is preferably 5 to 80 parts by weight. Moreover, the compounding quantity of a polymerization initiator, water, an organic solvent, and a filler is 0.01-10 weight part of polymerization initiator with respect to 100 weight part of all the polymerizable monomers, and 0.01-50 weight part of water. The organic solvent is preferably 2 to 400 parts by weight and the filler 2 to 100 parts by weight.

  In addition, these dental adhesives and dental pretreatment agents can be used for various adherends (dentities, metals, ceramics, resins, etc.) by mixing and using the respective components. It can be used as an adhesive. Each component may be packaged and mixed immediately before use, or when each component does not react and the storage stability is good, the components may be mixed in advance.

  When the use of the dental adhesive composition is a dental composite resin, preferred compositions are (a) a polymerizable monomer component represented by the general formula (1), and (b) an acidic group-containing polymerizable monomer component. (C) A composition containing a polymerization initiator and a filler. The blending ratio of the polymerizable monomer is (b) 95 to 20 parts by weight of the polymerizable monomer component represented by the general formula (1) in 100 parts by weight of the total polymerizable monomer component, and (b) acidic. The group-containing polymerizable monomer component is preferably 5 to 80 parts by weight. Moreover, it is suitable that the compounding quantity of a polymerization initiator and a filler is 0.01-10 weight part of polymerization initiators, and 100-2000 weight part of fillers with respect to 100 weight part of all the polymerizable monomers.

  When the dental adhesive composition is used for dental cement, preferred compositions are (a) a polymerizable monomer component represented by the general formula (1), and (b) an acidic group-containing polymerizable monomer. It becomes a composition containing a component, (c) a polymerization initiator, and a filler. The blending ratio of the polymerizable monomer is (B) 95 to 20 parts by weight of the polymerizable monomer component represented by the general formula (1) in 100 parts by weight of the total polymerizable monomer component. The amount of the acidic group-containing polymerizable monomer component is preferably 5 to 80 parts by weight. Moreover, it is suitable that the compounding quantity of a polymerization initiator and a filler is 0.01-10 weight part of polymerization initiators, and 100-2000 weight part of fillers with respect to 100 weight part of all the polymerizable monomers.

  In the case of a dental resin cement, a chemical polymerization type and a photopolymerization type are usually used in combination as the polymerization initiator. Chemical polymerization initiators are usually composed of two or more components, and when they are used, the polymerization initiating ability is demonstrated by mixing them. Therefore, in consideration of preservability, the packaging form is divided into two or more packages. become.

Hereinafter, the present invention will be described in detail by way of examples and comparative examples, but the present invention is not limited to these examples. Hereinafter, the abbreviations and abbreviations of the substances used in the preparation of the samples of the examples and the comparative examples, their structural formulas or substance names, various sample preparation methods, and various evaluation methods will be described.
(1) Abbreviations / abbreviations and structural formulas or substance names thereof [polymerizable monomer represented by the general formula (1)]

  In the above structural formula, the repeating numbers 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) 2 It is a mixture of more than one kind of polymerizable monomer molecules.

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 formula are average values of the mixture of the compounds (a), (b) and (c). The values g and h shown together with the above structural formula and the structural formula shown below mean an average value, but in each molecule, the values of g and h can take an integer value of 0, 1 or 2. . Except for the case where the average value of the values g and h is 0 or 2, the structural formulas indicating the average values of the values g and h are two or three types with different combinations of integer values (g, h). It means a mixture of structural isomers. Further, in the general formula (3), when Ar1 = Ar2 = phenylene group, the value g is a value corresponding to the value j shown in the general formula (3), and the value h is in the general formula (3). Is a value corresponding to the value k shown in FIG.

[(B) Acidic group-containing polymerizable monomer]
PM: Mixture obtained by mixing 2-methacryloyloxyethyl dihydrogen phosphate and bis (2-methacryloyloxyethyl) hydrogen phosphate in a molar ratio of 1: 1.
MDP: 10-methacryloyloxydecyl dihydrogen phosphate
Mac-10: 11-methacryloyloxy-1,1-undecanedicarboxylic acid
4-META: 4-methacryloxyethyl trimellitic anhydride
6-MHPP: 6-methacryloxyhexyl-3-phosphonopropionate

[Other polymerizable monomers]
3G: Triethylene glycol dimethacrylate
HEMA: 2-hydroxyethyl methacrylate
UDMA: 1.6-bis (methacrylethyloxycarbonylamino) -2,2,4, -trimethylhexane
MTU-6: 6-methacryloyloxyhexyl 2-thiouracil-5-carboxylate
MOOT-10: The following formula

MHDTA: 6- (N-methallyloyl) aminohexyl 6,8-dithioctic acid amide
MPS: 3-methacryloyloxypropyltrimethoxysilane
MDS: 10-methacryloyloxydecyltrimethoxysilane

[Organic solvent]
IPA: Isopropyl alcohol

[Polymerization initiator]
CQ: Camphorquinone
DMBE: ethyl p-N, N-dimethylaminobenzoate
DEPT: N, N-di (β-hydroxyethyl) -p-toluidine
TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
BTPO: Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide
BPO: Benzoyl peroxide
BMOV: Bis (maltolate) oxovanadium IV)
VOAA: Vanadium (IV) acetylacetonate
PhBTEOA: Tetraphenyl boron triethanolamine salt perocta H: 1,1,3,3-tetramethylbutyl hydroperoxide

[Filler]
Si-Zr1: Spherical silica-zirconia, γ-methacryloyloxypropyltrimethoxysilane surface-treated product (0.5 μm)
Si-Zr2: Amorphous silica-zirconia, γ-methacryloyloxypropyltrimethoxysilane surface-treated product (3 μm)
Si-Ti: Spherical silica-titania, γ-methacryloyloxypropyltrimethoxysilane surface-treated product (0.3 μm)
ZD-30S: Fumed silica (average particle size 0.02 μm) surface-treated with dimethyldichlorosilane and hexamethyldisilazane
DM-30: Fumed silica (average particle size 0.02 μm) surface-treated with dimethyldichlorosilane
MT-10: Fumed silica (average particle size 0.02 μm) surface-treated with methyltrichlorosilane

