Adhesive monomers for dental materials

Abstract

Provided are adhesive monomers for dental materials including compounds represented by the general formula (1) below, in which the core (X) and the terminal group (Y1) are bonded to each other directly or via the linking group (Z): X(Y1)n.sup.1a(Z—Y1)n.sup.1b(1) wherein n.sup.1a represents the number of terminal groups (Y1) directly bonded to the core (X), n.sup.1b represents the number of terminal groups (Y1) bonded to the core (X) via the linking group (Z), and the sum of n.sup.1a and n.sup.1b is equal to the valence of the core (X); the core (X), the linking group (Z) and the terminal group (Y1) are further defined. The adhesive monomers can enhance adhesive strength to the tooth in dental treatment, and impart high mechanical strength to cured products.

Claims

1. An adhesive monomer for dental materials comprising a compound represented by the general formula (1) below, in which the core (X) below and the terminal group (Y1) below are bonded to each other directly or via the linking group (Z) below:
X(Y1)n.sup.1a(Z—Y1)n.sup.1b  (1) wherein in the general formula (1), n.sup.1a represents the number of terminal groups (Y1) directly bonded to the core (X), n.sup.1b represents the number of terminal groups (Y1) bonded to the core (X) via the linking group (Z), and the sum of n.sup.1a and n.sup.1b is equal to the valence of the core (X); the core (X) is a C.sub.1-200 polyvalent organic group having a valence of 3 to 12 containing an oxygen atom or a nitrogen atom in which an atom bonded to the terminal group (Y1) or the linking group (Z) is the oxygen atom or the nitrogen atom; the terminal group (Y1) is a phosphorus-containing group represented by the general formula (2) below, a phosphorus-containing group represented by the general formula (3) below, a (meth)acryloyl group-containing group (Y2) represented by the general formula (4) below, a (meth)acryloyl group, a C.sub.1-20 hydrocarbon group or a hydrogen atom, and a plurality of terminal groups (Y1) may be the same as or different from each other, with the proviso that among all the terminal groups (Y1) in the compound represented by the general formula (1), one or more terminal groups are phosphorus-containing groups represented by the general formula (2) below or phosphorus-containing groups represented by the general formula (3) below, and one or more terminal groups are (meth)acryloyl group-containing groups (Y2); and the linking group (Z) is a divalent group represented by the general formula (5) below, and when the compound represented by the general formula (1) contains a plurality of linking groups (Z), the linking groups (Z) may be the same as or different from each other; ##STR00089## wherein in the general formula (3), one end of the group is bonded to the core (X) or the linking group (Z), and the other end of the group is bonded to the core (X) or the linking group (Z) present in another compound represented by the general formula (1); ##STR00090## wherein in the general formula (4), R.sup.4a represents a hydrogen atom or a methyl group, R.sup.4b represents a C.sub.2-6 linear alkylene group or a C.sub.2-6 linear oxyalkylene group, and the linear alkylene group or the linear oxyalkylene group is optionally substituted with a C.sub.1-6 alkyl group or a (meth)acryloyloxymethylene group in place of a hydrogen atom; and ##STR00091## wherein in the general formula (5), n.sup.5a, n.sup.5b, n.sup.5c and n.sup.5d represent the unit numbers of respective repeating units, and are each 0 to 100, the sum of n.sup.5a, n.sup.5b, n.sup.5c and n.sup.5d is 1 to 100, the left end of the group is bonded to the core (X), and the right end of the group is bonded to the terminal group (Y1).

2. The adhesive monomer for dental materials according to claim 1, wherein the terminal group (Y1) is a phosphorus-containing group represented by the general formula (2), a phosphorus-containing group represented by the general formula (3), a (meth)acryloyl group-containing group (Y2) represented by the general formula (4), or a hydrogen atom.

3. The adhesive monomer for dental materials according to claim 1, wherein the terminal group (Y1) is a phosphorus-containing group represented by the general formula (2), a phosphorus-containing group represented by the general formula (3), or a (meth)acryloyl group-containing group (Y2) represented by the general formula (4).

