JP2019099608A - Curable composition containing alicyclic (meth)acrylic compound - Google Patents

Abstract

To provide a curable composition providing a cured article having excellent mechanical physical properties and adhesiveness.SOLUTION: The curable composition is provided that contains: an alicyclic (meth)acrylic compound (A); an acidic group-containing (meth)acrylic compound (B); and a polymerization initiator (C), the alicyclic (meth)acrylic compound (A) is at least one kind of isosorbide di(meth)acrylate derivative selected from an alicyclic (meth)acrylic compound (A)-I represented by the formula [I] and an alicyclic (meth)acrylic compound (A)-II represented by the formula [II]. Rto Rare each independently a (meth)acryloyl group; X to Z are each independently a substituted/unsubstituted bivalent hydrocarbon group; m, n, p and q are each independently an integer of 0 to 30.SELECTED DRAWING: None

Description

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

  When filling or coating a restoration in a tooth defect, dental materials such as a dental composite resin, a dental cement, a dental adhesive and a dental primer are widely used.

  These dental materials are required to have mechanical properties similar to those of the dentin and to be integrated with the dentin, that is, to have a strength close to that of the dentin and good adhesion. Specifically, mechanical properties include strength, elastic modulus, hardness and the like. Furthermore, in order to develop these mechanical properties and adhesiveness, it is premised to have sufficient curability.

  Generally, as a means for imparting strength and curability, bisphenol A glycidyl dimethacrylate (generally called Bis-GMA), 2, 2- in which an aromatic group having a rigid structure such as bisphenol A is incorporated as a spacer in the molecule A dental material using bis (4-methacryloyloxypolyethoxyphenyl) propane (average added mole number of ethoxy group: 2.6) (generally called D2.6E) can be mentioned. On the other hand, from the viewpoint of safety, the tendency to avoid the use of bisphenol A derivatives is intensified, and dentistry using (meth) acrylic compounds such as a dimethacrylate compound or the like incorporating cyclic aliphatic group having rigid structure such as adamantane as a spacer Materials can also be mentioned (Patent Document 1). Furthermore, there is an example of a dimethacrylate compound having an isosorbide skeleton having an ether bond in an alicyclic structure (Patent Document 2).

JP, 2013-60373, A JP, 2011-84535, A

  Methods for imparting such strength and hardenability have been extremely effective for dental composite resins. On the other hand, in the case of a dental adhesive, it is necessary to penetrate into the dentine containing water to be cured in order to obtain good adhesion and to be hardened, so the hardenability composition used for the dental adhesive is hydrophilic. As required, the technique of Patent Document 1 has a problem in achieving both curability and hydrophilicity. Moreover, the technique of Patent Document 2 does not describe adhesion at all.

  Then, an object of this invention is to provide the curable composition in which hardened | cured material has the outstanding mechanical physical property and adhesiveness.

（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種である、硬化性組成物である。 The present invention achieving the above object comprises an alicyclic (meth) acrylic compound (A), an acidic group-containing (meth) acrylic compound (B), and a polymerization initiator (C), ) The acrylic compound (A) has 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) It is an integer of -30.)
(Meth) acrylic compound (A) -I represented by the formula, and the following general formula [II]

(Wherein, R ³ and R ⁴ are each independently a (meth) acryloyl group, and Y and Z are each independently a divalent unsubstituted or substituted hydrocarbon group, p and q Are each independently an integer of 0 to 30.)
It is a curable composition which is at least 1 sort (s) chosen from the group which consists of an alicyclic (meth) acryl compound (A) -II represented by these.

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

  In another embodiment, the alicyclic (meth) acrylic compound (A) is an alicyclic (meth) acrylic compound (A) -II represented by the general formula [II], and Y and Z are It is preferable that it is respectively independently a C2-C6 alkylene group.

In one embodiment, it is preferable that R ¹ , R ² , R ³ and R ^{4 of the} alicyclic (meth) acrylic compound (A) be a methacryloyl group.

  In one embodiment, it is preferable that the curable composition further contains a polymerization accelerator (D).

  In one embodiment, the curable composition further contains (meth) acrylate (E) other than the alicyclic (meth) acrylic compound (A) and the acidic group-containing (meth) acrylic compound (B). Is preferred.

  In one embodiment, it is preferable to contain a (meth) acrylate having a monofunctional hydroxyl group as the (meth) acrylate (E).

