JP2024017014A - Dental curable composition and kit - Google Patents

Abstract

PROBLEM TO BE SOLVED: 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

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to a curable composition that initiates polymerization by reacting an oxidizing agent and a reducing agent. In particular, the present invention relates to a dental curable composition having good curing behavior.

Materials based on (meth)acrylates are used in a wide range of fields such as paints, printing materials, adhesives and dental materials. For example, in the dental field, it is applied to various materials such as bonding materials, resin cements, resin-reinforced glass ionomers, and composite resins. These materials are typically cured by radical polymerization. Radicals are generated using one or more polymerization initiators selected from photopolymerization initiators, thermal polymerization initiators, and chemical (redox) polymerization initiators depending on the purpose.

Among these polymerization initiators, chemical polymerization initiators are particularly useful in applications where it is difficult to apply light or heat stimulation. Since chemical polymerization initiators contain a combination of a reducing agent and an oxidizing agent that can react immediately upon contact, they usually need to be stored in two or more separate parts. Examples of storage formats for storing chemical polymerization initiators separately include paste/paste, liquid/liquid, powder/liquid, and liquid/paste combinations.

It is desirable that the chemical polymerization initiator used for dental materials has temperature dependence of curing behavior such that curing is difficult to proceed at room temperature and hardening is easy to proceed in the oral cavity. A chemical polymerization initiator that has been known for a long time includes a chemical polymerization initiator that combines benzoyl peroxide and a tertiary aromatic amine compound. However, with this chemical polymerization initiator, the temperature dependence of curing behavior is small, and it is difficult to obtain the temperature dependence of curing behavior as described above. In addition, benzoyl peroxide has poor storage stability due to its low thermal stability.

On the other hand, in Patent Documents 1 and 2, radical polymerization initiators with improved storage stability are proposed. This radical polymerization initiator uses hydroperoxide as an oxidizing agent and various thiourea derivatives as a reducing agent. Hydroperoxide has high thermal stability and excellent storage stability compared to benzoyl peroxide and the like. However, even with this radical polymerization initiator, 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.

Japanese Patent Application Publication No. 2014-227370 International publication WO2014/156077 pamphlet

An object of the present invention is to provide a dental curable composition having a desirable curing behavior as a dental material.

The present inventors investigated dental curable compositions in order to solve the above problems. As a result, a dental curable composition having hardening behavior desirable as a dental material was discovered.
That is, the dental curable composition according to one embodiment of the present invention is
100 parts by mass of (A) polymerizable monomer,
0.05 to 5 parts by mass of (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 (D) saccharin compound,
0.05 to 2.5 parts by mass of (E) a reducing agent for copper;
It is characterized by containing.

The dental curable composition is characterized in that (E) comprises (e1) an aromatic amine compound having no electron-withdrawing group, (e2) a (thio)barbituric acid compound, and (e3) a thiourea compound. , (e4) a heterocyclic thiol compound.

In the above dental curable composition, the time from mixing the above (A) to (E) at 23°C until the temperature starts to rise after being held at 23°C is t1 (seconds), and at 37°C. If the time required for the temperature to reach the exothermic peak during holding is t2 (seconds), then t1-t2 is preferably 50 seconds or more.

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

A kit for preparing the dental curable composition according to one embodiment of the present invention includes:
Consisting of a first agent and a second agent that are isolated from each other,
(A) is included in at least one of the first agent and the second agent,
(B) and (C) are included in the first agent and not included in the second agent,
The above (D) and the above (E) are not included in the first agent but are included in the second agent.

According to the present invention, a dental curable composition having a desirable curing behavior as a dental material can be provided.

It is a graph for explaining operation time t1 of a dental curable composition. It is a graph for explaining the curing time t2 of the dental curable composition.

1. Overview of dental curable composition The dental curable composition according to one embodiment of the present invention is configured so that it can be suitably used as a dental material such as, for example, dental resin cement or dental abutment construction material. has been done. The dental curable composition according to the present embodiment comprises (A) a polymerizable monomer, (B) a peroxyester compound, (C) a divalent copper compound, (D) a saccharin compound, ( E) Contains a reducing agent for copper. Hereinafter, components that may be included in the dental curable composition according to this embodiment will be explained in detail.