[Polymerization inhibitor]
BHT: Dibutylhydroxytoluene

(2) Enamel and dentin adhesion test (when combining a dental pretreatment agent and a dental cement material Example: A-1 to A-50, Comparative example: A-1)
The cow was slaughtered and the front teeth of the cow were removed within 24 hours after slaughter. The extracted bovine front teeth were polished with # 600 emery paper under water injection, and the enamel and dentin planes were cut out so as to be parallel and flat to the lip surface. Next, compressed air was blown onto the machined plane for about 10 seconds to dry. Next, a double-sided tape having a hole with a diameter of 3 mm was attached to the flat surface, a dental pretreatment material was applied to the hole, left for 20 seconds, and then dried by blowing compressed air for about 10 seconds. On top of that, dental cement material 1 “Bistite II (including acidic group-containing polymerizable monomer)” (manufactured by Tokuyama Dental Co., Ltd.) or dental cement material 2 “Esthemu (acidic group-containing polymerizable monomer) (Not included) ”(manufactured by Tokuyama Dental Co., Ltd.) was applied, and a stainless steel attachment was further pressure-welded thereon. Next, after the dental cement material was cured at 37 ° C. for 1 hour, the adhesion test piece was immersed in water at 37 ° C. for 24 hours to obtain an adhesion test piece.

  This adhesion test piece was pulled at a crosshead speed of 2 mm / min using a universal testing machine (Autograph, manufactured by Shimadzu Corporation), and the tensile adhesive strength between the tooth and the cured composite resin was measured. The tensile bond strength between the tooth and the adhesive was measured for each of the four test specimens for each example or each comparative example. The average value of the four times of tensile adhesive strength was used as the adhesive strength of the corresponding Example or Comparative Example (composition: Table 1, Table 2 Adhesion test result: Table 3).

(3) Enamel and dentin adhesion test (when combining a dental pretreatment agent and a composite resin Example: A-1 to A-50, Comparative example: A-1)
The cow was slaughtered and the front teeth of the cow were removed within 24 hours after slaughter. The extracted bovine front teeth were polished with # 600 emery paper under water injection, and the enamel and dentin planes were cut out so as to be parallel and flat to the lip surface. Next, compressed air was blown onto the machined plane for about 10 seconds to dry. Next, a double-sided tape having a hole with a diameter of 3 mm was attached to the flat surface, a dental pretreatment material was applied to the hole, left for 20 seconds, and then dried by blowing compressed air for about 10 seconds. Thereafter, dental adhesive example D-2 was further applied to the hole, and compressed air was blown for about 10 seconds to dry or make the liquid level flat.

  Visible light irradiation was performed for 10 seconds with a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation) to cure the dental adhesive. Next, a paraffin wax having a hole with a thickness of 0.5 mm and a diameter of 8 mm is fixed by aligning the center of the hole of the paraffin wax with the center of the hole of the double-sided tape previously attached. Formed.

  In this simulated cavity, dental composite resin 1 “Esterite Σ Quick (without acidic group-containing polymerizable monomer)” (manufactured by Tokuyama Dental Co., Ltd.) or Dental Composite Resin 2 “Constick (containing acidic group) Filled with “polymeric monomer”) (manufactured by DMG) or dental composite resin 3 “primefill (including acidic group-containing polymerizable monomer and peroxide)” (manufactured by Tokuyama Dental Co., Ltd.) And press-contacted with a polyester sheet. Then, visible light irradiation was performed for 10 seconds with a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation), the dental composite resin was cured, and an adhesion test piece was produced.

  Resin cement (Bistite II made by Tokuyama Dental Co., Ltd.) was applied to the upper surface of the cured composite resin body of the adhesion test piece, and a cylindrical SUS attachment having a diameter of 8 mm and a length of 25 mm was further adhered. Next, after curing the resin cement at 37 ° C. for 15 minutes, the adhesion test piece was immersed in water at 37 ° C. for 24 hours to obtain an adhesion test piece I with an attachment. Thereafter, the adhesive strength was measured in the same manner as “(2) Enamel and dentin adhesion test” (composition: Table 1, Table 2 Adhesion test result: Table 3).

(4) Metal adhesion test (Examples: B-1 to B-47, C-1 to C-12, Comparative examples: B-1 to 2, C-1)
Dental gold-silver-palladium alloy “Gold Para 12” (10 × 10 × 3 mm manufactured by Towa Giken Co., Ltd.) as a precious metal alloy, and dental cobalt-chromium alloy “Work Lome” (10 × 10 × manufactured by Towa Giken Co., Ltd.) as a base metal alloy 3mm) is sandblasted after being polished with # 1500 water-resistant abrasive paper, and a double-sided tape having a hole with a diameter of 3 mm is pasted on the surface to be adhered. In the case of two liquids, equal amounts were mixed and then applied, allowed to stand for 20 seconds, and then dried by blowing compressed air for about 10 seconds.

  On top of that, dental cement material 1 “Bistite II (including acidic group-containing polymerizable monomer)” (manufactured by Tokuyama Dental Co., Ltd.) or dental cement material 2 “Esthemu (acidic group-containing polymerizable monomer) (Not included) ”(manufactured by Tokuyama Dental Co., Ltd.) was applied, and a stainless steel attachment was further pressure-welded thereon.

  Next, after the dental cement material was cured at 37 ° C. for 1 hour, the adhesion test piece was immersed in water at 37 ° C. for 24 hours to obtain an adhesion test piece. Thereafter, the adhesive strength was measured in the same manner as in “(2) Enamel and dentin adhesion test” (Composition: Table 4, Table 5, Table 8 Adhesion test results: Table 6, Table 7, Table 9). Table 10).

(5) Adhesion test of ceramics and adherend containing ceramics (Examples: B-1 to B-47, C-1 to C-12, Comparative Examples: B-1 to 2, C-1)
Dental ceramics (material: silicate glass) “Noritake Super Porcelain AAA” (10 × 10 × 3 mm manufactured by Kuraray Noritake Dental Co.), dental hybrid resin material “Pearl Este” (10 × 10 manufactured by Tokuyama Dental Co., Ltd.) × 3mm), zirconia “TZ-3Y-E sintered body” (10 × 10 × 3 mm manufactured by Tosoh Corporation), and in the case of “Noritake Super Porcelain AAA” and “Pearl Esthe”, polish with # 800 water-resistant abrasive paper In the case of “TZ-3Y-E sintered body”, sandblasting is performed after polishing with # 1500 water-resistant abrasive paper, and a double-sided tape having a hole with a diameter of 3 mm is attached to the adherend surface. The pretreatment material for application was applied, left for 20 seconds, and then dried by blowing compressed air for about 10 seconds.

