JP2018193342A - Curable compositions comprising alicyclic (meth)acryl compounds - Google Patents

Abstract

To provide curable compositions that provide cured products excellent in mechanical and esthetic properties with excellent operability.SOLUTION: Disclosed herein is a curable composition comprising an alicyclic (meth)acrylic compound (A), a polymerization initiator (B) and an inorganic particle (C), where the alicyclic (meth)acrylic compound (A) is selected from the group consisting of alicyclic (meth)acrylic compound (A)-I of Formula [I] and alicyclic (meth)acrylic compounds having amide bonds, and the average particle diameter of the inorganic particle (C) is 0.001-10 μm. In the Formula [I], R1 and R2 are independently (meth)acryloyl group, X is a divalent unsubstituted/substituted hydrocarbon group; m and n are independently an integer of 0-30.SELECTED DRAWING: None

Description

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

  Dental materials such as dental composite resins, dental cements, dental adhesives, and dental primers are widely used when filling or covering restorations on tooth defects.

  Among these dental materials, in particular, a dental composite resin and a dental cement are required to have mechanical properties and color similar to those of a tooth, that is, aesthetics. Specifically, mechanical properties include strength, elastic modulus, toughness, hardness and the like, and aesthetic properties include color, gloss, and the like. Furthermore, in recent years, the demand for ease of handling, that is, operability of dental materials has been increasing. Specifically, dental materials are easily extruded when used in a syringe, and a large amount is used at the time of use. It is important to be able to fill.

  In general, inorganic particles are blended as a means for imparting strength. However, when inorganic particles are blended, the toughness tends to decrease and the brittleness tends to break. In order to provide both strength and toughness, and also to impart aesthetics such as polishing and gloss, inorganic particles having a small particle size tend to be used. However, when inorganic particles having a small particle size are blended, the viscosity is increased, and it is difficult to extrude and the operability is lowered.

  The following techniques are known as techniques excellent in such mechanical properties, 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, by containing an isosorbide derivative, improves photosensitivity, air drying, hardness of a cured film, and the like, and suppresses problems such as curling of the cured film.

JP 2009-84221 A JP 2011-84535 A

  The dental composition of Patent Document 1 is excellent in transparency, but the mechanical properties 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 properties as a dental material, and does not specifically describe aesthetics and operability.

  Therefore, the present invention can provide a cured product having excellent mechanical properties and aesthetics and is excellent in operability, a method for producing a cured product for curing the curable composition, and the It aims at providing the hardening method of the curable composition which hardens a 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 comprises an alicyclic (meth) acrylic compound (A), a polymerization initiator (B) and inorganic particles (C), wherein the alicyclic (meth) acrylic compound (A) is The following general formula [I]

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

Wherein R ³ and R ⁴ are each independently a (meth) acryloyl group, Y and Z are each independently a divalent unsubstituted or substituted hydrocarbon group, and p and q are each It is an integer of 0-30 independently.)
And at least one selected from the group consisting of alicyclic (meth) acrylic compounds (A) -II represented by:
It is a curable composition whose average particle diameter of an inorganic particle (C) is 0.001-10 micrometers.

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

  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 it is a C2-C6 alkylene group each independently.

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

  The curable composition preferably further contains a polymerization accelerator (D).

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

  It is preferable that the curable composition 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.

  This invention also includes the manufacturing method of the hardened | cured material which hardens the curable composition of this invention.

  This invention also includes the hardening method of the curable composition which hardens the curable composition of this invention.

  The curable composition of the present invention can give 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]

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

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

  In the present specification, the notation of (meth) acryl is used to include both methacryl and acryl, and the notation of (meth) allyl is used to include both methallyl and allyl. In the present specification, the upper limit value and the lower limit value of the numerical ranges (content of each component, values calculated from each component, physical properties, etc.) can be appropriately combined.

[Alicyclic (meth) acrylic compound (A)]
In the curable composition of the present invention, the alicyclic (meth) acrylic compound (A) has an effect of relaxing polymerization shrinkage stress, imparting mechanical properties to the cured product, and reducing the viscosity of the composition. Therefore, the alicyclic (meth) acrylic compound (A) is preferably used as a substrate. The reason why the excellent effect as described above is exhibited by the curable composition of the present invention is not necessarily clear, but the alicyclic (meth) acrylic compound (A) is represented by the following formula [i]. By having a formula skeleton, it is presumed that a bulky and rigid ring structure contributes to the development of strength, and a bent structure that does not exist in a planar aromatic ring contributes to the relaxation of polymerization shrinkage stress. Furthermore, it is presumed that the cyclic ether structure in the alicyclic skeleton strongly contributes to the inorganic particles and contributes to improvement in operability by reducing the viscosity of the composition.

  The alicyclic skeleton represented by the formula [i] included 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 formula [i] -1, formula [i] -2, and formula [i] -3.

  These compounds in which hydrogen is bonded to both ends are ether diols derived from carbohydrates, which are obtained from natural biomass, and are one of so-called renewable resources. Diol compounds in which hydrogen is bonded to both ends of the alicyclic skeleton represented by [i] -1, [i] -2, and [i] -3 are respectively isosorbide (1,4: 3,6-dianhydro). -D-sorbitol), isomannide (1,4: 3,6-dianhydro-D-mannitol), and isoidide (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 be obtained by the same reaction except for the starting material. Among isosorbide, isomannide, and isoidide, an alicyclic skeleton derived from isosorbide is particularly preferable because it is easy to manufacture and has excellent heat resistance, and is difficult to deteriorate during processing.

Alicyclic (meth) acrylic compound (A) -I
Each symbol of the general formula [I] will be described. R ¹ and R ² are each independently a (meth) acryloyl group, X is a divalent unsubstituted or substituted hydrocarbon group, and m and n are each independently an integer of 0 to 30. .
In the 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. Among these, a curable composition From the viewpoint of viscosity, an aliphatic hydrocarbon group is preferable.

  Examples of the aliphatic hydrocarbon group include linear or branched alkylene groups and alkenylene groups. 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, and a 3-hexenylene group. Among these, ethylene group, 1,2-propylene group and 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, and a cyclooctylene group. Examples of the cycloalkenylene group include a cyclohexenylene group, a cycloheptenylene group, a cyclooctenylene group, a cyclononenylene group, and a cyclodecenylene group.

  Examples of the aromatic hydrocarbon group include an arylene group. Examples of the arylene group include phenylene group, tolylene group, methylphenylene group, xylylene group, naphthylene group, anthracenylene group, phenanthrylene group, biphenylene group, and fluoronylene group.

