Dental photocurable composition containing high soluble photoacid generator

Abstract

To provide a dental photocurable composition which can exhibit excellent mechanical characteristics even after returning from a low temperature to room temperature. To provide a dental photocurable composition, comprising (A) polymerizable monomer, (B) photosensitizer, (C) photoacid generator and (D) photopolymerization accelerator and the (C) photoacid generator may include only (C-1) iodonium salt-based compound of an anion having log S of −4 or less.

Claims

1. A dental photocurable composition, comprising (A) polymerizable monomer, (B) photosensitizer, (C) photoacid generator, and (D) photopolymerization accelerator, wherein, the (C) photoacid generator contains (C-1) iodonium salt-based compound of an anion having log S of −4 or less, and the dental photocurable composition comprises 0.5 parts by mass or more of the (C-1) iodonium salt-based compound of an anion having log S of −4 or less, with respect to 100 parts by mass of the (A) polymerizable monomer.

2. The dental photocurable composition according to claim 1, wherein the dental photocurable composition comprises an aryl iodonium salt consisting of an anion having an organic group and one or more atoms of P, B, Al, S and Ga, and an aryl iodonium cation as the (C-1) iodonium salt-based compound of an anion having log S of −4 or less.

3. The dental photocurable composition according to claim 1, wherein the dental photocurable composition comprises an aryl iodonium salt consisting of an anion having an organic group in which at least one H is substituted with F and one or more atoms of P, B, Al, S and Ga, and an aryl iodonium cation as the (C-1) iodonium salt-based compound of an anion having log S of −4 or less.

4. The dental photocurable composition according to claim 1, wherein the dental photocurable composition comprises aliphatic tertiary amine compound as (D) photopolymerization accelerator.

5. The dental photocurable composition according to claim 1, wherein the dental photocurable composition comprises (D-1) aliphatic tertiary amine compound not having two or more primary hydroxy groups as (D) photopolymerization accelerator.

6. The dental photocurable composition according to claim 1, wherein the dental photocurable composition is one pack type dental photocurable composition comprising, with respect to 100 parts by mass of the (A) polymerizable monomer, 0.005 to 1.0 parts by mass of the (B) photosensitizer, 0.5 to 10.0 parts by mass of the (C) photoacid generator, and 0.01 to 20.0 parts by mass of the (D) photopolymerization accelerator.

7. The dental photocurable composition according to claim 1, wherein the dental photocurable composition is two packs type dental photocurable composition consisting of a first paste and a second paste, wherein a specific gravity of the first paste and the second paste is 1:0.8 to 1:1.2, the dental photocurable composition comprises, with respect to 200 parts by mass of total of the (A) polymerizable monomer contained in the first paste and the second paste, 0.01 to 2.0 parts by mass of the (B) photosensitizer, 1.0 to 20.0 parts by mass of the (C) photoacid generator, and 0.02 to 40.0 parts by mass of the (D) photopolymerization accelerator.

8. The dental photocurable composition according to claim 2, wherein the dental photocurable composition comprises aliphatic tertiary amine compound as (D) photopolymerization accelerator.

9. The dental photocurable composition according to claim 2, wherein the dental photocurable composition comprises (D-1) aliphatic tertiary amine compound not having two or more primary hydroxy groups as (D) photopolymerization accelerator.

10. The dental photocurable composition according to claim 2, wherein the dental photocurable composition is one pack type dental photocurable composition comprising, with respect to 100 parts by mass of the (A) polymerizable monomer, 0.005 to 1.0 parts by mass of the (B) photosensitizer, 0.5 to 10.0 parts by mass of the (C) photoacid generator, and 0.01 to 20.0 parts by mass of the (D) photopolymerization accelerator.

11. The dental photocurable composition according to claim 2, wherein the dental photocurable composition is two packs type dental photocurable composition consisting of a first paste and a second paste, wherein a specific gravity of the first paste and the second paste is 1:0.8 to 1:1.2, the dental photocurable composition comprises, with respect to 200 parts by mass of total of the (A) polymerizable monomer contained in the first paste and the second paste, 0.01 to 2.0 parts by mass of the (B) photosensitizer, 1.0 to 20.0 parts by mass of the (C) photoacid generator, and 0.02 to 40.0 parts by mass of the (D) photopolymerization accelerator.

12. The dental photocurable composition according to claim 8, wherein the dental photocurable composition is one pack type dental photocurable composition comprising, with respect to 100 parts by mass of the (A) polymerizable monomer, 0.005 to 1.0 parts by mass of the (B) photosensitizer, 0.5 to 10.0 parts by mass of the (C) photoacid generator, and 0.01 to 20.0 parts by mass of the (D) photopolymerization accelerator.

13. The dental photocurable composition according to claim 8, wherein the dental photocurable composition is two packs type dental photocurable composition consisting of a first paste and a second paste, wherein a specific gravity of the first paste and the second paste is 1:0.8 to 1:1.2, the dental photocurable composition comprises, with respect to 200 parts by mass of total of the (A) polymerizable monomer contained in the first paste and the second paste, 0.01 to 2.0 parts by mass of the (B) photosensitizer, 1.0 to 20.0 parts by mass of the (C) photoacid generator, and 0.02 to 40.0 parts by mass of the (D) photopolymerization accelerator.

14. The dental photocurable composition according to claim 9, wherein the dental photocurable composition is one pack type dental photocurable composition comprising, with respect to 100 parts by mass of the (A) polymerizable monomer, 0.005 to 1.0 parts by mass of the (B) photosensitizer, 0.5 to 10.0 parts by mass of the (C) photoacid generator, and 0.01 to 20.0 parts by mass of the (D) photopolymerization accelerator.

15. The dental photocurable composition according to claim 9, wherein the dental photocurable composition is two packs type dental photocurable composition consisting of a first paste and a second paste, wherein a specific gravity of the first paste and the second paste is 1:0.8 to 1:1.2, the dental photocurable composition comprises, with respect to 200 parts by mass of total of the (A) polymerizable monomer contained in the first paste and the second paste, 0.01 to 2.0 parts by mass of the (B) photosensitizer, 1.0 to 20.0 parts by mass of the (C) photoacid generator, and 0.02 to 40.0 parts by mass of the (D) photopolymerization accelerator.

Description

EXAMPLES

(1) Hereinafter, example of the present disclosure are specifically described. However, the present disclosure is not intended to be limited to these Examples.

(2) The materials used in Examples and Comparative examples and their abbreviations are listed below.

(A) Polymerizable Monomer

(3) Bis-GM A: 2,2-bis [4-(3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane

(4) 2.6E: 2,2-bis (4-(meth) acryloyloxy polyethoxyphenyl) propane in which the average addition mole number of ethoxy groups is 2.6

(5) UDMA: N,N-(2,2,4-trimethyl hexamethylene) bis [2-(aminocarboxy) ethanol] methacrylate

(6) TEGDMA: triethyleneglycol dimethacrylate

(7) NPG: neopentyl glycol dimethacrylate

(8) HEMA: 2-hydroxyethyl methacrylate

(9) MDP: 10-methacryloyloxydecyl dihydrogen phosphate

(10) MHPA: 6-methacryloxyhexyl phosphonoacetate

(B) Photosensitizer

(11) CQ: camphorquinone

(12) BAPO: phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide

(D) Photopolymerization Accelerator

Alphatic Tertiary Amine

Aliphatic Tertiary Amine Compound Having No Primary Hydroxyl Group

(13) TBA: tribenzylamine

(14) DBGE: N,N-dibenzyl glycine ethyl

(15) DEAEMA: N,N-diethylamino ethylmethacrylate

(16) DMAEMA: N,N-dimethylamino ethylmethacrylate

Aliphatic Tertiary Amine Compound Having One Primary Hydroxyl Group

(17) DBAE: N,N-dibenzylamino ethanol

Aliphatic Tertiary Amine Compound Having Two Primary Hydroxyl Groups

(18) MDEOA: methyl diethanolamine

Aliphatic Tertiary Amine Compound Having Three Primary Hydroxyl Groups

(19) TEA: triethanolamine

Aromatic Tertiary Amine Compound

(20) DMBE: N,N-dimethylaminobenzoate ethyl

Organic Metal Compound

(21) DBTL: dibutyl-tin-dilaurate

(E) Filler

(22) The preparing method of each filler used for preparing the dental photocurable composition is shown below.

Filler 1

(23) A silane coupling treatment solution prepared by stirring 50.0 g of water, 35.0 g of ethanol, and 7.0 g of 8-methacryloxyoctyl trimethoxysilane as a silane coupling material at room temperature for 2 hours was added to 100.0 g of the zirconium silicate filler (average particle diameter: 1.2 μm, zirconia: 90 wt. %, silica:10 wt. %) and stirred for 30 minutes. Thereafter, a heat treatment was performed at 140° C. for 15 hours to obtain a filler 1.