  In one embodiment, it is preferable to contain, as the (meth) acrylate (E), an aliphatic compound-based difunctional (meth) acrylate.

  In one embodiment, it is preferable that the curable composition further contains (meth) acrylamide (F).

  In one embodiment, the curable composition preferably further contains water and / or a water-soluble organic solvent (G).

  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 dental adhesive.

  The present invention can provide a curable composition in which the cured product has excellent mechanical properties and adhesiveness. In addition, the present invention can provide a dental curable composition having excellent adhesion to dentin and having excellent mechanical properties. Furthermore, the present invention can provide a dental adhesive having excellent adhesion to dentine and having excellent mechanical properties.

（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種である。 The curable composition of the present invention contains an alicyclic (meth) acrylic compound (A), an acidic group-containing (meth) acrylic compound (B), and a polymerization initiator (C), and ) The acrylic compound (A) has 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 to 30) Is an integer of
(Meth) acrylic compound (A) -I represented by the formula, and 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 independently an integer of 0 to 30.)
Or at least one selected from the group consisting of alicyclic (meth) acrylic compounds (A) -II represented by

  In addition, in this specification, the description of (meth) acryl is used by the meaning which includes both methacryl and an acryl. In the present specification, the expression (meth) acryloyl is used to mean that both methacryloyl and acryloyl are included. In the present specification, the upper limit value and the lower limit value of the numerical range (the content of each component, the value calculated from each component, each physical property, etc.) can be combined as appropriate.

[Alicyclic (meth) acrylic compound (A)]
In the curable composition of the present invention, the alicyclic (meth) acrylic compound (A) imparts mechanical physical properties to a cured product, and has the effect of improving the hydrophilicity of the composition. Therefore, an alicyclic (meth) acrylic compound (A) is preferably used as a base material. The reason why the above-mentioned excellent effects are exhibited by the curable composition of the present invention is not necessarily clear, but the alicyclic (meth) acrylic compound (A) is an alicyclic compound 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 plurality of ether bonds contribute to hydrophilicity.

  The alicyclic skeleton represented by the above-mentioned formula [i], which the alicyclic (meth) acrylic compound (A) has, can be derived from an alicyclic diol having a corresponding ether bond. As a stereoisomer of alicyclic skeleton represented by said Formula [i], what is represented by following formula [i] -1, Formula [i] -2, and Formula [i] -3 is mentioned.

  A compound in which hydrogen is bonded to both ends of these is a sugar-derived ether diol, which can be obtained from natural biomass, and is 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 isosorbide (1,4: 3,6-dianhydro) respectively -D-sorbitol), isomannide (1,4: 3,6-dianhydro-D-mannitol), and isoidid (1,4: 3,6-dianhydro-L-iditol). Isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. The other diol compounds can be obtained by the same reaction except for the starting materials. Among isosorbide, isomannide, and isoidide, an alicyclic skeleton derived particularly from isosorbide is preferable because it is excellent in easiness of production and heat resistance and thus hardly deteriorates during processing.

· Alicyclic (meth) acrylic compounds (A) -I
Each symbol of the said general formula [I] is demonstrated. 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 .

  Examples of the hydrocarbon group represented by X in the above general formula [I] include aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups and the like, and among them, curable compositions Aliphatic hydrocarbon groups are preferred in view of their hydrophilicity.

  As said aliphatic hydrocarbon group, a linear or branched alkylene group, an alkenylene group, etc. are mentioned. Examples of the alkylene group include ethylene group, 1,2-propylene group, trimethylene group, butylene group, tetramethylene group, pentamethylene group, hexamethylene group and the like. As an alkenylene group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group etc. are mentioned, for example. Among these, ethylene, 1,2-propylene and trimethylene are preferable in view of viscosity and hydrophilicity.

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

  An arylene group is mentioned as said aromatic hydrocarbon group. Examples of the arylene group include phenylene group, tolylene group, methyl phenylene group, xylylene group, naphthylene group, anthracenylene group, phenanthrylene group, biphenylene group, fluorenylene group and the like.