  These hydrocarbon groups include isomers as long as they have the effects of the present invention. The hydrocarbon group may be a group combining two or more selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. For example, an alkylene 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.

  2-30 are preferable and, as for carbon number of the hydrocarbon group which X represents, 2-20 are more preferable. Among these, X is preferably an alkylene group having 2 to 6 carbon atoms in that the cured product of the resulting curable composition is excellent in strength. In view 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 possessed by 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 (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); a hydroxyl group, an amino group, a linear or branched alkoxy group having 1 to 12 carbon atoms, and the like. Is mentioned. These may be used alone or in combination of two or more. 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. In addition, when these substituents have an isomer, the isomer is included as long as it has the effect of the present invention. Among the above substituents, a hydroxyl group is preferable because the cured product of the curable composition is excellent in strength.

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

  The production method of the alicyclic (meth) acrylic compound (A) -I is not particularly limited. Regardless of the production method, the compound represented by the above general formula [I], and curing containing the compound The alicyclic (meth) acrylic compound (A) -I is preferably included in the scope of the present invention, and preferably used in JP 2011-84535 A, J Mater Sci: Mater Med (2012) 23 : 1149-1155 and the like. More specifically, the alicyclic (meth) acrylic compound (A) -I includes, for example, an alicyclic diol (isosorbide or the like) having an ether bond corresponding to the alicyclic skeleton represented by the formula [i]. ) As it is, or a method in which an epoxy compound such as ethylene oxide or propylene oxide is reacted therewith, and then a hydroxyl group is converted to a (meth) acryloyloxy group by an esterification reaction or the like; or in the formula [i] After reacting an alicyclic diol having an ether bond corresponding to the alicyclic skeleton represented (such as isosorbide) with a halogenated (meth) allyl such as allyl bromide, the double bond is epoxidized, Next, the epoxy group can be produced by a method of causing ring opening by reacting with (meth) acrylic acid or the like.

-Alicyclic (meth) acrylic compound (A) -II
Each symbol of the general formula [II] will be described. R ³ and R ⁴ are each independently a (meth) acryloyl group, Y and Z are each independently a divalent unsubstituted or substituted hydrocarbon group, and p and q are each independently 0 It is an integer of ~ 30.
In the general formula [II], examples of the hydrocarbon group represented by Y and Z include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. From the viewpoint of the viscosity of the adhesive composition, an aliphatic hydrocarbon group is preferred.

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

  The hydrocarbon groups represented by Y and Z, respectively, include isomers as long as they have the effects of the present invention. The hydrocarbon group may be a group combining two or more selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. For example, an alkylene 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.

  2-30 are preferable and, as for carbon number of the hydrocarbon group which Y and Z respectively represent, 2-20 are more preferable. Among them, it is preferable that Y and Z are each independently an alkylene group having 2 to 6 carbon atoms in that the obtained cured product of the curable composition is excellent in strength. In terms of the viscosity of the curable composition, Y and Z are each independently more preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. .

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

  In the general formula [II], p and q are each independently an integer of 0 to 30, and the cured product of the resulting curable composition is excellent in strength, and p and q are each independently 0 to 30. A range of 9 is preferred. Further, in terms of the viscosity of the curable composition, p and q are each preferably more preferably an integer of 0 to 6, more preferably each independently an integer of 0 to 3, and each independently. Is particularly preferably 0 or 1. p and q may be the same or different from each other, but p and q may be the same from the viewpoint of ease of production of the alicyclic (meth) acrylic compound (A) -II. preferable.

The production method of the alicyclic (meth) acrylic compound (A) -II is not particularly limited. 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 be preferably produced by the following method. That is, an alicyclic diol (such as isosorbide) having an ether bond corresponding to the alicyclic skeleton represented by the formula [i] is used as it is, or an epoxy compound such as ethylene oxide or propylene oxide is allowed to react therewith. Thereafter, the hydroxyl group is converted to an isocyanate compound represented by the general formula: R ³ —O—Z—NCO and an isocyanate compound represented by R ⁴ —O—Z—NCO (wherein R ³ , R ⁴ and Z are And having the same meaning as above).

  In the reaction between the hydroxyl group and the isocyanate compound, using a conventionally known urethanization catalyst, if necessary, a polymerization inhibitor is added, and both are reacted at a temperature of 40 to 90 ° C. The (meth) acrylic compound (A) -II can be obtained smoothly, which is preferable. As said polymerization inhibitor, the thing similar to the polymerization inhibitor which can be added to the curable composition of this invention mentioned later can be used.

Alicyclic (meth) acrylic compounds depending on the types of R ¹ , R ² , R ³ , R ⁴ , X, Y and Z, the numbers m, n, p and q in the general formulas [I] and [II] The properties of (A) are different. However, in general, the alicyclic (meth) acrylic compound (A) -I and the alicyclic (meth) acrylic compound (A) -II are often low-viscosity liquids at normal temperatures. When such a liquid alicyclic (meth) acrylic compound (A) is used at room temperature, a curable composition that is more excellent in handleability can be obtained.

As alicyclic (meth) acryl compound (A) -I, R ¹ and R ² are both methacryloyl groups, and X is a divalent unsubstituted or substituted hydrocarbon group having 2 to 6 carbon atoms. And alicyclic (meth) acrylic compounds wherein m and n are each independently an integer of 0 to 9 are preferred; R ¹ and R ² are both methacryloyl groups, and X is 2 having 2 to 4 carbon atoms. More preferably an alicyclic (meth) acrylic compound which is a valent unsubstituted or substituted hydrocarbon group and m and n are each independently an integer of 0 to 6; and R ¹ and R ² are both methacryloyl An alicyclic (meth) acrylic compound, wherein X is a divalent unsubstituted or substituted hydrocarbon group having 2 or 3 carbon atoms, and m and n are each independently an integer of 0 to 3 Is more preferable.

As alicyclic (meth) acrylic compound (A) -II, R ³ and R ⁴ are both methacryloyl groups, and Y and Z are each independently divalent unsubstituted or substituted having 2 to 6 carbon atoms. An alicyclic (meth) acrylic compound in which p and q are each independently an integer of 0 to 9; R ³ and R ⁴ are both methacryloyl groups, and Y and Z Are each independently a divalent unsubstituted or substituted hydrocarbon group having 2 to 4 carbon atoms, and p and q are each independently an integer of 0 to 6; More preferably; R ³ and R ⁴ are both methacryloyl groups, Y and Z are each independently a divalent unsubstituted or substituted hydrocarbon group having 2 or 3 carbon atoms, and p and q are each An alicyclic (meta) independently being an integer from 0 to 3 Krill compound is more preferable.