In this specification, unless otherwise specified, the notation "x to y" using numerical values x and y means "more than or equal to x and less than or equal to y." In such a notation, when a unit is attached only to the numerical value y, the unit shall also be applied to the numerical value x. In addition, in this specification, the term "(meth)acrylate" means both "acrylate" and "methacrylate", and the term "(meth)acryloyl" means both "acryloyl" and "methacryloyl". means.

2. Constituent Components of Dental Curable Composition 2-1 (A) Polymerizable Monomer In the dental curable composition according to this embodiment, (A) polymerizable monomer is used as the main component. (A) The polymerizable monomer 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).

As the polymerizable monomer (A), any known compound can be used without particular limitation as long as it contains one or more radically polymerizable unsaturated groups in one molecule. 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, at least one of an acryloyl group, a methacryloyl group, an acrylamide group, and a methacrylamide group is used as the polymerizable monomer (A). It is preferable to use a compound containing a saturated group.

Examples of monofunctional monomers and polyfunctional monomers that can be suitably used as the polymerizable monomer (A) 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, and polyethylene. Examples include glycol mono(meth)acrylate, allyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, and glyceryl mono(meth)acrylate. In addition, 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 and the like can be mentioned. (A) As the polymerizable monomer, only one type may be used, or two or more types may be used in combination.

2-2 (B) Peroxyester compound In the dental curable composition of this embodiment, (B) a peroxyester compound is used as an oxidizing agent. (B) The peroxyester compound generates initiating radicals necessary for curing through a redox reaction with (C) a divalent copper compound, (D) a saccharin compound, and (E) a reducing agent for copper. Guessed.

(B) Peroxyester compound refers to R-C(=O)-O-O-R' (where R and R' are any organic groups), or R-O-C(=O)-O It is a compound having a structure represented by -OR' (where R and R' are arbitrary organic groups). In this embodiment, a peroxyester compound having such a structure can be used as the oxidizing agent without any particular restriction. Specific examples of peroxy ester compounds that can be suitably used in this embodiment include cumyl peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxydecanoate, t-hexyl peroxy Neodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexano ate, 2,5-dimethyl 2,5-di(2-ethylhexanoylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, t-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, t-butylperoxybenzoate, etc. be able to. In the dental curable composition according to the present embodiment, from the viewpoint of polymerization activity and storage stability, it is preferable to use a peroxyester compound having a 10-hour half-life temperature of 80°C or higher as the peroxyester compound (B). Preferably, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxyacetate, t-butyl peroxy Particular preference is given to using at least one oxybenzoate. (B) As the peroxyester compound, only one type may be used, or two or more types may be used in combination.

Further, the blending amount of the (B) peroxyester compound in the dental curable composition according to the present embodiment is 0.05 to 5 parts by mass when the (A) polymerizable monomer is 100 parts by mass. From the viewpoint of curability, the amount is preferably 0.25 to 2.5 parts by mass.

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

(C) The divalent copper compound may be a hydrate or an anhydride. 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, and acetic acid. Copper (II) monohydrate, copper (II) acetylacetone, copper (II) naphthenate, copper (II) salicylate, copper (II) benzoate, copper (II) methacrylate, copper (II) butyl phthalate, Copper(II) gluconate, copper(II) dichloro(1,10-phenanthroline), copper(II) ethylenediaminetetraacetate disodium tetrahydrate, copper(II) dimethyldithiocarbamate, copper(II) diethylthiocarbamate , hexafluoroacetylacetonatocopper(II), bis(1,3-propanediamine)copper(II) dichloride, bis(8-quinolinolato)copper(II), and the like. In the dental curable composition according to the present embodiment, from the viewpoint of storage stability, at least one of copper(II) acetate monohydrate and copper(II) acetylacetone is used as the divalent copper compound (C). It is preferable to use (C) As the divalent copper compound, only one type may be used, or two or more types may be used in combination.

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

2-4 (D) Saccharin Compound In the dental curable composition according to this embodiment, (D) a saccharin compound is used as a polymerization accelerator. It is presumed that the saccharin compound (D) promotes the redox reaction through interaction with the divalent copper compound (C) and the reducing agent for copper (E).