  These hydrocarbon groups, if any, include isomers as long as they have the effect of the present invention. The hydrocarbon group may be a combination of two or more selected from the group consisting of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, for example, an alkylene group And a combination of a cycloalkylene group and an arylene group; a combination of an alkylene group and a cycloalkylene group; and 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 them, X is preferably an alkylene group having 2 to 6 carbon atoms in that the cured product of the curable composition obtained is excellent in strength. Further, in view of the hydrophilicity of the composition, X is more preferably an alkylene group having 2 to 4 carbon atoms, and still more preferably an alkylene group having 2 or 3 carbon atoms.

  The number of the substituents which the said hydrocarbon group has is 0-4 normally, 0-3 are preferable, 0-2 are more preferable, and 0 or 1 are more preferable. As a substituent of the said hydrocarbon group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); a hydroxyl group, an amino group, a C1-C12 linear or branched alkoxy group etc. are mentioned, for example Can be mentioned. These may be used alone or in combination of two or more. As the alkoxy group, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group , N-decyloxy group, n-dodecyloxy group and the like. In the case where an isomer is present, these substituents include the isomer as long as the effects of the present invention are obtained. Among the above-mentioned substituents, a hydroxyl group is preferable because the cured product of the curable composition is excellent in strength and hydrophilicity.

  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 10 in that the cured product of the curable composition obtained is excellent in strength. It is preferable that it is an integer of 9, It is more preferable that it is respectively independently the integer of 0-6, It is further more preferable that it is each independently the integer of 0-3, It is each independently 0 or 1. Is particularly preferred. m and n may be identical to or different from each other, but m and n may be identical to each other from the viewpoint of the ease of production of the alicyclic (meth) acrylic compound (A) -I, etc. preferable.

  The production method of the alicyclic (meth) acrylic compound (A) -I is not particularly limited, and the compound represented by the above general formula [I] regardless of the production method, and the curing containing the compound Although the organic composition is included in the scope of the present invention, the alicyclic (meth) acrylic compound (A) -I is preferably selected from 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 is, for example, an alicyclic diol (isosorbide or the like) having an ether bond corresponding to the alicyclic skeleton represented by the formula [i]. Or a method of converting a hydroxyl group to a (meth) acryloyloxy group by an esterification reaction or the like after reacting an epoxy compound such as ethylene oxide or propylene oxide with it as it is, or using the above formula [i] After reacting a halogenated (meth) allyl such as allyl bromide with an alicyclic diol (such as isosorbide) having an ether bond corresponding to the alicyclic skeleton represented, the double bond is epoxidized, Subsequently, it can manufacture by the method of making this epoxy group react with (meth) acrylic acid etc., and ring-opening.

· Alicyclic (meth) acrylic compounds (A) -II
Each symbol of the said general formula [II] is demonstrated. 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.

  Examples of the hydrocarbon group represented by Y and Z in the above general formula [II] include, for example, aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups and the like, and among them, curing is possible. Aliphatic hydrocarbon groups are preferred in view of the hydrophilicity of the sex composition.

  Examples and preferable examples of each of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group are the same as those described above as the explanation for X in the general formula [I], The explanation is omitted.

  The hydrocarbon group represented by Y and Z, if any, includes isomers as long as the effects of the present invention are obtained. The hydrocarbon group may be a combination of two or more selected from the group consisting of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, for example, an alkylene group And a combination of a cycloalkylene group and an arylene group; a combination of an alkylene group and a cycloalkylene group; and 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, Y and Z are preferably each independently an alkylene group having 2 to 6 carbon atoms in that the cured product of the curable composition obtained is excellent in strength. Further, in view of the hydrophilicity of the curable composition, Y and Z are each independently more preferably an alkylene group having 2 to 4 carbon atoms, and further preferably an alkylene group having 2 or 3 carbon atoms. preferable.

  The number of substituents which each of the hydrocarbon groups represented by Y and Z has, and the examples and preferable ones thereof are the same as those described above as the explanation for X in the above general formula [I], and the redundant explanation is omitted here. Do.

  In the above general formula [II], p and q are each independently an integer of 0 to 30, and p and q are each independently 0 to 10 in that the cured product of the curable composition obtained is excellent in strength. It is preferably in the range of 9, each independently preferably an integer of 0 to 6, and further preferably independently an integer of 0 to 3, further independently 0 or 1. Is particularly preferred. p and q may be identical to or different from each other, but p and q may be identical to each other from the viewpoint of ease of production of the alicyclic (meth) acrylic compound (A) -II, etc. preferable.