The curable composition of the present invention includes an alicyclic (meth) acrylic compound (A) and an alicyclic (meth) acrylic compound (A) -I and an alicyclic (meth) acrylic compound (A) -II. Only one of them may be contained, or both may be contained. As the alicyclic (meth) acrylic compound (A) -I, one type of compound may be used alone, or two or more types of compounds may be used in combination. Similarly, as the alicyclic (meth) acrylic compound (A) -II, one type of compound may be used alone, or two or more types of compounds may be used in combination. In the case where 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, 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, and 30 to 95% by mass in the total amount of the polymerizable monomer. It is more preferable that it is 50 to 90% by mass. In this 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 ( It means the total amount of (meth) acrylate (E), (meth) acrylamide (F) and other polymerizable monomers other than these.

[Polymerization initiator (B)]
As a polymerization initiator (B) used for this invention, it can select and use from the polymerization initiator currently used in the general industry, Among these, the polymerization initiator used for a dental use is used preferably. As the polymerization initiator (B), at least one selected from the group consisting of a photopolymerization initiator (B-1) and a 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, Examples include coumarins, anthraquinones, benzoin alkyl ether compounds, α-amino ketone compounds, and the like.

  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 even when any light source of a halogen lamp, a light emitting diode (LED), or a xenon lamp is used. 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) Phenyl) phosphonate, sodium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide, potassium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide And ammonium salts of 2,4,6-trimethylbenzoyl phenyl phosphine oxide.

  Among the (bis) acylphosphine oxides, examples of 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) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenyl Hosphy Oxide, bis (2,3,6-trimethylbenzoyl) -2,4,4-like trimethyl pentyl phosphine oxide.

  Further, (bis) acylphosphine oxides include compounds described in JP-A No. 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 and a sodium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide as the photopolymerization initiator (B-1).

  Examples of α-diketones include diacetyl, benzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′-oxybenzyl, acenaphthenequinone, 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 a chemical polymerization initiator (B-2) is not specifically limited, A well-known thing can be used. Typical organic peroxides include, for example, ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxy ketal, peroxy ester, peroxy dicarbonate and the like.

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

  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. Is mentioned.

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

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

  Examples of the peroxyketal include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 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.

  Examples of peroxyesters include α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-3, 3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxymaleate and the like can be mentioned.

  As peroxydicarbonate, for example, di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, di-n-propylperoxy Examples thereof include dicarbonate, di-2-ethoxyethyl peroxydicarbonate, diallyl peroxydicarbonate, and the like.

  Among these organic peroxides, hydroperoxide starts chemical polymerization due to a comprehensive balance of safety, storage stability, and radical generation ability in the presence of the alicyclic (meth) acrylic compound (A). It is preferably used as the agent (B-2). Among these, cumene hydroperoxide, t-butyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide are particularly preferably used as the chemical polymerization initiator (B-2).

  Although content of the polymerization initiator (B) in the curable composition of this invention is not specifically limited, From viewpoints, such as sclerosis | hardenability of the curable composition obtained, with respect to 100 mass parts of total amounts of a polymerizable monomer. In addition, the polymerization initiator (B) is preferably contained in an amount of 0.001 to 30 parts by mass. When content of a polymerization initiator (B) is 0.001 mass part or more, superposition | polymerization fully advances and stickiness can be prevented. As for content of a polymerization initiator (B), 0.05 mass part or more is more preferable, and 0.1 mass part or more is further more preferable. 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 this invention contains the inorganic particle (C) whose average particle diameter is 0.001-10 micrometers.

  Examples of the material for 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, 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 aluminosilicate glass and ytterbium fluoride. These can be used individually by 1 type or in combination of 2 or more types. The shape of the inorganic particles (C) is not particularly limited, and amorphous inorganic particles and spherical inorganic particles 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 operability of the resulting curable composition and the strength of the cured product are excellent. More preferably, barium glass is used.

  The inorganic particle (C) adjusts the miscibility with a polymerizable monomer other than the alicyclic (meth) acrylic compound (A) and the alicyclic (meth) acrylic compound (A). Alternatively, a surface treated in advance with a surface treating agent such as a silane coupling agent may be used. Examples of the surface treatment agent 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 spraying the surface treatment agent while stirring the inorganic particles vigorously; dispersing the inorganic particles and the surface treatment agent in a suitable solvent or A method of removing the solvent after dissolving; in the aqueous solution, the alkoxy group of the surface treatment agent is hydrolyzed with an acid catalyst to convert to a silanol group, and after adhering to the surface of the inorganic particles in the aqueous solution, The method of removing is mentioned. In any of the methods described above, the surface treatment can be carried out by heating the inorganic particle surface and the surface treatment agent by heating usually in the range of 50 to 150 ° C. In addition, the usage-amount in particular of a surface treating agent is not restrict | limited, For example, 1-10 mass parts of surface treating agents can be used with respect to 100 mass parts of inorganic particles before a process.

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

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

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

  The electron microscope observation is, for example, taking a scanning electron microscope (Hitachi, S-4000 type) photograph of particles, and analyzing the particle diameter of particles (200 or more) observed in the unit field of view of the photograph. It can obtain | require by measuring using a type | formula particle size distribution measurement software (Macview (Mounttech Co., Ltd.)). At this time, the particle diameter of the particles is obtained as an arithmetic average value of the longest length and the shortest length of the particles, and the average primary particle diameter is calculated from the number of particles and the particle diameter.

  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 polymerizable monomers, from the viewpoint of dischargeability and the strength of the cured product. More preferably, it is 50-750 mass parts, and it is further more preferable that it is 100-500 mass parts.

[Polymerization accelerator (D)]
The curable composition of the present invention preferably further contains a polymerization accelerator (D). Examples of the polymerization accelerator (D) include amines, sulfinic acid and salts thereof, sulfites, bisulfites, aldehydes, thiourea compounds, organophosphorus compounds, borate compounds, barbituric acid derivatives, triazine compounds, vanadium. Examples 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; secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine; N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate , Triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine, etc. And 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) benzoic acid n-butoxyethyl, 4- (N, N-dimethylamino) benzoic acid 2- (methacryloyloxy) ethyl, 4- (N, N-dimethylamino) benzophenone, 4- (N, N-dimethylamino) benzoic acid butyl and the like. Among these, from the viewpoint of imparting excellent curability to the curable composition, ethyl 4- (N, N-dimethylamino) benzoate, n-butoxyethyl 4- (N, N-dimethylamino) benzoate, 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 sulfate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinate, sodium 2,4,6-trimethylbenzenesulfinate, 2,4,6-trimethylbenzenesulfine Potassium acetate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinate, 2,4,6-to Sodium ethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzene Sulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, 2,4,6-triisopropyl Examples thereof include calcium benzenesulfinate.