Filler 2

(24) A silane coupling treatment solution prepared by stirring 50.0 g of water, 35.0 g of ethanol, and 7.0 g of 3-methacryloyloxypropyl trimethoxysilane as a silane coupling material at room temperature for 2 hours was added to 100.0 g of the zirconium silicate filler (average particle diameter: 0.8 μm, zirconia: 85 wt. %, silica:15 wt. %) and stirred for 30 minutes. Thereafter, a heat treatment was performed at 140° C. for 15 hours to obtain a filler 2.

Chemical Polymerization Initiator

(25) CHP: cumene hydroperoxide

(26) BPO: benzoyl peroxide

(27) TPE: 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate

Chemical Polymerization Accelerator

(28) PTU: (2-pyridyl) thiourea

(29) DEPT: N,N-dihydroxyethyl-p-toluidine

(30) DMPT: N,N-dimethyl-p-toluidine

(31) COA: acetylacetone copper

(32) VOA: vanadyl acetylacetonate

UV Absorber

(33) BT: 2-(2-hydroxy-5-methylphenyl benzotriazole

Polymerization Inhibitor

(34) BHT: 2,6-di-t-butyl-4-methylphenol

(35) MeHQ: p-methoxyphenol

Fluorescent Agent

(36) FA: 2.5-dihydroxyterephthalate diethyl

(C) Photoacid Generator

(37) The log S of the anion hydride of the iodonium salt was calculated using ChemDraw Professional ver 18.1.

(C-1) Iodonium Salt-Based Compound of an Anion Having log S of −4 or Less

C1: bis [4-(tert-butyl) phenyl] iodonium tetra (pentafluorophenyl) gallate (Log S: −15.1)

(38) ##STR00001##

C2: di-p-tolyleiodonium phenyl tris (pentafluorophenyl) borate (Log S: −11.3)

(39) ##STR00002##

C3: bis (4-tert-butylphenyl) iodonium tetra (nonafluoro-tert-butoxy) aluminate (Log S: −14.7)

(40) ##STR00003##

C4: p-cumenyl (p-tolyl) iodonium tris (pentafluoro ethanesulfonyl) methide (Log S: −5.3)

(41) ##STR00004##

C5: diphenyliodonium tris (nonafluorobutane sulfonyl) methide (Log S: −9.4)

(42) ##STR00005##

C.SUB.6: .bis (4-tert-butylphenyl) iodonium tris (pentafluoropropyl) trifluorophosphate (C Log P: −5.2)

(43) ##STR00006##

C7: p-cumenyl (p-tolyl) iodonium tris (pentafluoroethyl) trifluorophosphate (C Log P: −7.2)

(44) ##STR00007##

C8: p-cumenyl (p-tolyl) iodonium bis (trifluoromethyl) tetrafluorophosphate (C Log P: −4.7)

(45) ##STR00008##

C9: p-cumenyl (p-tolyl) iodonium (trifluoromethyl) pentafluorophosphate (C log P: −4.1)

(46) ##STR00009##

Photoacid Generator Containing Anion of Log S More Than −4

C11: bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate (Log S: −2.1)

(47) ##STR00010##

C12: Diphenyliodonium Trifluoromethane Sulfonic Acid (Log S: −0.7)

(48) ##STR00011##

C13: Diphenyliodonium Chloride (Log S: 0.2)

(49) ##STR00012##

C14: bis (4-tert-butylphenyl) iodonium hexafluorophosphate (Log S: −3.5)

(50) ##STR00013##

Preparing Method of one Pack Type Dental Photocurable Composition

(51) All components shown in Table 1 other than the filler (E) were put into a wide mouthed plastic container and mixed by using a mix rotor VMRC-5 under the condition of 100 rpm for 48 hours to prepare a matrix. Then, the matrix and the filler (E) were put into a kneader, stirred uniformly, and then defoamed under vacuum to prepare a dental photocurable composition. In the table 1, the content (parts by mass) of each component is indicated by the numerical value in parentheses after the abbreviation of each component.