The production method of the alicyclic (meth) acrylic compound (A) -II is not particularly limited, and the compound represented by the above general formula [II] regardless of the production method, 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 is reacted with an epoxy compound such as ethylene oxide or propylene oxide. And the isocyanate compound represented by the general formula: R ³ -O-Z-NCO and the isocyanate compound represented by R ⁴ -O-Z-NCO (wherein R ³ , R ⁴ and Z are It can be produced by the method of reacting with the same meaning as above.

  In the reaction of a hydroxyl group and an isocyanate compound, a polymerization inhibitor is added as necessary using a conventionally known urethanization catalyst, and when both are reacted at a temperature of 40 to 90 ° C., the target alicyclic 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 according to the types of R ¹ , R ² , R ³ , R ⁴ , X, Y and Z in the above general formulas [I] and [II], the number of m, n, p and q, etc. The nature of (A) is different. However, in general, the alicyclic (meth) acrylic compound (A) -I and the alicyclic (meth) acrylic compound (A) -II are often in the form of low viscosity liquid at normal temperature. If the liquid cycloaliphatic (meth) acrylic compound (A) is used at such normal temperature, a curable composition which is more excellent in handleability can be obtained.

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

As an alicyclic (meth) acrylic compound (A) -II, R ³ and R ⁴ are both methacryloyl groups, and Y and Z are each independently a divalent C ² to C 6 divalent unsubstituted or substituted Preferred are alicyclic (meth) acrylic compounds in which p and q are each independently an integer of 0 to 9; R ³ and R ⁴ are both methacryloyl groups, Y and Z The alicyclic (meth) acrylic compound in which each is 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 is R ³ and R ⁴ are both methacryloyl groups, and Y and Z are each independently a C 2 or C ³ divalent unsubstituted or substituted hydrocarbon group, and p and q are each Alicyclic (meth) which is an integer of 0 to 3 independently Krill compound is more preferable.

The curable composition of the present invention comprises, as the alicyclic (meth) acrylic compound (A), 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. Moreover, as alicyclic (meth) acryl compound (A) -I, even if 1 type of compounds are used independently, you may use together 2 or more types of compounds. Similarly, as the alicyclic (meth) acrylic compound (A) -II, one kind of compound may be used alone, or two or more kinds of compounds may be used in combination. When the curable composition of the present invention contains any one or both of an alicyclic (meth) acrylic compound (A) -I and an alicyclic (meth) acrylic compound (A) -II, R ¹ , R ² , R ³ and R ⁴ in 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 99% by mass, and 30 to 90% by mass, based on the total amount of polymerizable monomers. Is more preferably 50 to 85% by mass. In the present specification, the total amount of polymerizable monomers refers to the alicyclic (meth) acrylic compound (A), the acidic group-containing (meth) acrylic compound (B), and the alicyclic (meth) acrylic compound (A) And polymerizable groups other than the acidic group-containing (meth) acrylic compound (B) ((meth) acrylate (E), (meth) acrylamide (F) and other polymerizable monomers other than these) It means the total amount with.

[Acid group-containing (meth) acrylic compound (B)]
Examples of the acidic group-containing (meth) acrylic compound (B) used in the present invention include at least acidic groups such as phosphoric acid group, pyrophosphoric acid group, thiophosphoric acid group, phosphonic acid group, carboxylic acid group, and sulfonic acid group. The (meth) acryloyl compound which has one is mentioned. The acidic group-containing (meth) acrylic compounds (B) can be used singly or in appropriate combination of two or more. Specific examples of the acidic group-containing (meth) acrylic compound (B) will be described below.

  2- (Meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyl oxybutyl dihydrogen phosphate as a phosphate group-containing (meth) acrylic compound 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyl oxyheptyl dihydrogen phosphate, 8- (meth) acryloyl oxyoctyl dihydro Gen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyl oxydecyl dihydrogen phosphate, 11- (meth) a Lyloyl oxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxydodecyl dihydrogen phosphate, 16- (meth) acryloyl oxyhexadecyl dihydrogen phosphate, 20- (meth) acryloyl oxyicosyl dihydrogen 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) acryloyl Xyldecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl dihydrogen phosphate, 2- (meth) acryloyloxyethyl phenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl- (2-bromoethyl) hydro These include gen phosphate, 2-methacryloyloxyethyl- (4-methoxyphenyl) hydrogen phosphate, 2-methacryloyloxypropyl- (4-methoxyphenyl) hydrogen phosphate and their acid chlorides, alkali metal salts and amine salts. .

