Dental hardenable composition and kit

Abstract

To provide a dental curable composition having curing characteristics suitable for use as a dental material.SOLUTION: A dental curable composition comprises 100 pts.mass of (A) a polymerizable monomer, 0.05-5 pts.mass of (B) a peroxyester compound, 0.001-0.05 pt.mass of (C) a bivalent copper compound, 0.05-2.5 pts.mass of (D) a saccharin compound, and 0.05-2.5 pts.mass of (E) a reductant for copper.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a hardenable composition in which polymerization is initiated by reacting an oxidizing agent with a reducing agent, and more particularly to a dental hardenable composition having good hardening behavior. [Background technology]

[0002] (Meth)acrylate-based materials are used in a wide range of fields, including paints, printing materials, adhesives, and dental materials. For example, in the dental field, they are used in a variety of materials, including bonding agents, resin cements, resin-reinforced glass ionomers, and composite resins. These materials typically cure by radical polymerization. Radical generation is achieved by one or more polymerization initiators selected from photopolymerization initiators, thermal polymerization initiators, and chemical (redox) polymerization initiators, depending on the application.

[0003] Among these polymerization initiators, chemical polymerization initiators are particularly useful for applications where it is difficult to apply light or heat stimuli. Chemical polymerization initiators contain a combination of a reducing agent and an oxidizing agent that can react immediately upon contact, so they usually need to be stored in two or more separate forms. Forms in which chemical polymerization initiators are stored in two separate forms include paste / paste, liquid / liquid, powder / liquid, and liquid / paste combinations.

[0004] It is desirable that the chemical polymerization initiator used in dental materials has a temperature-dependent curing behavior that does not readily cure at room temperature but readily cures in the oral cavity. A long-known chemical polymerization initiator is a chemical polymerization initiator that combines benzoyl peroxide with a tertiary aromatic amine compound. However, this chemical polymerization initiator has a low temperature-dependent curing behavior, making it difficult to achieve the temperature-dependent curing behavior described above. In addition, benzoyl peroxide has poor storage stability due to its low thermal stability.

[0005] In response to this, Patent Documents 1 and 2 propose radical polymerization initiators with improved storage stability. These radical polymerization initiators use hydroperoxides as oxidizing agents and various thiourea derivatives as reducing agents. Hydroperoxides have higher thermal stability and superior storage stability compared to benzoyl peroxide and the like. However, even with these radical polymerization initiators, the temperature dependence of the curing behavior is not high, and it is still difficult to obtain the desired temperature dependence of the curing behavior. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-227370 [Patent Document 2] International Publication No. WO2014 / 156077 Brochure Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a dental hardenable composition that has desirable hardening behavior as a dental material. [Means for solving the problem]

[0008] The present inventors have investigated dental hardenable compositions to solve the above problems, and as a result have found dental hardenable compositions that have desirable hardening behavior as dental materials. That is, the dental curable composition according to one embodiment of the present invention comprises: 100 parts by mass of (A) polymerizable monomer; 0.05 to 5 parts by mass of a (B) peroxyester compound; 0.001 to 0.05 parts by mass of (C) a divalent copper compound; 0.05 to 2.5 parts by mass of a (D) saccharin compound; 0.05 to 2.5 parts by mass of (E) a reducing agent for copper; The compound is characterized by containing:

[0009] In the dental hardenable composition, (E) is preferably at least one of (e1) an aromatic amine compound having no electron-withdrawing group, (e2) a (thio)barbituric acid compound, (e3) a thiourea compound, and (e4) a heterocyclic thiol compound.

[0010] In the dental curable composition, when the time from mixing (A) to (E) at 23°C until the temperature starts to rise while maintaining the composition at 23°C is defined as t1 (seconds), and the time from maintaining the composition at 37°C until the temperature reaches an exothermic peak is defined as t2 (seconds), it is preferable that t1-t2 be 50 seconds or longer.

[0011] The dental curable composition preferably further contains 50 to 1500 parts by mass of a filler (F).