4. The adhesive monomer for dental materials according to claim 1, wherein in the linking group (Z) n.sup.5a, n.sup.5b, n.sup.5c and n.sup.5d are each 0 to 20, and the sum of n.sup.5a, n.sup.5b, n.sup.5c and n.sup.5d is 1 to 20.

5. The adhesive monomer for dental materials according to claim 1, wherein the linking group (Z) is a divalent group represented by the general formula (6) below: ##STR00092## wherein in the general formula (6), n.sup.6a, n.sup.6b and n.sup.6c represent the unit numbers of respective repeating units, and are each 0 to 20, the sum of n.sup.6a, n.sup.6b and n.sup.6c is 1 to 20, the left end of the group is bonded to the core (X), and the right end of the group is bonded to the terminal group (Y1).

6. The adhesive monomer for dental materials according to claim 1, wherein the linking group (Z) is a divalent group represented by the general formula (7) below: ##STR00093## wherein in the general formula (7), n.sup.7a and n.sup.7b represent the unit numbers of respective repeating units, and are each 0 to 20, the sum of n.sup.7a and n.sup.7b is 1 to 20, the left end of the group is bonded to the core (X), and the right end of the group is bonded to the terminal group (Y1).

7. The adhesive monomer for dental materials according to claim 1, wherein the core (X) is at least one selected from the group consisting of groups represented by the general formulas (8a) to (8j) below: ##STR00094## wherein in the general formula (8g), n.sup.8g is an integer of 1 to 40 ##STR00095##

8. The adhesive monomer for dental materials according to claim 1, wherein the (meth)acryloyl group-containing group (Y2) is at least one selected from the group consisting of groups represented by the general formulas (4a) to (4f) below: ##STR00096##

9. A monomer composition for dental materials comprising the adhesive monomer for dental materials according to claim 1.

10. The monomer composition for dental materials according to claim 9, wherein the monomer composition for dental materials is negative in a reverse mutation test.

11. A dental material comprising the adhesive monomer for dental materials according to claim 1.

12. The dental material according to claim 11, wherein the dental material is negative in a reverse mutation test.

13. A kit comprising the dental material according to claim 11.

Description

EXAMPLES

(1) The present invention will be described in further detail based on Examples hereinbelow without limiting the scope of the invention to such Examples.

Production Example 1

(2) A 500-milliliter four-necked flask equipped with a stirring blade, a thermometer and a reflux tube was loaded with 100 g (1.09 mol, the number of moles of OH groups: 3.27 mol) of glycerin (manufactured by Sigma-Aldrich Co. LLC), 0.43 g (1000 ppm based on the total weight of reactants) of dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.22 g (500 ppm based on the total weight of reactants) of 2,6-t-butyl-4-methylphenol (manufactured by Wako Pure Chemical Industries, Ltd.), and heated to 55° C. Subsequently, 337 g (2.17 mol, ⅔ equivalents based on the number of moles of OH of glycerin used) of 2-methacryloyloxyethyl isocyanate (KARENZ MOI (registered trademark), manufactured by Showa Denko K.K.) was added dropwise over a period of 30 minutes. Reaction was carried out for 4 hours at a temperature of 80 to 85° C. The infrared absorption spectrum IR was measured (Spectrum Two, manufactured by PerkinElmer), and the result showed that the isocyanate-derived vibration at 2267 cm.sup.−1 disappeared. A part of the product was taken, the hydroxyl group value thereof was measured in accordance with JIS K 0070, and the result showed that the hydroxyl group value was 138 mg KOH/g. The reaction product was subjected to liquid chromatography mass spectrometry (LC-MS analysis) (1.7 μm ACQUITY UPLC BEH C18 (2.1 mm×10 mm)/ACQUITY UPLC H-Class-SQ Detector 2, manufactured by Nihon Waters K.K.), and the result showed that the mass of [M-H].sup.+ was 403. This result demonstrated that the reaction product had a molecular weight of 402, and this molecular weight was consistent with that of the compound 1. The reaction product was discharged from the reaction vessel to give 417 g of a product containing the compound 1 below.