  As a pyrophosphate group-containing (meth) acrylic compound, bis [2- (meth) acryloyloxyethyl] pyrophosphate, bis [4- (meth) acryloyloxybutyl] pyrophosphate, bis [6- (meth) acryloyl pyrophosphate Oxyhexyl], bis [8- (meth) acryloyloxyoctyl] pyrophosphate, bis [10- (meth) acryloyloxydecyl] pyrophosphate, and their acid chlorides, alkali metal salts and amine salts.

  As the thiophosphoric acid group-containing (meth) acrylic compound, 2- (meth) acryloyloxyethyl dihydrogen thiophosphate, 3- (meth) acryloyloxypropyl dihydrogen thiophosphate, 4- (meth) acryloyloxybutyl dihydro Genthiophosphate, 5- (meth) acryloyloxypentyl dihydrogen thiophosphate, 6- (meth) acryloyloxyhexyl dihydrogen thiophosphate, 7- (meth) acryloyloxyheptyl dihydrogen thiophosphate, 8- (meth) ) Acryloyloxyoctyl dihydrogenthiophosphate, 9- (meth) acryloyloxynonyl dihydrogenthiophosphate, 10- (meth) acryloyloxydecyl dihydro Enthiophosphate, 11- (meth) acryloyloxyundecyl dihydrogen thiophosphate, 12- (meth) acryloyl oxydodecyl dihydrogen thiophosphate, 16- (meth) acryloyl oxyhexadecyl dihydrogen thiophosphate, 20 And (meth) acryloyloxyicosyl dihydrogen thiophosphates and their acid chlorides, alkali metal salts and ammonium salts.

  Examples of phosphonic acid group-containing (meth) acrylic compounds include 2- (meth) acryloyloxyethylphenyl phosphonate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl -3-phosphonopropionate, 10- (meth) acryloyloxydecyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl-3-phosphonoacetate, 10- (meth) acryloyloxydecyl 3-phosphonoacetates and their acid chlorides, alkali metal salts and ammonium salts.

  As a carboxylic acid group-containing (meth) acrylic compound, a monofunctional polymerizable monomer having one carboxyl group or its acid anhydride group in its molecule, or a plurality of carboxyl groups or its acid anhydride group in its molecule And monofunctional polymerizable monomers and the like.

  Examples of monofunctional (meth) acrylic compounds having one carboxyl group or its acid anhydride group in the molecule include (meth) acrylic acid, N- (meth) acryloyl glycine, N- (meth) acryloyl asparagine Acid, 2- (Meth) acryloyloxyethyl hydrogen succinate, 2- (Meth) acryloyloxyethyl hydrogen phthalate, 2- (Meth) acryloyl oxyethyl hydrogen malate, O- (Meth) acryloyl tyrosine, N- ( Meta) acryloyl tyrosine, N- (meth) acryloyl phenylalanine, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-o-aminobenzoic acid, 2- (meth) acryloyloxybenzoic acid, 3 -(Meth) acryloyloxybenzoic acid, 4- (4-) Data) acryloyloxy benzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid and compounds anhydride functionalized carboxyl group of these compounds.

  Examples of monofunctional (meth) acrylic compounds having a plurality of carboxyl groups or acid anhydride groups thereof in the molecule include, for example, 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid, 9- (meth) ) Acryloyloxynonane-1,1-dicarboxylic acid, 10- (meth) acryloyloxydecane-1,1-dicarboxylic acid, 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 12- (meth) acryloyl acid Oxidodecane-1,1-dicarboxylic acid, 13- (meth) acryloyloxytridecane-1,1-dicarboxylic acid, 4- (meth) acryloyloxyethyl trimellitate, 4- (meth) acryloyloxyethyl trimellitate Anhydride, 4- (meth) acryloyloxybutyl trimellitate, 4- (methyl) ) Acryloyloxyhexyl trimellitate, 4- (meth) acryloyloxydecyl trimellitate, 2- (meth) acryloyloxyethyl-3 '-(meth) acryloyloxy-2'-(3,4-dicarboxybenzoyloxy ) Propyl succinate, 6- (meth) acryloyloxyethyl naphthalene-1,2,6-tricarboxylic acid anhydride, 6- (meth) acryloyloxyethyl naphthalene-2,3,6-tricarboxylic acid anhydride, 4- ( Examples include meth) acryloyloxyethylcarbonylpropionoyl-1,8-naphthalic anhydride, 4- (meth) acryloyloxyethylnaphthalene-1,8-tricarboxylic anhydride and the like.