[0012] The kit for preparing the dental curable composition according to one aspect of the present invention includes: It consists of a first agent and a second agent that are isolated from each other, The (A) is contained in at least one of the first agent and the second agent, (B) and (C) are contained in the first agent but not in the second agent; The (D) and the (E) are not contained in the first agent but are contained in the second agent. It is characterized by the following. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a dental hardenable composition that has a hardening behavior desirable for a dental material. [Brief explanation of the drawings]

[0014] [Figure 1] 1 is a graph illustrating the operation time t1 of a dental hardenable composition. [Figure 2] 1 is a graph illustrating the hardening time t2 of a dental hardenable composition. DETAILED DESCRIPTION OF THE INVENTION

[0015] 1. Overview of dental hardenable compositions A dental hardenable composition according to one embodiment of the present invention is configured to be suitable for use as a dental material, such as a dental resin cement or a dental core material. The dental hardenable composition according to this embodiment contains (A) a polymerizable monomer, (B) a peroxyester compound, (C) a divalent copper compound, (D) a saccharin compound, and (E) a reducing agent for copper. Components that may be contained in the dental hardenable composition according to this embodiment are described in detail below.

[0016] In this specification, unless otherwise specified, the expression "x to y" using numerical values ​​x and y means "greater than or equal to x and less than or equal to y." In such an expression, when a unit is assigned only to the numerical value y, the unit also applies to the numerical value x. Furthermore, in this specification, the term "(meth)acrylate" means both "acrylate" and "methacrylate," and the term "(meth)acryloyl" means both "acryloyl" and "methacryloyl."

[0017] 2. Components of dental hardenable composition 2-1 (A) Polymerizable monomer The dental curable composition according to this embodiment uses a polymerizable monomer (A) as a main component. The polymerizable monomer (A) is a compound having at least one radically polymerizable unsaturated group in one molecule. The dental curable composition according to this embodiment is cured by radical polymerization of the polymerizable monomer (A).

[0018] The polymerizable monomer (A) can be any known compound containing one or more radically polymerizable unsaturated groups in one molecule, without any particular limitations. Examples of the radically polymerizable unsaturated group contained in the polymerizable monomer (A) include an acryloyl group, a methacryloyl group, an acrylamide group, a methacrylamide group, and a styryl group. In the dental curable composition according to this embodiment, from the viewpoint of curability, it is preferable to use, as the polymerizable monomer (A), a compound containing at least one of an acryloyl group, a methacryloyl group, an acrylamide group, and a methacrylamide group as the radically polymerizable unsaturated group.

[0019] Examples of monofunctional monomers and polyfunctional monomers that can be suitably used as the (A) polymerizable monomer include the following: That is, examples of monofunctional monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, glycidyl (meth)acrylate, 2-cyanomethyl (meth)acrylate, benzyl methacrylate, polyethylene glycol mono(meth)acrylate, allyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and glyceryl mono(meth)acrylate. Examples of polyfunctional monomers include 2,2'-bis{4-[2-hydroxy-3-(meth)acryloyloxypropoxy]phenyl}propane, triethylene glycol methacrylate, 2,2-bis[(4-(meth)acryloyloxypolyethoxyphenyl)propane], 1,6-bis(methacrylethyloxycarbonylamino)-2,2,4-trimethylhexane, 1,6-bis(methacrylethyloxycarbonylamino)-2,4,4-trimethylhexane, trimethylolpropane trimethacrylate, etc. As the (A) polymerizable monomer, one type may be used alone, or two or more types may be used in combination.

[0020] 2-2 (B) Peroxyester Compounds In the dental curable composition of this embodiment, a peroxyester compound (B) is used as an oxidizing agent. It is presumed that the peroxyester compound (B) undergoes an oxidation-reduction reaction with a divalent copper compound (C), a saccharin compound (D), and a reducing agent for copper (E), thereby generating initiating radicals necessary for curing.

