JP6892319B2 - Curable composition containing an alicyclic (meth) acrylic compound - Google Patents

Description

The present invention relates to a curable composition or the like suitable for dental materials or the like containing a specific alicyclic (meth) acrylic compound.

Dental materials such as dental composite resins, dental cements, dental adhesives and dental primers are commonly used to fill or coat restorations in tooth defects.

Among these dental materials, especially dental composite resins and dental cements are required to have mechanical characteristics and color tones similar to those of teeth, that is, aesthetics. Specifically, mechanical properties include strength, elastic modulus, toughness, hardness, and the like, and aesthetics include color, glossiness, and the like. Furthermore, in recent years, there has been an increasing demand for ease of handling of dental materials, that is, operability. Specifically, it is easy to extrude dental materials when they are packed in a syringe and used, and a large amount is used at one time. It is important to be able to fill.

In general, inorganic particles are blended as a means for imparting strength, but when inorganic particles are blended, the toughness tends to decrease and the particles tend to be brittle and fragile. Inorganic particles with a small particle size tend to be used in order to achieve both strength and toughness, as well as aesthetics such as abrasiveness and luster. However, when inorganic particles having a small particle size are blended, there is a problem that the viscosity increases, it becomes difficult to extrude, and the operability decreases.

The following techniques are known as techniques having excellent mechanical characteristics, aesthetics, and operability. Patent Document 1 reports a dental composition having improved transparency by containing an adamantane derivative. Patent Document 2 reports a composition that improves photosensitivity, air-drying property, hardness of a cured film, and the like by containing an isosorbide derivative, and suppresses defects such as curling of the cured film.

Japanese Unexamined Patent Publication No. 2009-84221 Japanese Unexamined Patent Publication No. 2011-84535

The dental composition of Patent Document 1 is excellent in transparency, but the mechanical characteristics are not specifically described, and nothing is described about operability. On the other hand, the composition containing the isosorbide derivative described in Patent Document 2 has insufficient mechanical characteristics as a dental material, and does not specifically describe aesthetics and operability.

Therefore, the present invention provides a curable composition that can provide a cured product having excellent mechanical properties and aesthetic properties and is also excellent in operability, a method for producing a cured product that cures the curable composition, and the present invention. It is an object of the present invention to provide a method for curing a curable composition, which cures the curable composition.

（式中、Ｒ¹及びＲ²はそれぞれ独立して（メタ）アクリロイル基であり、Ｘは２価の非置換又は置換された炭化水素基であり、ｍ及びｎはそれぞれ独立して０〜３０の整数である。）
で表される脂環式（メタ）アクリル化合物（Ａ）−Ｉ、及び下記一般式〔II〕

（式中、Ｒ³及びＲ⁴はそれぞれ独立して（メタ）アクリロイル基であり、Ｙ及びＺはそれぞれ独立して２価の非置換又は置換された炭化水素基であり、ｐ及びｑはそれぞれ独立して０〜３０の整数である。）
で表される脂環式（メタ）アクリル化合物（Ａ）−IIからなる群から選ばれる少なくとも１種であり、
無機粒子（Ｃ）の平均粒子径が０．００１〜１０μｍである、硬化性組成物である。 The present invention that has achieved the above object contains an alicyclic (meth) acrylic compound (A), a polymerization initiator (B) and inorganic particles (C), and the alicyclic (meth) acrylic compound (A) is , The following general formula [I]

(In the formula, R ¹ and R ² are independently (meth) acryloyl groups, X is a divalent unsubstituted or substituted hydrocarbon group, and m and n are independently 0 to 30 respectively. Is an integer of.)
The alicyclic (meth) acrylic compound (A) -I represented by, and the following general formula [II].

(In the formula, R ³ and R ⁴ are independently (meth) acryloyl groups, Y and Z are independently divalent unsubstituted or substituted hydrocarbon groups, and p and q are respectively. It is an integer from 0 to 30 independently.)
It is at least one selected from the group consisting of alicyclic (meth) acrylic compounds (A) -II represented by.
A curable composition having an average particle size of the inorganic particles (C) of 0.001 to 10 μm.

In one embodiment, the alicyclic (meth) acrylic compound (A) is an alicyclic (meth) acrylic compound (A) -I represented by the general formula [I], where X has 2 to 6 carbon atoms. It is preferably an alkylene group of.

In another embodiment, the alicyclic (meth) acrylic compound (A) is an alicyclic (meth) acrylic compound (A) -II represented by the general formula [II], and Y and Z are It is preferable that each of them is an alkylene group having 2 to 6 carbon atoms independently.

It is preferable that ^{R 1} , R ² , R ³ and R ^{4 of the} alicyclic (meth) acrylic compound (A) are methacryloyl groups.

It is preferable that the curable composition further contains the polymerization accelerator (D).

It is preferable that the curable composition further contains a (meth) acrylate (E) other than the alicyclic (meth) acrylic compound (A).

The curable composition preferably further contains (meth) acrylamide (F).

The curable composition of the present invention is suitable as a dental curable composition.

The curable composition of the present invention is suitable as a curable composition for dental hard tissues.

The curable composition of the present invention is suitable as a dental composite resin.

The curable composition of the present invention is suitable as a dental cement.

The present invention also includes a method for producing a cured product that cures the curable composition of the present invention.

The present invention also includes a method for curing a curable composition, which cures the curable composition of the present invention.

The curable composition of the present invention can provide a cured product having excellent mechanical properties and aesthetics, and is also excellent in operability.

（式中、Ｒ¹及びＲ²はそれぞれ独立して（メタ）アクリロイル基であり、Ｘは２価の非置換又は置換された炭化水素基であり、ｍ及びｎはそれぞれ独立して０〜３０の整数である。）
で表される脂環式（メタ）アクリル化合物（Ａ）−Ｉ、及び下記一般式〔II〕

（式中、Ｒ³及びＲ⁴はそれぞれ独立して（メタ）アクリロイル基であり、Ｙ及びＺはそれぞれ独立して２価の非置換又は置換された炭化水素基であり、ｐ及びｑはそれぞれ独立して０〜３０の整数である。）
で表される脂環式（メタ）アクリル化合物（Ａ）−IIからなる群から選ばれる少なくとも１種であり、
無機粒子（Ｃ）の平均粒子径が０．００１〜１０μｍである。 The curable composition of the present invention contains an alicyclic (meth) acrylic compound (A), a polymerization initiator (B) and inorganic particles (C), and the alicyclic (meth) acrylic compound (A) is , The following general formula [I]

(In the formula, R ¹ and R ² are independently (meth) acryloyl groups, X is a divalent unsubstituted or substituted hydrocarbon group, and m and n are independently 0 to 30 respectively. Is an integer of.)
The alicyclic (meth) acrylic compound (A) -I represented by, and the following general formula [II].

(In the formula, R ³ and R ⁴ are independently (meth) acryloyl groups, Y and Z are independently divalent unsubstituted or substituted hydrocarbon groups, and p and q are respectively. It is an integer from 0 to 30 independently.)
It is at least one selected from the group consisting of alicyclic (meth) acrylic compounds (A) -II represented by.
The average particle size of the inorganic particles (C) is 0.001 to 10 μm.

In the present specification, the notation of (meth) acrylic is used to include both methacrylic and acrylic, and the notation of (meth) allyl is used to include both methacrylic and allyl. In the present specification, the upper limit value and the lower limit value of the numerical range (content of each component, value calculated from each component, each physical property, etc.) can be appropriately combined.

[Alicyclic (meth) acrylic compound (A)]
The alicyclic (meth) acrylic compound (A) has the effect of relaxing the polymerization shrinkage stress, imparting mechanical properties to the cured product, and reducing the viscosity of the composition in the curable composition of the present invention. Therefore, the alicyclic (meth) acrylic compound (A) is preferably used as a base material. The reason why the curable composition of the present invention exerts the above-mentioned excellent effects is not necessarily clear, but the alicyclic (meth) acrylic compound (A) is represented by the following formula [i]. It is presumed that the bulky and rigid ring structure contributes to the development of strength and the bent structure, which is not found in the planar aromatic ring, contributes to the relaxation of the polymerization shrinkage stress by having the formula skeleton. Further, it is presumed that the cyclic ether structure in the alicyclic skeleton has a strong affinity for the inorganic particles and contributes to the improvement of operability by reducing the viscosity of the composition.

The alicyclic skeleton represented by the above formula [i] contained in the alicyclic (meth) acrylic compound (A) can be derived from an alicyclic diol having a corresponding ether bond. Examples of the stereoisomer of the alicyclic skeleton represented by the formula [i] include those represented by the following formulas [i] -1, formula [i] -2, and formula [i] -3.

These compounds in which hydrogen is bonded to both ends are ether diols derived from sugars, which are also obtained from natural biomass, and are one of the so-called renewable resources. The diol compounds in which hydrogen is bonded to both ends of the alicyclic skeleton represented by [i] -1, [i] -2, and [i] -3 are isosorbide (1,4: 3,6-dianhydro), respectively. They are called −D-sorbitol), isomannide (1,4: 3,6-dianhydro-D-mannitol), and isohydrate (1,4: 3,6-dianhydro-L-iditol). Isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. Other diol compounds can also be obtained by the same reaction except for the starting material. Among isosorbide, isomannide, and isoidide, the alicyclic skeleton derived from isosorbide is particularly preferable because it is easy to manufacture and has excellent heat resistance and is not easily deteriorated during processing.

-Alicyclic (meth) acrylic compound (A) -I
Each symbol of the above general formula [I] will be described. R ¹ and R ² are independent (meth) acryloyl groups, X is a divalent unsubstituted or substituted hydrocarbon group, and m and n are each independently an integer of 0 to 30. ..
In the above general formula [I], examples of the hydrocarbon group represented by X include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and the like, and among them, a curable composition. An aliphatic hydrocarbon group is preferable in terms of the viscosity of the group.