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

  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-propylthio Urea, tetracyclohexylthiourea, 3,3-dimethylethylenethiourea, 4,4-dimethyl-2-imidazolinethione and the like can be mentioned. 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 -Imidazolinethione is preferably used as the polymerization accelerator (D).

  Examples of the organic phosphorus compound include triphenylphosphine, 2-methyltriphenylphosphine, 4-methyltriphenylphosphine, 2-methoxytriphenylphosphine, 4-methoxytriphenylphosphine, tri-n-butylphosphine, triisobutylphosphine, And tri-t-butylphosphine.

  As the borate compound, an aryl borate compound is preferable. When the aryl borate compound used suitably is illustrated specifically, as a borate compound which has one aryl group in 1 molecule, a trialkylphenyl boron, a trialkyl (p-chlorophenyl) boron, a 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-butyloxyph) Nyl) boron, trialkyl (p-octyloxyphenyl) boron and trialkyl (m-octyloxyphenyl) boron (wherein the alkyl group is selected from the group consisting of n-butyl group, n-octyl group and n-dodecyl group, etc.) And at least one of these salts (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.).

  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) And dialkyldi (m-octyloxyphenyl) boron (wherein the alkyl group is at least one selected from the group consisting of n-butyl group, n-octyl group and n-dodecyl group) 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 butylquinoli Nium salt).

  Examples of the borate compound having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, monoalkyltri [3 , 5-Bis (trifluoromethyl) phenyl] boron, monoalkyltri [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, mono 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, Noalkyltri (p-octyloxyphenyl) boron and monoalkyltri (m-octyloxyphenyl) boron (the alkyl group is one selected from n-butyl group, n-octyl group or n-dodecyl group) and These salts (sodium, lithium, potassium, magnesium, tetrabutylammonium, tetramethylammonium, tetraethylammonium, methylpyridinium, ethylpyridinium, butylpyridinium, methylquinolinium, Norinium salt, butylquinolinium salt, etc.).

  Examples of the borate compound having four aryl groups in one molecule include tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, 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-octyl) Xylphenyl) boron, (p-fluorophenyl) triphenylboron, [3,5-bis (trifluoromethyl) phenyl] triphenylboron, (p-nitrophenyl) triphenylboron, (m-butyloxyphenyl) triphenyl Boron, (p-butyloxyphenyl) triphenylboron, (m-octyloxyphenyl) triphenylboron and (p-octyloxyphenyl) triphenylboron and their salts (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.) It is below.

  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. These aryl borate compounds may be used alone or in combination of two or more.

  Examples of the barbituric acid derivative include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, and 5-ethyl. Barbituric acid, 5-isopropyl barbituric 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-phen Rubarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethylbarbituric 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 Hexyl barbituric acid, 5-butyl-1-cyclohexyl barbituric acid, 1-benzyl-5-phenylbarbituric acid and thiobarbituric acids, and salts thereof (especially preferred are alkali metals or alkaline earth metals) Is mentioned. Examples of salts of these barbituric acids include sodium 5-butyl barbiturate, 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, 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- Methoxyphenyl) 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) -s-triazine, 2- [2- {N-hydroxyethyl-N-methylamino} ethoxy] -4,6-bis (trichloromethyl)- Examples include s-triazine, 2- [2- {N, N-diallylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine.

  As the vanadium compound, IV and / or V valent vanadium compounds are preferable. Examples of the IV-valent and / or V-valent vanadium compounds include vanadium tetroxide (IV), vanadyl acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl- 1,3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), and ammonium metavanadate (V). 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-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, and di-n-butyltin dilaurate. Among these, 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, vanadium compounds, and copper compounds are particularly preferably used, and among these, 1- (2-pyridyl) -2-thiourea, 4- ( N, N-dimethylamino) ethyl benzoate, 4,4-dimethyl-2-imidazolinethione, vanadyl acetylacetonate (IV), copper acetylacetone, and cupric acetate are most preferably used as the polymerization accelerator (D). .

  Although content of the polymerization accelerator (D) in the curable composition of this invention is not specifically limited, From viewpoints, such as sclerosis | hardenability of the curable composition obtained, with respect to 100 mass parts of total amounts of a polymerizable monomer. The polymerization accelerator (D) is preferably contained in an amount of 0.001 to 30 parts by mass. When content of a polymerization accelerator (D) is 0.001 mass part or more, superposition | polymerization can fully advance and stickiness can be prevented. As for content of a polymerization accelerator (D), 0.05 mass part or more is more preferable, and 0.1 mass part or more is further more preferable. On the other hand, even when the polymerization performance of the polymerization initiator (B) used is low due to the content of the polymerization accelerator (D) being 30 parts by mass or less, the polymerization initiator (B ) Can be prevented. 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.

  In the present invention, the chemical polymerization initiator (B-2) and the polymerization accelerator (D) may be combined to form 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 including 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 type 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 a two-paste type in which both the first material and the second material are pasty. 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 isolated from each other, and the two pastes are kneaded and chemical polymerization proceeds immediately before use. When the curable composition further contains a photopolymerization initiator (B-1), it is preferable to cure the curable composition by proceeding with photopolymerization in addition to chemical polymerization.

[(Meth) 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 (meth) acrylate (E) include monofunctional (meth) acrylate having one (meth) acryloyl group, and polyfunctional (meth) acrylate having a plurality of (meth) acryloyl groups. 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, 6 -(Meth) 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; (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl Alkyl (meth) acrylates such as ru (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate; cyclohexyl (meth) acrylate , Cycloaliphatic (meth) acrylates such as isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isosorbide mono (meth) acrylate, isomannide mono (meth) acrylate, isoid mono (meth) acrylate; benzyl (meth) Aromatic group-containing (meth) acrylates such as acrylate; methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate Ether group-containing (meth) acrylates such as butoxydiethylene glycol (meth) acrylate; bromine-containing (meth) acrylates such as 2,3-dibromopropyl (meth) acrylate; 3- (meth) acryloyloxypropyltrimethoxysilane, 11- ( Examples include silyl group-containing (meth) acrylates such as (meth) acryloyloxyundecyltrimethoxysilane. These may be used alone or in combination of two or more. Among these, alkyl (meth) acrylate and alicyclic (meth) acrylate are preferable in terms of good miscibility with the alicyclic (meth) acrylic compound (A) and excellent curability of the curable composition. More preferred are methyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isosorbide mono (meth) acrylate, isomannide mono (meth) acrylate and isoid mono (meth) acrylate. .