[0021] (B) The peroxyester compound is a compound having a structure represented by RC(=O)-OO-R' (where R and R' are any organic groups) or ROC(=O)-OO-R' (where R and R' are any organic groups). In this embodiment, peroxyester compounds having such a structure can be used as the oxidizing agent without any particular limitation. Specific examples of peroxyester compounds that can be suitably used in this embodiment include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxydecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, t-hexyl peroxy-2-ethylhexanoate, t- Examples of the peroxyalkylene compounds include butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, t-butylperoxy-3-methylbenzoate, and t-butylperoxybenzoate. In the dental curable composition according to this embodiment, from the viewpoints of polymerization activity and storage stability, it is preferable to use a peroxyester compound (B) having a 10-hour half-life temperature of 80°C or higher, and it is particularly preferable to use at least one of t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxy-2-ethylhexylmonocarbonate, t-butylperoxyacetate, and t-butylperoxybenzoate. As the (B) peroxyester compound, one type may be used alone, or two or more types may be used in combination.

[0022] Furthermore, the blending amount of the (B) peroxyester compound in the dental curable composition according to this embodiment is 0.05 to 5 parts by mass, and preferably 0.25 to 2.5 parts by mass from the viewpoint of curability, relative to 100 parts by mass of the (A) polymerizable monomer.

[0023] 2-3 (C) Divalent Copper Compounds In the dental curable composition according to this embodiment, a divalent copper compound (C) is used as a catalyst. The divalent copper compound (C) is reduced by a saccharin compound (D) and a reducing agent for copper (E). It is presumed that the reduced copper compound undergoes a redox reaction with a peroxyester compound (B) to generate an initiating radical.

[0024] (C) The divalent copper compound may be a hydrate or anhydrous. Examples of divalent copper compounds that can be suitably used in this embodiment include copper(II) chloride, copper(II) sulfate pentahydrate, copper(II) nitrate, copper(II) trifluoromethanesulfonate, copper(II) acetate monohydrate, copper(II) acetylacetonate, copper(II) naphthenate, copper(II) salicylate, copper(II) benzoate, copper(II) methacrylate, copper(II) butyl phthalate, copper(II) gluconate, dichloro(1,10-phenanthroline)copper(II), ethylenediaminetetraacetate copper(II) disodium tetraacetate tetrahydrate, copper(II) dimethyldithiocarbamate, copper(II) diethylthiocarbamate, copper(II) hexafluoroacetylacetonate, bis(1,3-propanediamine)copper(II) dichloride, and bis(8-quinolinolato)copper(II). In the dental curable composition according to this embodiment, from the viewpoint of storage stability, it is preferable to use at least one of copper acetate (II) monohydrate and copper acetylacetonate (II) as the divalent copper compound (C). As the divalent copper compound (C), one kind may be used alone, or two or more kinds may be used in combination.

[0025] Furthermore, the blending amount of the divalent copper compound (C) in the dental curable composition according to this embodiment is 0.001 to 0.05 parts by mass, and preferably 0.005 to 0.03 parts by mass from the viewpoint of storage stability, relative to 100 parts by mass of the polymerizable monomer (A).

[0026] 2-4 (D) Saccharin compounds In the dental curable composition according to this embodiment, a saccharin compound (D) is used as a polymerization accelerator. It is presumed that the saccharin compound (D) accelerates the oxidation-reduction reaction by interacting with the divalent copper compound (C) and the reducing agent for copper (E).

[0027] (D) The saccharin compound is a compound represented by the following general formula (1). [ka] (Here, in general formula (1), M represents a hydrogen atom or a metal atom. R1 represents an alkyl group having 1 to 5 carbon atoms, an unsaturated chain hydrocarbon group having 2 to 5 carbon atoms, a halogen atom, a silyl group, or an alkylsilyl group. n represents an integer of 0 to 4. However, when n is 2 to 4 and multiple R1s are present, the multiple R1s may be the same or different.)

[0028] In the dental curable composition according to this embodiment, it is preferable to use at least one of saccharin, saccharin sodium, and saccharin denatonium as the saccharin compound (D), and it is more preferable to use saccharin from the viewpoint of solubility in the polymerizable monomer (A).