  As a sulfonic acid group containing (meth) acryl compound, 2-sulfoethyl (meth) acrylate is mentioned.

  Among the above-mentioned acidic group-containing (meth) acrylic compounds (B), from the viewpoint of good adhesion when used as a dental adhesive, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 4- (Meth) acryloyloxyethyl trimellitate anhydride, 4- (meth) acryloyloxyethyl trimellitate, 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, and 2-methacryloyloxyethyl dihydrogen Mixtures of phosphate and bis (2-methacryloyloxyethyl) hydrogen phosphate are preferred, 10- (meth) acryloyloxydecyl dihydrogen phosphate and 4- (meth) acryloyloxyethyl trimellitate anhydride being more preferred , 10- (meth) acryloyloxydecyl dihydrogen phosphate is most preferred.

  The content of the acidic group-containing (meth) acrylic compound (B) in the curable composition of the present invention is preferably 1 to 50% by mass, based on the total amount of the polymerizable monomers, and is preferably 2.5 to 40. It is more preferable that it is mass%, and it is further more preferable that it is 5-30 mass%.

[Polymerization initiator (C)]
As a polymerization initiator (C) used for this invention, it can be selected and used from the polymerization initiator used by the general industrial field, Especially the polymerization initiator used for dental use is used preferably. As the polymerization initiator (C), particularly, at least one selected from the group consisting of a photopolymerization initiator (C-1) and a chemical polymerization initiator (C-2) can be used.

  As the photopolymerization initiator (C-1), for example, (bis) acylphosphine oxides (including salts), thioxanthones (including salts such as quaternary ammonium salts), ketals, α-diketones, Coumarins, anthraquinones, benzoin alkyl ether compounds, α-amino ketone compounds and the like can be mentioned.

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

  Among the (bis) acyl phosphine oxides, as an acyl phosphine oxide, for example, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2,6-dimethoxy benzoyl diphenyl phosphine oxide, 2,6-dichloro benzoyl diphenyl phosphine oxide 2,4,6-trimethylbenzoyl methoxyphenyl phosphine oxide, 2,4,6-trimethyl benzoyl ethoxy phenyl phosphine oxide, 2,3,5,6- tetramethyl benzoyl diphenyl phosphine oxide, benzoyl di- (2, 6 dimethyl Phenyl) phosphonate, sodium salt of 2,4,6-trimethyl benzoyl phenyl phosphine oxide, potassium salt of 2,4,6-trimethyl benzoyl phenyl phosphine oxide And ammonium salts of 2,4,6-trimethylbenzoyl phenyl phosphine oxide.

  Among the (bis) acyl phosphine oxides, as bisacyl phosphine oxides, for example, bis (2,6-dichlorobenzoyl) phenyl phosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenyl phosphine Oxides, bis (2,6-dichlorobenzoyl) -4-propylphenyl phosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthyl phosphine oxide, bis (2,6-dimethoxybenzoyl) phenyl phosphine oxide, bis ( 2,6-Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenyl Hosphi Oxide, bis (2,3,6-trimethylbenzoyl) -2,4,4-like trimethyl pentyl phosphine oxide.

  Furthermore, as (bis) acyl phosphine oxides, the compound described in Unexamined-Japanese-Patent No. 2000-159621 is mentioned.

  Among these (bis) acyl phosphine oxides, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2,4,6- trimethyl benzoyl methoxy phenyl phosphine oxide, bis (2,4,6- trimethyl benzoyl) phenyl phosphine It is particularly preferred to use the sodium salt of oxide, 2,4,6-trimethyl benzoylphenyl phosphine oxide as the photoinitiator (C-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, camphor quinone is particularly preferable from the viewpoint of having a maximum absorption wavelength in the visible light region.

  As a chemical polymerization initiator (C-2), an organic peroxide is preferably used. The organic peroxide used as the chemical polymerization initiator (C-2) is not particularly limited, and known ones can be used. Representative organic peroxides include, for example, ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxy esters, peroxy dicarbonates, and the like.

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

  As the hydroperoxide, for example, 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, etc. Can be 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.