  Examples of polyfunctional (meth) acrylates include aliphatic compound-based bifunctional (meth) acrylates, aromatic compound-based bifunctional (meth) acrylates, and trifunctional or higher (meth) acrylates. Etc.

  Examples of aliphatic compound-based bifunctional (meth) acrylates include glycerol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and propylene. Glycol di (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- Kanji ol di (meth) acrylate, 1,2-bis (3- (meth) acryloyloxy-2-hydroxypropoxy) ethane. Among these, glycerol di (meth) acrylate and triethylene glycol are excellent in miscibility with the alicyclic (meth) acrylic compound (A) and excellent in the strength and toughness of the cured product of the resulting 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 (Meth) acrylate, 1,9-nonanediol di (meth) acrylate and 1,10-decanol di (meth) acrylate 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) Having an added mole number of about 2.6), 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- ( Ta) acryloyloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- ( (Meth) acryloyloxyethoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2- (4- (meth) acryloyloxy Dipropoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2,2-bis (4- (meth)) Acryloyloxyisopropoxyphenyl) propane, etc. It is below.

  Examples of tri- or higher functional (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Examples include erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, 1,7-di (meth) acryloyloxy-2,2,6,6-tetra (meth) acryloyloxymethyl-4-oxyheptane, and the like. It is done. Among these, trimethylolpropane tri (meth) acrylate is preferable because it is miscible with the alicyclic (meth) acrylic compound (A) and is excellent in the strength of the cured product of the curable composition.

  In addition, 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 coloring resistance to a pigment or the like. Examples of such fluorine-containing (meth) acrylates include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, and 2- (par Fluorobutyl) ethyl (meth) acrylate, 3- (perfluorobutyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl ( (Meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) Acrylate, 1H, 1H, 7H-dodecafluoro Heptyl (meth) acrylate, IH-1-(trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, such 3H- hexafluorobutyl (meth) acrylate. Among these, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, and 1H, 1H, 5H-octafluoropentyl (meth) are excellent in coloring resistance. Acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate are preferably used. .

  In addition, the curable composition of the present invention contains an acidic group-containing (meth) acrylate as at least a part of (meth) acrylate (E) for the purpose of imparting adhesion to a metal, other resin, or tooth. May be included. Examples of such an acidic group-containing (meth) acrylate include at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group (meth). An acrylate is mentioned. 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, 4- (meth) acryloyloxybutyl dihydro Genphosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) acryloyloxyoctyl Dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (Meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxy hexadecyl dihydrogen phosphate, 20- (meth) acryloyloxyicosyl dihydrogen phosphate 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- (meth) acryloyloxynonyl] hydrogen phosphate, bis [10- (meth) a Liloyloxydecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl-2-bromo Examples thereof include ethyl hydrogen phosphate, bis [2- (meth) acryloyloxy- (1-hydroxymethyl) ethyl] hydrogen phosphate, and acid chlorides, alkali metal salts, and ammonium salts thereof. These may be used alone or in combination of two or more.

  The content of the acidic group-containing (meth) acrylate is preferably 1 to 30% by mass, more preferably 2 to 25% by mass in the total amount of the polymerizable monomer, from the viewpoint of adhesiveness. More preferably, it is 3-20 mass%.

  Moreover, the curable composition of this invention may also contain the (meth) acrylate which has a urethane bond as at least one part of (meth) acrylate (E) from a 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) described later to 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, tricyclodecane diisocyanate (TCDDI), adamantane diisocyanate (ADI), dicyclomethane diisocyanate (hydrogenated MDI), cyclohexylmethane diisocyanate (hydrogenated TDI), naphthalene diisocyanate (NDI).

  Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 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] Eniru] propane, 1,2-bis [3- (meth) acryloyloxy-2-hydroxypropoxy] ethane, pentaerythritol tri (meth) acrylate, tri or tetra (meth) acrylate of dipentaerythritol.

  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.

  As the (meth) acrylate having a urethane bond, the monofunctional (meth) acrylate having a urethane bond, for example, 2- (methylaminocarboxy) ethane-1-ol (meth) acrylate, 2- (ethylamino) Carboxy) 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 -All (meth) acrylate, 2- (ethoxycarbonylamino) ethane-1-ol (meth) acrylate, 2- (propoxycarbonylamino) ethane-1-ol (meth) acrylate, 2- (butoxycarbonylamino) ethane- Examples include 1-ol (meth) acrylate and 2- (phenoxycarbonylamino) ethane-1-ol (meth) acrylate. In addition, as the polyfunctional (meth) acrylate having a urethane bond, for example, one selected from one or more compounds selected from the above-mentioned compounds having an isocyanate group and (meth) acrylates having a hydroxyl group Examples include reactants in any combination of two or more compounds.

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

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

  The content of the (meth) acrylate having a urethane bond is preferably 10 to 70% by mass and more preferably 15 to 60% by mass in the total amount of the polymerizable monomer from the viewpoint of toughness. More preferably, it is 20-40 mass%.

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

[(Meth) 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. ) Acrylamide and cycloaliphatic (meth) acrylamide are preferred.

  Examples of (meth) acrylamide (F) include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, and N-isopropyl ( (Meth) 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) acryloylmorpholine, N, N-dimethylamino Ethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-di Lopylaminoethyl (meth) acrylamide, N, N-dibutylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dipropyl Aminopropyl (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 ′ '-G (Meth) acryloyl diethylenetriamine, N, N ', N' ', N' '' - such as tetra (meth) acryloyl triethylenetetramine. These may be used alone or in combination of two or more.