(3) ##STR00044##

(4) Subsequently, a 300-milliliter four-necked flask equipped with a stirring blade, a thermometer and a reflux tube was loaded with 152 g (hydroxyl group value: 138 mg KOH/g, equivalent of OH: 0.374 mol) of the reaction product containing the compound 1, 450 mL of ultradehydrated methylene chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.093 g (500 ppm based on the total weight of reactants) of 2,6-t-butyl-4-methylphenol. Subsequently, 34.1 g (0.240 mol, P equivalent: 0.480 mol) of diphosphorus pentaoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in three separate portions. Reaction was carried out for 6 hours at a reaction temperature equal to or higher than room temperature and not higher than 30° C. Thereafter, 150 mL of water was slowly added into the apparatus to completely deactivate unreacted diphosphorus pentaoxide at room temperature. The organic layer was extracted, and volatile components were distilled off. The reaction product was discharged from the reaction vessel to give 150 g of a product containing a phosphoric acid ester-containing urethane methacrylic compound of the structural formulas of the compounds 2-1 and 2-2 below. The reaction product was subjected to LC-MS analysis, and the result showed that the masses of [M-H].sup.+ were 483 and 867. This result indicated that the main products had a molecular weight of 482 and a molecular weight of 866, which were consistent with the molecular weight of the compound 2-1 below and the molecular weight of the compound 2-2 below, respectively.

(5) ##STR00045##

Production Example 2

(6) Except that diglycerin (manufactured by NACALAI TESQUE, INC.) was used in place of the glycerin described in Production Example 1, the same synthesis operation as in Production Example 1 was carried out to give a product containing a compound 3 of the structural formula of the compound 3 below, and a phosphoric acid ester-containing compound 4 of the structural formula of the compound 4 below.

(7) ##STR00046##

Production 3

(8) Except that KARENZ MOI-EG (registered trademark) (manufactured by Showa Denko K.K.) containing oxyethylene units in the molecule was used in place of the 2-methacryloyloxyethyl isocyanate (KARENZ MOI (registered trademark)) described in Production Example 1, the same synthesis operation as in Production Example 1 was carried out to give a product containing a compound 5 of the structural formula of the compound 5 below, and a phosphoric acid ester-containing compound 6 of the structural formula of the compound 6 below.

(9) ##STR00047##

Production Example 4

(10) A 300-milliliter four-necked flask equipped with a stirring blade, a thermometer and a reflux tube was loaded with 99.0 g of a polyol 1 (OH group: 1.63 mol) of the structural formula in Table 1 below (ACTCOL (registered trademark), manufactured by Mitsui Chemicals, Inc., average molecular weight: 182, hydroxyl group value: 926 mg KOH/g), 0.27 g (1000 ppm based on the total weight of reactants) of dibutyltin dilaurate and 0.14 g (500 ppm based on the total weight of reactants) of 2,6-t-butyl-4-methylphenol, and heated to 55° C. Subsequently, 171 g (1.10 mol, ⅔ equivalents based on the number of moles of OH of the polyol 1 used) of KARENZ MOI was added dropwise over a period of 20 minutes. Reaction was carried out for 8 hours at a reaction temperature of 80 to 85° C. IR measurement was performed, and the result showed that the isocyanate-derived vibration at 2267 cm.sup.−1 disappeared. A part of the product was taken, the hydroxyl group value thereof was measured in accordance with JIS K 0070, and the result showed that the hydroxyl group value was 119 mg KOH/g. The reaction product was subjected to LC-MS analysis, and the result showed that the mass of [M-H].sup.+ was 489 and the mass of [M-Na].sup.+ was 511. This result demonstrated that the main product had a molecular weight of 488, and this molecular weight was consistent with that of the compound 1 in which one oxyethylene unit is introduced and a+b+c is equal to 1. The reaction product was discharged from the reaction vessel to give 260 g of a product containing a hydroxyl group-containing monomer represented by the structural formula of the compound 7 below.