  On top of that, dental cement material 1 “Bistite II (including acidic group-containing polymerizable monomer)” (manufactured by Tokuyama Dental Co., Ltd.) or dental cement material 2 “Esthemu (acidic group-containing polymerizable monomer) (Not included) ”(manufactured by Tokuyama Dental Co., Ltd.) was applied, and a stainless steel attachment was further pressure-welded thereon. Next, after the dental cement material was cured at 37 ° C. for 1 hour, the adhesion test piece was immersed in water at 37 ° C. for 24 hours to obtain an adhesion test piece. Thereafter, the adhesive strength was measured in the same manner as in “(2) Enamel and dentin adhesion test” (Composition: Table 4, Table 5, Table 8 Adhesion test results: Table 6, Table 7, Table 9). Table 10).

(6) Enamel and dentin adhesion test (when a dental adhesive and a dental composite resin are combined Example: D-1 to D-67, E-1 to E-8, Comparative example: D-1 , E-1)
The cow was slaughtered and the front teeth of the cow were removed within 24 hours after slaughter. The extracted bovine front teeth were polished with # 600 emery paper under water injection, and the enamel and dentin planes were cut out so as to be parallel and flat to the lip surface. Next, compressed air was blown onto the machined plane for about 10 seconds to dry. Next, a double-sided tape having a hole with a diameter of 3 mm is affixed to this plane, and the dental adhesive is applied to the hole as it is in the case of the one-component type, and in the case of the two-component type, the equal amount is mixed and then applied. After leaving for 20 seconds, it was dried by blowing compressed air for about 10 seconds. Visible light irradiation was performed for 10 seconds with a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation) to cure the dental adhesive. Next, a paraffin wax having a hole with a thickness of 0.5 mm and a diameter of 8 mm is fixed by aligning the center of the hole of the paraffin wax with the center of the hole of the double-sided tape previously attached. Formed.

  In this simulated cavity, dental composite resin 1 “Esterite Σ Quick (without acidic group-containing polymerizable monomer)” (manufactured by Tokuyama Dental Co., Ltd.) or Dental Composite Resin 2 “Constick (containing acidic group) Filled with “polymeric monomer”) (manufactured by DMG) or dental composite resin 3 “primefill (including acidic group-containing polymerizable monomer and peroxide)” (manufactured by Tokuyama Dental Co., Ltd.) And press-contacted with a polyester sheet. Then, visible light irradiation was performed for 10 seconds with a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation), the dental composite resin was cured, and an adhesion test piece was produced.

  Resin cement (Bistite II made by Tokuyama Dental Co., Ltd.) was applied to the upper surface of the cured composite resin body of the adhesion test piece, and a cylindrical SUS attachment having a diameter of 8 mm and a length of 25 mm was further adhered. Next, after curing the resin cement at 37 ° C. for 15 minutes, the adhesion test piece was immersed in water at 37 ° C. for 24 hours to obtain an adhesion test piece I with an attachment. Thereafter, the adhesive strength was measured in the same manner as in “(2) Enamel and dentin adhesion test” (Composition: Table 11, Table 12, Table 14, Table 15 Adhesion test results: Table 13, Table 16). ).

(7) Enamel and dentin adhesion test (when two-component dental adhesive and dental resin cement are combined Example: E-1 to E-8, Comparative example: E-1)
The cow was slaughtered and the front teeth of the cow were removed within 24 hours after slaughter. The extracted bovine front teeth were polished with # 600 emery paper under water injection, and the enamel and dentin planes were cut out so as to be parallel and flat to the lip surface. Next, compressed air was blown onto the machined plane for about 10 seconds to dry. Next, a double-sided tape having a hole with a diameter of 3 mm is affixed to this plane, and an equal amount of two-component dental adhesive is mixed and applied to the hole. After leaving for 20 seconds, compressed air is blown for about 10 seconds. Dried. On top of that, dental cement material 2 “estesem (not containing an acidic group-containing polymerizable monomer)” (manufactured by Tokuyama Dental Co., Ltd.) was applied, and a stainless steel attachment was further pressure-welded thereon. Next, after the dental cement material was cured at 37 ° C. for 1 hour, the adhesion test piece was immersed in water at 37 ° C. for 24 hours to obtain an adhesion test piece. Then, the adhesive strength was measured in the same manner as in “(2) Enamel and dentin adhesion test” (composition: Table 14, Table 15 Adhesion test results: Table 16).

(8) Enamel and dentin adhesion test (when using a dental pretreatment material for dental adhesive cement material: Examples F-1 to F-56, Comparative example: F-1)
The cow was slaughtered and the front teeth of the cow were removed within 24 hours after slaughter. The extracted bovine front teeth were polished with # 600 emery paper under water injection, and the enamel and dentin planes were cut out so as to be parallel and flat to the lip surface. Next, compressed air was blown onto the machined plane for about 10 seconds to dry. Next, a double-sided tape having a hole with a diameter of 3 mm was attached to this plane. A dental pretreatment material (Example: A-5) was applied to the holes, allowed to stand for 20 seconds, and then dried by blowing compressed air for about 10 seconds. A dental adhesive cement material was applied thereon, and a stainless steel attachment was further pressure-welded thereon. Next, after the dental cement material was cured at 37 ° C. for 1 hour, the adhesion test piece was immersed in water at 37 ° C. for 24 hours to obtain an adhesion test piece. Thereafter, the adhesion strength was measured in the same manner as in “(2) Enamel and dentin adhesion test” (composition: Table 17, Table 18 Adhesion test results: Table 19, Table 20).