(52) TABLE-US-00001 TABLE 1 One pack (C) Photoacid type dental generator (D) Photo photocurable (A) Polymerizable (B) Photo Other polymerization Polymerization composition monomer sensitizer (C-1) than (C-1) accelerator (E) Filler inhibitor Others Example A1 Bis-GMA(60), CQ(0.3) C1(2.0) — TBA(0.8) Filler1(250) MeHQ(0.005) FA(0.01) TEGDMA(40) Example A2 2.6E(80), CQ(0.2) C2(5.0) — DEAEMA(1.5) Filler2(250) MeHQ(0.005) — TEGDMA(20) Example A3 UDMA(70), CQ(0.1) C3(1.0) — DBGE(2.0) Filler1(250) MeHQ(0.005) FA(0.01) TEGDMA(30) Example A4 Bis-GMA(60), CQ(0.5) C4(2.0) — DEAEMA(2.0) Filler2(250) MeHQ(0.005) — TEGDMA(20), MDP(20) Example A5 Bis-GMA(60), CQ(0.1) C5(1.0) — DEAEMA(2.0) Filler1(250) MeHQ(0.005) FA(0.01) TEGDMA(40) Example A6 2.6E(80), CQ(0.7) C6(2.0) — DEAEMA(0.5) Filler2(250) MeHQ(0.005) — TEGDMA(20) Example A7 UDMA(70), CQ(0.2) C7(3.0) — TBA(0.5) Filler1(250) MeHQ(0.005) FA(0.01) TEGDMA(30) Example A8 Bis-GMA(60), CQ(0.1) C8(0.5) — TBA(5.0) Filler2(250) MeHQ(0.005) FA(0.01) TEGDMA(40) Example A9 Bis-GMA(60), CQ(0.2) C9(0.5) — DEAEMA(5.0) Filler1(250) MeHQ(0.005) — TEGDMA(40) Example A10 Bis-GMA(60), CQ(0.1) C8(2.0) — DEAEMA(2.0) Filler2(250) MeHQ(0.005) — TEGDMA(40) Example A11 Bis-GMA(60), CQ(0.2) C9(2.0) — TBA(2.0) Filler1(250) MeHQ(0.005) FA(0.01) TEGDMA(40) Example A12 Bis-GMA(60), CQ(0.1) C8(10.0) — DEAEMA(2.0) Filler2(250) MeHQ(0.005) — TEGDMA(40) Example A13 Bis-GMA(60), CQ(0.2) C9(10.0) — TBA(2.0) Filler1(250) MeHQ(0.005) FA(0.01) TEGDMA(40) Example A14 Bis-GMA(60), CQ(0.1) C7(10.0) — DMAEMA(2.0) Filler2(250) MeHQ(0.005) FA(0.01) TEGDMA(40) Example A15 Bis-GMA(60), CQ(0.4) C7(0.5) — DEAEMA(2.0) Filler1(250) MeHQ(0.005) — TEGDMA(40) Example A16 Bis-GMA(60), CQ(0.4) C7(0.4) C13(0.1) DEAEMA(2.0) Filler2(250) MeHQ(0.005) — TEGDMA(40) Example A17 Bis-GMA(60), CQ(0.3) C6(0.9) C14(0.1) TBA(2.0) Filler2(250) MeHQ(0.005) — TEGDMA(40) Example A18 Bis-GMA(60), CQ(0.3) C5(2.0) — DEAEMA(0.01) Filler1(250) MeHQ(0.005) — TEGDMA(40) Example A19 Bis-GMA(60), CQ(0.3) C6(1.0) — TBA(20.0) Filler2(250) MeHQ(0.005) FA(0.01) TEGDMA(40) Example A20 Bis-GMA(60), CQ(0.2) C7(1.5) — DEAEMA(20.0) Filler1(250) MeHQ(0.005) — TEGDMA(40) Example A21 Bis-GMA(60), CQ(1.2) C1(1.5) — DEAEMA(2.0) Filler2(250) MeHQ(0.005) FA(0.01) TEGDMA(40) Example A22 Bis-GMA(60), CQ(0.005) C1(1.5) — DEAEMA(2.0) Filler1(250) MeHQ(0.005) — TEGDMA(40) Example A23 Bis-GMA(60), CQ(0.005) C7(0.5) — DMAEMA(0.5) Filler2(250) MeHQ(0.005) — TEGDMA(40) Example A24 Bis-GMA(60), CQ(0.3) C6(1.5) — DEAEMA(2.0) Filler1(250) MeHQ(0.005) FA(0.01) TEGDMA(40) Example A25 Bis-GMA(60), CQ(0.3) C6(3.0) — DMAEMA(2.0) Filler2(250) MeHQ(0.005) — TEGDMA(40) Example A26 2.6E(80), CQ(0.1) C5(1.5) — DBAE(2.0) Filler1(250) MeHQ(0.005) — TEGDMA(20) Example A27 UDMA(70), CQ(0.3) C6(2.0) — DBAE(2.0) Filler2(250) MeHQ(0.005) FA(0.01) TEGDMA(30) Example A28 Bis-GMA(60), CQ(0.3) C4(2.0) — MDEOA(0.3) Filler1(250) MeHQ(0.005) — TEGDMA(40) Example A29 Bis-GMA(60), CQ(0.3) C4(2.0) — TEA(0.5) Filler2(250) MeHQ(0.005) — TEGDMA(40) Example A30 Bis-GMA(60), CQ(0.3) C6(2.0) — DMBE(0.35) Filler1(250) MeHQ(0.005) FA(0.01) TEGDMA(40) Example A31 Bis-GMA(60), CQ(0.3) C6(1.5) — DMBE(0.3), Filler2(250) MeHQ(0.005) — TEGDMA(40) MDEOA(0.5) Example A32 Bis-GMA(60), CQ(0.3) C7(2.0) — TBA(1.0), Filler1(250) MeHQ(0.005) FA(0.01) TEGDMA(40) DMBE(0.3) Example A33 Bis-GMA(60), CQ(0.3) C6(1.5) — DBGE(1.5), Filler2(250) MeHQ(0.005) BT(0.5) TEGDMA(40) DMBE(0.3) Example A34 Bis-GMA(60), CQ(0.3) C7(2.0) — DEAEMA( 1.3), Filler1(250) MeHQ(0.005) BT(0.5) TEGDMA(40) DMBE(0.2) Example A35 Bis-GMA(60), CQ(0.3) C7(1.5) — DBTL(1.0) Filler2(250) MeHQ(0.005) — TEGDMA(40) Example A36 Bis-GMA(60), BAPO(0.4) C3(2.0) — TBA(2.0) Filler1(250) MeHQ(0.01) FA(0.01) TEGDMA(40) Example A37 Bis-GMA(60), CQ(0.2) C6(1.5) — DBGE(2.0) Filler2(250) MeHQ(0.005) FA(0.01) TEGDMA(40) Example A38 Bis-GMA(60), CQ(0.3) C7(1.0) — DEAEMA(1.5) Filler1(800) MeHQ(0.005) — TEGDMA(40) Example A39 Bis-GMA(60), CQ(0.3) C7(1.5) — DMAEMA(2.0) Filler2(1000) MeHQ(0.005) — TEGDMA(40) Example A40 Bis-GMA(60), CQ(0.3) C7(2.0) — TBA(2.0) Filler1(400) MeHQ(0.005) — TEGDMA(40) Example A41 Bis-GMA(60), CQ(0.3) C1(1.5) — DMAEMA(2.0) Filler1(20) MeHQ(0.005) FA(0.01) TEGDMA(40) Example A42 Bis-GMA(60), CQ(0.2) C1(4.0) — TBA(2.0) — MeHQ(0.005) — TEGDMA(40) Example A43 Bis-GMA(60), CQ(0.003) C1(1.5) — DEAEMA(2.0) Filler1(250) MeHQ(0.005) — TEGDMA(40) Example A44 Bis-GMA(60), CQ(0.2) C9(12.0) — TBA(2.0) Filler1(250) MeHQ(0.005) FA(0.01) TEGDMA(40) Example A45 Bis-GMA(60), CQ(0.2) C7(1.5) — DEAEMA(40.0) Filler1(250) MeHQ(0.005) — TEGDMA(40) Example A46 Bis-GMA(60), CQ(0.05) C5(1.0) — DEAEMA(2.0) Filler1(250) MeHQ(0.005) FA(0.01) TEGDMA(40) Example A47 Bis-GMA(60), CQ(2.0) C5(1.0) — DEAEMA(2.0) Filler1(250) MeHQ(0.005) FA(0.01) TEGDMA(40) Example A48 Bis-GMA(60), CQ(0.1) C5(1.0) — DEAEMA(0.01) Filler1(250) MeHQ(0.005) FA(0.01) TEGDMA(40) Comparative Bis-GMA(60), — C2(2.0) — MDEOA(1.0) Filler1(250) MeHQ(0.005) — Example CA1 TEGDMA(40) Comparative Bis-GMA(60), CQ(0.5) C3(5.0) — — Filler1(250) MeHQ(0.005) — Example CA2 TEGDMA(40) Comparative Bis-GMA(60), CQ(1.2) — — DEAEMA(10.0) Filler1(250) — Example CA3 TEGDMA(40) Comparative Bis-GMA(60), CQ(0.3) — C11(0.2) TBA(2.0) Filler2(250) MeHQ(0.005) — Example CA4 TEGDMA(40) Comparative Bis-GMA(60), CQ(0.3) — C12(0.2) TBA(2.0) Filler1(250) MeHQ(0.005) — Example CA5 TEGDMA(40) Comparative Bis-GMA(60), CQ(0.3) — C11(0.5) MDEOA(1.0) Filler1(250) MeHQ(0.005) — Example CA6 TEGDMA(40) Comparative Bis-GMA(60), CQ(0.2) — C12(0.6) TBA(2.0) Filler2(250) MeHQ(0.005) — Example CA7 TEGDMA(40) Comparative Bis-GMA(60), CQ(0.3) — C13(0.5) MDEOA(1.0) Filler1(250) MeHQ(0.005) — Example CA8 TEGDMA(40) Comparative Bis-GMA(60), CQ(0.2) — C14(0.5) DEAEMA(2.0) Filler1(250) MeHQ(0.005) — Example CA9 TEGDMA(40) Comparative Bis-GMA(60), CQ(0.3) — C1K2.0) MDEOA(1.0) Filler2(250) MeHQ(0.005) — Example CA10 TEGDMA(40) Comparative Bis-GMA(60), CQ(0.2) — C12(1.5) DEAEMA(2.0) Filler1(250) MeHQ(0.005) — Example CA11 TEGDMA(40) Comparative Bis-GMA(60), CQ(0.3) — C13(3.0) MDEOA(1.0) Filler2(250) MeHQ(0.005) — Example CA12 TEGDMA(40) Comparative Bis-GMA(60), CQ(0.2) — C14(3.0) TBA(2.0) Filler1(250) MeHQ(0.005) — Example CA13 TEGDMA(40)

Preparing Method of Two Packs Type Dental Photocurable Composition

(53) All components shown in Table 2 other than the filler (E) were put into a wide mouthed plastic container and mixed by using a mix rotor VMRC-5 under the condition of 100 rpm for 48 hours to prepare a matrix. Then, the matrix and the filler (E) were put into a kneader, stirred uniformly, and then defoamed under vacuum to prepare a first paste and a second paste, and then the first paste and the second paste were filled into a double syringe (5 mL) manufactured by Mixpack Co., Ltd. to prepare a dental photocurable composition. For the two packs type dental photocurable composition, a paste prepared by mixing the first paste and the second paste with a mixing chip manufactured by Mixpack Co., Ltd. was used. The mixing chip manufactured by Mixpack Co., Ltd. is a static mixer, and when using it, the first paste and the second paste can be kneaded at a volume ratio of 0.9 to 1.1:1.0. The first paste and the second paste were kneaded so as to have a mass ratio of 0.8 to 1.2:1.0 and used. In the table 2, the content (parts by mass) of each component is indicated by the numerical value in parentheses after the abbreviation of each component.