Examples of the aliphatic hydrocarbon group include a linear or branched chain alkylene group and an alkaneylene group. Examples of the alkylene group include an ethylene group, a 1,2-propylene group, a trimethylene group, a butylene group, a tetramethylene group, a pentamethylene group and a hexamethylene group. Examples of the alkenylene group include a 1-hexenylene group, a 2-hexenylene group, a 3-hexenylene group and the like. Among these, an ethylene group, a 1,2-propylene group and a trimethylene group are preferable in terms of viscosity and strength.

Examples of the alicyclic hydrocarbon group include a cycloalkylene group and a cycloalkenylene group. Examples of the cycloalkylene group include a cyclohexylene group, a methylcyclohexylene group, an ethylcyclohexylene group, a dimethylcyclohexylene group, a cycloheptylene group, a cyclooctylene group and the like. Examples of the cycloalkenylene group include a cyclohexenylene group, a cycloheptenylene group, a cyclooctenylene group, a cyclononenylene group, a cyclodecenylene group and the like.

Examples of the aromatic hydrocarbon group include an arylene group. Examples of the arylene group include a phenylene group, a trilene group, a methylphenylene group, a xylylene group, a naphthylene group, an anthracenylene group, a phenylene trilene group, a biphenylene group, a fluorylene group and the like.

These hydrocarbon groups, if present, contain isomers as long as they have the effect of the present invention. Further, the hydrocarbon group may be a group in which two or more kinds selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group are combined, for example, an alkylene group. And an arylene group; a combination of a cycloalkylene group and an arylene group; a combination of an alkylene group and a cycloalkylene group; a combination of an alkylene group, a cycloalkylene group and an arylene group may be used.

The hydrocarbon group represented by X preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms. Among them, X is preferably an alkylene group having 2 to 6 carbon atoms in that the cured product of the obtained curable composition is excellent in strength. Further, in terms of the viscosity of the curable composition, X is more preferably an alkylene group having 2 to 4 carbon atoms, and further preferably an alkylene group having 2 or 3 carbon atoms.

The number of substituents contained in the hydrocarbon group is usually 0 to 4, preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1. Examples of the substituent of the hydrocarbon group include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom); a hydroxyl group, an amino group, a linear or branched alkoxy group having 1 to 12 carbon atoms, and the like. Can be mentioned. These may be one kind alone or may contain two or more kinds. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group and an n-octyloxy group. , N-decyloxy group, n-dodecyloxy group and the like. If there is an isomer, these substituents include the isomer as long as it has the effect of the present invention. Among the above-mentioned substituents, a hydroxyl group is preferable because the cured product of the curable composition has excellent strength.

In the above general formula [I], m and n are independently integers of 0 to 30, and m and n are independently 0 to 0 in that the cured product of the obtained curable composition is excellent in strength. It is preferably an integer of 9. Further, in terms of the viscosity of the curable composition, m and n are more preferably integers of 0 to 6 independently, and further preferably integers of 0 to 3 independently, respectively. It is particularly preferable that the value is 0 or 1. Although m and n may be the same as or different from each other, m and n may be the same as each other from the viewpoint of ease of production of the alicyclic (meth) acrylic compound (A) -I. preferable.

The method for producing the alicyclic (meth) acrylic compound (A) -I is not particularly limited, and regardless of the production method, the compound represented by the above general formula [I] and the curing containing the compound. Although the sex composition is included in the scope of the present invention, the alicyclic (meth) acrylic compound (A) -I is preferably obtained from JP-A-2011-84535, J Mater Sci: Mater Med (2012) 23. It can be manufactured by the method described in: 1149-1155 and the like. More specifically, the alicyclic (meth) acrylic compound (A) -I is, for example, an alicyclic diol (isosorbide or the like) having an ether bond corresponding to the alicyclic skeleton represented by the above formula [i]. ) Is used as it is, or an epoxy compound such as ethylene oxide or propylene oxide is reacted with the same, and then the hydroxyl group is converted into a (meth) acryloyloxy group by an esterification reaction or the like; or by the above formula [i]. After reacting an alicyclic diol (isosorbide, etc.) having an ether bond corresponding to the represented alicyclic skeleton with a halogenated (meth) allyl such as allyl bromide, the double bond is epoxidized. Then, the epoxy group can be produced by reacting with (meth) acrylic acid or the like to open the ring.

-Alicyclic (meth) acrylic compound (A) -II
Each symbol of the above general formula [II] will be described. R ³ and R ⁴ are independently (meth) acryloyl groups, Y and Z are independently divalent unsubstituted or substituted hydrocarbon groups, and p and q are independently 0. It is an integer of ~ 30.
In the above general formula [II], examples of the hydrocarbon group represented by Y and Z include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and the like, and among them, curing An aliphatic hydrocarbon group is preferable in terms of the viscosity of the sex composition.

Examples and preferred examples of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group are the same as those described above as the explanation in X of the general formula [I], and are duplicated here. The explanation to be given is omitted.

The hydrocarbon groups represented by Y and Z, if any, contain isomers as long as they have the effects of the present invention. Further, the hydrocarbon group may be a group in which two or more kinds selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group are combined, for example, an alkylene group. And an arylene group; a combination of a cycloalkylene group and an arylene group; a combination of an alkylene group and a cycloalkylene group; a combination of an alkylene group, a cycloalkylene group and an arylene group may be used.

The number of carbon atoms of the hydrocarbon group represented by Y and Z is preferably 2 to 30, and more preferably 2 to 20. Among them, Y and Z are preferably alkylene groups having 2 to 6 carbon atoms independently, respectively, in that the cured product of the obtained curable composition is excellent in strength. Further, in terms of the viscosity of the curable composition, Y and Z are each independently preferably an alkylene group having 2 to 4 carbon atoms, and further preferably an alkylene group having 2 or 3 carbon atoms. ..

The number of substituents of the hydrocarbon groups represented by Y and Z, examples thereof, and preferable ones are the same as those described above as the explanation in X of the above general formula [I], and duplicate description is omitted here. To do.

In the above general formula [II], p and q are independently integers of 0 to 30, and p and q are independently 0 to 0 in that the cured product of the obtained curable composition is excellent in strength. It is preferably in the range of 9. Further, in terms of the viscosity of the curable composition, p and q are more preferably independent integers of 0 to 6, and further preferably independent integers of 0 to 3, respectively. It is particularly preferable that the value is 0 or 1. Although p and q may be the same as or different from each other, p and q may be the same as each other from the viewpoint of ease of production of the alicyclic (meth) acrylic compound (A) -II. preferable.

The method for producing the alicyclic (meth) acrylic compound (A) -II is not particularly limited, and regardless of the production method, the compound represented by the above general formula [II] and the curability containing the compound. Although the composition is included in the scope of the present invention, the alicyclic (meth) acrylic compound (A) -II can preferably be produced by the following method. That is, an alicyclic diol (isosorbide or the like) having an ether bond corresponding to the alicyclic skeleton represented by the above formula [i] is used as it is, or an epoxy compound such as ethylene oxide or propylene oxide is reacted with this as it is. After that, the hydroxyl group is changed ^{to the isocyanate compound represented by the general formula: R 3-} O-Z-NCO and the isocyanate compound represented by R ^4- O-Z-NCO (in the formula, R ³ , R ⁴ and Z are It can be produced by a method of reacting with (having the same meaning as described above).

In the reaction between the hydroxyl group and the isocyanate compound, a conventionally known urethanization catalyst is used, a polymerization inhibitor is added as necessary, and the two are reacted at a temperature of 40 to 90 ° C. to obtain the desired alicyclic system. The (meth) acrylic compound (A) -II can be obtained smoothly, which is preferable. As the polymerization inhibitor, the same polymerization inhibitor that can be added to the curable composition of the present invention described later can be used.

^{Alicyclic (meth) acrylic compounds according to the types of R 1} , R ² , R ³ , R ⁴ , X, Y and Z in the above general formulas [I] and [II], the number of m, n, p and q, etc. The properties of (A) are different. However, in general, both the alicyclic (meth) acrylic compound (A) -I and the alicyclic (meth) acrylic compound (A) -II are often low-viscosity liquids at room temperature. By using such an alicyclic (meth) acrylic compound (A) that is liquid at room temperature, a curable composition that is even more excellent in handleability can be obtained.

As the alicyclic (meth) acrylic compound (A) -I, ^{both R 1} and R ² are methacryloyl groups, and X is a divalent, unsubstituted or substituted hydrocarbon group having 2 to 6 carbon atoms. Alicyclic (meth) acrylic compounds in which m and n are independently integers of 0 to 9 are preferable; ^{both R 1} and R ² are methacryloyl groups, and X is 2 with 2 to 4 carbon atoms. More preferred are alicyclic (meth) acrylic compounds that are valence-unsubstituted or substituted hydrocarbon groups in which m and n are independently integers of 0-6; ^{both R 1} and R ² are methacryloyl. An alicyclic (meth) acrylic compound in which X is a divalent, unsubstituted or substituted hydrocarbon group having 2 or 3 carbon atoms, and m and n are independently integers of 0 to 3. Is even more preferable.

As the alicyclic (meth) acrylic compound (A) -II, ^{both R 3} and R ⁴ are methacryloyl groups, and Y and Z are independently divalent unsubstituted or substituted with 2 to 6 carbon atoms, respectively. Alicyclic (meth) acrylic compounds are preferred, each of which is a hydrocarbon group and p and q are each independently an integer of 0-9; R ³ and R ⁴ are both methacryloyl groups, Y and Z. Are independently divalent, unsubstituted or substituted hydrocarbon groups having 2 to 4 carbon atoms, and p and q are independently integers of 0 to 6 in an alicyclic (meth) acrylic compound. More preferably; R ³ and R ⁴ are both methacryloyl groups, Y and Z are independently divalent, unsubstituted or substituted hydrocarbon groups having 2 or 3 carbon atoms, and p and q are respectively. An alicyclic (meth) acrylic compound, which is independently an integer of 0 to 3, is more preferred.