(9) Metal adhesion test (When using dental pretreatment material of dental adhesive cement material: Examples F-1 to F-56, Comparative example: F-1)
Dental gold-silver-palladium alloy “Gold Para 12” (10 × 10 × 3 mm manufactured by Towa Giken Co., Ltd.) as a precious metal alloy, and dental cobalt-chromium alloy “Work Lome” (10 × 10 × manufactured by Towa Giken Co., Ltd.) as a base metal alloy 3mm) is sandblasted after being polished with # 1500 water-resistant abrasive paper, and a double-sided tape having a 3 mm diameter hole is affixed to the adherend surface, and a dental pretreatment material (Example: C-6) Equal amounts were mixed and applied, left for 20 seconds, and then dried by blowing compressed air for about 10 seconds. A dental adhesive cement material was applied thereon, and a stainless steel attachment was further pressure-welded thereon. Next, after the dental cement material was cured at 37 ° C. for 1 hour, the adhesion test piece was immersed in water at 37 ° C. for 24 hours to obtain an adhesion test piece. Thereafter, the adhesion strength was measured in the same manner as in “(2) Enamel and dentin adhesion test” (composition: Table 17, Table 18 Adhesion test results: Table 19, Table 20).

(10) Ceramic adhesion test (when using dental pretreatment material of dental adhesive cement material: Examples F-1 to F-56, Comparative example: F-1)
Dental ceramics (material: silicate glass) “Noritake Super Porcelain AAA” (10 × 10 × 3 mm manufactured by Kuraray Noritake Dental Co.), dental hybrid resin material “Pearl Este” (10 × 10 manufactured by Tokuyama Dental Co., Ltd.) × 3mm), zirconia “TZ-3Y-E sintered body” (10 × 10 × 3 mm manufactured by Tosoh Corporation), and in the case of “Noritake Super Porcelain AAA” and “Pearl Esthe”, polish with # 800 water-resistant abrasive paper In the case of “TZ-3Y-E sintered body”, sandblasting is performed after polishing with # 1500 water-resistant abrasive paper, and a double-sided tape having a hole with a diameter of 3 mm is attached to the adherend surface. A pretreatment material for use (Example: C-6) was mixed and applied in an equal amount, allowed to stand for 20 seconds, and then dried by blowing compressed air for about 10 seconds. A dental adhesive cement material was applied thereon, and a stainless steel attachment was further pressure-welded thereon. Next, after the dental cement material was cured at 37 ° C. for 1 hour, the adhesion test piece was immersed in water at 37 ° C. for 24 hours to obtain an adhesion test piece. Thereafter, the adhesion strength was measured in the same manner as in “(2) Enamel and dentin adhesion test” (composition: Table 17, Table 18 Adhesion test results: Table 19, Table 20).

(11) Enamel and dentin adhesion test (for dental adhesive cement material only: Examples F-1 to F-56, comparative example: F-1)
The cow was slaughtered and the front teeth of the cow were removed within 24 hours after slaughter. The extracted bovine front teeth were polished with # 600 emery paper under water injection, and the enamel and dentin planes were cut out so as to be parallel and flat to the lip surface. Next, compressed air was blown onto the machined plane for about 10 seconds to dry. Next, a double-sided tape having a hole with a diameter of 3 mm was attached to this plane. A dental adhesive cement material was applied to the hole, and a stainless steel attachment was pressed thereon. Next, after the dental cement material was cured at 37 ° C. for 1 hour, the adhesion test piece was immersed in water at 37 ° C. for 24 hours to obtain an adhesion test piece. Thereafter, the adhesive strength was measured in the same manner as “(2) Enamel and dentin adhesion test” (composition: Table 17, Table 18 Adhesion test results: Table 21).

(12) Metal adhesion test (For dental adhesive cement material only: Examples F-1 to F-56, Comparative example: F-1)
Dental gold-silver-palladium alloy “Gold Para 12” (10 × 10 × 3 mm manufactured by Towa Giken Co., Ltd.) as a precious metal alloy, and dental cobalt-chromium alloy “Work Lome” (10 × 10 × manufactured by Towa Giken Co., Ltd.) as a base metal alloy 3mm) is sandblasted after being polished with # 1500 water-resistant abrasive paper, and a double-sided tape having a hole with a diameter of 3 mm is applied to the adherend surface, and a dental adhesive cement material is applied to the hole, A stainless steel attachment was pressed on top. Next, after the dental cement material was cured at 37 ° C. for 1 hour, the adhesion test piece was immersed in water at 37 ° C. for 24 hours to obtain an adhesion test piece. Thereafter, the adhesive strength was measured in the same manner as “(2) Enamel and dentin adhesion test” (composition: Table 17, Table 18 Adhesion test results: Table 21).

(13) Ceramics adhesion test (for dental adhesive cement material only: Examples F-1 to F-56, Comparative example: F-1)
Dental ceramics (material: silicate glass) “Noritake Super Porcelain AAA” (10 × 10 × 3 mm manufactured by Kuraray Noritake Dental Co.), dental hybrid resin material “Pearl Este” (10 × 10 manufactured by Tokuyama Dental Co., Ltd.) × 3mm), zirconia “TZ-3Y-E sintered body” (10 × 10 × 3 mm manufactured by Tosoh Corporation), and in the case of “Noritake Super Porcelain AAA” and “Pearl Esthe”, polish with # 800 water-resistant abrasive paper In the case of “TZ-3Y-E sintered body”, sandblasting was performed after polishing with # 1500 water-resistant abrasive paper, and a double-sided tape having a hole with a diameter of 3 mm was attached to the surface to be adhered, A dental adhesive cement material was applied, and a stainless steel attachment was further pressure-welded thereon. Next, after the dental cement material was cured at 37 ° C. for 1 hour, the adhesion test piece was immersed in water at 37 ° C. for 24 hours to obtain an adhesion test piece. Thereafter, the adhesive strength was measured in the same manner as “(2) Enamel and dentin adhesion test” (composition: Table 17, Table 18 Adhesion test results: Table 21).

(14) Enamel and dentin adhesion test (in the case of dental adhesive composite resin: Examples: G-1 to G-57, Comparative Example: G-1)
The cow was slaughtered and the front teeth of the cow were removed within 24 hours after slaughter. The extracted bovine front teeth were polished with # 600 emery paper under water injection, and the enamel and dentin planes were cut out so as to be parallel and flat to the lip surface. Next, compressed air was blown onto the machined plane for about 10 seconds to dry. Next, a double-sided tape having a hole with a diameter of 3 mm is affixed to this plane, and a paraffin wax having a hole with a thickness of 0.5 mm and a diameter of 8 mm is placed on the double-sided tape. In addition, a simulated cavity was formed by fixing the center of the paraffin wax hole together. The simulated cavity was filled with a dental adhesive composite resin and pressed with a polyester sheet. Then, visible light irradiation was performed for 20 seconds with a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation), the dental composite resin was cured, and an adhesion test piece was produced.