(11) ##STR00048##

(12) Subsequently, the obtained product was reacted with the diphosphorus pentaoxide described in Production Example 1 to give a product containing a phosphoric acid ester-containing compound represented by the structural formula of the compound 8 below.

(13) ##STR00049##

Production Examples 5 to 9 and 13

(14) Except that the polyols shown in Table 1 below were used in place of the polyol described in Production Example 4, the same synthesis operation as in Production Example 4 was carried out to give products containing compounds represented by the structural formulas of the compounds 9 to 18, 25 and 26 below.

Production Examples 10 and 11

(15) Except that the polyols shown in Table 1 below was used in place of the polyol described in Production Example 3, the same synthesis operation as in Production Example 4 was carried out to give products containing compounds represented by the structural formulas of the compounds 19 to 22 below.

Production Example 12

(16) Except that ½ equivalents of KARENZ MOI-EG based on the number of moles of OH of the polyol shown in Table 1 below was used in place of KARENZ MOI described in Production Example 4, the same synthesis operation as in Production Example 4 was carried out to give products containing compounds represented by the structural formulas of the compounds 23 and 24 below.

(17) TABLE-US-00001 TABLE 1 Pro- Structural Structural formulas of duc- formulas monophosphoric acid Monophosphoric tion of polyol raw ester group- acid Ex- materials/hydroxyl containing compound ester group- am- group values precursors/hydroxyl containing ples (mgKOH/g) group values (mgKOH/g) compounds 1 0 2 3 4 0 5 6 7 0 8 9 10 11 0 12 13

Example 1

(18) 1.80 g (1.7 mmol) of the compound 2 obtained in Production Example 1, 2.5 g (5.3 mmol) of UDMA (2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate) and 0.74 g (2.6 mmol) of TEGDMA (triethylene glycol dimethacrylate: NK Ester 3G, manufactured by Shin-Nakamura Chemical Co, Ltd.) were added into a container, and stirred to uniformity at 50° C. to give a polymerizable monomer composition. 0.5 parts by weight of TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide: IRGACURE TPO, manufactured by BASF SE) was then added to and mixed with 100 parts by weight of the polymerizable monomer composition to give a uniform pasty composition to be used as a dental material. The composition of Example 1 is an example of compositions suitable for evaluation of performance as a resin.

(19) [Bending Strength Test Method]

(20) The composition prepared as described above was packed in a 2×2×25 mm SUS mold, covered with a cover film, and then irradiated with light from a dental visible light irradiator (α Light V, manufactured by J. Morita Tokyo MFG. Corp.) for 3 minutes on each side, namely, for a total of 6 minutes on both sides to cure the composition. The cured product was stored in deionized water at 37° C. for 24 hours, and then subjected to a three-point bending test with a general-purpose tester (Precise Versatile Material Tester 210X, manufactured by INTESCO Co., Ltd.) under conditions in which the distance between supports was 20 mm and the cross head speed was 1.0 mm/min. The results of the bending test of the cured products of the compositions to be used as the dental materials are shown in Table 2.

(21) [Adhesive Strength Test Method]

(22) A bovine lower anterior tooth extracted and kept in a frozen state was thawed by injection of water, and subjected to root amputation and pulp extirpation treatment. This was placed in a plastic cylindrical container having a diameter of 25 mm and a depth of 25 mm, and embedded in an acrylic resin. The surface thereof was wet-polished with #120 and #400 emery papers to expose enamel in a state of being parallel to the lip surface.