(54) TABLE-US-00002 TABLE 2 (C) Photoacid generator (D) Photo Two packs type dental (B) Photo Other polymerization photocurable composition (A) Polymerizable monomer sensitizer (C-1) than (C-1) accelerator Example B1 First paste Bis-GMA(60), TEGDMA(40) CQ(0.6) — — TBA(3.0) Second paste UDMA(70), TEGDMA(30) — C1(4.0) — — Example B2 First paste 2.6E(80), TEGDMA(20) CQ(0.4) — — DEAEMA(2.0) Second paste Bis-GMA(60), TEGDMA(40) — C2(5.0) — — Example B3 First paste UDMA(70), TEGDMA(30) CQ(0.2) C3(4.0) — — Second paste 2.6E(80), TEGDMA(20) — — — TBA(2.0) Example B4 First paste UDMA(70), TEGDMA(30) — — — DEAEMA(1.5) Second paste Bis-GMA(65), HEMA(25), MDP(10) CQ(1.0) C4(2.0) — — Example B5 First paste Bis-GMA(60), TEGDMA(20), MHPA(20) CQ(0.2) C5(3.0) — TEA(1.5) Second paste Bis-GMA(60), TEGDMA(40) — — — — Example B6 First paste 2.6E(80), TEGDMA(20) CQ( 1.4) C6(3.0) — DEAEMA(0.5) Second paste Bis-GMA(60), TEGDMA(40) — — — — Example B7 First paste Bis-GMA(65), HEMA(25), MDP(10) CQ(0.4) C7(5.0) — TBA(0.5) Second paste 2.6E(80), TEGDMA(20) — — — — Example B8 First paste Bis-GMA(60), TEGDMA(40) — C8(0.5) — TBA(2.0) Second paste Bis-GMA(60), TEGDMA(40) CQ(0.2) C8(0.5) — — Example B9 First paste Bis-GMA(60), TEGDMA(40) CQ(0.4) — — DEAEMA(4.0) Second paste Bis-GMA(60), TEGDMA(40) — C9(1.0) — — Example B10 First paste Bis-GMA(60), TEGDMA(40) — C8(3.0) — — Second paste Bis-GMA(60), TEGDMA(40) CQ(0.2) — — DEAEMA(2.0) Example B11 First paste Bis-GMA(60), TEGDMA(40) CQ(0.4) C9(3.0) — DBGE(2.0) Second paste Bis-GMA(60), TEGDMA(40) — — — — Example B12 First paste Bis-GMA(60), TEGDMA(40) CQ(0.3) C8(10.0) — DEAEMA(2.0) Second paste Bis-GMA(60), TEGDMA(40) — — — — Example B13 First paste Bis-GMA(60), TEGDMA(40) CQ(0.8) — — TBA(4.0) Second paste Bis-GMA(60), TEGDMA(40) — C9(10.0) — — Example B14 First paste Bis-GMA(60), TEGDMA(40) — C7(20.0) — — Second paste Bis-GMA(60), TEGDMA(35), MDP(5) CQ(0.4) — — DMAEMA(2.0) Example B15 First paste Bis-GMA(60), TEGDMA(40) CQ( 1.6) C7(1.0) — DEAEMA(2.0) Second paste Bis-GMA(60), TEGDMA(35), MDP(5) — — — — Example B16 First paste Bis-GMA(40), UDMA(20), NPG(40) — C7(0.9) C12(0.1) DEAEMA(2.0) Second paste Bis-GMA(40), UDMA(20), NPG(40) CQ(0.8) — — — Example B17 First paste Bis-GMA(40), UDMA(20), NPG(40) CQ(0.5) — — TBA(2.0) Second paste Bis-GMA(40), UDMA(20), NPG(40) — C6(0.9) C14(0.1) — Example B18 First paste Bis-GMA(40), UDMA(20), NPG(40) CQ(0.4) — — DEAEMA(0.1) Second paste Bis-GMA(40), UDMA(20), NPG(40) — C5(2.0) — — Example B19 First paste Bis-GMA(40), UDMA(20), NPG(40) CQ(0.6) — — TBA(2.0) Second paste Bis-GMA(40), UDMA(20), NPG(40) — C6(2.0) — — Example B20 First paste Bis-GMA(40), UDMA(20), NPG(40) CQ(0.4) C7(2.0) — DEAEMA(40.0) Second paste Bis-GMA(40), UDMA(20), NPG(40) — — — — Example B21 First paste UDMA(70), TEGDMA(30) CQ(2.4) — — DEAEMA(3.0) Second paste UDMA(70), TEGDMA(30) — C1(2.5) — — Example B22 First paste UDMA(70), TEGDMA(30) CQ(0.01) — — DEAEMA(3.0) Second paste UDMA(70), TEGDMA(30) — C1(2.0) — — Example B23 First paste UDMA(70), TEGDMA(30) CQ(0.01) — — DMAEMA(1.0) Second paste UDMA(70), TEGDMA(30) — C7(1.0) — — Example B24 First paste UDMA(70), TEGDMA(30) CQ(0.5) — — DEAEMA(2.0) Second paste UDMA(70), TEGDMA(20), MDP(10) — C6(3.0) — — Example B25 First paste Bis-GMA(60), TEGDMA(40) — C6(3.0) — DMAEMA(2.0) Second paste UDMA(70), TEGDMA(20), MDP(10) CQ(0.5) — — — Example B26 First paste 2.6E(80), TEGDMA(20) — — — DBAE(2.0) Second paste 2.6E(80), TEGDMA(20) CQ(0.4) C5(3.0) — — Example B27 First paste UDMA(70), TEGDMA(30) CQ(0.6) C6(2.0) — — Second paste UDMA(70), TEGDMA(30) — — — DBAE(1.0) Example B28 First paste Bis-GMA(60), TEGDMA(40) CQ(0.5) C4(2.0) — — Second paste UDMA(70), TEGDMA(20), MDP(10) — — — MDEOA(0.5) Example B29 First paste UDMA(70), TEGDMA(20), MDP(10) CQ(0.5) — — TEA(0.5) Second paste Bis-GMA(60), TEGDMA(40) — C4(2.0) — — Example B30 First paste Bis-GMA(60), TEGDMA(40) — C6(2.0) — DMBE(1.0) Second paste Bis-GMA(60), TEGDMA(40) CQ(0.6) — — — Example B31 First paste Bis-GMA(60), TEGDMA(40) CQ(0.6) — — DMBE(0.4), MDEOA(1.5) Second paste Bis-GMA(60), TEGDMA(40) — C6(1.5) — — Example B32 First paste Bis-GMA(60), TEGDMA(40) CQ(0.5) — — TBA(2.0) Second paste Bis-GMA(60), TEGDMA(40) — C7(2.0) — DMBE(0.5) Example B33 First paste Bis-GMA(60), TEGDMA(40) CQ(0.5) — — TBA(1.5), DMBE(0.5) Second paste Bis-GMA(60), TEGDMA(40) — C6(2.0) — — Example B34 First paste Bis-GMA(60), TEGDMA(40) — C7(2.0) — DEAEMA(1.5) Second paste Bis-GMA(60), TEGDMA(40) CQ(0.6) — — DMBE(0.3) Example B35 First paste Bis-GMA(60), TEGDMA(40) CQ(0.6) — — DBTL(1.0) Second paste Bis-GMA(60), TEGDMA(40) — C7(1.5) — — Example B36 First paste Bis-GMA(60), TEGDMA(40) BAPO(1.0) C3(2.0) — TBA(2.0) Second paste Bis-GMA(60), TEGDMA(40) — — — — Example B37 First paste Bis-GMA(60), TEGDMA(40) CQ(0.4) — — TBA(2.0) Second paste Bis-GMA(60), TEGDMA(40) — C6(3.0) — — Example B38 First paste Bis-GMA(60), TEGDMA(40) — C7(2.0) — — Second paste UDMA(70), TEGDMA(20), MDP(10) CQ(0.3) — — DEAEMA(1.5) Example B39 First paste Bis-GMA(60), TEGDMA(40) CQ(0.3) — — DMAEMA(2.0) Second paste UDMA(70), TEGDMA(20), MDP(10) — C7(3.0) — — Example B40 First paste Bis-GMA(60), TEGDMA(40) CQ(0.3) — — TBA(2.0) Second paste UDMA(70), TEGDMA(20), MDP(10) — C7(2.0) — — Example B41 First paste UDMA(70), TEGDMA(30) CQ(0.6) — — TBA(3.0) Second paste UDMA(70), TEGDMA(30) — C1(4.0) — — Example B42 First paste Bis-GMA(60), TEGDMA(40) CQ(0.6) — — TBA(3.0) Second paste UDMA(70), TEGDMA(30) — C3(4.0) — — Example B43 First paste Bis-GMA(60), TEGDMA(40) CQ(0.6) — — TBA(3.0) Second paste UDMA(70), TEGDMA(20), MDP(10) — C3(4.0) — — Example B44 First paste Bis-GMA(60), TEGDMA(40) CQ(0.4) — — DEAEMA(2.0) Second paste UDMA(70), TEGDMA(20), MDP(10) — C5(2.0) — — Example B45 First paste Bis-GMA(60), TEGDMA(40) CQ(0.4) — — DEAEMA(2.0) Second paste Bis-GMA(60), TEGDMA(40) — C4(3,0) — — Comparative First paste Bis-GMA(60), TEGDMA(40) — C2(2.0) — TBA(1.0) Example CB1 Second paste Bis-GMA(60), TEGDMA(40) — — — — Comparative First paste Bis-GMA(60), TEGDMA(40) CQ(0.5) — — — Example CB2 Second paste Bis-GMA(60), TEGDMA(40) — — — — Comparative First paste Bis-GMA(60), TEGDMA(40) CQ(0.5) C3(5.0) — — Example CB3 Second paste Bis-GMA(60), TEGDMA(40) — — — — Comparative First paste Bis-GMA(60), TEGDMA(40) — — C11(0.2) — Example CB4 Second paste Bis-GMA(60), TEGDMA(40) CQ(0.6) — — TBA(2.0) Comparative First paste Bis-GMA(60), TEGDMA(40) CQ(0.6) — — TBA(2.0) Example CB5 Second paste Bis-GMA(60), TEGDMA(40) — — C12(0.2) — Comparative First paste Bis-GMA(60), TEGDMA(40) CQ(0.6) — C11(1.0) — Example CB6 Second paste Bis-GMA(60), TEGDMA(40) — — — MDEOA(3.0) Comparative First paste Bis-GMA(60), TEGDMA(40) CQ(0.6) — — TBA(2.0) Example CB7 Second paste Bis-GMA(60), TEGDMA(40) — — C12(1.0) — Comparative First paste Bis-GMA(60), TEGDMA(40) CQ(0.6) — — — Example CB8 Second paste Bis-GMA(60), TEGDMA(40) — — C13(1.0) MDEOA(3.0) Comparative First paste Bis-GMA(60), TEGDMA(40) — — C14(1.0) DEAEMA(4.0) Example CB9 Second paste Bis-GMA(60), TEGDMA(40) CQ(0.6) — — — Comparative First paste Bis-GMA(60), TEGDMA(40) — — — MDEOA(3.0) Example CB10 Second paste Bis-GMA(60), TEGDMA(40) CQ(0.6) — C11(4.0) — Comparative First paste Bis-GMA(60), TEGDMA(40) — — — DEAEMA(2.0) Example CB11 Second paste Bis-GMA(60), TEGDMA(40) CQ(0.6) — C12(4.0) — Comparative First paste