  Resin cement (Bistite II made by Tokuyama Dental Co., Ltd.) was applied to the upper surface of the cured composite resin body of the adhesion test piece, and a cylindrical SUS attachment having a diameter of 8 mm and a length of 25 mm was further adhered. Next, after curing the resin cement at 37 ° C. for 15 minutes, the adhesion test piece was immersed in water at 37 ° C. for 24 hours to obtain an adhesion test piece I with an attachment. Then, the adhesive strength was measured in the same manner as in “(2) Enamel and dentin adhesion test” (composition: Table 22, Table 23 Adhesion test results: Table 24).

(15) 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 Borin) equipped with a cone / plate geometry 4 cm / 2 ° and a temperature control system was used. Then, the measurement was performed three times under the measurement conditions of the measurement temperature (plate temperature) 25 ° C. and the shear rate of 1 rps, and the average value of the three measurements was taken as the viscosity (Table 25).

(16) Synthesizing procedure of polymerizable monomer (a) The monomer corresponding to the polymerizable monomer represented by the general formula (1) was synthesized by the following procedure.

<Synthesis of Acid Chloride (A)>
A first mixed solution of 25.3 g (0.096 mol) of 4,4′-diphenyl ether dicarboxylic acid, 0.85 g (0.012 mol) of dimethylformamide and 80 ml of toluene was prepared. A second mixed solution consisting of 58.4 g (0.46 mol) thionyl chloride and 20 ml of toluene was gradually added dropwise to the stirred first mixed solution at room temperature. The liquid obtained after completion of the dropwise addition was heated to 95 ° C. and refluxed for 3 hours. The yellow transparent liquid obtained after heating / refluxing is allowed to cool, and may be referred to as 4,4′-diphenyl ether dicarboxylic acid chloride (hereinafter referred to as “acid chloride (A)”) having the molecular structure shown below. There was obtained a toluene solution. Furthermore, this toluene solution was subjected 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′-diphenyl ether dicarboxylic acid chloride solid. It was.

<Synthesis of 1.4-DPEHE>
A dispersion containing the acid chloride (A) was obtained by adding 120 ml of methylene chloride to 15.3 g (0.052 mol) of the acid chloride (A). A mixed solution of 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 to the dispersion of the acid chloride (A) at −78 ° C. using a dropping funnel and further stirred for 5 hours.

Water was added to the liquid obtained after dropping and stirring, and the solvent was removed using a rotary evaporator. The residue obtained after removal of the solvent was dissolved in 100 ml of toluene, washed with 0.5 N hydrochloric acid solution, washed with saturated brine, dried over magnesium sulfate, and filtered. The obtained filtrate was concentrated with a rotary evaporator, and then the concentrated solution was further vacuum-dried to obtain 4-DPEHE (yield 19.0 g, yield 76%, HPLC purity 97%). In addition, the data of 1H NMR spectrum of the obtained 4-DPEHE were as follows.
1H 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 2.4-DPEHH>
According to the synthesis method shown in Process 1 of <Synthesis of 4-DPEHB> except that 23.6 g of 1,6-hexanediol was used instead of 18.0 g of 1,4-butanediol, 19.7 g of 6-hydroxyhexyl methacrylate (Yield 53%) 16.0 g (43% yield) was obtained.

Subsequently, according to the synthesis method shown in Process 2 of <Synthesis of 4-DPEHB> except that 4.1 g of 6-hydroxyhexyl methacrylate was used instead of 4-hydroxybutyl methacrylate, 6-hydroxyhexyl methacrylate and acid chloride (A ) To give 4-DPEHH (yield 4.6 g, yield 78%, HPLC purity 98%). In addition, the data of 1H NMR spectrum of the obtained 4-DPEHH were as follows.
1H 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)

<3.4-DPEPE>
Except that 12.6 g of 2-hydroxyethyl methacrylate was used, 22.6 g (0.13 mol) of polyethylene glycol monomethacrylate (average of ethylene glycol chain (-CH2CH2O-) n repetition number n≈2) was used. 4-DPEPE (yield 22.5 g, yield 78%, HPLC purity 97%) was synthesized by the same method as the synthesis method of -DPEHE. In addition, the data of 1H NMR spectrum of the obtained 4-DPEPE were as follows.
1H NMR δ 1.93 (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), 7.9 (d, 4H)

<Synthesis of 4.4-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, the mixture was stirred. And cooled to 0 ° C. Next, a solution obtained by dissolving 44.8 g (0.2 mol) of the acid chloride (A) in methylene chloride (200 ml) was slowly added dropwise to this solution over 2 hours. The solution obtained after the dropwise addition was further stirred for 1 hour, water was added, and the solvent was removed using a rotary evaporator. The residue obtained after removal of the solvent was dissolved in 100 ml of toluene, washed with 0.5 N hydrochloric acid solution, washed with saturated brine, dried over magnesium sulfate, and filtered. The obtained filtrate was concentrated again with a rotary evaporator, and then the concentrated solution was purified by silica gel column chromatography to obtain 41.6 g (yield 60%) of 4,4′-bis (2-hydroxyethoxycarbonyl) diphenyl ether. .

Into a solution obtained by dissolving 34.6 g (0.1 mol) of 4,4′-bis (2-hydroxyethoxycarbonyl) diphenyl ether and 3.2 g (5 mmol) of dibutyltin dilaurate in 100 ml of anhydrous dimethylformamide. Further, 31.0 g (0.2 mol) of 2-methacryloyloxyethyl isocyanate was added, and the mixture was stirred at room temperature for 3 hours. To the solution after stirring, 100 ml of methylene chloride was added, washed three times with distilled water using a separatory funnel, and the methylene chloride layer was dried using magnesium sulfate. After drying, magnesium sulfate was filtered off, the filtrate was concentrated on a rotary evaporator, and the concentrate was further vacuum dried to obtain 4-DPEU (yield 63.7 g, yield 97%, HPLC purity 94%). . In addition, the data of 1H NMR spectrum of the obtained 4-DPEU were as follows.
1H 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 5.4-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 was dissolved. 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, this reaction solution was stirred for 5 hours, and then the reaction solution was acidified with 1N hydrochloric acid solution to precipitate a solid. Subsequently, the reaction solution in which the solid was precipitated was subjected to suction filtration, and then the precipitated solid was washed with water. The solid (compound) obtained after washing was vacuum-dried to obtain 4,4′-dicarboxydiphenyl sulfide (yield 45.5 g, yield 83%).