The curable composition of the present invention comprises, as the alicyclic (meth) acrylic compound (A), the alicyclic (meth) acrylic compound (A) -I and the alicyclic (meth) acrylic compound (A) -II. It may contain only one of them, or may contain both. Further, as the alicyclic (meth) acrylic compound (A) -I, one kind of compound may be used alone, or two or more kinds of compounds may be used in combination. Similarly, as the alicyclic (meth) acrylic compound (A) -II, one kind of compound may be used alone, or two or more kinds of compounds may be used in combination. When the curable composition of the present invention contains one or both of the alicyclic (meth) acrylic compound (A) -I and the alicyclic (meth) acrylic compound (A) -II, the fat ^{R 1} , R ² , R ³ and R ⁴ of the cyclic (meth) acrylic compound (A) are preferably methacryloyl groups.

The content of the alicyclic (meth) acrylic compound (A) in the curable composition of the present invention is preferably 10 to 100% by mass, preferably 30 to 95% by mass, based on the total amount of the polymerizable monomers. Is more preferable, and 50 to 90% by mass is further preferable. In the present specification, the total amount of the polymerizable monomer is a polymerizable monomer other than the alicyclic (meth) acrylic compound (A) and the alicyclic (meth) acrylic compound (A) (described later (described later). Means the total amount of (meth) acrylate (E), (meth) acrylamide (F) and other polymerizable monomers).

[Polymerization initiator (B)]
As the polymerization initiator (B) used in the present invention, it can be selected from the polymerization initiators used in the general industry, and among them, the polymerization initiator used for dental applications is preferably used. As the polymerization initiator (B), in particular, at least one selected from the group consisting of the photopolymerization initiator (B-1) and the chemical polymerization initiator (B-2) can be used.

Examples of the photopolymerization initiator (B-1) include (bis) acylphosphine oxides (including salts), thioxanthones (including salts such as quaternary ammonium salts), ketals, α-diketones, and the like. Examples thereof include coumarins, anthraquinones, benzoin alkyl ether compounds, and α-aminoketone compounds.

Among these photopolymerization initiators (B-1), it is preferable to use at least one selected from the group consisting of (bis) acylphosphine oxides and α-diketones. As a result, a curable composition having excellent photocurability in the visible light region and the near-ultraviolet region and exhibiting sufficient photocurability regardless of the light source of a halogen lamp, a light emitting diode (LED), or a xenon lamp can be obtained. can get.

Among the (bis) acylphosphine oxides, examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 2,6-dichlorobenzoyldiphenylphosphine oxide. , 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6-dimethyl) Phosphine) phosphonate, sodium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide, potassium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide, ammonium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide, etc. Can be mentioned.

Among the (bis) acylphosphine oxides, examples of the bisacylphosphine oxides include bis (2,6-dichlorobenzoyl) phenylphosphine oxide and bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine. Oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenyl Phosphine oxide, bis (2,3,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like can be mentioned.

Further, examples of the (bis) acylphosphine oxides include compounds described in JP-A-2000-159621.

Among these (bis) acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine It is particularly preferable to use an oxide, a sodium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide, as a photopolymerization initiator (B-1).

Examples of α-diketones include diacetyl, benzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4'-oxybenzyl, acenaphthenicone and the like. .. Among these, camphorquinone is particularly preferable from the viewpoint of having a maximum absorption wavelength in the visible light region.

As the chemical polymerization initiator (B-2), an organic peroxide is preferably used. The organic peroxide used as the chemical polymerization initiator (B-2) is not particularly limited, and known ones can be used. Typical organic peroxides include, for example, ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, peroxydicarbonates and the like.

Examples of the ketone peroxide include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methyl cyclohexanone peroxide, cyclohexanone peroxide and the like.

Examples of the hydroperoxide include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide and the like. Can be mentioned.

Examples of the diacyl peroxide include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoy peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide.

Examples of the dialkyl peroxide include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and 1,3-bis (. Examples thereof include t-butylperoxyisopropyl) benzene and 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexine.

Examples of the peroxyketal include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, and 2,2-bis (t-butyl). Peroxy) butane, 2,2-bis (t-butylperoxy) octane, 4,4-bis (t-butylperoxy) valeric acid n-butyl ester and the like can be mentioned.

Examples of the peroxy ester include α-cumyl peroxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentylperoxy-2-ethylhexanoate, and the like. t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-3, Examples thereof include 3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, and t-butylperoxymaleate.

Examples of the peroxydicarbonate include di-3-methoxyperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, and di-n-propylperoxy. Examples thereof include dicarbonate, di-2-ethoxyethylperoxydicarbonate, and diallylperoxydicarbonate.

Among these organic peroxides, hydroperoxides initiate chemical polymerization due to the overall balance between safety, storage stability, and the ability to generate radicals in the presence of the alicyclic (meth) acrylic compound (A). It is preferably used as an agent (B-2). Among them, cumene hydroperoxide, t-butyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide are particularly preferably used as the chemical polymerization initiator (B-2).

The content of the polymerization initiator (B) in the curable composition of the present invention is not particularly limited, but from the viewpoint of curability of the obtained curable composition, etc., with respect to 100 parts by mass of the total amount of the polymerizable monomer. Therefore, it is preferable that the polymerization initiator (B) is contained in an amount of 0.001 to 30 parts by mass. When the content of the polymerization initiator (B) is 0.001 part by mass or more, the polymerization proceeds sufficiently and stickiness can be prevented. The content of the polymerization initiator (B) is more preferably 0.05 parts by mass or more, and further preferably 0.1 parts by mass or more. On the other hand, when the content of the polymerization initiator (B) is 30 parts by mass or less, precipitation from the curable composition can be prevented even when the polymerization performance of the polymerization initiator (B) itself is low. The content of the polymerization initiator (B) is more preferably 20 parts by mass or less, further preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less.

[Inorganic particles (C)]
The curable composition of the present invention contains inorganic particles (C) having an average particle size of 0.001 to 10 μm.

Examples of the material of the inorganic particles (C) include quartz, silica, alumina, zirconia, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, and barium. Glass, strontium glass, glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoro Examples include aluminum silicate glass and itterbium fluoride. These can be used alone or in combination of two or more. The shape of the inorganic particles (C) is not particularly limited, and amorphous inorganic particles, spherical inorganic particles, and the like can be appropriately selected and used. Among these, quartz, silica, alumina, zirconia, barium glass, and fluoroaluminosilicate glass are preferably used, and more preferably silica and barium glass, because the obtained curable composition is excellent in operability and the strength of the cured product. Is used, and more preferably barium glass is used.

The inorganic particles (C) are required to be mixed with polymerizable monomers other than the alicyclic (meth) acrylic compound (A) and the alicyclic (meth) acrylic compound (A), if necessary. A surface-treated agent such as a silane coupling agent may be used. Examples of such surface treatment agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, 3-methacryloyloxypropyltrimethoxysilane, and 11-methacryloyloxyundecyltrimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like.

As a surface treatment method, a known method can be used, for example, a method of spray-adding the surface treatment agent while vigorously stirring the inorganic particles; or dispersing the inorganic particles and the surface treatment agent in an appropriate solvent or A method of removing the solvent after dissolution; the alkoxy group of the surface treatment agent is hydrolyzed in an aqueous solution by an acid catalyst to convert it into a silanol group, which is adhered to the surface of inorganic particles in the aqueous solution, and then water is added. Examples include a method of removing. In any of the above methods, the reaction between the surface of the inorganic particles and the surface treatment agent can be completed and the surface treatment can be performed by heating in the range of usually 50 to 150 ° C. The amount of the surface treatment agent used is not particularly limited, and for example, 1 to 10 parts by mass of the surface treatment agent can be used with respect to 100 parts by mass of the inorganic particles before treatment.

The average particle size of the inorganic particles (C) is 0.001 to 10 μm from the viewpoint of the handleability of the obtained curable composition and the mechanical properties and aesthetics of the cured product, and is 0.01 to 5. It is preferably 0 μm, more preferably 0.1 to 1.0 μm.

In the present specification, the average particle size of the inorganic particles can be determined by a laser diffraction / scattering method or an electron microscope observation of the particles. Specifically, the laser diffraction / scattering method is convenient for measuring the particle size of particles of 0.10 μm or more, and the electron microscope observation is convenient for measuring the particle size of ultrafine particles of less than 0.10 μm.

The laser diffraction / scattering method can be measured by using, for example, a laser diffraction type particle size distribution measuring device (SALD-2100: manufactured by Shimadzu Corporation) using a 0.2% aqueous sodium hexametaphosphate solution as a dispersion medium.

In electron microscope observation, for example, a scanning electron microscope (manufactured by Hitachi, Ltd., S-4000 type) photograph of particles is taken, and the particle size of particles (200 or more) observed in the unit field of view of the photograph is analyzed. It can be obtained by measuring using a formula particle size distribution measurement software (Macview (Mount Tech Co., Ltd.)). At this time, the particle size of the particles is obtained as an arithmetic mean value of the longest length and the shortest length of the particles, and the average primary particle size is calculated from the number of particles and the particle size thereof.

The content of the inorganic particles (C) is not particularly limited, but is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer from the viewpoint of ejection property and strength of the cured product. It is more preferably 50 to 750 parts by mass, and even more preferably 100 to 500 parts by mass.

[Polymerization accelerator (D)]
The curable composition of the present invention preferably further contains the polymerization accelerator (D). Examples of the polymerization accelerator (D) include amines, sulfic acid and salts thereof, sulfites, hydrogen sulfites, aldehydes, thiourea compounds, organic phosphorus compounds, borate compounds, barbituric acid derivatives, triazine compounds, and vanadium. Examples thereof include compounds, copper compounds, tin compounds, cobalt compounds, halogen compounds and thiol compounds.