Bis-GMA(60), TEGDMA(40) CQ(0.6) — — MDEOA(3.0) Example CB12 Second paste Bis-GMA(60), TEGDMA(40) — — C13(4.0) — Comparative First paste Bis-GMA(60), TEGDMA(40) CQ(0.6) — — TBA(2.0) Example CB13 Second paste Bis-GMA(60), TEGDMA(40) — — C14(5.0) — Chemical polymerization initiator or Chemical Two packs type dental polymerization Polymerization photocurable composition (E) Filler accelerator inhibitor Others Example B1 First paste Filler1(200) PTU(1.0) MeHQ(0.005) FA(0.01) Second paste Filler1(200) CHP(1.5) BHT(0.1) Example B2 First paste Filler2(200) PTU(1.0) MeHQ(0.005) Second paste Filler2(200) CHP(1.5) BHT(0.1) Example B3 First paste Filler1(200) PTU(1.0), VOA(0.01) MeHQ(0.005) FA(0.01) Second paste Filler1(200) CHP(1.5) BHT(0.1) Example B4 First paste Filler2(200) PTU(1.0), COA(0.1) MeHQ(0.005) Second paste Filler2(200) CHP(1.5) BHT(0.1) Example B5 First paste Filler1(200) PTU(1.0), COA(0.1) MeHQ(0.005) FA(0.01) Second paste Filler1(200) CHP(1.5) BHT(0.1) — Example B6 First paste Filler2(200) PTU(2.0), VOA(0.01) MeHQ(0.005) — Second paste Filler2(200) CHP(3.0) BHT(0.1) — Example B7 First paste Filler1(200) PTU(2.0), VOA(0.001) MeHQ(0.005) FA(0.01) Second paste Filler1(200) CHP(3.0) BHT(0.1) — Example B8 First paste Filler2(200) PTU(2.0), VOA(0.1) MeHQ(0.005) FA(0.01) Second paste Filler2(200) CHP(3.0) BHT(0.1) — Example B9 First paste Filler1(200) PTU(1.0), COA(0.01) MeHQ(0.005) — Second paste Filler1(200) CHP(1.5) BHT(0.1) — Example B10 First paste Filler2(200) PTU(1.0), COA(0.01) MeHQ(0.005) — Second paste Filler2(200) CHP(1.5) BHT(0.3) — Example B11 First paste Filler1(200) PTU(1.0), COA(0.01) MeHQ(0.005) FA(0.01) Second paste Filler1(200) CHP(1.5) BHT(0.3) — Example B12 First paste Filler2(200) PTU(1.0), COA(0.01) MeHQ(0.005) — Second paste Filler2(200) CHP(1.5) BHT(0.3) — Example B13 First paste Filler1(200) PTU(1.0), COA(0.01) MeHQ(0.005) FA(0.01) Second paste Filler1(200) CHP(1.5) BHT(0.3) — Example B14 First paste Filler2(200) PTU(1.0), COA(0.01) MeHQ(0.005) FA(0.01) Second paste Filler2(200) CHP(1.5) BHT(0.3) — Example B15 First paste Filler1(200) PTU(1.0), COA(0.01) MeHQ(0.01) — Second paste Filler1(200) CHP(1.5) BHT(0.3) — Example B16 First paste Filler2(200) PTU(1.0), COA(0.01) BHT(0.1) — Second paste Filler2(200) CHP(1.5) BHT(0.3) — Example B17 First paste Filler1(200) PTU(1.0), VOA(0.01) BHT(0.1) — Second paste Filler1(200) CHP(1.5) BHT(0.1) — Example B18 First paste Filler2(200) PTU(1.0), COA(0.1) MeHQ(0.005) — Second paste Filler2(200) CHP(1.5) BHT(0.1) — Example B19 First paste Filler1(200) VOA(0.1), COA(0.01) MeHQ(0.005) FA(0.01) Second paste Filler1(200) TPE(2) BHT(0.1) — Example B20 First paste Filler2(200) PTU(1.0), COA(0.01) MeHQ(0.005) — Second paste Filler2(200) CHP(1.5) BHT(0.1) — Example B21 First paste Filler1(200) PTU(1.6), COA(0.01) MeHQ(0.005) FA(0.01) Second paste Filler1(200) CHP(1.8) BHT(0.1) — Example B22 First paste Filler2(200) PTU(2.0) MeHQ(0.005) — Second paste Filler2(200) CHP(3.0) BHT(0.1) — Example B23 First paste Filler1(200) PTU(2.0), VOA(0.005) MeHQ(0.005) — Second paste Filler1(200) CHP(3.0) BHT(0.1) — Example B24 First paste Filler2(200) PTU(2.0) MeHQ(0.005) FA(0.01) Second paste Filler2(200) CHP(3.0) BHT(0.1) — Example B25 First paste Filler1(200) PTU(2.0), VOA(0.005) MeHQ(0.005) — Second paste Filler1(200) CHP(3.0) BHT(0.1) — Example B26 First paste Filler2(200) PTU(2.0) MeHQ(0.005) — Second paste Filler2(200) CHP(3.0) BHT(0.1) — Example B27 First paste Filler1(200) PTU(2.0), VOA(0.005) MeHQ(0.005) FA(0.01) Second paste Filler1(200) CHP(3.0) BHT(0.1) — Example B28 First paste Filler2(200) PTU(2.0) MeHQ(0.005) — Second paste Filler2(200) CHP(3.0) BHT(0.1) — Example B29 First paste Filler1(200) PTU(2.0), VOA(0.005) MeHQ(0.005) — Second paste Filler1(200) CHP(3.0) BHT(0.1) — Example B30 First paste Filler2(200) PTU(2.0), VOA(0.005) MeHQ(0.005) FA(0.01) Second paste Filler2(200) CHP(3.0) BHT(0.1) — Example B31 First paste Filler1(200) PTU(1.5), VOA(0.005) MeHQ(0.005) — Second paste Filler1(200) CHP(2.0) BHT(0.1) — Example B32 First paste Filler2(200) PTU(1.5), VOA(0.005) MeHQ(0.005) FA(0.01) Second paste Filler2(200) CHP(2.0) BHT(0.1) — Example B33 First paste Filler1(200) PTU(1.5), VOA(0.005) MeHQ(0.005) BT(1) Second paste Filler1(200) CHP(2.0) BHT(0.1) — Example B34 First paste Filler1(200) PTU(1.5), VOA(0.005) MeHQ(0.005) BT(1) Second paste Filler1(200) CHP(2.0) BHT(0.1) — Example B35 First paste Filler1(200) PTU(1.5), VOA(0.005) MeHQ(0.005) — Second paste Filler1(200) CHP(2.0) BHT(0.1) — Example B36 First paste Filler1(200) CHP(2.0) MeHQ(0.01) FA(0.01) Second paste Filler1(200) PTU(1.5), VOA(0.005) BHT(0.1) — Example B37 First paste Filler2(400) PTU(1.6), COA(0.01) MeHQ(0.005) FA(0.01) Second paste Filler2(400) CHP(1.8) BHT(0.1) — Example B38 First paste Filler1(400) CHP(2.0) MeHQ(0.005) — Second paste Filler1(400) PTU(1.5), VOA(0.005) BHT(0.1) — Example B39 First paste Filler2(50) PTU(1.6), COA(0.01) MeHQ(0.005) — Second paste Filler2(50) CHP(1.8) BHT(0.1) — Example B40 First paste — PTU(1.6), COA(0.01) MeHQ(0.005) — Second paste — CHP(1.8) BHT(0.1) — Example B41 First paste Filler1(200) DMPT(0.5) BHT(0.1) — Second paste Filler1(200) BPO(1.5) BHT(0.1) — Example B42 First paste Filler1(200) DEPT(1.0) — FA(0.01) Second paste Filler1(200) BPO(1.5) BHT(0.1) — Example B43 First paste Filler1(200) VOA(0.1), COA(0.01) BHT(0.1) FA(0.01) Second paste Filler1(200) BPO(1.0), TPE(1.0) BHT(0.1) — Example B44 First paste Filler2(400) DEPT(1.0) BHT(0.1) — Second paste Filler2(400) BPO(1.5) BHT(0.1) — Example B45 First paste Filler2(400) DEPT(1.0) BHT(0.1) — Second paste Filler2(400) BPO(1.5) BHT(0.1) — Comparative First paste Filler1(200) PTU(1.6), COA(0.01) MeHQ(0.005) — Example CB1 Second paste Filler1(200) CHP(1.8) BHT(0.1) — Comparative First paste Filler2(200) PTU(1.6), COA(0.01) MeHQ(0.005) — Example CB2 Second paste Filler2(200) CHP(1.8) BHT(0.1) — Comparative First paste Filler1(200) CHP(2.0) MeHQ(0.005) — Example CB3 Second paste Filler1(200) PTU(1.5), VOA(0.01) BHT(0.1) — Comparative First paste Filler2(200) CHP(2.0) MeHQ(0.005) — Example CB4 Second paste Filler2(200) PTU(1.5), VOA(0.01) BHT(0.1) — Comparative First paste Filler1(200) CHP(2.0) MeHQ(0.005) — Example CB5 Second paste Filler1(200) PTU(1.5), VOA(0.01) BHT(0.1) — Comparative First paste Filler2(200) PTU(1.5), VOA(0.01) MeHQ(0.005) — Example CB6 Second paste Filler2(200) CHP(2.0) BHT(0.1) — Comparative First paste Filler1(200) PTU(1.5), VOA(0.01) MeHQ(0.005) — Example CB7 Second paste Filler1(200) CHP(2.0) BHT(0.1) — Comparative First paste Filler2(200) PTU(1.5), VOA(0.01) MeHQ(0.005) — Example CB8 Second paste Filler2(200) PTU(1.5), VOA(0.01) BHT(0.1) — Comparative First paste Filler1(200) CHP(2.0) MeHQ(0.005) — Example CB9 Second paste Filler1(200) PTU(1.5), VOA(0.01) BHT(0.1) — Comparative First paste Filler2(200) CHP(2.0) MeHQ(0.005) — Example CB10 Second paste Filler2(200) PTU(1), COA(0.01) BHT(0.1) — Comparative First paste Filler1(200) CHP(2.0) MeHQ(0.005) — Example CB11 Second paste Filler1(200) PTU(1.6), COA(0.01) BHT(0.1) — Comparative First paste Filler2(200) CHP(1.8) MeHQ(0.005) — Example CB 12 Second paste Filler2(200) PTU(1.5), VOA(0.01) BHT(0.1) — Comparative First paste Filler1(200) CHP(2.0) MeHQ(0.005) — Example CB13 Second paste Filler1(200) PTU(1.5), VOA(0.01) BHT(0.1) —