  Next, an 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′-diphenylsulfide dicarboxylic acid chloride was synthesized by the same method as in the synthesis method.

Subsequently, a method similar to the synthesis method of 4-DPEHE was conducted except that 16.1 g (0.052 mol) of 4,4′-diphenylsulfide dicarboxylic acid chloride was used instead of 15.3 g of acid chloride (A). -DPSHE (yield 18.9 g, yield 73%, HPLC purity 91%) was obtained. The data of 1H NMR spectrum of the obtained 4-DPSHE was as follows.
1H 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 6.4-DPEGMA>
12.8 g of glycidyl methacrylate (0.09 mol), 12.9 g (0.05 mol) of 4,4′-diphenyl ether dicarboxylic 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 make a uniform solution. Next, this solution was transferred to a separatory funnel, washed with 40 ml of 10 wt% aqueous potassium carbonate solution three times, and further washed three times with distilled water, and then the ethyl acetate layer was recovered. Thereafter, magnesium sulfate was added to the recovered 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 by a rotary evaporator to obtain a concentrate. This concentrate was further dried in vacuo to give 4-DPEGMA (22.8 g, 84% yield, 95% HPLC purity). The data of 1H NMR spectrum of the obtained 4-DPEGMA was as follows.
1H NMR δ 1.93 (s, 6H), 3.90 (d, 0.8H), 4.30 to 4.70 (m, 9.2H), 5.59 (s, 2H), 6.16 ( s, 2H), 7.07 (d, 4H), 8.07 (d, 4H)

<Synthesis of 7.4-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 dropping and stirring was washed 3 times with 60 ml of 0.4 mol / L hydrochloric acid aqueous solution, then 3 times with 60 ml of 10 wt% aqueous potassium carbonate solution, and further washed 3 times with distilled water, and then methylene chloride. The layer was collected. Thereafter, magnesium sulfate was added to the recovered 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 obtain 4-DPEGMAI (25.9 g, yield 92%, HPLC purity 97%). The data of 1H NMR spectrum of the obtained 4-DPEGMAI was as follows.
1H NMR δ 1.93 (s, 6H), 3.90 (d, 0.2H), 4.30 to 4.70 (m, 9.8H), 5.59 (s, 2H), 6.16 ( s, 2H), 7.07 (d, 4H), 8.07 (d, 4H)

<Synthesis of 8.4-DPEGMAII>
12.8 g of glycidyl methacrylate (0.09 mol), 12.9 g (0.05 mol) of 4,4′-diphenyl ether dicarboxylic acid, 0.02 g (0.00009 mol) of tetrabutylammonium bromide, 0.02 g of BHT ( 0.00009 mol) and 20 g of dimethylacetamide were reacted at 100 ° C. for 4 hours. 40 ml of ethyl acetate was added to the liquid obtained by the reaction to make a uniform solution. Next, this solution was transferred to a separatory funnel, washed with 40 ml of 10 wt% aqueous potassium carbonate solution three times, and further washed three times with distilled water, and then the ethyl acetate layer was recovered. Thereafter, magnesium sulfate was added to the recovered 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 by a rotary evaporator to obtain a concentrate. The concentrate was further dried in vacuo to give 4-DPEGMAII (Yield 25.3 g, 90% yield, HPLC purity 95%). The data of 1H NMR spectrum of the obtained 4-DPEGMAII was as follows.
1H NMR δ 1.93 (s, 6H), 3.90 (d, 0.4H), 4.30 to 4.70 (m, 9.6H), 5.62 (s, 2H), 6.16 ( s, 2H), 7.07 (d, 4H), 8.07 (d, 4H)

<Synthesis of 9.4-DPEGMAIII>
4-DPEGMAII is synthesized by the above method and then purified by silica gel column chromatography (filler: SiO2, developing solvent: ethyl acetate / hexane = 3/1 to 2/1) to give 4-DPEGMAIII (yield 18 0.7 g, yield 69%, HPLC purity 99%). The data of 1H NMR spectrum of the obtained 4-DPEGMAIII were as follows.
1H 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 10.4-DPEGMIV>
After 4-DPEGMA is synthesized by the above method, it is purified by silica gel column chromatography (filler: SiO2, developing solvent: ethyl acetate / hexane = 3/1 to 2/1) to give 4-DPEGMAIV (yield 2 0.2 g, yield 8%, HPLC purity 99%). The data of 1H NMR spectrum of the obtained 4-DPEGMAIV was as follows.
1H NMR δ 1.93 (s, 6H), 3.90 (d, 3.2H), 4.30 to 4.70 (m, 7.8H), 5.62 (s, 2H), 6.16 ( s, 2H), 7.07 (d, 4H), 8.07 (d, 4H)

<Synthesis of 11.4-DPEGA>
4-DPEGA (yield 21.21) was obtained in the same manner as the 4-DPEGMA synthesis method except that 11.5 g (0.09 mol) of glycidyl acrylate was used instead of 12.8 g (0.09 mol) of glycidyl methacrylate. 8 g, yield 85%, HPLC purity 96%). The data of 1H NMR spectrum of the obtained 4-DPEGA was as follows.
1H 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 12.2-DPEGMA>
The same synthesis method of 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 data of 1H NMR spectrum of the obtained 2-DPEGMA was as follows.
1H NMR δ 1.93 (s, 6H), 3.80 (d, 1.8H), 4.00 to 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 13.4-DPEHGMA>
After 5-hexen-1-ol (30.1 g, 0.3 mol) was dissolved 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 added. The added solution was adjusted, and this solution was ice-cooled. 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. The solution obtained after completion of the dropwise addition was stirred at room temperature for 3 hours, and then 100 ml of distilled water was added, followed by extraction with methylene chloride three times. The residue was obtained by removing the solvent from the methylene chloride layer obtained by extraction using a rotary evaporator. Furthermore, the obtained residue was dissolved in 100 ml toluene. The obtained toluene solution was washed 3 times with 0.5 N hydrochloric acid solution, then 3 times with saturated saline solution, and dried with magnesium sulfate solution. After drying, the magnesium sulfate solution was filtered off, the filtrate was concentrated with a rotary evaporator, and the concentrate was further dried under vacuum to obtain 46.4 g (yield 92%) of 5-hexen-1-yl methacrylate.