[0029] Furthermore, the blending amount of the (D) saccharin compound in the dental hardenable composition according to this embodiment is 0.05 to 2.5 parts by mass, and preferably 0.3 to 1 part by mass from the viewpoint of hardenability, relative to 100 parts by mass of the (A) polymerizable monomer.

[0030] 2-5 (E) Reducing agent for copper The dental hardenable composition according to this embodiment uses a copper reducing agent (E). The copper reducing agent (E) can be any compound capable of reducing the divalent copper contained in the divalent copper compound (C) to monovalent copper or zero-valent copper, and is not particularly limited. The dental hardenable composition according to this embodiment preferably uses at least one of the following reducing agents for copper (E): (e1) an aromatic amine compound having no electron-withdrawing group, (e2) a (thio)barbituric acid compound, (e3) a thiourea compound, and (e4) a heterocyclic thiol compound.

[0031] (e1) The aromatic amine compound having no electron-withdrawing group is characterized in that the aromatic ring does not have an electron-withdrawing group such as an ester group, an amide group, a nitrile group, or a nitro group. Examples of compounds used as the (e1) aromatic amine compound having no electron-withdrawing group include p-dimethylaminotoluidine, p-diethylaminotoluidine, p-diethanolaminotoluidine, p-dimethylaniline, and p-dimethylamino tertiary butylbenzene. In the dental curable composition according to this embodiment, it is preferable to use p-diethylaminotoluidine as the (e1) aromatic amine compound having no electron-withdrawing group, from the viewpoint of storage stability.

[0032] (e2) The (thio)barbituric acid compound is a compound represented by the following general formula (2). [ka] (Here, in general formula (2), X represents O or S. R2, R3, R4, and R5 each represent hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a halogen group such as a chloro group, a hydroxyl group, an amino group, or a nitro group. R2, R3, R 4、 and R5 may be the same or different.

[0033] (e2) Examples of (thio)barbituric acid compounds include barbituric acid, thiobarbituric acid, 1,3,5-trimethylbarbituric acid, 1-phenyl-5-benzylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 5-laurylbarbituric acid, 5-butylbarbituric acid, 5-allylbarbituric acid, 5-hydroxy-5-butylbarbituric acid, 5-phenylthiobarbituric acid, 1,3-dimethylthiobarbituric acid, 5,5-dibromobarbituric acid, trichlorobarbituric acid, 5-nitrobarbituric acid, 5-aminobarbituric acid, 5-hydroxybarbituric acid, and 5,5-dihydroxybarbituric acid. In the dental hardenable composition according to this embodiment, it is preferable to use 1-cyclohexyl-5-ethylbarbituric acid as the (thio)barbituric acid compound (e2) from the viewpoint of hardenability.

[0034] (e3) Thiourea compound refers to a compound having the structure =NC(=S)-N=. As (e3) thiourea compound, it is preferable to use a thiourea compound represented by the following general formula (3). [ka] (Here, in general formula (3), R6, R7, and R8 each represent a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted alkenyl group. R7 may bond with R6 or R8 to form a ring.)

[0035] In the dental hardenable composition according to this embodiment, it is preferable to use N-benzoylthiourea, (2-pyridyl)thiourea, or ethylenethiourea as the thiourea compound (e3) from the viewpoint of hardenability.

[0036] (e4) The heterocyclic thiol compound is a compound represented by the following general formula (4): [ka] (wherein, in general formula (4), X is O, S, or NR 11 Represents R9, R 10 , R 11 R and R each represent hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a halogen group such as a chloro group, a hydroxyl group, an amino group, or a nitro group. 10 , R 11 R may be the same or different. 10 may be bonded to R9 to form a ring.

[0037] Examples of the (e4) heterocyclic thiol compound include 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptooxazole, 2-mercaptoimidazole, 2-mercaptothiazole, 6-methyl-1,3-benzoxazole-2-thiol, 5-phenylbenzoxazole-2-thiol, 4,5-diphenyl-2-mercaptooxazole, etc. In the dental hardenable composition according to this embodiment, from the viewpoint of hardenability, it is preferable to use at least one of 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, and 2-mercaptobenzothiazole as the (e4) heterocyclic thiol compound, and it is more preferable to use 2-mercaptobenzoxazole.