Acceleration Test Condition

(55) One pack type dental photocurable composition and two packs type dental photocurable composition filled in each container was left to stand in a storage room set at 40° C. (Yamato Scientific Co., Ltd.) and in a storage room set at −5° C. (KGT-4010HC, Nihon Freezer Co., Ltd.) and stored for 6 months.

Evaluation 1: Confirmation of Appearance

(56) After taking out one pack type dental photocurable composition and two packs type dental photocurable composition stored at −5° C. from the storage, these were allowed to stand at room temperature of 15 to 25° C. for 1 week, and 1 g of paste was discharged from the container. Evaluation criteria were as follows.

(57) A (good): no precipitate was visually confirmed.

(58) B (within permissible range): 1 or more and 5 or less precipitates were visually confirmed.

(59) C (there was a problem in appearance): more than 5 were visually confirmed.

Evaluation 2: Confirmation of Storage Stability by Flexural Strength

(60) The prepared dental photocurable composition was filled into a stainless steel mold, and the cover glasses were placed on both sides to press with a glass kneading plate. Thereafter, light was irradiated for 10 seconds to 5 locations by using the photopolymerization irradiator (PEN Bright manufactured SHOFU Inc.) to cure the dental curable composition. After curing, the cured product was removed from the mold, and light was irradiated to the backside in the same manner again to use as a test specimen (25×2×2 mm rectangular shape). The test specimen was immersed in water at 37° C. for 24 hours, and thereafter flexural test was performed. For two packs type dental photocurable composition, flexural test was performed within 1 hour after irradiating the test specimen with light. The flexural test was conducted at a distance between supporting points of 20 mm and at a crosshead speed of 1 mm/min using an Instron universal testing machine (manufactured by Instron). The evaluation of storage stability based on the results of the flexural test was performed by using Formula (2). When the change from before storage was more than −5%, it was determined to have high storage stability. When the change from before storage was −5% to −15%, it was determined that the storage stability was slightly poor. When the change from before storage was less than −15%, it was determined that the storage stability was extremely poor.
((flexural strength after storage (MPa)−flexural strength before storage (MPa))/(flexural strength before storage (MPa))×100 [%]  [Formula (2)]

(61) Furthermore, the flexural strength before the acceleration test was separately evaluated. In the case of containing 100 parts by mass or more of the (E) filler with respect to 100 parts by mass of the polymerizable monomer, evaluation criteria for flexural strength of the one pack type dental photocurable composition and the two packs type dental photocurable composition were as follows.

(62) Good: More than 100 MPa

(63) Applicable: 80 MPa or more and 100 MPa or less than

(64) Insufficient: less than 80 MPa

(65) In the case of containing less than 100 parts by mass of the (E) filler with respect to 100 parts by mass of the polymerizable monomer, evaluation criteria for flexural strength of the one pack type dental photocurable composition and the two packs type dental photocurable composition were as follows.

(66) Good: More than 90 MPa

(67) Applicable: 60 MPa or more and 90 MPa or less than

(68) Insufficient: less than 60 MPa

(69) Since the flexural strength differs depending on the compounding amount of the filler, different criteria were set.

Evaluation 3: Sensitivity to Light

(70) The height of the dental lamp (Luna-Vue S, manufactured by Morita Manufacturing Co., Ltd.) was adjusted so that the sample installation part was exposed to light with an illuminance of 8000±1000 1× using an illuminometer. A slide glass (26×16 mm, thickness 2 mm) was placed on a glass mixing plate lined with no gloss black paper, and then a sample of about 30 mg was collected on the slide glass. After exposing the sample for 60±5 seconds on the sample installation section, the sample was taken out from the sample installation section and immediately pressed against another slide glass to form a thin layer. When the state of the sample at this time was not physically uniform, it was determined that curing had started, and the time until curing was evaluated in 5-second increments. The longer this time, the better the sensitivity to light. Evaluation criteria were as follows.

(71) Good: 90 seconds or more

(72) Applicable: 60 seconds or more and less than 90 seconds

(73) Insufficient: less than 60 seconds

(74) The sensitivity to light indicates the time in which it is possible to sufficiently change the shape without being cured by environmental light such as a fluorescent lamp between discharging the dental photocurable composition from the container and to adapting. Since the oral cavity is a narrow space, it is not easy to operate. Further, the shape of natural tooth is complicated for each individual. Therefore, it is preferable that the sensitivity to light is long in order to adapt to various cases.

Evaluation 4: Color Stability After Irradiation

(75) Each prepared dental photocurable composition was fully filled into a mold (in a shape of a disc having a diameter of 15 mm and a thickness of 1 mm) made of stainless steel. Thereafter, a cover glass was placed on upper side of the stainless mold to apply pressure with glass plate. Subsequently, light irradiation was performed for 1 minute using a photopolymerization irradiator (Grip Light II, manufactured by SHOFU Inc.) via the cover glass to prepare a cured material. The cured material was taken out of the mold, the cover glass was removed and the test specimen was measured for color tone. Color measurement was performed by placing the test specimen on the background of a standard white plate (D65/10°, X=81.07, Y=86.15, Z=93.38) and using a spectrocolorimeter (manufactured by BYK-Chemie GmbH) under predetermined condition (light source: C, viewing angle: 2°, measurement area: 11 mm). Then, after exposing the test specimen to light for 24 hours with a xenon lamp light exposure tester (Suntest CPS+), the color tone of the test specimen was measured again, and the difference in discoloration was represented by ΔE calculated from the following formula.
ΔE=((ΔL*).sup.2+(Δa*).sup.2+(Δb*).sup.2).sup.1/2
ΔL*=L1*.Math.L2*
Δa*=a1*.Math.a2*
Δb*=b1*.Math.b2*

(76) In the formula, L1* is the brightness index before light exposure, L2* is the brightness index after light exposure, a1* and b1* are the color quality index before light exposure, and a2* and b2* are the color quality index after light exposure. Evaluation criteria were as follows.