(D) The saccharin compound is a compound represented by the following general formula (1).
(Here, in general formula (1), M represents a hydrogen atom or a metal atom. R ₁ is an alkyl group having 1 to 5 carbon atoms, or an unsaturated chain hydrocarbon group having 2 to 5 carbon atoms. , represents 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 _1s exist, the multiple R _1s are the same. (It may be different or different.)

In the dental curable composition according to the present embodiment, it is preferable to use at least one of saccharin, saccharin sodium, and saccharin denatonium as the (D) saccharin compound, and (A) the solubility in the polymerizable monomer is From this point of view, it is more preferable to use saccharin.

Further, the amount of the saccharin compound (D) in the dental curable composition according to the present embodiment is 0.05 to 2.5 parts by mass when the polymerizable monomer (A) is 100 parts by mass. From the viewpoint of curability, the amount is preferably 0.3 to 1 part by mass.

2-5 (E) Reducing agent for copper In the dental curable composition according to this embodiment, (E) a reducing agent for copper is used. (E) As a reducing agent for copper, any compound having the ability to reduce divalent copper contained in the divalent copper compound to monovalent copper or zero-valent copper can be used without particular restriction. can. In the dental curable composition according to the present embodiment, (E) as a reducing agent for copper, (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 are preferably used.

(e1) The aromatic amine compound having no electron-withdrawing group is characterized in that the aromatic ring does not have an electron-withdrawing group represented by an ester group, an amide group, a nitrile group, a nitro group, or the like. (e1) Compounds used as aromatic amine compounds having no electron-withdrawing group include, for example, p-dimethylaminotoluidine, p-diethylaminotoluidine, p-diethanolaminotoluidine, p-dimethylaniline, p-dimethylaminotoluidine, and p-dimethylaminotoluidine. Li-butylbenzene and the like can be mentioned. In the dental curable composition according to the present embodiment, from the viewpoint of storage stability, p-diethylaminotoluidine is preferably used as (e1) the aromatic amine compound having no electron-withdrawing group.

(e2) The (thio)barbituric acid compound is a compound represented by the following general formula (2).
(Here, in general formula (2), X represents O or S. _{R 2} , R ₃ , R ₄ and R ₅ are each hydrogen, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, halogen group such as chloro group, hydroxyl group, amino group, or nitro group. R ₂ , R ₃ , R _{4 ,} and R ₅ may be the same or different.)

(e2) (Thio)barbituric acid compounds include, for example, barbituric acid, thiobarbituric acid, 1,3,5-trimethylbarbituric acid, 1-phenyl-5-benzylbarbituric acid, 1-benzyl- 5-phenyl-barbituric 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, Examples include trichlorobarbituric acid, 5-nitrobarbituric acid, 5-aminobarbituric acid, 5-hydroxybarbituric acid, 5,5-dihydroxybarbituric acid and the like. In the dental curable composition according to this embodiment, from the viewpoint of curability, it is preferable to use 1-cyclohexyl-5-ethylbarbituric acid as the (e2) (thio)barbituric acid compound.

(e3) Thiourea compound refers to a compound having the structure =NC(=S)-N=. (e3) As the thiourea compound, it is preferable to use a thiourea compound represented by the following general formula (3).
(Here, in general formula (3), R ₆ , R ₇ and R ₈ are each a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted Represents an 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. _{R 7} is bonded to R ₆ or R ₈ may form a ring.)

In the dental curable composition according to the present embodiment, from the viewpoint of curability, it is preferable to use N-benzoylthiourea, (2-pyridyl)thiourea, or ethylenethiourea as the (e3) thiourea compound.

(e4) The heterocyclic thiol compound is a compound represented by the following general formula (4).
(Here _, in general formula ( _{4 ) ,} Represents a substituted 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. _{R 9} , R ₁₀ , and R ₁₁ are , may be the same or different. R ₁₀ may be combined with R ₉ to form a ring.)

(e4) Examples of the heterocyclic thiol compound include 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptooxazole, 2-mercaptoimidazole, 2-mercaptothiazole, 6-methyl- Examples include 1,3-benzoxazole-2-thiol, 5-phenylbenzoxazole-2-thiol, and 4,5-diphenyl-2-mercaptooxazole. In the dental curable composition according to the present embodiment, from the viewpoint of curability, at least one of 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, and 2-mercaptobenzothiazole is used as the (e4) heterocyclic thiol compound. It is preferable to use 2-mercaptobenzoxazole, and more preferably 2-mercaptobenzoxazole.