[0038] In the dental hardenable composition according to this embodiment, from the viewpoint of aesthetics, it is preferable to use at least one of (e2) a (thio)barbituric acid compound, (e3) a thiourea compound, and (e4) a heterocyclic thiol compound as the reducing agent for copper (E). Furthermore, in the dental hardenable composition according to this embodiment, it is more preferable to use (e4) a heterocyclic thiol compound as the reducing agent for copper (E), taking into consideration hardenability. Only one type of (E) copper reducing agent may be used, or two or more types may be used in combination.

[0039] Furthermore, the blending amount of the reducing agent relative to (E) copper in the dental curable composition according to this embodiment is 0.05 to 2.5 parts by mass, and from the viewpoint of curing, is preferably 0.25 to 1 part by mass, per 100 parts by mass of (A) polymerizable monomer.

[0040] 2-6 Other ingredients The dental curable composition according to this embodiment may contain other components as appropriate, provided that the effects of the invention are not impaired. Examples of other components include (F) a filler, a polymerization inhibitor, an ultraviolet absorber, and a pigment.

[0041] Specifically, in the dental curable composition according to this embodiment, it is preferable to use at least one of silica, zirconia, silica-zirconia, and polymethacrylic acid as the (F) filler in order to improve polishability and mechanical strength. The (F) filler may be treated with a surface treatment agent, such as a silane coupling agent. The amount of the (F) filler is preferably 50 to 1500 parts by mass, more preferably 70 to 1000 parts by mass, per 100 parts by mass of the (A) polymerizable monomer.

[0042] In the dental curable composition according to this embodiment, for example, at least one of hydroquinone, hydroquinone monomethyl ether, and dibutylhydroxytoluene can be used as the polymerization inhibitor.

[0043] 3. Hardening behavior of dental hardenable compositions The dental hardenable composition is configured to be hardened in the oral cavity after preparation by mixing or other operations outside the oral cavity during patient treatment. For this reason, it is preferable that the dental hardenable composition does not harden outside the oral cavity from the viewpoint of ensuring sufficient time for preparation so as to ensure the reliability of treatment. On the other hand, it is preferable that the dental hardenable composition hardens easily inside the oral cavity from the viewpoint of reducing the burden on the patient due to restrictions on movement during hardening, etc. Based on these requirements, the dental hardenable composition according to this embodiment is configured to easily achieve both hardness in hardening outside the oral cavity and easy hardening in the oral cavity.

[0044] In this embodiment, assuming that the room temperature outside the oral cavity is 23°C, the extraoral curing behavior of the dental hardenable composition is evaluated based on the working time t1, which is the time required for the dental hardenable composition to start hardening after mixing the components ((A) to (E) above) at 23°C and maintaining the mixture at 23°C. For the dental hardenable composition, the working time t1 corresponds to the time required for various preparatory operations. Because the hardening reaction of the dental hardenable composition is an exothermic reaction, the working time t1 can be defined as the time from the start of mixing the components to the start of a temperature rise. For the dental hardenable composition according to this embodiment, the working time t1 is preferably appropriately long, for example, preferably 90 to 720 seconds, and more preferably 150 to 360 seconds.

[0045] In this embodiment, an example of a method for determining the operation time t1 of the dental hardenable composition will be described. FIG. 1 is a graph in which the horizontal axis represents the time elapsed since the start of mixing of the components, and the vertical axis represents the temperature of the dental hardenable composition. FIG. 1 also shows a curve obtained by plotting the measured temperature values ​​of the dental hardenable composition at each time. In this embodiment, the operation time t1 can be determined as the time at which the temperature changes from a constant linear portion to a monotonically increasing portion of the curve.