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

2,3.0 g (0.125 mol) of 5,6-epoxyhexane-1-yl methacrylate obtained, 12.9 g (0.05 mol) of 4,4′-diphenyl ether dicarboxylic acid, 0.045 g of benzyltriethylammonium chloride (0.2 mmol) and a mixed solution obtained by mixing 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, this concentrate was vacuum-dried to obtain 4-DPEHGMA (yield 29.0 g, 0.046 mol, yield 93%, HPLC purity 95%). The data of 1H NMR spectrum of the obtained 4-DPEHGMA was as follows.
1H NMR δ 1.29 (t, 4H), 1.44 (m, 4H), 1.57 (t, 4H), 1.93 (s, 6H), 3.85 (d, 1.9H), 4 .15-4.70 (m, 8.1H), 5.59 (s, 2H), 6.16 (s, 2H), 7.05 (d, 4H), 7.95 (d, 4H)

<Synthesis of 14.4-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 obtained by dissolving 31.4 g (0.3 mol) of methacrylic acid chloride in 50 ml of methylene chloride was added dropwise to this solution. The solution obtained after completion of the dropwise addition was stirred at room temperature for 3 hours, and then 100 ml of distilled water was added and extracted with methylene chloride three times. Next, a toluene solution was obtained by dissolving a residue obtained by removing the solvent from the obtained methylene chloride layer using a rotary evaporator in 100 ml of toluene. The toluene solution was washed three times with a 0.5 N hydrochloric acid solution, then washed 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 vacuum-dried to obtain 46.0 g (90% yield) of allyloxyethyl methacrylate.

  A solution prepared by dissolving 46.0 g (0.27 mol) of allyloxyethyl methacrylate obtained in 100 ml of methylene chloride and further adding 196 g (corresponding to 0.675 mol) of a 60% by weight metachloroperbenzoic acid / water mixture was prepared. And stirred at room temperature for 10 hours. By-product metachlorobenzoic acid was filtered off from the stirred solution, and the filtrate was reduced 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 mass% aqueous potassium carbonate solution, dried over magnesium sulfate, and then concentrated by a rotary evaporator to obtain a concentrate. Further, this concentrate was vacuum-dried to obtain 47.3 g (yield 94%) of glycidyloxyethyl methacrylate.

The obtained methacrylic acid-glycidyloxyethyl 23.3 g (0.125 mol), 4,4′-diphenyl ether dicarboxylic acid 12.9 g (0.05 mol), benzyltriethylammonium chloride 0.045 g (0.2 mmol), And the liquid mixture which mixed p-methoxyphenol 0.03g was stirred at 90 degreeC 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 with a rotary evaporator to obtain a concentrate. Finally, this concentrate was vacuum-dried to obtain 4-DPEEGMA (yield 29.0 g, yield 92%, HPLC purity 94%). The data of 1H NMR spectrum of the obtained 4-DPEHGMA was as follows.
1H 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 15.4-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 A reaction solution was prepared by adding 50 ml of an aqueous sodium oxyhydrogen solution, 140 g (2 mol) of 2-methyl-2-butene, and further adding 36 g (0.4 mol) of sodium chlorite. Next, this reaction solution was stirred for 5 hours, and then the reaction solution was acidified with 1N hydrochloric acid solution to precipitate a solid. Subsequently, the reaction solution in which the solid was precipitated was subjected to suction filtration, and then the precipitated solid was washed with water. The solid (compound) obtained after the washing was vacuum-dried to obtain 45.5 g (yield 83%) of 4,4′-dicarboxydiphenyl sulfide.

Subsequently, the same method as 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. 4-DPSGMA (22.3 g, yield 80%, HPLC purity 95%) was obtained by the above method. In addition, the data of 1H NMR spectrum of the obtained 4-DPSGMA were as follows.
1H 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 16.4-DPSOGMMA>
A method similar to the method for synthesizing 4-DPEGMA, except that 15.3 g (0.05 mol) of 4,4′-dicarboxydiphenyl sulfone was used instead of 12.9 g of 4,4′-diphenyl ether dicarboxylic acid. -DPSOGMA (Yield 24.5 g, Yield 83%, HPLC purity 97%) was obtained. The data of 1H NMR spectrum of the obtained 4-DPSOGMA was as follows.
1H 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 17.4-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, phosphorus A reaction solution was prepared by adding 50 ml of an aqueous sodium oxyhydrogen solution, 140 g (2 mol) of 2-methyl-2-butene, and further adding 36 g (0.4 mol) of sodium chlorite. Next, this reaction solution was stirred for 5 hours, and then the reaction solution was acidified with 1N hydrochloric acid solution to precipitate a solid. Subsequently, the reaction solution in which the solid was precipitated was subjected to suction filtration, and then the precipitated solid was washed with water. The solid (compound) obtained after washing was vacuum-dried to obtain 39.8 g (yield 78%) of 4,4′-dicarboxydiphenylmethane.

Subsequently, in place of 12.9 g of 4,4′-diphenyl ether dicarboxylic acid, 12.8 g (0.05 mol) of 4,4′-dicarboxydiphenylmethane obtained above was used. 4-DPFGMA (yield 22.1 g, yield 82%, HPLC purity 94%) was obtained in the same manner. In addition, the data of 1H NMR spectrum of the obtained 4-DPFGMA were as follows.
1H 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 18.4-DPAGMA>
Other than using 12.9 g of 4,4′-diphenyl ether dicarboxylic acid and using 2,2-bis (4-carboxyphenyl) propane 14.2 (0.05 mol) synthesized by the synthesis method described in British Patent GB753384 Obtained 4-DPAGMA (yield 22.7 g, yield 80%, HPLC purity 93%) in the same manner as the synthesis method of 4-DPEGMA. The data of 1H NMR spectrum of the obtained 4-DPAGMA were as follows.
1H 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 19.4-DPBGMA>
After dissolving 50.8 g (0.2 mol) of 4-formylphenyl-4′-formylbenzoate synthesized by the synthesis method described in JP-A-2007-1067779 in 200 ml of t-butanol and 50 ml of water A reaction solution was prepared by adding 50 ml of an aqueous sodium hydrogenphosphate solution, 140 g (2 mol) of 2-methyl-2-butene, and further adding 36 g (0.4 mol) of sodium chlorite. Next, this reaction solution was stirred for 5 hours, and then the reaction solution was acidified with 1N hydrochloric acid solution to precipitate a solid. Subsequently, the reaction solution in which the solid was precipitated was subjected to suction filtration, and then the precipitated solid was washed with water. The solid (compound) obtained after washing was vacuum-dried to obtain 45.4 g of 4-carboxyphenyl-4′-carboxybenzoate (yield 79%).