In the dental curable composition according to the present embodiment, from the aesthetic point of view, (E) as a reducing agent for copper, (e2) (thio)barbituric acid compound, (e3) thiourea compound, (e4) complex Preferably, at least one cyclic thiol compound is used. Further, in the dental curable composition according to the present embodiment, in consideration of curability, it is more preferable to use (e4) a heterocyclic thiol compound as the (E) reducing agent for copper. (E) As the reducing agent for copper, only one type may be used, or two or more types may be used in combination.

In addition, the amount of the reducing agent for (E) copper in the dental curable composition according to the present embodiment is 0.05 to 2.5 parts by mass when the amount of (A) polymerizable monomer is 100 parts by mass. part, and from the viewpoint of curing, it is preferably 0.25 to 1 part by mass.

2-6 Other Components The dental curable composition according to the present embodiment may contain other components as appropriate to the extent that the effects of the invention are not impaired. Examples of other components include (F) fillers, polymerization inhibitors, ultraviolet absorbers, and pigments.

Specifically, in the dental curable composition according to the present embodiment, at least one of silica, zirconia, silica-zirconia, and polymethacrylic acid is used as the filler (F) in order to improve polishability and mechanical strength. Preferably, one is used. (F) The filler may be treated with a surface treatment agent, such as a silane coupling agent. The blending amount of the filler (F) is preferably 50 to 1,500 parts by mass, more preferably 70 to 1,000 parts by mass, based on 100 parts by mass of the polymerizable monomer (A).

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

3. Curing behavior of dental curable composition The dental curable composition is configured to be prepared by operations such as mixing outside the oral cavity during patient treatment, and then cured within the oral cavity. Therefore, in the dental curable composition, it is preferable that hardening is difficult to proceed outside the oral cavity from the viewpoint of ensuring sufficient time for preparation so as to ensure reliability of treatment. On the other hand, in the dental curable composition, it is preferable that the curing progresses easily in the oral cavity from the viewpoint of reducing the burden on the patient due to restrictions on movement during curing. Based on such requirements, the dental curable composition according to the present embodiment is configured to easily achieve both of hardening that hardens outside the oral cavity and hardens that hardens easily inside the oral cavity. has been done.

In this embodiment, assuming that the room temperature outside the oral cavity is 23°C, the hardening behavior of the dental curable composition outside the oral cavity is evaluated by mixing each component ((A) to (E) above) at 23°C. The evaluation is based on the operating time t1 until the dental curable composition starts to harden when the dental curable composition is maintained at 23°C. For dental curable compositions, the operation time t1 corresponds to the time during which various operations for preparation are possible. In the dental curable composition, since the reaction during curing is an exothermic reaction, the operation time t1 can be defined as the time from the time when mixing of each component is started until the temperature starts to rise. In the dental curable composition according to the present embodiment, the operation time t1 is preferably appropriately long, for example, preferably 90 to 720 seconds, more preferably 150 to 360 seconds.

An example of a method for determining the operation time t1 of the dental curable composition in this embodiment will be described. FIG. 1 is a graph in which the horizontal axis is the elapsed time from the time when mixing of each component was started, and the vertical axis is the temperature of the dental curable composition. FIG. 1 shows a curve obtained by plotting the measured temperature of the dental curable composition at each time. In this embodiment, the time at which the temperature changes from a constant straight line portion to a monotonically increasing point in the curve can be set as the operation time t1.

In addition, in this embodiment, assuming that the temperature in the oral cavity is 37°C, the curing behavior of the dental curable composition in the oral cavity is evaluated by adding each component ((A) to (E) above) at 23°C. The evaluation is based on the curing time t2 until the curing of the dental curable composition is completed when the dental curable composition is held at 37° C. after mixing. In the dental curable composition, since the reaction during curing is an exothermic reaction, the curing time t2 can be defined as the time from the time when mixing of each component is started until the temperature reaches the exothermic peak. In the dental curable composition according to the present embodiment, the curing time t2 is preferably appropriately short, for example, preferably 120 to 600 seconds, more preferably 150 to 300 seconds.