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

  As peroxyketal, for example, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butyl) Examples include peroxy) butane, 2,2-bis (t-butylperoxy) octane, 4,4-bis (t-butylperoxy) valeric acid n-butyl ester and the like.

  As peroxy esters, for example, 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.

  Examples of peroxydicarbonates include di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, di-n-propylperoxy Dicarbonate, di-2-ethoxyethylperoxydicarbonate, diallylperoxydicarbonate and the like can be mentioned.

  Among these organic peroxides, hydroperoxides initiate chemical polymerization from the comprehensive balance of safety, storage stability, and radical formation ability in the presence of the alicyclic (meth) acrylic compound (A). It is preferably used as an agent (C-2). Among them, cumene hydroperoxide, t-butyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide are particularly preferably used as the chemical polymerization initiator (C-2).

  The content of the polymerization initiator (C) in the curable composition of the present invention is not particularly limited, but from the viewpoint of the curability of the curable composition to be obtained, 100 parts by mass of the total of the polymerizable monomers Preferably, the polymerization initiator (C) is contained in an amount of 0.001 to 30 parts by mass. When the content of the polymerization initiator (C) is 0.001 parts by mass or more, the polymerization proceeds sufficiently, and stickiness can be prevented. The content of the polymerization initiator (C) is more preferably 0.05 parts by mass or more, further preferably 0.1 parts by mass or more. On the other hand, when the content of the polymerization initiator (C) is 30 parts by mass or less, precipitation from the curable composition can be prevented even when the polymerization performance of the polymerization initiator (C) itself is low. As for content of a polymerization initiator (C), 20 mass parts or less are more preferable, 10 mass parts or less are more preferable, 5 mass parts or less are especially preferable.

[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, organic phosphorus compounds, borate compounds, barbituric acid derivatives, triazine compounds, vanadium Examples thereof include compounds, copper compounds, tin compounds, cobalt compounds, halogen compounds, and thiol compounds. A polymerization accelerator (D) may be used individually by 1 type, and may use 2 or more types together.

  Amines are divided into aliphatic amines and aromatic amines. Examples of aliphatic amines include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; and secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine. N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate , Triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine etc. And aliphatic amines.

  Also, as the aromatic amine, for example, N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-bis (2-hydroxyethyl) -p-toluidine, 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-tert-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-toluy 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-tert-butylaniline, N, N-dimethyl-3,5-di-tert-butylaniline, ethyl 4- (N, N-dimethylamino) benzoate, 4- (N, N -Dimethylamino) benzoate, 4- (N, N-dimethylamino) benzoate n-butoxyethyl, 4- (N, N-dimethylamino) benzoate 2- (methacryloyloxy) ethyl, 4- (N, N-dimethylamino) benzophenone, butyl 4- (N, N-dimethylamino) benzoate and the like can be mentioned. Among these, ethyl 4- (N, N-dimethylamino) benzoate, n-butoxyethyl 4- (N, N-dimethylamino) benzoate, from the viewpoint of imparting excellent curability to the curable composition, And at least one selected from the group consisting of 4- (N, N-dimethylamino) benzophenone is preferably used.

  Examples of sulfinic acid and salts thereof include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, benzenesulfin Sodium acid, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinate, sodium 2,4,6-trimethylbenzenesulfinate, 2,4,6-trimethylbenzenesulfine Acid potassium, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid, 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 include calcium benzenesulfinate and the like.

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

  Examples of aldehydes include terephthalaldehyde and benzaldehyde derivatives. Examples of benzaldehyde derivatives include dimethylamino benzaldehyde, p-methyloxy benzaldehyde, p-ethyloxy benzaldehyde, p-n-octyloxy benzaldehyde and the like.

  As a thiourea compound, for example, 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, tetracyclohexyl thiourea, 3, 3- dimethyl ethylene thio urea, 4, 4- dimethyl -2- imidazolidine thione etc. are mentioned. Among these, 1- (2-pyridyl) -2-thiourea or 4,4-dimethyl-2 from the viewpoint of the curability of the curable composition in the presence of the alicyclic (meth) acrylic compound (A). -Imidazolidinethione is preferably used as a polymerization accelerator (D).

  Examples of organophosphorus compounds include triphenylphosphine, 2-methyltriphenylphosphine, 4-methyltriphenylphosphine, 2-methoxytriphenylphosphine, 4-methoxytriphenylphosphine, tri n-butylphosphine, triisobutylphosphine, Tri-t-butyl phosphine etc. are mentioned.