(77) Good: ΔE was less than 5

(78) Applicable: ΔE was 5 or more and 10 or less than

(79) Insufficient: ΔE was more than 10

(80) When the color stability after irradiation is good, discoloration is small in the case of using, and a highly aesthetic property can be maintained.

Evaluation 5: Thermal Color Stability

(81) Each prepared dental photocurable composition was fully filled into a mold (in a shape of a disc having a diameter of 15 mm and a thickness of 1 mm) made of stainless steel. Thereafter, a cover glass that is colorless and transparent was placed on upper side of the stainless mold to apply pressure with glass plate. Subsequently, light irradiation was performed for 1 minute using a photopolymerization irradiator (Grip Light II, manufactured by SHOFU Inc.) via the cover glass to prepare a cured material. The cured material was taken out of the mold, the cover glass was removed and the test specimen was measured for color tone. Color measurement was performed by placing the test specimen on the background of a standard white plate (D65/10°, X=81.07, Y=86.15, Z=93.38) and using a spectrocolorimeter (manufactured by BYK-Chemie GmbH) under predetermined condition (light source: C, viewing angle: 2°, measurement area: 11 mm). Then, the test specimen was immersed in 10 mL of water in a container in an incubator set at 70° C., allowed to stand for one week, and was measured again for the color tone, and the difference in discoloration was represented by ΔE calculated from the following formula.
ΔE=((ΔL*).sup.2+(Δa*).sup.2+(Δb*).sup.2).sup.1/2
ΔL*=L1*.Math.L2*
Δa*=a1*.Math.a2*
Δb*=b1*.Math.b2*

(82) In the formula, L1* is the brightness index before immersion and stand, L2* is index after immersion and stand, a1* and b1* are the color quality index before immersion and stand, and a2* and b2* are the color quality index after immersion and stand. Evaluation criteria were as follows.

(83) Good: ΔE was less than 5

(84) Applicable: ΔE was 5 or more and 10 or less than

(85) Insufficient: ΔE was more than 10

(86) When the thermal stability is good, discoloration is small in the case of using the dental material in the oral cavity for a long period of time, and a highly aesthetic state can be maintained for a long period of time.

(87) The results shown in Tables 3 and 4 will be described.

(88) TABLE-US-00003 TABLE 3 After storing at −5° After storing at Color C. for 6 months 40° for 6 months stability Thermal Flexural Flexural strength Flexural strength after color strength change rate change rate Sensitivity irradiation stability (Mpa) Precipitate (%) (%) to light ΔE ΔE Example A1 107 A −2.7 −1.2 125 1.6 2.1 Example A2 102 A −2.4 −0.7 125 4.0 1.6 Example A3 110 A −0.9 −0.2 95 2.5 1.6 Example A4 124 A −0.9 −0.4 95 4.0 2.7 Example A5 126 A −0.3 −1.3 100 3.0 2.4 Example A6 116 A −2.3 −2.4 90 3.8 1.5 Example A7 115 A −0.8 −2.5 115 1.2 3.0 Example A8 85 A −1.4 −0.4 110 1.4 3.2 Example A9 81 A −0.1 −2.5 125 2.7 2.0 Example A10 123 A −6.5 −1.7 115 4.3 1.5 Example A11 122 A −6.6 −2.5 100 4.1 1.8 Example A12 135 B −6.7 −8.6 100 7.9 2.4 Example A13 134 B −7.6 −8.2 100 8.0 2.2 Example A14 137 A −1.6 −8.1 100 4.4 1.9 Example A15 81 A −2.0 −1.4 160 2.0 3.1 Example A16 83 A −4.8 −0.2 155 4.3 2.9 Example A17 100 A −4.4 −0.9 90 4.3 1.5 Example A18 85 A −2.1 −2.0 145 2.1 2.9 Example A19 139 A −0.1 −0.8 60 6.7 3.6 Example A20 125 A −1.8 −1.1 65 7.3 2.3 Example A21 138 A −1.6 −0.3 75 7.8 2.0 Example A22 85 A −0.1 −1.4 180 2.5 2.5 Example A23 80 A −2.9 −0.2 200 3.2 1.2 Example A24 125 A −1.0 −2.6 150 1.1 1.3 Example A25 134 A −0.4 −2.6 155 2.7 2.4 Example A26 104 A −0.1 −0.2 105 3.2 4.2 Example A27 119 A −2.3 −0.5 110 1.6 5.6 Example A28 101 A −0.2 −2.8 105 3.8 8.0 Example A29 103 A −2.5 −2.9 110 3.2 9.3 Example A30 100 A −2.6 −0.9 70 9.8 3.1 Example A31 84 A −1.5 −1.3 90 7.2 8.6 Example A32 123 A −2.6 −0.3 95 7.5 2.1 Example A33 124 A −2.4 −2.4 95 3.9 2.2 Example A34 133 A −2.6 −0.2 90 2.0 1.6 Example A35 112 A −1.0 −1.7 160 1.3 2.7 Example A36 81 A −0.9 −0.9 80 3.7 2.0 Example A37 114 A −3.0 −1.9 90 3.8 3.7 Example A38 130 A −2.6 −1.2 160 3.7 2.7 Example A39 165 A −0.4 −2.6 150 1.8 1.8 Example A40 141 A −0.2 −1.2 155 1.8 2.2 Example A41 102 A −0.1 −2.5 90 2.8 3.9 Example A42 90 A −0.7 −0.7 95 3.9 2.5 Example A43 80 A −0.1 −1.4 240 2.2 2.3 Example A44 138 B −8.0 −9.2 80 9.1 3.9 Example A45 125 A −3.8 −4.3 60 9.0 4.0 Example A46 114 A −2.7 −0.1 125 1.7 2.9 Example A47 138 A −1.6 −0.8 65 9.8 4.5 Example A48 82 A −1.8 −0.1 130 1.8 2.0 Comparative Uncured A Uncured Uncured Uncured Uncured Uncured Example CA1 Comparative 71 A −1.3 −1.7 180 1.2 3.3 Example CA2 Comparative 74 A −1.3 −1.9 180 14.8 3.2 Example CA3 Comparative 71 A −4.5 −0.4 220 1.9 2.6 Example CA4 Comparative 69 A −4.3 −1.1 225 2.0 1.8 Example CA5 Comparative 93 C −17.7 −3.1 125 7.0 11.4 Example CA6 Comparative 94 C −15.1 −3.3 110 7.1 3.0 Example CA7 Comparative 98 C −18.3 −4.7 125 7.2 12.6 Example CA8 Comparative 98 C −17.0 −4.3 95 7.9 3.4 Example CA9 Comparative 102 C −16.3 −20.5 70 13.4 12.3 Example CA10 Comparative 113 C −15.3 −20.8 70 15.7 2.7 Example CA11 Comparative 115 C −16.0 −20.7 80 14.2 12.6 Example CA12 Comparative 104 C −18.5 −20.5 75 13.8 3.4 Example CA13