  Among these, N, N-dimethyl (meth) acrylamide, N, N- is preferable in that the miscibility with the alicyclic (meth) acrylic compound (A) is good and the toughness of the cured product of the curable composition is excellent. Diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide, N- (2-hydroxyethyl) (Meth) acrylamide, N- (meth) acryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dimethylaminobutyl (meth) acrylic N, N-diethylaminobutyl (meth) acrylamide, N- (meth) acryloyloxyethyl (meth) acrylamide, N- (meth) acryloyloxypropyl (meth) acrylamide, N, N ′, N ″ -tri ( (Meth) acryloyldiethylenetriamine, N, N ′, N ″, N ′ ″-tetra (meth) acryloyltriethylenetetramine are preferred, and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (meth) acryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) Acrylamide, N, N-dimethylami Propyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N- (meth) acryloyloxyethyl (meth) acrylamide, N- (meth) acryloyloxypropyl (meth) acrylamide, N, N ′, N ′ '-Tri (meth) acryloyldiethylenetriamine, N, N ′, N ″, N ′ ″-tetra (meth) acryloyltriethylenetetramine are more preferred, N, N-dimethylacrylamide, N, N-diethylacrylamide, N -Isopropylacrylamide, N- (2-hydroxyethyl) acrylamide, N-acryloylmorpholine, N, N-dimethylaminoethylacrylamide, N, N-diethylaminoethylacrylamide, N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropyl 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 more preferable, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-acryloylmorpholine, N, N-dimethyl Aminopropylacrylamide, N- (meth) acryloyloxyethyl (meth) acrylamide, N- (meth) acryloyloxypropyl (meth) acrylamide, N, N ′, N ″ -tri (meth) acryloyldiethylenetriamine, N, N ′ , N '' N '' '- tetra (meth) acryloyl triethylenetetramine are particularly preferable.

  The content of (meth) acrylamide (F) in the curable composition of the present invention is 1 to 80 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 a polymer other than the alicyclic (meth) acrylic compound (A), methacrylate (E) and (meth) acrylamide (F) within the range not impairing the effects of the present invention. An additional monomer may be further contained. Examples of other polymerizable monomers include, for example, vinyl monomers having a carboxyl group such as (meth) acrylic acid, maleic acid, and maleic anhydride; aromatics such as styrene, α-methylstyrene, and p-methylstyrene. Group vinyl monomers; conjugated diene monomers such as butadiene and isoprene; olefin monomers such as ethylene and propylene; and lactone monomers such as ε-caprolactone and valerolactone.

  Moreover, a well-known additive can be mix | blended with the curable composition of this invention in the range which does not reduce performance. 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, dibutyl hydroquinone, hydroquinone monomethyl ether, dibutyl hydroquinone monomethyl ether, t-butylcatechol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butylphenol, Phenols such as 3,5-di-t-butyl-4-hydroxytoluene; quinones such as p-benzoquinone, 2,5-diphenyl-p-benzoquinone, p-toluquinone and p-xyloquinone. As for content of a polymerization inhibitor, 0.001-1.0 mass part is preferable with respect to 100 mass parts of total amounts of a polymerizable monomer.

[Use]
The curable composition of the present invention can give 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 used for dental hard tissues 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.

  1 shows an example of a preferred embodiment of a dental composite resin. Preferred embodiments of the dental composite resin (CR-1) include an alicyclic (meth) acrylic compound (A), a photopolymerization initiator (B-1), inorganic particles (C), and a polymerization accelerator (D ), A dental composite resin containing (meth) acrylate (E) and / or (meth) acrylamide (F) as an optional component. In the dental composite resin of the embodiment (CR-1), 10 to 100% by mass of the alicyclic (meth) acrylic compound (A) and (meth) acrylate (E) in the total amount of the polymerizable monomer. And / 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) with respect to 100 parts by mass of the total amount of polymerizable monomers. It is preferable to contain 0.001-30 mass parts of polymerization accelerators (D), and 10-1000 mass parts of inorganic particles (C). In the total amount of polymerizable monomers, alicyclic (meth) acrylic compounds ( 30) to 95% by mass of A), 2.5 to 60% by mass of (meth) acrylate (E) and / or (meth) acrylamide (F), and 100 parts by mass of the total amount of polymerizable monomers, 0.05-20 parts by mass of photopolymerization initiator (B-1) It is more preferable to contain 0.05-20 mass parts of polymerization accelerators (D) and 50-750 mass parts of inorganic particles (C), and the alicyclic (meth) acrylic compound in the total amount of polymerizable monomers. 50 to 90% by mass of (A), 5 to 40% by mass of (meth) acrylate (E) and / or (meth) acrylamide (F), and light with respect to 100 parts by mass of the total amount of polymerizable monomers. It is more preferable to contain 0.1 to 10 parts by mass of the polymerization initiator (B-1), 0.1 to 10 parts by mass of the polymerization accelerator (D), and 100 to 500 parts by mass of the inorganic particles (C).

  An example of suitable embodiment of dental cement is shown. As an embodiment (S-1) of a suitable dental cement, an alicyclic (meth) acrylic compound (A), a photopolymerization initiator (B-1), a chemical polymerization initiator (B-2), and inorganic particles Dental cement containing (C), polymerization accelerator (D), and (meth) acrylate (E) and / or (meth) acrylamide (F) as an optional component may be mentioned. In the dental cement of the embodiment (S-1), 10 to 100% by mass of the alicyclic (meth) acrylic compound (A), (meth) acrylate (E) and And / or (meth) acrylamide (F) is contained in an amount of 0 to 80% by mass, and the photopolymerization initiator (B-1) is added in an amount of 0.001 to 30 parts by mass with respect to 100 parts by mass of the total amount of polymerizable monomers. It is preferable to contain 0.001-30 mass parts of polymerization initiators (B-2), 0.001-30 mass parts of polymerization accelerators (D), and 10-1000 mass parts of inorganic particles (C). In the total amount of the ionic monomer, the alicyclic (meth) acrylic compound (A) is 30 to 95% by mass, and the (meth) acrylate (E) and / or (meth) acrylamide (F) is 2.5 to 60 mass. % Of photopolymerization with respect to 100 parts by mass of the total amount of polymerizable monomers 0.05-20 parts by mass of initiator (B-1), 0.05-20 parts by mass of chemical polymerization initiator (B-2), 0.05-20 parts by mass of polymerization accelerator (D), inorganic More preferably, the particle (C) is contained in an amount of 50 to 500 parts by mass. In the total amount of the polymerizable monomer, 50 to 90% by mass of the alicyclic (meth) acrylic compound (A) and (meth) acrylate (E ) And / or (meth) acrylamide (F) in an amount of 5 to 40% by mass, and 0.1 to 10 parts by mass of the photopolymerization initiator (B-1) with respect to 100 parts by mass of the total amount of polymerizable monomers. Further, 0.1 to 10 parts by mass of the chemical polymerization initiator (B-2), 0.1 to 10 parts by mass of the polymerization accelerator (D), and 100 to 300 parts by mass of the inorganic particles (C) are further contained. preferable.

  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 the ranges described separately in this specification. Can be appropriately selected and changed.