Amines are divided into aliphatic amines and aromatic amines. Examples of the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; and secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine; N-Methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethylmethacrylate, N-methyldiethanolaminedimethacrylate, N-ethyldiethanolaminedimethacrylate, triethanolamine monomethacrylate , Triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine and other tertiary aliphatic amines.

Examples of the aromatic amine include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-bis (2-hydroxyethyl) -p-toluidine, and N, N-bis. (2-Hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-isopropylaniline, N, N-bis (2-hydroxyethyl)- 3,5-Di-t-butylaniline, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N- Dimethyl-4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, ethyl 4- (N, N-dimethylamino) benzoate, 4- (N, N-dimethylamino) Methyl benzoate, 4- (N, N-dimethylamino) n-butoxyethyl benzoate, 4- (N, N-dimethylamino) 2- (methacryloyloxy) ethyl benzoate, 4- (N, N-dimethylamino) ) Benzophenone, butyl 4- (N, N-dimethylamino) benzoate and the like. Among these, ethyl 4- (N, N-dimethylamino) benzoate, n-butoxyethyl 4- (N, N-dimethylamino) benzoate, from the viewpoint of imparting excellent curability to the curable composition, And at least one selected from the group consisting of 4- (N, N-dimethylamino) benzophenone is preferably used.

Examples of sulfinic acid and salts thereof include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, and benzenesulfin. Sodium acid, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, 2,4,6-trimethylbenzenesulfinate Potassium acid, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, Potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinate, 2, Sodium 4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, calcium 2,4,6-triisopropylbenzenesulfinate, etc. Can be mentioned.

Examples of the sulfite and hydrogen sulfite include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite and the like.

Examples of aldehydes include terephthalaldehyde and benzaldehyde derivatives. Examples of the benzaldehyde derivative include dimethylaminobenzaldehyde, p-methyloxybenzaldehyde, p-ethyloxybenzaldehyde, pn-octyloxybenzaldehyde and the like.

Examples of the thiourea compound include 1- (2-pyridyl) -2-thiourea, thiourea, methylthiourea, ethylthiourea, N, N'-dimethylthiourea, N, N'-diethylthiourea, N, N'. -Di-n-propylthiourea, N, N'-dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea Examples thereof include urea, tetracyclohexylthiourea, 3,3-dimethylethylenethiourea and 4,4-dimethyl-2-imidazolinthione. Among these, from the viewpoint of curability of the curable composition in the presence of the alicyclic (meth) acrylic compound (A), 1- (2-pyridyl) -2-thiourea or 4,4-dimethyl-2. -Imidazoline thion is preferably used as the polymerization accelerator (D).

Examples of the organophosphorus compound include triphenylphosphine, 2-methyltriphenylphosphine, 4-methyltriphenylphosphine, 2-methoxytriphenylphosphine, 4-methoxytriphenylphosphine, trin-butylphosphine, triisobutylphosphine, and the like. Examples thereof include tri-t-butylphosphine.

As the borate compound, an aryl borate compound is preferable. Specific examples of preferably used arylborate compounds include trialkylphenylboron, trialkyl (p-chlorophenyl) boron, and trialkyl (, for example, trialkylphenylboron, trialkyl (p-chlorophenyl) boron, and trialkyl). p-fluorophenyl) boron, trialkyl [3,5-bis (trifluoromethyl) phenyl] boron, trialkyl [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy) -2-propyl) phenyl] boron, trialkyl (p-nitrophenyl) boron, trialkyl (m-nitrophenyl) boron, trialkyl (p-butylphenyl) boron, trialkyl (m-butylphenyl) boron, tri Alkyl (p-butyloxyphenyl) boron, trialkyl (m-butyloxyphenyl) boron, trialkyl (p-octyloxyphenyl) boron and trialkyl (m-octyloxyphenyl) boron (alkyl group is n-butyl group) , At least one selected from the group consisting of n-octyl group, n-dodecyl group, etc.) and salts thereof (sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt). , Tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, etc.) and the like.

Examples of the borate compound having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, and dialkyldi [3,5-bis (trifluoromethyl). ) Phenyl] boron, dialkyldi [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyldi (p-nitrophenyl) boron, dialkyldi () m-nitrophenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi (p-octyl) Oxyphenyl) boron and dialkyldi (m-octyloxyphenyl) boron (alkyl group is at least one selected from the group consisting of n-butyl group, n-octyl group, n-dodecyl group and the like) and salts thereof. (Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt Butyl quinolinium salt, etc.) and the like.

Examples of the borate compound having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, and monoalkyltri [3]. , 5-bis (trifluoromethyl) phenyl] boron, monoalkyltri [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, monoalkyl Alkyltri (p-nitrophenyl) boron, monoalkyltri (m-nitrophenyl) boron, monoalkyltri (p-butylphenyl) boron, monoalkyltri (m-butylphenyl) boron, monoalkyltri (p-butyl) Oxyphenyl) boron, monoalkyltri (m-butyloxyphenyl) boron, monoalkyltri (p-octyloxyphenyl) boron and monoalkyltri (m-octyloxyphenyl) boron (alkyl groups are n-butyl group, n -One selected from octyl group, n-dodecyl group, etc.) and salts thereof (sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methyl Pyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, etc.) and the like.

Examples of the borate compound having four aryl groups in one molecule include tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, and tetrakis [3,5-bis (trifluoromethyl). ) Phenyl] boron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis ( m-nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis (p-octyl) Oxyphenyl) boron, tetrakis (m-octyloxyphenyl) boron, (p-fluorophenyl) triphenylboron, [3,5-bis (trifluoromethyl) phenyl] triphenylboron, (p-nitrophenyl) triphenyl Boron, (m-butyloxyphenyl) triphenylboron, (p-butyloxyphenyl) triphenylboron, (m-octyloxyphenyl) triphenylboron and (p-octyloxyphenyl) triphenylboron and salts thereof ( Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, Butyl quinolinium salt, etc.) and the like.

Among these aryl borate compounds, it is more preferable to use a borate compound having 3 or 4 aryl groups in one molecule from the viewpoint of storage stability. In addition, these aryl borate compounds can be used alone or in admixture of two or more.

Examples of barbituric acid derivatives include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, and 5-ethyl. Barbituric acid, 5-isopropylbarbituric acid, 5-cyclohexyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-5- n-butyl barbituric acid, 1,3-dimethyl-5-isobutyl barbituric acid, 1,3-dimethyl-5-cyclopentyl barbituric acid, 1,3-dimethyl-5-cyclohexyl barbituric acid, 1,3- Dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethyl Barbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5- Examples thereof include phenylbarbituric acids and thiobarbituric acids, and salts thereof (particularly alkali metals or alkaline earth metals are preferable). Examples of these salts of barbituric acids include sodium 5-butylbarbiturate, sodium 1,3,5-trimethylbarbiturate, sodium 1-cyclohexyl-5-ethylbarbiturate and the like.

Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, and 2-methyl-4,6-bis ( Trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-) Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-bromophenyl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s- Triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2-[ 2- (p-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (o-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s -Triazine, 2- [2- (p-butoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6 -Bis (trichloromethyl) -s-triazine, 2- [2- (3,4,5-trimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (1-naphthyl) ) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-biphenylyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N, N-bis ( 2-Hydroxyethyl) amino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N-hydroxyethyl-N-ethylamino} ethoxy] -4,6-bis (trichloromethyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- [2- {N-hydroxyethyl-N-methylamino} ethoxy] -4,6-bis (trichloromethyl) Examples thereof include −s-triazine, 2- [2- {N, N-diallylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine.

As the vanadium compound, an IV-valent and / or V-valent vanadium compound is preferable. Examples of the IV-valent and / or V-valent vanadium compounds include divanadium tetraoxide (IV), vanadyl acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), and oxobis (1-phenyl-). 1,3-Butandionate) vanadium (IV), bis (maltlate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), ammon metavanadate (V) and the like. Among these, vanadyl acetylacetonate (IV) is preferably used as the polymerization accelerator (D) from the viewpoint of curability of the curable composition in the presence of the alicyclic (meth) acrylic compound (A).

Examples of the copper compound include acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like. Among these, acetylacetone copper or cupric acetate is preferably used as the polymerization accelerator (D) from the viewpoint of curability of the curable composition in the presence of the alicyclic (meth) acrylic compound (A).

Examples of the tin compound include di-n-butyl tin dilaurate, di-n-octyl tin dilaurate, di-n-octyl tin dilaurate, and di-n-butyl tin dilaurate. Among them, di-n-octyltin dilaurate or di-n-butyltin dilaurate is preferably used as the polymerization accelerator (D).

Examples of the cobalt compound include acetylacetone cobalt, cobalt acetate, cobalt oleate, cobalt chloride, and cobalt bromide.

As the halogen compound, for example, dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide and the like are preferably used.

Examples of the thiol compound include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

Among these polymerization accelerators (D), amines, thiourea compounds, vanadyl compounds, and copper compounds are particularly preferably used, and among these, 1- (2-pyridyl) -2-thiourea, 4-( Ethyl N, N-dimethylamino) benzoate, 4,4-dimethyl-2-imidazolinthione, vanadyl acetylacetonate (IV), acetylacetone copper, and cupric acetate are most preferably used as the polymerization accelerator (D). ..

The content of the polymerization accelerator (D) in the curable composition of the present invention is not particularly limited, but from the viewpoint of curability of the obtained curable composition, etc., with respect to 100 parts by mass of the total amount of the polymerizable monomer. Therefore, it is preferable that the polymerization accelerator (D) is contained in an amount of 0.001 to 30 parts by mass. When the content of the polymerization accelerator (D) is 0.001 part by mass or more, the polymerization proceeds sufficiently and stickiness can be prevented. The content of the polymerization accelerator (D) is more preferably 0.05 parts by mass or more, and further preferably 0.1 parts by mass or more. On the other hand, since the content of the polymerization accelerator (D) is 30 parts by mass or less, even when the polymerization performance of the polymerization initiator (B) used is low, the polymerization initiator (B) from the curable composition ) Can be prevented from precipitating. The content of the polymerization accelerator (D) is more preferably 20 parts by mass or less, and further preferably 10 parts by mass or less.