(23) Next, compressed air was blown onto the flat surface for about 1 second, the prepared composition was then applied to the enamel flat surface, and compressed air was blown with a low blowing force. This surface was irradiated with light from a visible light irradiator (Translux 2Wave, manufactured by Heraeus Kulzer GmbH) for 20 seconds. Further, a plastic mold having a diameter of 2.38 mm (manufactured by Ultradent Products, Inc.) was then placed thereon, and a dental composite resin (Venus Diamond, manufactured by Heraeus Kulzer GmbH) was packed, irradiated with light from the visible light irradiator for 20 seconds, and thereby cured. Thereafter, the mold was removed to prepare an adhesive sample. The sample was stored in warm water at 37° C. for 24 hours, and a shear load which was parallel to the enamel and in contact with the surface of the bovine tooth was then applied at a cross head speed of 1.0 mm/min using a general-purpose tester (Precise Versatile Material Tester 210X, manufactured by INTESCO Co., Ltd.). The shear adhesive strength was determined from the shear load at the time when the columnar composition formed on the bovine tooth surface was separated from the surface.

(24) The result of the shear test of the dental composition for dental materials is shown in Table 2.

Example 2 to 8

(25) Except that the monophosphoric acid ester group-containing methacrylate compounds 4, 6, 8, 14, 18, 20 and 26 obtained in the above Production Examples were used in place of the compound 2, the same operation as in Example 1 was carried out to prepare polymerizable monomer compositions, and compositions to be used as dental materials. Subsequently, the same tests as in Example 1 were conducted to obtain bending strength and shear test results. The results are shown in Table 2.

Comparative Example 1

(26) Except that MDP (10-methacryloyloxydecyl dihydrogen phosphate) was used in place of the compound 2, the same operation as in Example 1 was carried out to prepare a polymerizable monomer composition, and a composition to be used as a dental material. Subsequently, the same tests as in Example 1 were conducted to obtain bending strength and shear test results. The results are shown in Table 2.

(27) TABLE-US-00002 TABLE 2 Phosphoric Results of Cured product acid ester shear test bending test result group-containing on bovine Maximum Elastic methacrylic tooth stress modulus compounds (MPa) (MPa) (GPa) Example 1 Compound 2  17.7 ± 3.4 102 2.3 Example 2 Compound 4  18.1 ± 4.9 102 2.4 Example 3 Compound 6  15.2 ± 5.4 89 2.0 Example 4 Compound 8  17.4 ± 6.7 106 2.2 Example 5 Compound 14 15.8 ± 2.6 95 2.1 Example 6 Compound 18 16.5 ± 4.8 97 2.0 Example 7 Compound 20 17.4 ± 5.7 93 2.0 Example 8 Compound 26 13.4 ± 1.5 93 2.1 Comparative MDP 14.5 ± 2.4 85 1.7 Example 2

(28) The results in Table 2 reveal that the compositions containing the adhesive monomers for dental materials of the invention have higher adhesive strength with the tooth as compared to the composition containing the conventional adhesive monomer for dental materials, and the cured products of the compositions containing the adhesive monomers for dental materials of the invention have more excellent strength as compared to the cured product of the composition containing the conventional adhesive monomer for dental materials. Thus, use of the adhesive monomer for dental materials of the present invention ensures that a dental adhesive material having high adhesive strength with the tooth and a dental cured product having high strength can be provided.

Example 9

(29) 1.2 g (60 parts by weight) of the compound 2 obtained in Production Example 1, 0.6 g (30 parts by weight) of UDMA (2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate) and 0.2 g (10 parts by weight) of TEGDMA (triethylene glycol dimethacrylate: NK Ester 3G, manufactured by Shin-Nakamura Chemical Co, Ltd.) were added into a container, and stirred to uniformity at 50° C. to give a polymerizable monomer composition. 0.5 parts by weight of TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide: IRGACURE TPO, manufactured by BASF SE) was then added to and mixed with 100 parts by weight of the polymerizable monomer composition to give a uniform pasty composition to be used as a dental material. The composition of Example 9 is an example of compositions suitable for evaluation of performance as a resin. Except that bovine tooth enamel and bovine tooth dentin were used, the same tests as in Example 1 were conducted to obtain bending strength and shear test results. The results are shown in Table 3.

Examples 10 to 17

(30) Except that the phosphoric acid ester group-containing methacrylates 4, 6, 8, 14, 16, 18, 20 and 26 obtained in the above Production Examples were used in place of the compound 2, the same operation as in Example 9 was carried out to prepare compositions to be used as dental materials. Subsequently, the same tests as in Example 9 were conducted to obtain bending strength and shear test results. The results are shown in Table 3.