[0046] In this embodiment, the intraoral temperature is assumed to be 37°C, and the curing behavior of the dental curable composition in the oral cavity is evaluated based on the curing time t2, which is the time required for the dental curable composition to completely harden when the components (A) to (E) above) are mixed at 23°C and then maintained at 37°C. Because the curing reaction of the dental curable composition is an exothermic reaction, the curing time t2 can be defined as the time from the start of mixing the components until the temperature reaches an exothermic peak. For the dental curable composition according to this embodiment, the curing time t2 is preferably appropriately short, for example, preferably 120 to 600 seconds, and more preferably 150 to 300 seconds.

[0047] In this embodiment, an example of a method for determining the curing time t2 of a dental curable composition will be described. FIG. 2 is a graph in which the horizontal axis represents the time elapsed since the start of mixing of the components and the vertical axis represents the temperature of the dental curable composition. FIG. 2 shows a curve obtained by plotting the measured temperature values ​​of the dental curable composition at each time. In this embodiment, the curing time t2 can be determined as the time at which the exothermic peak is reached on the curve. The position of the exothermic peak on the curve can be obtained as the intersection of a horizontal line L1 tangent to the highest temperature portion of the curve and an extrapolated line L2 of the portion where the temperature rise can be considered to be substantially constant.

[0048] As described above, in the dental hardenable composition according to this embodiment, in order to achieve both resistance to hardening outside the oral cavity and ease of hardening inside the oral cavity, it is preferable that the manipulation time t1 be sufficiently longer than the hardening time t2. Specifically, in the dental hardenable composition according to this embodiment, in order to obtain more desirable hardening behavior as a dental material, it is preferable that the difference (t1-t2) between the manipulation time t1 (seconds) and the hardening time t2 (seconds) is 50 seconds or more.

[0049] 4. Kit for preparing dental hardenable composition The dental curable composition according to this embodiment is prepared as a kit consisting of a first agent and a second agent that are isolated from each other to prevent progress of curing during storage or distribution. In the kit according to this embodiment, the first agent and the second agent are isolated by an inhibitor that inhibits molecular diffusion between them, thereby preventing physical contact between them. Typically, in the kit according to this embodiment, the first agent and the second agent are individually contained and held in various containers, such as syringes, bags, and bottles, that serve as inhibitors. The containers and bags that contain the first agent and the second agent are preferably capable of blocking external air and external light, and can be formed, for example, from resin, glass, metal, ceramics, etc. However, the inhibitor is not limited to the above configuration as long as it can isolate the first agent and the second agent.

[0050] In the kit according to this embodiment, from the viewpoint of storage stability, it is preferable that the components contained in the first agent and the second agent are a combination of components that do not react with each other. From this viewpoint, for example, a combination of (B) a peroxyester compound and (C) a divalent copper compound, which do not react with each other, can be configured to be contained in the first agent but not in the second agent. In this case, a combination of (D) a saccharin compound and (E) a reducing agent for copper, which do not react with each other, can be configured to be contained in the second agent but not in the first agent. The (A) polymerizable monomer can be contained in at least one of the first agent and the second agent; that is, it may be contained in either the first agent or the second agent, or in both the first agent and the second agent.

[0051] 5. Working Example The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0052] 5-1 Raw materials First, the substances used as raw materials in the examples and comparative examples and their abbreviations are shown below.

[0053] -(A) polymerizable monomer Bis-GMA: 2,2'-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane 3G: Triethylene glycol dimethacrylate · D-2,6E: 2,2-bis(4-methacryloyloxypolyethoxyphenyl).

[0054] -(B) Peroxyester Compound BPT: t-butylperoxy-3,5,5-trimethylhexanoate ·BPB: t-butyl peroxybenzoate.

[0055] -(C) Divalent copper compounds Cu(acac)2: Acetylacetonate copper(II) Cu(OAc)2: Copper(II) acetate monohydrate · Cu(OTf)2: Copper(II) trifluoromethanesulfonate.

[0056] -(D) Saccharin compounds ·saccharin.