[Cured product]
A cured product can be obtained by curing the curable composition of the present invention. There is no particular limitation on the curing method. For example, when the curable composition of the present invention is a two-material type including at least the first material and the second material, the first material and the second material. Mixing etc. are mentioned.

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

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples at all, and many variations are within the technical idea of the present invention. This is possible by those with ordinary knowledge. In addition, unless otherwise indicated, the part in an example is a mass part.

[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). ^The apparatus and conditions used for ¹ H-NMR and UPLC measurement are as follows.

^[1 apparatus and conditions H-NMR measurement]
Apparatus: Nuclear magnetic resonance apparatus “JNM-LA400” (manufactured by JEOL Ltd.)
Deuterated solvent: Deuterated chloroform

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

[Average particle size of inorganic particles]
Moreover, the average particle diameter of the inorganic particles (filler) used in the following examples was measured by a laser diffraction particle size distribution measuring device. The apparatus and conditions used for the measurement are as follows.
Apparatus: Laser diffraction particle size distribution measuring apparatus “SALD-2100” (manufactured by Shimadzu Corporation)
Dispersion medium: 0.2% sodium hexametaphosphate aqueous solution

  Next, the manufacturing method of the component of the curable composition of an Example and a comparative example or its content is described below with an abbreviation.

[Alicyclic (meth) acrylic compounds]
Production Example 1 Synthesis of isosorbide dimethacrylate 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 were charged in a 2 L four-necked flask. 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 confirming the heat of reaction. After completion of the dropwise addition, the mixture was continuously stirred for 5 hours under ice cooling. Then, it returned to room temperature and stirred for further 3 hours, and reaction was complete | finished.

  After completion of the reaction, the reaction 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 ¹ H-NMR measurement and UPLC analysis described above were performed using the obtained liquid, it was found to be isosorbide dimethacrylate (yield 90.4% based on 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。

Was used as the 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)

  In a 2 L four-necked flask, 146 g (1 mol) of isosorbide was dissolved in 670 g of a 50% by weight aqueous potassium hydroxide solution. ) And heated under reflux for 7 hours, and then distilled under reduced pressure to obtain 217 g (yield 96%) of isosorbide diallyl ether.

  113 g (0.5 mol) of the obtained isosorbide diallyl ether was dissolved in 500 mL of methylene chloride, 79.8 g (1.1 mol) of m-chloroperbenzoic acid was added, and the mixture was stirred at room temperature for 24 hours. Washing, filtration, and drying yielded 117 g (90% yield) of isosorbide diglycidyl ether.

  104 g (0.4 mol) of the obtained isosorbide diglycidyl ether, 42.1 (0.5 mol) of methacrylic acid, 0.44 g of triphenylphosphine and 0.15 g of hydroquinone were added, and the mixture was stirred at 75 ° C. for 1 hour in a nitrogen atmosphere. Subsequently, the mixture was stirred at 100 ° C. for 3 hours, 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.

Using the obtained liquid, the above-described ¹ H-NMR measurement and UPLC analysis were performed, and it was found that the compound was represented by the above formula (yield 78% based on 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)

  In a 2 L four-necked flask, 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 were charged. At 60 ° C., 310 g (2 mol) of methacryloyloxyethyl isocyanate was slowly added dropwise using a dropping funnel while confirming the heat of reaction. After completion of dropping, the mixture was continuously stirred at 60 ° C. for 12 hours.

  After completion of the reaction, the reaction solution was returned to room temperature, 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 ¹ H-NMR measurement and UPLC analysis described above were performed using the obtained liquid, it was found to be a compound represented by the above formula (yield based on raw material isosorbide 92.3%). 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 In a 300 mL three-necked flask, 30.4 g of 1,3-bis (4-glycidyloxyphenyl) adamantane (70 3 mmol), 1,2-dichloroethane 50 mL, and triethylamine 5.0 g (50 mmol) were added, and the mixture was stirred with a stirrer chip at 25 ° C. in the atmosphere. 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. A part of the reaction product was sampled and subjected to UPLC measurement. As a result, disappearance of 1,3-bis (4-glycidyloxyphenyl) adamantane was confirmed.

The reaction mixture was washed successively with saturated aqueous NaHCO ₃ solution (100 mL × 2), 1N HCl (100 mL × 1) and distilled water (100 mL × 1), and the organic layer was dried over anhydrous MgSO ₄ . The organic layer was filtered and then concentrated using an evaporator. The concentrate was vacuum-dried to obtain 1,3-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] adamantane (36.8 g, yield 88%). This was used as Comparative Example 1 as 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-tetramethylbutyl hydroperoxide

[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-methacryloyloxydecyl dihydrogen phosphate (E) -2 UDMA: 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (E) -3 3G: tri Ethylene glycol dimethacrylate

[(Meth) acrylamide (F)]
(F) -1 DEAA: N, N-dimethylacrylamide (F) -2 ACMO: N-acryloylmorpholine

(Polymerization inhibitor)
BHT: 3,5-di-tert-butyl-4-hydroxytoluene

Examples 1-14 and Comparative Examples 1-3
The raw materials shown in Tables 1 to 3 were mixed at room temperature (23 ° C.) in the dark to prepare each paste (curable composition).
About these pastes, the characteristic was investigated in accordance with the method of the following test examples 1-4. In Examples 1 to 7 and Comparative Examples 1 to 3, each property was examined using a one-material paste (one-material curable composition) having the composition shown in Tables 1 and 3. On the other hand, in Examples 8-14, each characteristic was used using the mixture obtained by mixing the 2 material type paste (2 material type curable composition) which consists of A material and B material of the composition shown in Table 2, respectively. (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 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 upper and lower sides (2 mm × 25 mm surface) of the paste were pressed with a slide glass. Next, the paste was cured by irradiating the back and front of the paste with 5 portions on one side through a slide glass 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), bending strength, bending elastic modulus, and displacement at break. Was measured. The results are shown in Tables 1-3. In this measurement, the higher the bending strength, the higher the strength of the cured product. The higher the flexural modulus, the better the cured product, and the greater the breaking point displacement, the harder the cured product is. When the bending strength is 100 MPa or more, the flexural modulus is 5 GPa or more, and the displacement at break is 1.0 mm or more, the cured product is excellent in toughness.