Further, in the present invention, the chemical polymerization initiator (B-2) and the polymerization accelerator (D) may be combined as a redox polymerization initiator. At this time, from the viewpoint of storage stability, the chemical polymerization initiator (B-2) and the polymerization accelerator (D) are preferably stored in separate containers. In this case, the curable composition is provided containing at least a first material containing a chemical polymerization initiator (B-2) and a second material containing a polymerization accelerator (D). The curable composition is preferably provided as a kit used in the form of a two-material mold composed of the first material and the second material. In this case, it is more preferable that the curable composition is provided as a kit used in the form of a two-paste type in which both the first material and the second material are in the form of a paste. When the curable composition is provided as a kit in the form of a two-paste type, each paste is stored in a state where the pastes are separated from each other, and the two pastes are kneaded immediately before use to proceed with chemical polymerization. When the curable composition further contains a photopolymerization initiator (B-1), it is preferable to proceed with photopolymerization in addition to chemical polymerization to cure the curable composition.

[(Meta) acrylate (E) other than alicyclic (meth) acrylic compound (A)]
The curable composition of the present invention preferably further contains (meth) acrylate (E) other than the alicyclic (meth) acrylic compound for the purpose of improving operability or adjusting the physical properties of the cured product. Examples of the (meth) acrylate (E) include a monofunctional (meth) acrylate having one (meth) acryloyl group, a polyfunctional (meth) acrylate having a plurality of (meth) acryloyl groups, and the like. The (meth) acrylate (E) is preferably methacrylate.

Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6. (Meta) acrylate having a hydroxyl group such as −hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate; methyl ( Meta) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) Alkyl (meth) acrylates such as acrylates, n-hexyl (meth) acrylates, lauryl (meth) acrylates, cetyl (meth) acrylates, stearyl (meth) acrylates; cyclohexyl (meth) acrylates, isobornyl (meth) acrylates, tetrahydrofurfuryl Alicyclic (meth) acrylates such as (meth) acrylates, isosorbide mono (meth) acrylates, isomannide mono (meth) acrylates, and isoided mono (meth) acrylates; containing aromatic groups such as benzyl (meth) acrylates (meth). Acrylate; Ether group-containing (meth) acrylate such as methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, butoxydiethylene glycol (meth) acrylate; 2,3-dibromopropyl (meth) acrylate, etc. Bromine-containing (meth) acrylates; silyl group-containing (meth) acrylates such as 3- (meth) acryloyloxypropyltrimethoxysilane and 11- (meth) acryloyloxyundecyltrimethoxysilane. These may be used alone or in combination of two or more. Among these, alkyl (meth) acrylates and alicyclic (meth) acrylates are preferable because they have good compatibility with the alicyclic (meth) acrylic compound (A) and the curable composition has excellent curability. Methyl (meth) acrylates, cyclohexyl (meth) acrylates, isobornyl (meth) acrylates, tetrahydrofurfuryl (meth) acrylates, isosorbide mono (meth) acrylates, isomannide mono (meth) acrylates and isoided mono (meth) acrylates are more preferred. ..

Examples of the polyfunctional (meth) acrylate include an aliphatic compound-based bifunctional (meth) acrylate, an aromatic compound-based bifunctional (meth) acrylate, and a trifunctional or higher (meth) acrylate. And so on.

Examples of the aliphatic compound-based bifunctional (meth) acrylate include glycerol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and propylene. Glycoldi (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-ethyl-1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10- Examples thereof include decanediol di (meth) acrylate and 1,2-bis (3- (meth) acryloyloxy-2-hydroxypropoxy) ethane. Among these, glycerol di (meth) acrylate and triethylene glycol are excellent in compatibility with the alicyclic (meth) acrylic compound (A) and excellent strength and toughness of the cured product of the obtained curable composition. Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-ethyl-1,6-hexanediol di (Meta) acrylates, 1,9-nonanediol di (meth) acrylates and 1,10-decaneol di (meth) acrylates are preferred. These may be used alone or in combination of two or more.

Examples of the aromatic compound-based bifunctional (meth) acrylate include 2,2-bis ((meth) acryloyloxyphenyl) propane and 2,2-bis [4- (3- (meth) acryloyloxy-). 2-Hydroxypropoxy) phenyl] propane, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane (average of ethoxy groups) 2,2-Bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyl) Oxydipropoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxyethoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) ) -2- (4- (Meta) acryloyloxytriethoxyphenyl) propane, 2- (4- (meth) acryloyloxydipropoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2 , 2-Bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane and the like.

Examples of the trifunctional or higher (meth) acrylate include trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and penta. Elythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, 1,7-di (meth) acryloyloxy-2,2,6,6-tetra (meth) acryloyloxymethyl-4-oxyheptane, etc. Be done. Among these, trimethylolpropane tri (meth) acrylate is preferable because it is excellent in miscibility with the alicyclic (meth) acrylic compound (A) and the strength of the cured product of the curable composition.

Further, the curable composition of the present invention may contain a fluorine-containing (meth) acrylate as at least a part of the (meth) acrylate (E) for the purpose of adjusting the color resistance to a dye or the like. Examples of such fluorine-containing (meth) acrylate include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, and 2- (per). Fluorobutyl) ethyl (meth) acrylate, 3- (perfluorobutyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl ( Meta) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) Examples thereof include acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, and the like. .. Among these, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) are excellent in color resistance. Acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate are preferably used. ..

Further, the curable composition of the present invention contains an acidic group-containing (meth) acrylate as at least a part of the (meth) acrylate (E) for the purpose of imparting adhesiveness to a metal, another resin, or a dentin. It may be included. Such an acidic group-containing (meth) acrylate has, for example, at least one acidic group such as a phosphoric acid group, a pyrophosphate group, a thiophosphate group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group (meth). Examples include acrylate. As the acidic group-containing (meth) acrylate, a (meth) acrylate having a phosphoric acid group is preferable.

Examples of the (meth) acrylate having a phosphoric acid group include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, and 4- (meth) acryloyloxybutyl dihydro. Genphosphate, 5- (meth) acryloyloxypentyl dihydrogenphosphate, 6- (meth) acryloyloxyhexyl dihydrogenphosphate, 7- (meth) acryloyloxyheptyl dihydrogenphosphate, 8- (meth) acryloyloxyoctyl Dihydrogenphosphate, 9- (meth) acryloyloxynonyl dihydrogenphosphate, 10- (meth) acryloyloxydecyldihydrogenphosphate, 11- (meth) acryloyloxyundecyldihydrogenphosphate, 12- (meth) Acryloyl oxide decyldihydrogen phosphate, 16- (meth) acryloyloxyhexadecyldihydrogen phosphate, 20- (meth) acryloyloxyicosyldihydrogen phosphate, bis [2- (meth) acryloyloxyethyl] hydrogen phosphate , Bis [4- (meth) acryloyloxybutyl] hydrogen phosphate, bis [6- (meth) acryloyloxyhexyl] hydrogen phosphate, bis [8- (meth) acryloyloxyoctyl] hydrogen phosphate, bis [9- (Meta) acryloyloxynonyl] hydrogen phosphate, bis [10- (meth) acryloyloxydecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyldihydrogenphosphate, 2- (meth) acryloyloxyethyl Phenylhydrogen phosphate, 2- (meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis [2- (meth) acryloyloxy- (1-hydroxymethyl) ethyl] hydrogen phosphate, and their acid salts. , Alkali metal salt, ammonium salt and the like. These may be used alone or in combination of two or more.

From the viewpoint of adhesiveness, the content of the acidic group-containing (meth) acrylate is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, based on the total amount of the polymerizable monomer. It is more preferably 3 to 20% by mass.

Further, the curable composition of the present invention may contain (meth) acrylate having a urethane bond as at least a part of (meth) acrylate (E) from the viewpoint of toughness. The (meth) acrylate having a urethane bond may be monofunctional or polyfunctional. The (meth) acrylate having a urethane bond is preferably 2 to 4 functional, and more preferably bifunctional, from the viewpoint of excellent toughness.

The (meth) acrylate having a urethane bond can be easily synthesized, for example, by subjecting a compound having an isocyanate group (-NCO), which will be described later, to an addition reaction with a (meth) acrylate having a hydroxyl group (-OH). ..

Examples of the compound having an isocyanate group include hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), 2,2,4-trimethyl. Hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, tricyclodecanediisocyanate (TCDDI), adamantan diisocyanate (ADI), dicyclomethane diisocyanate (hydrogenated MDI), cyclohexylmethane diisocyanate (hydrogenated TDI), naphthalenediocyanate (NDI) and the like.

Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. 4-Hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) ) Acrylate, glycerin mono (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, 2,2-bis [4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl ] Propane, 1,2-bis [3- (meth) acryloyloxy-2-hydroxypropoxy] ethane, pentaerythritol tri (meth) acrylate, dipentaerythritol tri or tetra (meth) acrylate and the like can be mentioned.

The addition reaction between the compound having an isocyanate group and the (meth) acrylate having a hydroxyl group can be carried out according to a known method, and is not particularly limited.

The obtained (meth) acrylate having a urethane bond includes, for example, 2- (methylaminocarboxy) ethane-1-ol (meth) acrylate and 2- (ethylamino) as a monofunctional (meth) acrylate having a urethane bond. Carboxylate ethane-1-ol (meth) acrylate, 2- (propylaminocarboxy) ethane-1-ol (meth) acrylate, 2- (butylaminocarboxy) ethane-1-ol (meth) acrylate, 2- (hexyl) Aminocarboxy) ethane-1-ol (meth) acrylate, 2- (cyclohexylaminocarboxy) ethane-1-ol (meth) acrylate, 2- (phenylaminocarboxy) ethane-1-ol (meth) acrylate, 2-( Methoxycarbonylamino) ethane-1-ol (meth) acrylate, 2- (ethoxycarbonylamino) ethane-1-ol (meth) acrylate, 2- (propoxycarbonylamino) ethane-1-ol (meth) acrylate, 2- Examples thereof include (butoxycarbonylamino) ethane-1-ol (meth) acrylate and 2- (phenoxycarbonylamino) ethane-1-ol (meth) acrylate. Further, as the polyfunctional (meth) acrylate having a urethane bond, for example, one or more compounds selected from the above-mentioned compounds having an isocyanate group and (meth) acrylate having a hydroxyl group are selected 1. Examples thereof include reactants of any combination of compounds of more than one species.