In this embodiment, an example of a method for determining the curing time t2 of the dental curable composition will be described. FIG. 2 is a graph in which the horizontal axis is the elapsed time from the time when mixing of each component was started, and the vertical axis is the temperature of the dental curable composition. FIG. 2 shows a curve obtained by plotting the measured temperature of the dental curable composition at each time. In this embodiment, the time to reach the exothermic peak in the curve can be set as the curing time t2. The position of the exothermic peak in the curve can be obtained as the intersection of the horizontal straight line L1 that is in contact with the highest temperature part of the curve and the extrapolated line L2 of the part where the temperature rise can be considered to be substantially constant.

As mentioned above, in the dental curable composition according to the present embodiment, the operating time t1 is longer than the curing time t2 in order to achieve both the difficulty of curing outside the oral cavity and the ease of curing within the oral cavity. It is preferable that it be long. Specifically, in the dental curable composition according to the present embodiment, in order to obtain more desirable curing behavior as a dental material, the difference (t1-t2) between the operation time t1 (seconds) and the curing time t2 (seconds) is preferably 50 seconds or more.

4. Kit for preparing dental curable composition The dental curable composition according to the present embodiment includes a first agent and a second agent that are separated from each other in order to prevent the progress of hardening during storage and distribution. It is prepared as a kit consisting of two drugs. In the kit according to the present embodiment, the first agent and the second agent are separated by an inhibiting member that inhibits molecular diffusion between them, so that they cannot physically come into contact with each other. Typically, in the kit according to the present embodiment, the first agent and the second agent are individually housed in various containers such as syringes, bags, bottles, etc. as inhibiting members. The container or bag containing the first and second agents is preferably capable of blocking outside air and light, and can be made of, for example, resin, glass, metal, ceramics, or the like. However, the inhibiting member is not limited to the above configuration as long as it can isolate the first agent and the second agent.

In the kit according to the present embodiment, from the viewpoint of storage stability, it is preferable that both the components contained in the first agent and the components contained in the second agent be a combination of components that do not react with each other. From this point of view, for example, the combination of (B) peroxyester compound and (C) divalent copper compound, which do not react with each other, is included in the first part and not included in the second part. be able to. 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 included in the second part and not included in the first part. (A) The polymerizable monomer can be included in at least one of the first agent and the second agent, that is, even if it is included in either the first agent or the second agent, the polymerizable monomer and the second agent.

5. Examples Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

5-1 Raw materials First, each substance used as a raw material in Examples and Comparative Examples and its abbreviations are shown below.

-(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).

-(B) Peroxy ester compound - BPT: t-butyl peroxy-3,5,5-trimethylhexanoate - BPB: t-butyl peroxy-benzoate.

-(C) Divalent copper compound Cu(acac)2: acetylacetone copper(II)
-Cu(OAc)2: Copper(II) acetate monohydrate.Cu(OTf)2: Copper(II) trifluoromethanesulfonate.

-(D) Saccharin compound/saccharin.

-(E) 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.

-(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.

-Other components・BHT: dibutylhydroxytoluene・BPO: benzoyl peroxide・TMBH: 1,1,3,3-tetramethylbutyl hydroperoxide.

5-2 Preparation of dental curable composition Dental curable compositions were prepared for Examples 1 to 22 and Comparative Examples 1 to 6. Each dental curable composition according to each Example and Comparative Example was prepared as a kit consisting of a first part and a second part. That is, in each of the Examples and Comparative Examples, a dental curable composition is obtained by mixing the first agent and the second agent at a volume ratio of 1:1. Table 1 shows the compositions other than the (F) filler of the first and second parts according to Examples 1 to 22, and Table 2 shows the compositions other than the (F) filler of the first and second parts according to Comparative Examples 1 to 6. Indicates composition other than filler. In any 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 as (F) filler to each of the first and second agents. . In Tables 1 and 2, the numerical value in parentheses for each component represents the amount (parts by mass) of each component, and the upward arrow means the same configuration as in the column directly above.