Test example 2 Abrasion resistance test (evaluation of sliding durability)
The sliding durability was evaluated based on the change in gloss before and after the abrasion resistance test. Specifically, it is as follows. The produced paste (curable composition) was filled in a SUS mold (length 30 mm × width 20 mm × thickness 2 mm), and the upper and lower sides (30 mm × 20 mm surface) of the paste were pressed with a slide glass. Subsequently, the paste was cured by irradiating light on both sides of the paste for 180 seconds through a slide glass with a visible light irradiator for dental technology (α light V, manufactured by Morita). The obtained cured product was used as a test piece, and 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 test piece after buffing was subjected to an abrasion resistance test. For the buffing, a dental abrasive (trade name: POCENY HYDON, manufactured by Tokyo Teeth Co., Ltd.) was used.The gloss (G1) of the test piece before the abrasion resistance test was measured using a gloss meter (VG-107 The ratio of the mirror was 100%, and the measurement angle was 60 ° .Toothbrush wear tester (Daiei Scientific Instruments) Manufactured by Seiko Seisakusho Co., Ltd.) and a wear resistance test of 40000 cycles under a load of 250 g using a suspension of a dentifrice and a commercially available toothbrush. The dentifrice / distilled water was prepared at a mass ratio of 60/40, and the glossiness (G2) of the surface of the test piece after the abrasion resistance test was determined in the same manner as before the abrasion resistance test. Based on the glossiness of the surface of the test piece, the sliding durability (%) is determined by {( G2) × 100} / (G1) The results are shown in Tables 1 to 3. Lubrication durability of 70% or more is preferable from the viewpoint of aesthetics.

Test Example 3 Measurement of polymerization shrinkage stress A paste (curable composition) prepared in a ring-shaped mold (made of stainless steel, inner diameter 5.5 mm × thickness 0.8 mm) placed on a glass plate having a thickness of 4.0 mm. Product). The glass plate used was sandblasted with alumina powder having a particle size of 50 μm. On the filled paste, a stainless steel jig (φ5 mm) connected to a universal testing machine (Autograph AG-100kNI, manufactured by Shimadzu Corporation) was installed. Next, using a dental visible light irradiator (Pencure 2000, manufactured by Morita), the paste was cured by irradiating the paste with light through a glass plate for 20 seconds. Under the present circumstances, the polymerization shrinkage stress accompanying the superposition | polymerization (hardening) of the curable composition which advances by this light irradiation was measured with the said universal testing machine. 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 the curable composition is used for dental use, it becomes possible to fill more curable composition at once, 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 specimen is a one-material curable composition (Examples 1 to 7 and Comparative Examples 1 to 3), Clearfill Majesty LV A syringe container (manufactured by Kurarenoritake Dental Co., Ltd.) was used with a guide chip attached to the tip of the syringe container. As for the size of the syringe container, the length of the cylindrical portion was 7.5 cm, and the inner diameter of the opening was 0.8 cm. The guide tip size was 1.5 cm in length and the inner diameter of the opening was 0.8 mm. When the test specimen is a two-material curable composition (Examples 8 to 14), a clear-filled Panavia V5 (Kurarenoritake Dental Co., Ltd., total volume 5 mL) syringe container was placed at the tip of the syringe container with an inner diameter of 0. Used with a 8 mm mixing tip.

  The paste (curable composition) was stored in a syringe container and stored at 25 ° C. for 1 week to stabilize the properties of the curable composition. Then, the extrusion member (presser) was made to enter the syringe container, and the paste in the container was discharged from the discharge part of the chip through the guide chip or the mixing chip. The force required to extrude the paste from the syringe container at this time was measured using a universal testing machine (Autograph AGI-100, manufactured by Shimadzu Corporation) as the discharge force. Specifically, the syringe container is set up vertically, the crosshead equipped with the jig for 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. Power. The discharge force was measured at 25 ° C. When the ejection force is 40 N or less, ejection can be performed easily and the ejection performance is good. Although ejection is possible at a value exceeding 40N and not exceeding 60N, the ejection performance is poor. If it exceeds 60 N, ejection is difficult.

  From the results of Tables 1 to 3, the cured products of the curable compositions of the examples have large bending strength and displacement, and are excellent in toughness while having a large bending elastic modulus. In addition to excellent lubrication durability, the polymerization shrinkage stress is low, and since the force when filling and discharging the container is small, the operability is also excellent. On the other hand, the compositions of Comparative Examples 1 and 2 that do not contain the alicyclic (meth) acrylic compound (A) are poor in toughness of the cured product, are brittle, and have high ejection force. Moreover, the hardened | cured material of the composition which mix | blended the inorganic particle which the average particle diameter of the comparative example 3 exceeds 10 micrometers has bad toughness and lubricous durability.

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

Claims (13)

Containing an alicyclic (meth) acrylic compound (A), a polymerization initiator (B) and inorganic particles (C),
The alicyclic (meth) acrylic compound (A) is represented by the following general formula [I]

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

Wherein R ³ and R ⁴ are each independently a (meth) acryloyl group, Y and Z are each independently a divalent unsubstituted or substituted hydrocarbon group, and p and q are each It is an integer of 0-30 independently.)
And at least one selected from the group consisting of alicyclic (meth) acrylic compounds (A) -II represented by:
The curable composition whose average particle diameter of an inorganic particle (C) is 0.001-10 micrometers.   The alicyclic (meth) acrylic compound (A) is an alicyclic (meth) acrylic compound (A) -I represented by the general formula [I], and X is an alkylene group having 2 to 6 carbon atoms. The curable composition according to claim 1.   The alicyclic (meth) acrylic compound (A) is an alicyclic (meth) acrylic compound (A) -II represented by the general formula [II], and Y and Z each independently have 2 to 2 carbon atoms. The curable composition according to claim 1, which is 6 alkylene groups. The curable composition according to any one of claims 1 to ^3, wherein R ¹ , R ² , R ³ and R ^{4 of the} alicyclic (meth) acrylic compound (A) are methacryloyl groups.   Furthermore, the curable composition of any one of Claims 1-4 containing a polymerization accelerator (D).   Furthermore, the curable composition of any one of Claims 1-5 containing (meth) acrylate (E) other than the said alicyclic (meth) acrylic compound (A).   Furthermore, the curable composition of any one of Claims 1-6 containing (meth) acrylamide (F).   The curable composition according to any one of claims 1 to 7, which is a dental curable composition.   The curable composition of Claim 8 which is a curable composition for dental hard tissues.   The curable composition according to claim 9, which is a dental composite resin.   The curable composition according to claim 9, which is a dental cement.   The manufacturing method of the hardened | cured material which hardens the curable composition of any one of Claims 1-11.   The hardening method of the curable composition which hardens the curable composition of any one of Claims 1-11.