Comparative Example 2

(31) Except that MDP (10-methacryloyloxydecyl dihydrogen phosphate) was used in place of the compound 2, the same operation as in Example 9 was carried out to prepare a composition to be used as a dental material. Subsequently, the same test as in Example 9 was conducted to obtain a shear test result. The result is shown in Table 3.

(32) TABLE-US-00003 TABLE 3 Phosphoric acid ester Results of shear test Cured product group-containing on bovine tooth bending test result methacrylic Enamel Dentin Maximum Elastic compounds (MPa) (MPa) stress (MPa) modulus (GPa) Example 9 Compound 2   7.9 ± 3.0 7.7 ± 2.7 92 2.2 Example 10 Compound 4  14.0 ± 1.8 7.5 ± 2.0 88 2.3 Example 11 Compound 6   7.1 ± 2.7 6.1 ± 2.4 66 1.3 Example 12 Compound 8   9.0 ± 3.2 7.6 ± 1.4 68 1.4 Example 13 Compound 14  9.6 ± 2.7 5.2 ± 2.3 75 1.6 Example 14 Compound 16 14.3 ± 3.1 8.7 ± 2.1 51 0.94 Example 15 Compound 18  8.3 ± 1.8 8.8 ± 2.7 79 1.8 Example 16 Compound 20  9.4 ± 3.5 6.7 ± 1.6 62 1.2 Example 17 Compound 26  6.9 ± 3.7 8.4 ± 1.0 81 2.0 Comparative MDP  0.5 ± 1.0 0.5 ± 0.6 22 0.32 Example 2

Examples 18 to 21

(33) Except that the phosphoric acid ester group-containing methacrylates 10, 12, 22 and 24 obtained in the above Production Examples were used in place of the compound 2, the same operation as in Example 9 was carried out to prepare compositions to be used as dental materials. Subsequently, the same test as in Example 9 was conducted to obtain a shear test result. The result is shown in Table 4.

(34) TABLE-US-00004 TABLE 4 Results of shear test Phosphoric acid ester on bovine tooth group-containing Enamel Dentin methacrylic compounds (MPa) (MPa) Example 18 Compound 10 4.6 ± 2.5 6.9 ± 1.7 Example 19 Compound 12 8.9 ± 1.5 7.7 ± 1.6 Example 20 Compound 22 3.2 ± 1.6 4.5 ± 1.2 Example 21 Compound 24 8.7 ± 1.6 3.0 ± 0.9 Comparative MDP 0.5 ± 1.0 0.5 ± 0.6 Example 2

(35) The results in Table 4 have also revealed that the compositions containing the adhesive monomers for dental materials of the invention have higher adhesive strength with the tooth as compared to the composition containing the conventional adhesive monomer for dental materials.

Example 22

(36) 0.48 g (8.0 parts by weight) of the compound 2 obtained in Production Example 1, 1.2 g (20 parts by weight) of UDMA (2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate), 0.6 g (10 parts by weight) of TEGDMA (triethylene glycol dimethacrylate: NK Ester 3G, manufactured by Shin-Nakamura Chemical Co, Ltd.), 0.12 g (2.0 parts by weight) of 4-META (4-methacryloyloxyethyl trimellitic anhydride, manufactured by Wako Pure Chemical Industries, Ltd.), 0.012 g (0.2 parts by weight) of CQ (camphaquinone, manufactured by Wako Pure Chemical Industries, Ltd.) and 0.024 g (0.4 parts by weight) of 2-butoxyethyl 4-(dimethylamino)benzoate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added into a container, and stirred to uniformity at 50° C. to give a mixture. To the mixture was added 3.6 g (59 parts by weight) of a barium aluminum borosilicate glass filler (GM 27884, particle diameter: 1.5 μm, 1.6% silane-treated product, manufactured by NEC SCHOTT Components Corporation), and the resulting mixture was mixed to give a uniform pasty composition to be used as a dental material. The composition of Example 22 is an example of compositions suitable for evaluation of performance as a resin. Except that bovine tooth dentin was used, a plastic mold was placed on a dentin flat surface blown with compressed air, the composition was packed in two portions, and a dental composite resin (Venus Diamond) was not used, the same tests as in Example 1 were conducted to obtain bending test and shear test results. The results are shown in Table 4.