Example 1 will be specifically described. Bis-GMA: 5 parts by mass, 3G: 20 parts by mass, D-2,6E: 25 parts by mass (A) polymerizable monomer: 50 parts by mass, BPT: 1.5 parts by mass, Cu (acac A first agent was prepared by mixing 0.01 parts by mass of )2, 75 parts by mass of F1, and 50 parts by mass of F2. In addition, (A) polymerizable monomer: 50 parts by mass consisting of Bis-GMA: 5 parts by mass, 3G: 20 parts by mass, D-2,6E: 25 parts by mass, saccharin: 0.75 parts by mass, MBO : 0.5 parts by mass, F1: 75 parts by mass, and F2: 50 parts by mass to prepare a second agent. The first agent and second agent prepared in this way were filled into a paste container of an automix syringe "Estecem II" (manufactured by Tokuyama Dental Co., Ltd.). In addition, when mixing the first agent and the second agent to obtain a dental curable composition, attach a mixing tip for cement (manufactured by Tokuyama Dental Co., Ltd.) to the tip of the paste container, and mix the first agent and the second agent. and the second agent were mixed in equal amounts at a volume ratio of 1:1 to obtain a dental curable composition.

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

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

For the operation time t1, a composition obtained by mixing the first and second parts of the dental curable compositions according to each example and comparative example at a volume ratio of 1:1 using a mixing tip, Immediately after mixing, the mixture was placed into a mold of a thermocouple device maintained at 23±1°C. In the obtained curve, the starting point that moves away from the straight line part where the temperature became constant after charging toward the high temperature side with time was determined, and the time from the time when mixing was started to the starting point was defined as the operation time t1. Each dental curable composition was judged to be good when the operation time t1 was 90 seconds or more. Further, each dental curable composition was judged to be "uncured" if no curing was confirmed even after 720 seconds.

Regarding the curing time t2, a composition obtained by mixing the first part and the second part of the dental curable composition according to each example and comparative example at a volume ratio of 1:1 using a mixing tip, After 30 seconds of mixing, it was placed in a mold in a thermocouple device maintained at 37±1°C. In the obtained curve, find the intersection of the horizontal line touching the highest temperature part and the extrapolated line of the part where the temperature rise is considered to be substantially constant, and calculate the curing time from the time when mixing started to the intersection. It was set as t2. Each dental curable composition was judged to be good if the curing time t2 was within 600 seconds. In addition, each dental curable composition was judged to be "uncured" if no curing was confirmed even after 600 seconds.

Further, for the dental curable compositions according to Examples 1 to 22 and Comparative Examples 1 to 6, the operating time t1 (seconds) and the curing time t2 ( The difference (t1-t2) between the two seconds (seconds) was calculated. Each dental curable composition was judged to be good if t1-t2 was 50 seconds or more.

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. In addition, in Tables 3 and 4, if the operation time t1, curing time t2, and t1-t2 are all good, it is considered to be a pass, and at least one of the operation time t1, curing time t2, and t1-t2 is The result of the pass/fail judgment is shown, in which the test is judged as a failure if the test is not satisfactory.

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. Specifically, (B) Comparative Example 1 which does not contain a peroxyester compound, (C) Comparative Example 2 which does not contain a divalent copper compound, (D) Comparative Example 3 which does not contain a saccharin compound, and (E) Copper. Comparative Example 4, which did not contain a reducing agent, was rejected due to uncured. Furthermore, Comparative Examples 5 and 6 using chemical polymerization initiators with different configurations from those of the above embodiments were rejected because t1-t2 was less than 50 seconds.

Claims (5)

100 parts by mass of (A) polymerizable monomer,
0.05 to 5 parts by mass of (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 (D) saccharin compound,
0.05 to 2.5 parts by mass of (E) a reducing agent for copper;
A dental curable composition comprising: (E) is (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 curable composition according to claim 1, characterized in that it is at least one of the following. After mixing the above (A) to (E) at 23 ° C., the time from when the mixture is held at 23 ° C. until the temperature starts to rise is t1 (seconds), and when the temperature is held at 37 ° C., the temperature reaches the exothermic peak. 2. The dental curable composition according to claim 1, wherein t1-t2 is 50 seconds or more, where t2 (seconds) is the time it takes to achieve this. The dental curable composition according to any one of claims 1 to 3, further comprising 50 to 1500 parts by mass of (F) filler. Consisting of a first agent and a second agent that are isolated from each other,
(A) is included in at least one of the first agent and the second agent,
(B) and (C) are included in the first agent and not included in the second agent,
The kit for preparing a dental curable composition according to claim 1, wherein the (D) and the (E) are not included in the first agent but are included in the second agent.

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