Subsequently, in place of 12.9 g of 4,4′-diphenyl ether dicarboxylic acid, 14.3 g (0.05 mol) of 4-carboxyphenyl-4′-carboxybenzoate described above was used. 4-DPBGMA (yield 22.8 g, yield 80%, HPLC purity 94%) was obtained in the same manner. In addition, the data of 1H NMR spectrum of the obtained 4-DPBGMA were as follows.
1H 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 20.4-DPALGMMA>
After dissolving 1,1-bis (4-formylphenyl) cyclohexane (58.4 g, 0.2 mol) synthesized by the synthesis method described in Japanese Patent No. 3076603 in 200 ml of t-butanol and 50 ml of water The reaction solution was prepared by adding 50 ml of sodium hydrogenphosphate aqueous solution, 140 g (2 mol) of 2-methyl-2-butene, and further adding 36 g (0.4 mol) of sodium chlorite. Next, this reaction solution was stirred for 5 hours, and then the reaction solution was acidified with 1N hydrochloric acid solution to precipitate a solid. Subsequently, the reaction solution in which the solid was precipitated was subjected to suction filtration, and then the precipitated solid was washed with water. The solid (compound) obtained after washing was vacuum-dried to obtain 54.4 g (yield 84%) of 1,1-bis (4-carboxylphenyl) cyclohexane.

Next, a synthesis method of 4-DPEGMA, 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′-diphenyl ether dicarboxylic acid. 4-DPALGMMA (yield 23.7 g, yield 78%, HPLC purity 92%) was obtained in the same manner. The data of 1H NMR spectrum of the obtained 4-DPALGMMA was as follows.
1H 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)

(10) Preparation of dental pretreatment agent and dental adhesive sample (A) Polymerizable monomer, acidic group-containing polymerizable monomer, other polymerizable monomer represented by the general formula (1), water The organic solvent, the polymerization inhibitor, and the polymerization initiator were weighed at the predetermined mass ratios shown in Tables 1 to 5 and mixed in the dark until uniform, to prepare a sample.

  In the case of using Bis-GMA as a polymerizable monomer, the sample was weighed in a state where Bis-GMA was heated to 60 ° C. in an incubator during weighing.

  Moreover, when adding ion, the isopropoxide of each ion is weighed out so that the amount of ions becomes a predetermined mass ratio shown in Tables 1 to 5, and a predetermined mass shown in Tables 1 to 5 is obtained. It was reacted with a ratio of acidic group-containing polymerizable monomers. After isopropanol produced by the reaction was removed by vacuum drying, other necessary components were added so as to have a predetermined mass ratio shown in Tables 1 to 5, and mixed in a dark place until uniform to prepare a sample.

(11) Preparation of dental adhesive cement material and dental adhesive composite resin sample (a) Polymerizable monomer represented by general formula (1), acidic group-containing polymerizable monomer, other polymerizable monomer Then, a polymerization inhibitor and a polymerization initiator were weighed at predetermined mass ratios shown in Tables 6 to 7, and mixed in a dark place until uniform, to prepare a matrix monomer.
The matrix monomer was adjusted by weighing Bis-GMA at 60 ° C. in an incubator during weighing when Bis-GMA was used as the polymerizable monomer.

  Moreover, when adding ion, the isopropoxide of each ion is weighed so that the amount of ions becomes a predetermined mass ratio shown in Tables 6 to 7, and a predetermined mass shown in Tables 6 to 7 is obtained. It was reacted with a ratio of acidic group-containing polymerizable monomers. After isopropanol produced by the reaction was removed by vacuum drying, other necessary components were added so as to have the predetermined mass ratios shown in Tables 6 to 7, and mixed in the dark until uniform to prepare a matrix monomer. .

  The prepared matrix monomer and filler were weighed so as to have a predetermined mass ratio shown in Tables 6 to 7, and mixed in an agate mortar to obtain a mixture. Subsequently, the mixture was defoamed under vacuum to remove bubbles to obtain a paste-like sample.

(12) Evaluation results (a) Tables 1 to 5 show the compositions and adhesive evaluation results of dental pretreatment agents prepared using the polymerizable monomer represented by the general formula (1). Table 6 shows the composition and evaluation results of the adhesive properties, and Table 7 shows the composition and adhesive evaluation results of the dental adhesive composite resin. Table 8 shows the viscosity measurement results of the polymerizable monomer represented by (a) the general formula (1).

Claims (7)

(B) a polymerizable monomer which is shown by the following general formula (1), dental adhesive composition characterized by containing a (b) acidic group-containing polymerizable monomer.

[In the general formula (1), X represents —O— , and Ar ¹ and Ar ² each represents an unsubstituted aromatic group having any valence selected from divalent to tetravalent. Each may be the same or different, and each of L ¹ and L ² has any number of main chain atoms within the range of 2 to 60 and is 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. Moreover, m1, m2, n1, and n2 are each an integer selected from the range of 1-3. ] The dental adhesive composition according to claim 1 , wherein at least one of L1 and L2 in the general formula (1) contains a hydroxyl group. Wherein (i) a heavy polymerizable monomer dental adhesive composition according to claim 1 or 2, characterized in that a polymerizable monomer 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 shown in the general formula (1). ] Furthermore, (C) Dental adhesive composition as described in any one of Claims 1-3 containing a polymerization initiator. Furthermore, (D) Dental adhesive composition as described in any one of Claims 1-4 containing a filler. The dental adhesive composition according to any one of claims 1 to 5 , which is used as a dental pretreatment material. The dental adhesive composition according to any one of claims 1 to 6 , which is used as any one of a dental adhesive, a dental adhesive composite resin, and a dental adhesive cement.