(89) TABLE-US-00004 TABLE 4 After storing at −5° C. for 6 months After storing at Color Flexural 40° for 6 months stability Thermal Flexural strength Flexural strength after color strength change rate change rate Sensitivity irradiation stability (Mpa) Precipitate (%) (%) to light ΔE ΔE Example B1 126 A −2.4 −3.1 115 1.3 3.6 Example B2 127 A −1.7 −3.1 95 3.4 2.1 Example B3 118 A −2.8 −4.5 115 1.4 2.9 Example B4 115 A −1.4 −4.2 110 1.5 2.8 Example B5 125 A −2.8 −3.6 100 2.4 1.3 Example B6 115 A −2.4 −3.2 125 2.1 3.3 Example B7 129 A −2.8 −3.8 100 1.3 2.3 Example B8 83 A −0.6 −3.8 90 3.2 2.1 Example B9 81 A −4.3 −4.3 105 3.5 1.1 Example B10 122 A −5.0 −4.2 110 4.4 2.6 Example B11 122 A −6.3 −3.5 125 4.2 1.7 Example B12 128 B −7.0 −6.1 100 4.5 3.2 Example B13 110 B −7.1 −7.2 90 4.3 3.9 Example B14 121 A −0.6 −8.1 90 4.0 1.1 Example B15 82 A −0.6 −3.6 145 1.9 2.5 Example B16 84 A −4.1 −3.1 165 4.0 3.7 Example B17 98 A −4.1 −4.6 90 4.9 2.8 Example B18 85 A −2.8 −4.3 155 2.2 2.0 Example B19 120 A −1.1 −3.6 165 2.7 1.1 Example B20 137 A −0.7 −3.2 65 5.2 1.9 Example B21 136 A −1.5 −3.9 60 8.5 1.7 Example B22 85 A −2.3 −4.5 185 1.4 1.6 Example B23 80 A −1.0 −4.5 190 2.0 3.5 Example B24 132 A −1.3 −4.3 150 3.9 1.9 Example B25 136 A −2.3 −4.5 145 3.6 1.5 Example B26 103 A −1.0 −4.0 95 2.6 4.6 Example B27 102 A −0.7 −4.3 120 3.9 5.4 Example B28 139 A −1.4 −4.4 95 2.7 8.7 Example B29 125 A −2.0 −4.6 105 2.0 9.1 Example B30 99 A −1.6 −4.1 70 9.8 1.5 Example B31 80 A −1.6 −4.5 95 8.0 9.5 Example B32 126 A −0.1 −3.4 90 6.5 3.9 Example B33 124 A −2.2 −4.0 90 2.9 2.8 Example B34 125 A −1.2 −4.8 90 2.4 2.2 Example B35 124 A −0.5 −4.1 145 3.3 1.1 Example B36 80 A −2.8 −4.0 60 3.9 2.3 Example B37 115 A −2.1 −3.7 105 1.6 1.8 Example B38 162 A −2.1 −4.9 175 2.3 2.6 Example B39 108 A −2.6 −4.1 90 1.3 2.8 Example B40 90 A −0.6 −4.6 100 2.1 1.4 Example B41 111 A −2.4 −4.4 105 7.6 1.6 Example B42 108 A −1.5 −4.2 90 7.7 9.6 Example B43 116 A −2.9 −4.4 110 3.0 2.9 Example B44 110 A −1.3 −3.6 110 7.1 9.9 Example B45 105 A −2.6 −3.3 100 7.1 9.8 Comparative 10 A −1.8 −3.4 600 2.9 2.6 Example CB1 Comparative 70 A −1.7 −4.3 190 3.8 3.4 Example CB2 Comparative 70 A −2.2 −3.7 160 1.3 2.6 Example CB3 Comparative 60 A −4.2 −4.3 200 1.7 2.3 Example CB4 Comparative 58 A −4.3 −3.4 220 2.2 2.6 Example CB5 Comparative 88 C −17.9 −3.8 100 7.7 11.7 Example CB6 Comparative 82 C −15.9 −4.4 90 7.9 2.1 Example CB7 Comparative 93 C −15.1 −2.7 95 7.3 11.6 Example CB8 Comparative 97 C −19.8 −2.3 125 7.3 3.4 Example CB9 Comparative 129 C −16.4 −20.3 85 13.8 12.0 Example CB10 Comparative 121 C −16.6 −20.2 70 13.4 2.0 Example CB11 Comparative 115 C −18.6 −20.8 70 13.8 11.9 Example CB12 Comparative 103 C −19.3 −20.9 70 15.8 1.4 Example CB13

(90) It was confirmed that the compositions described in Examples exhibited a flexural strength of 80 MPa or more in the preparation stage, and the flexural strength did not significantly decrease even when stored at a low temperature for a long period of time.

(91) In Examples A8, A9, A15, A16, A23, B8, B9, B15, B16, and B17, the flexural strength was slightly low because the compounding amount of the photoacid generator was slightly small. On the other hand, when the compounding amount of the photoacid generator was slightly large as in Examples A12, A13, A14 and B14, it was confirmed that the flexural strength tended to decrease when the storage test at a high temperature such as 40° C. was performed, and the sensitivity to light was shortened and the color stability after irradiation was reduced. In the case of containing C8 or C9 which were an iodonium salt compound which was a salt of an anion having log S of −4 to -5 and an iodonium cation as the photoacid generator, when the compounding amount was small as in Examples A8, A9, B8, B9, there was no problem even if it was stored at low temperature. In Examples A10, A11, B10, B11 in which the compounding amount was increased and in Examples A12, A13, B12, B13 in which the compounding amount was further increased, the storage stability tended to be slightly lowered, and some precipitates were confirmed and the color stability after irradiation tended to be slightly deteriorated in the case of storing at low temperature. However, the change was within the range in which it could be used without problems. Further, it was confirmed that although Examples A16 and A17 contained an iodonium salt compound which is a salt of an anion having log S exceeding −4 and an iodonium cation, the compounding amount was the trace amount such as 0.1 part by mass with respect to 100 parts by mass of the polymerizable monomer, therefore storage stability was not significantly affected.

(92) It was confirmed that in Examples A22 and B22, the flexural strength tended to be low because the compounding amount of the photosensitizer was slightly small, and in Examples A21, A47 and B21, because the compounding amount of the photosensitizer was slightly large, the flexural strength was high, but sensitivity to light and the color stability after irradiation tended to decrease. Further, in Examples A36 and B36 containing BAPO, which is an acylphosphine oxide, as a photosensitizer, there was a tendency that the flexural strength was lower than a composition containing an α-diketone compound as a photosensitizer.

(93) It was confirmed that in Examples A18, A48 and B18, the flexural strength tended to low because the compounding amount of the photopolymerization accelerator was slightly small, and in Examples A19, A20 and B20, because the compounding amount of the photosensitizer was slightly large, the flexural strength was high, but sensitivity to light and the color stability after irradiation tended to decrease.

(94) Examples A26, A27, B26 and B27 contained dibenzylaminoethanol (DBAE) having one primary hydroxy group as a photopolymerization accelerator, Examples A28 and B28 contained methyldiethanolamine having two primary hydroxy groups as a photopolymerization accelerator, and Examples A29 and B29 contained triethanolamine having three primary hydroxy groups as a photopolymerization accelerator. Comparing these, it was confirmed that the thermal color stability tended to decrease as the number of primary hydroxy group increases, and in particular, by having two or more primary hydroxy groups, the thermal color stability was significantly reduced.

(95) Examples A30, A31, A32, B30, B31 and B32 contained DMBE which is an aromatic amine as a photopolymerization accelerator. It was confirmed that the color stability after irradiation was lowered when the aromatic amine was contained. On the other hand, in the case of a composition containing an aromatic amine and an ultraviolet absorber at the same time as in Examples A33, A34, B33 and B34, it was possible to prevent a decrease in color stability after irradiation. However, it was more preferable not to compound the ultraviolet absorber because the yellowing of the cured product may increase and the large amount of the ultraviolet absorber may cause a decrease in mechanical strength because it did not contribute to the improvement of the physical properties.

(96) Examples B41, B42, B44 and B45 contained an aromatic amine as a chemical polymerization accelerator. The photocolor stability tended to decrease as in the case of containing an aromatic amine as a photopolymerization accelerator. In addition, Examples B42, B44 and B45 containing an aromatic amine having two primary hydroxy groups in the molecule, such as DEPT, tended to have a reduced thermal color stability.

(97) Because Comparative Examples CA1 and CB1 did not contain a photosensitizer, these were not cured, or their flexural strength was significantly reduced. Since Comparative Examples CA2 and CB3 did not contain a photoacid generator, the flexural strength was remarkably low. Since Comparative Examples CA3 and CB2 did not contain a photopolymerization accelerator, the flexural strength was remarkably low. Comparative Examples CA4 to CA13 and CB4 to CB13 contained an iodonium salt compound which is a salt of an anion having log S exceeding −4 and iodonium cation. In Comparative Examples CA4, CA5, CB5 and CB6 in which the compounding amount of such a photoacid generator was small, no decrease in storage stability was confirmed, but the flexural strength was insufficient. When the compounding amount of the photoacid generator was increased as in Comparative Examples CA6 to CA9 and Comparative Examples CB6 to CB9, it was confirmed that there was a tendency that the flexural strength was improved, but precipitates were confirmed when the photoacid generator was stored at a low temperature, and the flexural strength was lowered. Furthermore, a decrease in color stability after irradiation was also confirmed. Further, in Comparative Examples CA10 to CA13 and Comparative Examples CB10 to CB13 in which the compounding amount of the photoacid generator was increased, it was confirmed that the flexural strength was further improved, but the storage stability and color stability after irradiation during low temperature storage and high temperature storage were lowered. The solubility of the photoacid generator affects storage stability and color stability.

(98) The dental photocurable composition of the present disclosure evaluated in Examples can be used for any known dental photocurable composition without any problem. The dental photocurable composition of the present disclosure may be used for a dental adhesive material, a dental composite resin, a dental core build-up material, a dental resin cement, a dental coating material, a dental sealant material, a dental manicure material, a dental splinting material, a dental glass ionomer cement, a dental hard resin, a dental CAD-CAM restoration material, a dental 3D printer material and the like. With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context.

(99) Although the description herein has been given with reference to the drawings and embodiments, it should be noted that those skilled in the art may make various changes and modifications on the basis of this invention without difficulty. Accordingly, any such changes and modifications are intended to be included in the scope of the embodiments.

INDUSTRIAL APPLICABILITY

(100) According to the present disclosure, it is possible to provide a dental photocurable composition which can exhibit excellent mechanical characteristics even after returning from a low temperature to room temperature.