[0057] -(E) a reducing agent for copper CEBA: 1-cyclohexyl-5-ethyl-barbituric acid PEAT: N,N-diethylamino-p-toluidine BzTU: N-benzoylthiourea MBT: 2-mercaptobenzothiazole MBO: 2-mercaptobenzoxazole ·DEPT: p-Diethanolaminotoluidine · PyTU: (2-pyridyl)thiourea.

[0058] -(F) Filler · F1: Silica zirconia filler with an average particle size of 3 μm · F2: Silica zirconia filler with an average particle size of 0.2 μm.

[0059] -Other ingredients BHT: Dibutylhydroxytoluene BPO: Benzoyl peroxide ·TMBH: 1,1,3,3-tetramethylbutyl hydroperoxide.

[0060] 5-2 Preparation of dental hardenable composition Dental hardenable compositions were prepared for Examples 1 to 22 and Comparative Examples 1 to 6. Each dental hardenable composition according to each Example and Comparative Example was prepared as a kit consisting of a first part and a second part. That is, for each Example and Comparative Example, the dental hardenable composition was obtained by mixing the first part and the second part at a volume ratio of 1:1. Table 1 shows the compositions of the first and second parts according to Examples 1 to 22, excluding the (F) filler, and Table 2 shows the compositions of the first and second parts according to Comparative Examples 1 to 6, excluding the (F) filler. In each of Examples 1 to 22 and Comparative Examples 1 to 6, 75 parts by mass of F1 and 50 parts by mass of F2 were added to the first and second parts, respectively. In Tables 1 and 2, the parenthesized numbers for each component indicate the amount (parts by mass) of each component, and an upward arrow indicates the same composition as the column immediately above.

[0061] Example 1 will be specifically described. A first agent was prepared by mixing 50 parts by weight of (A) polymerizable monomer consisting of 5 parts by weight of Bis-GMA, 20 parts by weight of 3G, and 25 parts by weight of D-2,6E with 1.5 parts by weight of BPT, 0.01 parts by weight of Cu(acac)2, 75 parts by weight of F1, and 50 parts by weight of F2. A second agent was prepared by mixing 50 parts by weight of (A) polymerizable monomer consisting of 5 parts by weight of Bis-GMA, 20 parts by weight of 3G, and 25 parts by weight of D-2,6E with 0.75 parts by weight of saccharin, 0.5 parts by weight of MBO, 75 parts by weight of F1, and 50 parts by weight of F2. The first and second agents thus prepared were filled into the paste container of an automix syringe "Estecem II" (manufactured by Tokuyama Dental Co., Ltd.). When mixing the first and second agents to obtain a dental hardenable composition, a mixing tip for cement (manufactured by Tokuyama Dental Co., Ltd.) was attached to the tip of the paste container, and equal amounts of the first and second agents were mixed at a volume ratio of 1:1 to obtain a dental hardenable composition.

[0062] For Examples 2 to 22 and Comparative Examples 1 to 6, dental curable compositions were prepared in the same manner as in Example 1 above, except that only the composition was changed as shown in Tables 1 and 2.

[0063] [Table 1]

[0064] [Table 2]

[0065] 5-3 Evaluation of dental hardenable compositions The dental curable compositions according to Examples 1 to 22 and Comparative Examples 1 to 6 were evaluated for working time t1 and curing time t2.

[0066] For the operation time t1, the first and second parts of the dental hardenable compositions of each Example and Comparative Example were mixed at a volume ratio of 1:1 using a mixing tip, and the resulting composition was immediately loaded into a mold for a thermocouple device maintained at 23±1°C. In the resulting curve, the starting point, which deviates from the linear portion where the temperature remained constant after loading and moves toward a higher temperature over time, was determined, and the operation time t1 was defined as the time from the start of mixing to the starting point. For each dental hardenable composition, an operation time t1 of 90 seconds or longer was considered to be satisfactory. Furthermore, for each dental hardenable composition, if no hardening was confirmed after 720 seconds, it was considered to be "unhardened."