Among these, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (commonly known as UDMA), N, N'-from the viewpoint of excellent operability of the curable composition and toughness of the cured product. Reaction of (2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propan-1,3-diol] tetramethacrylate (commonly known as U4TH), alicyclic diisocyanate with 2-hydroxyethyl (meth) acrylate A product, for example, a reaction product of IPDI and 2-hydroxyethyl (meth) acrylate, a reaction product of TCDDI and 2-hydroxyethyl (meth) acrylate, and a reaction product of ADI and 2-hydroxyethyl (meth) acrylate are preferable. .. These may be used alone or in combination of two or more.

In addition, macromonomers having (meth) acrylic groups at both ends of polyurethane obtained by reacting diol and diisocyanate can also be used.

From the viewpoint of toughness, the content of the (meth) acrylate having a urethane bond is preferably 10 to 70% by mass, more preferably 15 to 60% by mass, based on the total amount of the polymerizable monomer. It is more preferably 20 to 40% by mass.

The total content of the (meth) acrylate (E) in the curable composition of the present invention is 1 to 1 in the total amount of the polymerizable monomer from the viewpoint of the toughness of the cured product of the curable composition of the present invention. It is preferably 80% by mass, more preferably 2.5 to 60% by mass, and even more preferably 5 to 40% by mass.

[(Meta) Acrylamide (F)]
The curable composition of the present invention preferably further contains (meth) acrylamide (F) for the purpose of improving operability or adjusting the physical properties of the cured product. The (meth) acrylamide (F) may be an aliphatic (meth) acrylamide, an alicyclic (meth) acrylamide, or an aromatic (meth) acrylamide, and may be an aliphatic (meth) acrylamide. ) Acrylamide and alicyclic (meth) acrylamide are preferred.

Examples of the (meth) acrylamide (F) include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, and N-isopropyl ( Meta) acrylamide, N, N-di-n-butyl (meth) acrylamide, N, N-di-n-hexyl (meth) acrylamide, N, N-di-n-octyl (meth) acrylamide, N, N- Di-2-ethylhexyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N- (dihydroxyethyl) (meth) acrylamide, N- (meth) acryloylmorpholin, N, N-dimethylamino Ethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dipropylaminoethyl (meth) acrylamide, N, N-dibutylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl ( Meta) Acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dipropylaminopropyl (meth) acrylamide, N, N-dibutylaminopropyl (meth) acrylamide, N, N-dimethylaminobutyl (meth) Acrylamide, N, N-diethylaminobutyl (meth) acrylamide, N, N-dipropylaminobutyl (meth) acrylamide, N, N-dibutylaminobutyl (meth) acrylamide, N- (meth) acryloyloxyethyl (meth) acrylamide , N- (meth) acryloyloxypropyl (meth) acrylamide, N, N', N''-tri (meth) acryloyldiethylenetriamine, N, N', N'', N''''-tetra (meth) acryloyltri Examples include ethylenetetramine. These may be used alone or in combination of two or more.

Among these, N, N-dimethyl (meth) acrylamide, N, N- are excellent in compatibility with the acryloyl (meth) acrylic compound (A) and excellent toughness of the cured product of the curable composition. Diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide, N- (2-hydroxyethyl) (Meta) acrylamide, N- (meth) acryloyl morpholine, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dimethylaminobutyl (meth) acrylamide, N, N-diethylaminobutyl (meth) acrylamide, N- (meth) acryloyloxyethyl (meth) acrylamide, N- (meth) Acryloyloxypropyl (meth) acrylamide, N, N', N''-tri (meth) acryloyl diethylenetriamine, N, N', N'', N''''-tetra (meth) acryloyltriethylenetetramine is preferred, N , N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (meth) acryloylmorpholin, N, N-Dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N- (meth) acryloyl Oxyethyl (meth) acrylamide, N- (meth) acryloyloxypropyl (meth) acrylamide, N, N', N''-tri (meth) acryloyldiethylenetriamine, N, N', N'', N'''- Tetra (meth) acryloyltriethylenetetramine is more preferred, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N- (2-hydroxyethyl) acrylamide, N-acryloylmorpholin, N, N- Dimethylaminoethylacrylamide, N, N-diethylaminoethylacrylamide, N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide, N- (meth) acryloyloxyethyl (meth) acrylamide, N- (meth) acryloyloxypropyl (meth) acrylamide, N, N', N''-tri (meth) acryloyldiethylenetriamine, N, N', N'', N'''-tetra (meth) acryloyltriethylenetetramine is more preferred, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-acryloylmorpholin, N, N-dimethyl. Aminopropyl acrylamide, N- (meth) acryloyloxyethyl (meth) acrylamide, N- (meth) acryloyloxypropyl (meth) acrylamide, N, N', N''-tri (meth) acryloyldiethylenetriamine, N, N' , N'', N''''-tetra (meth) acryloyltriethylenetetramine is particularly preferred.

The content of (meth) acrylamide (F) in the curable composition of the present invention is 1 to 80 mass by mass in the total amount of the polymerizable monomer from the viewpoint of the toughness of the cured product of the curable composition of the present invention. %, More preferably 2.5 to 60% by mass, and even more preferably 5 to 40% by mass.

[Other ingredients]
The curable composition of the present invention is polymerized other than the alicyclic (meth) acrylic compound (A), methacrylate (E) and (meth) acrylamide (F) as long as the effects of the present invention are not impaired. It may further contain a sex monomer. Other polymerizable monomers include, for example, vinyl-based monomers having a carboxyl group such as (meth) acrylic acid, maleic acid, and maleic anhydride; fragrances such as styrene, α-methylstyrene, and p-methylstyrene. Group vinyl monomers; conjugated diene-based monomers such as butadiene and isoprene; olefin-based monomers such as ethylene and propylene; lactone-based monomers such as ε-caprolactone and valerolactone.

In addition, a known additive can be added to the curable composition of the present invention as long as the performance is not deteriorated. Examples of such additives include polymerization inhibitors, antioxidants, pigments, dyes, ultraviolet absorbers, organic solvents, thickeners and the like.

Examples of the polymerization inhibitor include hydroquinone, dibutylhydroquinone, hydroquinone monomethyl ether, dibutyl hydroquinone monomethyl ether, t-butyl catechol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butylphenol, and the like. Phenols such as 3,5-di-t-butyl-4-hydroxytoluene; quinones such as p-benzoquinone, 2,5-diphenyl-p-benzoquinone, p-tolucinone, p-xylokinone and the like can be mentioned. The content of the polymerization inhibitor is preferably 0.001 to 1.0 part by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer.

[Use]
The curable composition of the present invention can provide a cured product having excellent mechanical properties and aesthetics, and is also excellent in operability. Therefore, the curable composition of the present invention is preferably used for dental applications, and more preferably for dental hard tissue applications such as teeth and bones. Examples of such dental hard tissue applications include dental composite resins and dental cements. The curable composition of the present invention may be either a one-material type or a two-material type.

An example of a preferred embodiment of a dental composite resin is shown. Suitable dental composite resin embodiments (CR-1) include alicyclic (meth) acrylic compounds (A), photopolymerization initiators (B-1), inorganic particles (C), and polymerization accelerators (D). ), Dental composite resins containing (meth) acrylate (E) and / or (meth) acrylamide (F) as optional components. In the dental composite resin of the embodiment (CR-1), 10 to 100% by mass of the alicyclic (meth) acrylic compound (A) was added to the total amount of the polymerizable monomer, and the (meth) acrylate (E) was added. And / or containing 0 to 80% by mass of (meth) acrylamide (F), 0.001 to 30 parts by mass of the photopolymerization initiator (B-1) with respect to 100 parts by mass of the total amount of the polymerizable monomer. It is preferable that the polymerization accelerator (D) is contained in an amount of 0.001 to 30 parts by mass and the inorganic particles (C) are contained in an amount of 10 to 1000 parts by mass. A) is contained in an amount of 30 to 95% by mass, (meth) acrylate (E) and / or (meth) acrylamide (F) is contained in an amount of 2.5 to 60% by mass, based on 100 parts by mass of the total amount of the polymerizable monomer. It is more preferable to contain 0.05 to 20 parts by mass of the photopolymerization initiator (B-1), 0.05 to 20 parts by mass of the polymerization accelerator (D), and 50 to 750 parts by mass of the inorganic particles (C). , 50 to 90% by mass of the alicyclic (meth) acrylic compound (A) and 5 to 40% by mass of (meth) acrylate (E) and / or (meth) acrylamide (F) in the total amount of the polymerizable monomer. % To 10 parts by mass of the photopolymerization initiator (B-1) and 0.1 to 10 parts by mass of the polymerization accelerator (D) with respect to 100 parts by mass of the total amount of the polymerizable monomer. It is more preferable to contain 100 to 500 parts by mass of the inorganic particles (C).