Comparative Example 3

(37) Except that MDP (10-methacryloyloxydecyl dihydrogen phosphate) was used in place of the compound 2, the same operation as in Example 22 was carried out to prepare a composition to be used as a dental material. Subsequently, the same tests as in Example 22 were conducted to obtain bending test and shear test results. The results are shown in Table 5.

(38) TABLE-US-00005 TABLE 5 Phosphoric acid ester Results of group-containing shear test on Cured product methacrylic bovine tooth bending test result compounds Dentin (MPa) Elastic modulus (GPa) Example 22 Compound 2 20.2 ± 4.0 6.5 Comparative MDP 10.4 ± 2.8 5.7 Example 3

Example 23

(39) 1.0 g (4.7 parts by weight) of the compound 2 obtained in Production Example 1, 6.0 g (28 parts by weight) of Bis-GMA (bisphenol A diglycidyl methacrylate, manufactured by Shin-Nakamura Chemical Co, Ltd.), 6.0 g (28 parts by weight) of HEMA (Acryester HO (registered trademark), manufactured by Mitsubishi Rayon Co., Ltd.), 0.020 g (0.94 parts by weight) of TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide: IRGACURE TPO, manufactured by BASF SE), 0.40 g (1.9 parts by weight) of CQ (camphaquinone, manufactured by Wako Pure Chemical Industries, Ltd.), 0.20 g (0.94 parts by weight) of ethyl 4-(dimethylamino)benzoate (manufactured by Wako Pure Chemical Industries, Ltd.), 0.20 g (0.94 parts by weight) of p-tolyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.0 g (14 parts by weight) of BHT (dibutylhydroxytoluene: manufactured by Wako Pure Chemical Industries, Ltd.), 3.0 g (14 parts by weight) of ethanol (ultradehydrated: manufactured by Wako Pure Chemical Industries, Ltd.) and 3.0 g (14 parts by weight) of distilled water were added into a container, and stirred to uniformity at 50° C. to give a mixture. To the mixture was added 1.2 g (5.7 parts by weight) of a barium aluminum borosilicate glass filler (GM 27884, particle diameter: 1.5 μm, 1.6% silane-treated product, manufactured by NEC SCHOTT Components Corporation), and the resulting mixture was mixed to give a uniform liquid composition to be used as a dental material. The composition of Example 22 is an example of compositions suitable for evaluation of performance as a resin. Except that bovine tooth dentin was used, and after application of the composition, compressed air was blown with a low blowing force to remove the solvent, the same test as in Example 1 was conducted to obtain a shear test result. The result is shown in Table 6.

Comparative Example 4

(40) Except that MDP (10-methacryloyloxydecyl dihydrogen phosphate) was used in place of the compound 2, the same operation as in Example 23 was carried out to prepare a composition to be used as a dental material. Subsequently, the same test as in Example 23 was conducted to obtain a shear test result. The result is shown in Table 6.

(41) TABLE-US-00006 TABLE 6 Phosphoric acid ester group- Results of shear test on containing methacrylic bovine tooth compounds Dentin (MPa) Example 23 Compound 2 28.5 ± 04.9 Comparative MDP 19.4 ± 5.8 Example 4

(42) The results in Tables 5 and 6 have also revealed that the compositions containing the adhesive monomers for dental materials of the invention have higher adhesive strength with the tooth as compared to the compositions containing the conventional adhesive monomers for dental materials, and the cured products of the compositions containing the adhesive monomers for dental materials of the invention have more sufficient mechanical strength as compared to the cured products of the compositions containing the conventional adhesive monomers for dental materials.