[0067] For the curing time t2, the first and second parts of each dental hardenable composition of each Example and Comparative Example were mixed at a volume ratio of 1:1 using a mixing tip, and the resulting composition was placed in a mold of a thermocouple device maintained at 37±1°C 30 seconds after mixing. The intersection of the horizontal line tangent to the highest temperature and the extrapolated line of the portion where the temperature rise could be considered substantially constant was determined for the resulting curve. The curing time t2 was determined as the time from the start of mixing to the intersection. For each dental hardenable composition, a curing time t2 of 600 seconds or less was considered to be satisfactory. Furthermore, for each dental hardenable composition, if no hardening was confirmed after 600 seconds, it was considered to be "unhardened."

[0068] Furthermore, the difference (t1-t2) between the operation time t1 (seconds) and the curing time t2 (seconds) was calculated using the operation time t1 and the curing time t2 calculated as described above for the dental curable compositions of Examples 1 to 22 and Comparative Examples 1 to 6. For each dental curable composition, a difference (t1-t2) of 50 seconds or more was determined to be good.

[0069] Table 3 shows the evaluation results of the dental curable compositions according to Examples 1 to 22, and Table 4 shows the evaluation results of the dental curable compositions according to Comparative Examples 1 to 6. Tables 3 and 4 also show the pass / fail judgment results, in which a sample was deemed to have passed if the operation time t1, the curing time t2, and t1-t2 were all satisfactory, and a sample was deemed to have failed if at least one of the operation time t1, the curing time t2, and t1-t2 was not satisfactory.

[0070] As shown in Table 3, all of the dental curable compositions according to Examples 1 to 22 passed the test. On the other hand, as shown in Table 4, all of the dental curable compositions according to Comparative Examples 1 to 6 failed the test. Specifically, Comparative Example 1, which did not contain (B) a peroxyester compound, Comparative Example 2, which did not contain (C) a divalent copper compound, Comparative Example 3, which did not contain (D) a saccharin compound, and Comparative Example 4, which did not contain a reducing agent for copper, failed because they were not cured. Furthermore, Comparative Examples 5 and 6, which used a chemical polymerization initiator with a different configuration from the above embodiment, failed because t1-t2 was less than 50 seconds.

[0071] Table 3

[0072] Table 4

Claims

1. 100 parts by mass of (A) polymerizable monomer; 0.05 to 5 parts by mass of a peroxyester compound (B); 0.001 to 0.05 parts by mass of (C) a divalent copper compound; 0.05 to 2.5 parts by mass of a saccharin compound (D) represented by the following general formula (1); 0.05 to 2.5 parts by mass of (E) a reducing agent for copper; Contains When the time from mixing (A) to (E) at 23°C until the temperature starts to rise while maintaining the temperature at 23°C is t1 (seconds), and the time from maintaining the temperature at 37°C until the temperature reaches an exothermic peak while maintaining the temperature at 37°C is t2 (seconds), t1 - t2 is 50 seconds or more. A dental hardenable composition comprising: 【Chemistry 1】 (In general formula (1), M represents a hydrogen atom or a metal atom. R 1 represents an alkyl group having 1 to 5 carbon atoms, an unsaturated chain hydrocarbon group having 2 to 5 carbon atoms, a halogen atom, a silyl group, or an alkylsilyl group. n represents an integer of 0 to 4. However, when n is 2 to 4 and multiple R 1 s are present, the multiple R 1 s may be the same or different.)

2. (E) is at least one of (e1) an aromatic amine compound having no electron-withdrawing group, (e2) a (thio)barbituric acid compound, (e3) a thiourea compound, and (e4) a heterocyclic thiol compound. The dental hardenable composition according to claim 1 .

3. Further contains 50 to 1500 parts by mass of (F) filler.

3. The dental hardenable composition according to claim 1 or 2.

4. It is composed of a first agent and a second agent that are isolated from each other, (A) is contained in at least one of the first agent and the second agent, (B) and (C) are contained in the first agent but not in the second agent; The (D) and the (E) are not contained in the first agent but are contained in the second agent.

2. A kit for preparing the dental hardenable composition according to claim 1.

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