An example of a preferred embodiment of dental cement is shown. Suitable dental cement embodiments (S-1) include alicyclic (meth) acrylic compounds (A), photopolymerization initiators (B-1), chemical polymerization initiators (B-2), and inorganic particles. Examples thereof include (C), a polymerization accelerator (D), and a dental cement containing (meth) acrylate (E) and / or (meth) acrylamide (F) as optional components. In the dental cement of the embodiment (S-1), the alicyclic (meth) acrylic compound (A) is contained in an amount of 10 to 100% by mass, the (meth) acrylate (E) and the (meth) acrylate (E) in the total amount of the polymerizable monomer. / Or (meth) acrylamide (F) is contained in an amount of 0 to 80% by mass, and 0.001 to 30 parts by mass of the photopolymerization initiator (B-1) is added to 100 parts by mass of the total amount of the polymerizable monomer. It is preferable that the polymerization initiator (B-2) is contained in an amount of 0.001 to 30 parts by mass, the polymerization accelerator (D) is contained in an amount of 0.001 to 30 parts by mass, and the inorganic particles (C) are contained in an amount of 10 to 1000 parts by mass. Among the total amount of the sex monomers, 30 to 95% by mass of the alicyclic (meth) acrylic compound (A) and 2.5 to 60% by mass of the (meth) acrylate (E) and / or (meth) acrylamide (F). % 20 parts by mass of the photopolymerization initiator (B-1) and 0.05 to 20 parts by mass of the chemical polymerization initiator (B-2) with respect to 100 parts by mass of the total amount of the polymerizable monomer. It is more preferable to contain 0.05 to 20 parts by mass of the polymerization accelerator (D) and 50 to 500 parts by mass of the inorganic particles (C), and the alicyclic type (meth) is contained in the total amount of the polymerizable monomer. ) Acrylic compound (A) is contained in an amount of 50 to 90% by mass, (meth) acrylate (E) and / or (meth) acrylamide (F) is contained in an amount of 5 to 40% by mass, and the total amount of the polymerizable monomer is 100 parts by mass. On the other hand, the photopolymerization initiator (B-1) is 0.1 to 10 parts by mass, the chemical polymerization initiator (B-2) is 0.1 to 10 parts by mass, and the polymerization accelerator (D) is 0.1 to 10 parts by mass. It is more preferable to contain 100 to 300 parts by mass of the inorganic particles (C).

Conditions such as the type and content of each component in the preferred embodiment (CR-1) of the dental composite resin and the preferred embodiment (S-1) of the dental cement are within the scope separately described in this specification. Can be selected and changed as appropriate.

[Cured product]
A cured product can be obtained by curing the curable composition of the present invention. The curing method is not particularly limited. For example, when the curable composition of the present invention is a two-material type containing at least the first material and the second material, the first material and the second material are used. Mixing and the like can be mentioned.

The present invention includes embodiments in which the above configurations are variously combined within the technical scope of the present invention as long as the effects of the present invention are exhibited.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples, and many modifications are made in the art within the technical idea of the present invention. It is possible by a person with ordinary knowledge. The part in the example is a mass part unless otherwise specified.

[Analysis of alicyclic (meth) acrylic compounds]
In the following production examples, the alicyclic (meth) acrylic compound ^{was identified by 1} H-NMR measurement. The purity of the alicyclic (meth) acrylic compound was measured by UPLC (Ultra-Performance Liquid Chromatography). ^{1 The} equipment and conditions used for 1 H-NMR and UPLC measurements are as follows.

[ ¹ Equipment and conditions for 1 H-NMR measurement]
Device: Nuclear magnetic resonance device "JNM-LA400" (manufactured by JEOL Ltd.)
Deuterated solvent: Deuterated chloroform

[Analysis of purity by UPLC]
Equipment: ACQUITY UPLC (manufactured by Japan Waters Corp.)
Column: ACQUITY UPLC BEH C18 1.7 μm (manufactured by Japan Waters Corp.)
Mobile phase: Methanol / water = 45/55
Flow rate: 0.5 mL / min
Detector: RI, UV
Column temperature: 50 ° C
Injection volume: 1.0 μL

[Average particle size of inorganic particles]
The average particle size of the inorganic particles (fillers) used in the following examples was measured by a laser diffraction type particle size distribution measuring device. The equipment and conditions used for the measurement are as follows.
Device: Laser diffraction type particle size distribution measuring device "SALD-2100" (manufactured by Shimadzu Corporation)
Dispersion medium: 0.2% aqueous sodium hexametaphosphate solution

Next, the methods for producing the components of the curable compositions of Examples and Comparative Examples or their contents are described below together with abbreviations.

[Alicyclic (meth) acrylic compound]
Production Example 1 Synthesis of Isosorbide Dimethacrylate A 2L four-necked flask was charged with 146 g (1 mol) of isosorbide, 209.1 g (2 mol) of methacrylic acid chloride, 0.15 g (0.0014 mol) of p-benzoquinone, and 700 g of toluene. The mixture was cooled to 5 ° C. in an ice bath, and 202 g (2.0 mol) of triethylamine was slowly added dropwise using a dropping funnel while checking the heat of reaction. After completion of the dropping, the mixture was continuously stirred under ice-cooling for 5 hours. Then, the temperature was returned to room temperature and the mixture was further stirred for 3 hours to complete the reaction.

After completion of the reaction, the mixture was washed with 100 mL of distilled water, 0.025 g of hydroquinone was added, and the solvent was removed under reduced pressure to obtain a pale yellow viscous liquid.

When the above-mentioned ¹ H-NMR measurement and UPLC analysis were performed using the obtained liquid, it was found to be isosorbide dimethacrylate (yield 90.4% based on the raw material isosorbide). Hereinafter, in the examples, the following formula;

で表されるイソソルビドジメタクリレートを脂環式（メタ）アクリル化合物（Ａ）−Ｉ−１として用いた。

Isosorbide dimethacrylate represented by (1) was used as an alicyclic (meth) acrylic compound (A) -I-1.

Production Example 2 Synthesis of a compound represented by the following formula (alicyclic (meth) acrylic compound (A) -I-2)

146 g (1 mol) of isosorbide was dissolved in 670 g of a 50 mass% potassium hydroxide aqueous solution in a 2 L four-necked flask, and 19.3 g (0.06 mol) of tetrabutylammonium bromide and 726 g (6.0 mol) of allyl bromide were used as a phase transfer catalyst. ) Was added, and the mixture was heated under reflux for 7 hours and then distilled under reduced pressure to obtain 217 g (yield 96%) of isosorbidodialyl ether.

113 g (0.5 mol) of the obtained isosorbide diallyl ether is dissolved in 500 mL of methylene chloride, 79.8 g (1.1 mol) of m-chloroperbenzoic acid is added, and the mixture is stirred at room temperature for 24 hours and then with an aqueous potassium carbonate solution. It was washed, filtered and dried to obtain 117 g (yield 90%) of isosorbide diglycidyl ether.

104 g (0.4 mol) of the obtained isosorbidodiglycidyl ether, 42.1 (0.5 mol) of methacrylate, 0.44 g of triphenylphosphine and 0.15 g of hydroquinone were added, and the mixture was stirred at 75 ° C. for 1 hour under a nitrogen atmosphere. Then, after stirring at 100 ° C. for 3 hours, the mixture was dissolved in 400 mL of methylene chloride, washed with an aqueous potassium carbonate solution, filtered and dried to obtain 101.6 g (yield 90%) of a viscous liquid.

When the above-mentioned ¹ H-NMR measurement and UPLC analysis were performed using the obtained liquid, it was found that the compound was represented by the above formula (yield 78% based on the raw material isosorbide). Hereinafter, in the examples, the compound represented by the above formula was used as the alicyclic (meth) acrylic compound (A) -I-2.

Production Example 3 Synthesis of a compound represented by the following formula (alicyclic (meth) acrylic compound (A) -II-1)

A 2 L four-necked flask was charged with 146 g (1 mol) of isosorbide, 0.15 g of di-n-butyltin dilaurate, 0.15 g (0.0014 mol) of p-benzoquinone, and 500 mL of toluene. At 60 ° C., 310 g (2 mol) of methacryloyloxyethyl isocyanate was slowly added dropwise using a dropping funnel while checking the heat of reaction. After completion of the dropping, the mixture was continuously stirred at 60 ° C. for 12 hours.

After completion of the reaction, the temperature was returned to room temperature, the mixture was washed with 100 mL of distilled water, 0.025 g of hydroquinone was added, and the solvent was removed under reduced pressure to obtain a pale yellow viscous liquid.

When the above-mentioned ¹ H-NMR measurement and UPLC analysis were performed using the obtained liquid, it was found that the compound was represented by the above formula (yield 92.3% based on the raw material isosorbide). Hereinafter, in the examples, the compound represented by the above formula was used as the alicyclic (meth) acrylic compound (A) -II-1.

Production Example 4 Synthesis of 1,3-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] adamantane 30.4 g (70) of 1,3-bis (4-glycidyloxyphenyl) adamantane in a 300 mL three-necked flask. .3 mmol), 50 mL of 1,2-dichloroethane and 5.0 g (50 mmol) of triethylamine were added, and the mixture was stirred with a stirrer chip at 25 ° C. in the air. 20 g (224 mmol) of methacrylic acid was added, the temperature was raised in an oil bath, and the mixture was stirred at 80 to 85 ° C. for 5 hours. As a result of sampling a part of the reaction product and performing UPLC measurement, disappearance of 1,3-bis (4-glycidyloxyphenyl) adamantane was confirmed.

The reaction mixture was washed successively with saturated _{aqueous NaHCO 3} solution (100 mL x 2), 1N HCl (100 mL x 1) and distilled water (100 mL x 1), and the organic layer was dried over anhydrous sulfonyl ₄ . After filtering the organic layer, it was concentrated using an evaporator. The concentrate was vacuum dried to give 1,3-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] adamantane (36.8 g, 88% yield). This was used as Comparative Example 1 as an alicyclic (meth) acrylic compound 1.

[Photopolymerization Initiator (B-1)]
(B-1) -1 CQ: Camphorquinone (B-1) -2 BAPO: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide

[Chemical polymerization initiator (B-2)]
(B-2) -1 THP: 1,1,3,3-tetramethylbutylhydroperoxide

[Inorganic particles (C)]
Inorganic particles (C) -1: 3-methacryloyloxypropyltrimethoxysilane surface-treated barium glass powder, "GM27884 NF180" manufactured by SCHOTT, average particle size 0.18 μm
Inorganic particles (C) -2: 3-methacryloyloxypropyltrimethoxysilane surface-treated barium glass powder, "GM27884 UF0.4" manufactured by SCHOTT, average particle size 0.4 μm

[Polymerization accelerator (D)]
(D) -1 PDE: 4- (N, N-dimethylamino) ethyl benzoate (D) -2 PTU: 1- (2-pyridyl) -2-thiourea (D) -3 VOAA: vanadyl acetylacetonate (IV)

[Methacrylate (E)]
(E) -1 MDP: 10-methacryloyloxydecyldihydrogen phosphate (E) -2 UDMA: 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (E) -3 3G: Tri Ethylene glycol dimethacrylate

[(Meta) Acrylamide (F)]
(F) -1 DEAA: N, N-dimethylacrylamide (F) -2 ACMO: N-acryloyl morpholine

[Polymerization inhibitor]
BHT: 3,5-di-t-butyl-4-hydroxytoluene

Examples 1-14 and Comparative Examples 1-3
The raw materials shown in Tables 1 to 3 were mixed in a dark place at room temperature (23 ° C.) to prepare each paste (curable composition).
The characteristics of these pastes were examined according to the methods of Test Examples 1 to 4 below. In Examples 1 to 7 and Comparative Examples 1 to 3, each characteristic was examined using a one-material paste (one-material curable composition) having the compositions shown in Tables 1 and 3. On the other hand, in Examples 8 to 14, each characteristic was used by using a mixture obtained by mixing a two-material type paste (two-material type curable composition) composed of materials A and B having the compositions shown in Table 2. (However, the discharge property was evaluated by the method described later). The results are shown in Tables 1-3.

Test Example 1 Evaluation of toughness The toughness was evaluated by a bending test in accordance with ISO 4049: 2009. Specifically, it is as follows. The prepared paste (curable composition) was filled in a SUS mold (length 2 mm × width 25 mm × thickness 2 mm), and the top and bottom (2 mm × 25 mm surfaces) of the paste were pressure-welded with a slide glass. Next, the paste was cured by irradiating the front and back of the paste with light through a slide glass at 5 locations on each side for 10 seconds with a dental visible light irradiator (Pencure 2000, manufactured by Morita). The obtained cured product was subjected to a bending test at a crosshead speed of 1 mm / min using a universal testing machine (Autograph AG-100kNI, manufactured by Shimadzu Corporation), and the bending strength, flexural modulus and breaking point displacement were performed. Was measured. The results are shown in Tables 1-3. In this measurement, the greater the bending strength, the higher the strength of the cured product, the higher the flexural modulus, the more excellent the hardness, and the larger the displacement at the breaking point, the more difficult the cured product to break. When the bending strength is 100 MPa or more, the flexural modulus is 5 GPa or more, and the fracture point displacement is 1.0 mm or more, the cured product has excellent toughness.

Test Example 2 Abrasion resistance test (evaluation of sliding durability)
The sliding durability was evaluated based on the change in glossiness before and after the wear resistance test. Specifically, it is as follows. The prepared paste (curable composition) was filled in a SUS mold (length 30 mm × width 20 mm × thickness 2 mm), and the top and bottom (30 mm × 20 mm surfaces) of the paste were pressure-welded with a slide glass. Next, the paste was cured by irradiating the front and back of the paste with light through a slide glass for 180 seconds each with a visible light irradiator for dental technicians (α-light V, manufactured by Morita Co., Ltd.). Using the obtained cured product as a test piece, this surface was polished with No. 1500 water resistant abrasive paper. Next, the polished surface was buffed at 3000 rpm for 20 seconds using a technical polishing box (EWL80, manufactured by KaVo). The buffed test piece was subjected to an abrasion resistance test. For buffing, a dental abrasive (trade name: PORTENY HYDON, manufactured by Tokyo Tooth Materials Co., Ltd.) was used. The glossiness (G1) of the test piece before the abrasion resistance test was measured by a gloss meter (VG-107). , Nippon Denshoku Kogyo Co., Ltd.) was used to determine the ratio when the mirror was set to 100%. The measurement angle was 60 °. The test piece was used as a toothbrush wear tester (Daei Kagaku Seiki Co., Ltd.). A wear resistance test was conducted for 40,000 cycles under a load of 250 g using a suspension of dentifrice material and a commercially available toothbrush. The suspension of dentifrice material was prepared using a commercially available toothpaste material. , Abrasive / distilled water was prepared at a mass ratio of 60/40. The glossiness (G2) of the surface of the test piece after the wear resistance test was determined by the same method as before the wear resistance test. Before and after the wear resistance test. Based on the glossiness of the surface of the test piece, the abrasive durability (%) was expressed as {(G2) × 100} / (G1). The results are shown in Tables 1 to 3. It is suitable from the viewpoint of aesthetics.

Test Example 3 Measurement of polymerization shrinkage stress A paste (curable composition) prepared in a ring-shaped mold (stainless steel, inner diameter 5.5 mm × thickness 0.8 mm) installed on a glass plate having a thickness of 4.0 mm. Thing) was filled. The glass plate used was sandblasted with alumina powder having a particle size of 50 μm. A stainless steel jig (φ5 mm) connected to a universal testing machine (Autograph AG-100kNI, manufactured by Shimadzu Corporation) was installed on the filled paste. Then, using a dental visible light irradiator (Pencure 2000, manufactured by Morita Co., Ltd.), the paste was irradiated with light for 20 seconds through a glass plate to cure the paste. At this time, the polymerization shrinkage stress associated with the polymerization (curing) of the curable composition progressed by such light irradiation was measured by the above-mentioned universal tester. The results are shown in Tables 1-3. The smaller the polymerization shrinkage stress, the smaller the risk of peeling due to shrinkage. For example, when a curable composition is used for dental applications, more curable composition can be filled at one time. Operability is improved. The polymerization shrinkage stress is preferably 100 N or less, and more preferably less than 85 N.

Test Example 4 Evaluation of Dischargeability (Discharge Force) In the measurement of discharge force, when the test piece is a one-material curable composition (Examples 1 to 7 and Comparative Examples 1 to 3), Clearfill Majesty LV A syringe container (manufactured by Clarenori Take Dental Co., Ltd.) was used with a guide tip attached to the tip of the syringe container. The size of the syringe container was 7.5 cm in the length of the cylindrical portion and 0.8 cm in the inner diameter of the opening. The guide tip size was 1.5 cm in length and 0.8 mm in inner diameter of the opening. When the test piece is a two-material curable composition (Examples 8 to 14), a syringe container of Clearfill Panavia V5 (manufactured by Kuraray Noritake Dental Co., Ltd., total capacity 5 mL) is placed at the tip of the syringe container with an inner diameter of 0. A 0.8 mm mixing tip was attached and used.

The paste (curable composition) was placed in a syringe container and stored at 25 ° C. for one week to stabilize the properties of the curable composition. After that, the extrusion member (push) was made to enter the syringe container, and the paste in the container was discharged from the ejection portion of the insert through the guide tip or the mixing tip. At this time, the force required to extrude the paste from the syringe container was measured as a discharge force using a universal testing machine (Autograph AGI-100, manufactured by Shimadzu Corporation). Specifically, the syringe container is erected vertically, the crosshead equipped with the jig for the compressive strength test is lowered at 4 mm / min, and the paste is discharged while applying a load, and the maximum load at that time is discharged. It was a force. The discharge force was measured at 25 ° C. When the discharge force is 40 N or less, it can be easily discharged and the discharge property is good. Discharge is possible at more than 40 N and 60 N or less, but the discharge property is poor. Discharge is difficult above 60N.

From the results shown in Tables 1 to 3, the cured product of the curable composition of the example has a large flexural modulus and is hard, but has a large flexural strength and displacement, and is excellent in toughness. In addition, it is excellent in smoothing durability, low polymerization shrinkage stress, and small force when it is filled in a container and discharged, so that it is also excellent in operability. On the other hand, the compositions of Comparative Examples 1 and 2 which do not contain the alicyclic (meth) acrylic compound (A) have poor toughness of the cured product, are brittle, and have a large ejection force. Further, the cured product of the composition containing the inorganic particles having an average particle diameter of more than 10 μm in Comparative Example 3 has poor toughness and smoothing durability.

The curable composition of the present invention can be suitably used for dental applications such as dental composite resins and dental cements.

Claims (12)

It contains an alicyclic (meth) acrylic compound (A), a polymerization initiator (B) and inorganic particles (C).
The alicyclic (meth) acrylic compound (A) has the following general formula [I].

(In the formula, R ¹ and R ² are independently (meth) acryloyl groups, X is a divalent unsubstituted or substituted hydrocarbon group, and m and n are independently 0 to 30 respectively. Is an integer of.)
It is an alicyclic (meth) acrylic compound (A) -I represented by
A curable composition having an average particle size of the inorganic particles (C) of 0.1 to 1.0 μm. The curable composition according to claim 1, wherein X is an alkylene group having 2 to 6 carbon atoms. The curable composition according to claim 1 or 2 ^{, wherein R 1} and R ^{2 of the} alicyclic (meth) acrylic compound (A) are methacryloyl groups. The curable composition according to any one of claims 1 to 3 , further containing a polymerization accelerator (D). The curable composition according to any one of claims 1 to 4 , further containing a (meth) acrylate (E) other than the alicyclic (meth) acrylic compound (A). The curable composition according to any one of claims 1 to 5 , further containing (meth) acrylamide (F). The curable composition according to any one of claims 1 to 6 , which is a dental curable composition. The curable composition according to claim 7 , which is a curable composition for dental hard tissue. The curable composition according to claim 8 , which is a dental composite resin. The curable composition according to claim 8 , which is a dental cement. A method for producing a cured product, which cures the curable composition according to any one of claims 1 to 10. A method for curing a curable composition according to any one of claims 1 to 10.