  As the borate compound, an aryl borate compound is preferable. Specific examples of the aryl borate compound suitably used include, as a borate compound having one aryl group in one molecule, for example, trialkylphenyl boron, trialkyl (p-chlorophenyl) boron, 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, Trialkyl (p-butyloxyphenyl) boron, trialkyl (m-butyloxy (Phenyl) boron, trialkyl (p-octyloxyphenyl) boron and trialkyl (m-octyloxyphenyl) boron (alkyl is selected from the group consisting of n-butyl, n-octyl and n-dodecyl) And salts thereof (sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutyl ammonium salt, tetramethyl ammonium salt, tetraethyl ammonium salt, methyl pyridinium salt, ethyl pyridinium salt, butyl pyridinium salt, And methyl quinolinium salts, ethyl quinolinium salts, butyl quinolinium salts and the like.

  Examples of borate compounds having two aryl groups in one molecule include dialkyl diphenyl boron, dialkyl di (p-chlorophenyl) boron, dialkyl di (p- fluorophenyl) boron and dialkyl di [3,5- bis (trifluoromethyl) ) Phenyl] boron, dialkyldi [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyldi (p-nitrophenyl) boron, dialkyldi) (M-nitrophenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi (p- Octyl oxyphenyl) Boron and dialkyldi (m-octyloxyphenyl) boron (wherein the alkyl group is at least one selected from the group consisting of n-butyl, n-octyl and n-dodecyl), etc. and salts thereof (sodium Salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts butylki And the like.

  Examples of borate compounds 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, Monoalkyltri (p-nitrophenyl) boron, monoalkyltri (m-nitrophenyl) boron, monoalkyltri (p-butylphenyl) boron, monoalkyltri (m-butylphenyl) boron, monoalkyltri (p-) Butyloxyphenyl) boron, monoalkyltri (m-butyloxyphenyl) boron Monoalkyl tri (p-octyloxyphenyl) boron and monoalkyltri (m-octyloxyphenyl) boron (wherein the alkyl group is one selected from n-butyl, n-octyl or n-dodecyl) And their salts (sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutyl ammonium salt, tetramethyl ammonium salt, tetraethyl ammonium salt, methyl pyridinium salt, ethyl pyridinium salt, butyl pyridinium salt, methyl quinolinium salt, And ethyl quinolinium salts, butyl quinolinium salts and the like.

  Examples of borate compounds having four aryl groups in one molecule include tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, and tetrakis [3,5-bis (trifluoromethyl). ) Phenyl] boron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis (M-nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis (p-butyl) Octyl oxyphenyl) boron, tetrakis (m-ok Roxyphenyl) boron, (p-fluorophenyl) triphenylboron, [3,5-bis (trifluoromethyl) phenyl] triphenylboron, (p-nitrophenyl) triphenylboron, (m-butyloxyphenyl) Triphenylboron, (p-butyloxyphenyl) triphenylboron, (m-octyloxyphenyl) triphenylboron and (p-octyloxyphenyl) triphenylboron and salts thereof (sodium salt, lithium salt, potassium salt, Magnesium salt, tetrabutyl ammonium salt, tetramethyl ammonium salt, tetraethyl ammonium salt, methyl pyridinium salt, ethyl pyridinium salt, butyl pyridinium salt, methyl quinolinium salt, ethyl quinolinium salt, butyl quinolinium salt, etc. And the like.

  Among these aryl borate compounds, it is more preferable to use a borate compound having three or four aryl groups in one molecule from the viewpoint of storage stability. Moreover, it is also possible to use these aryl borate compounds individually by 1 type or in mixture of 2 or more types.

  Examples of barbituric acid derivatives include barbituric acid, 1,3-dimethyl barbituric acid, 1,3-diphenyl barbituric acid, 1,5-dimethyl barbituric acid, 5-butyl barbituric acid, 5-ethyl barbituric acid Barbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric 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-phenyl barbituric acid, 1-cyclohexyl-1-ethyl barbituric acid, 1-benzyl-5-fe 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-yl Hexyl barbituric acid, 5-butyl-1-cyclohexyl barbituric acid, 1-benzyl-5-phenyl barbituric acid and thiobarbituric acids, and salts thereof (particularly, alkali metal or alkaline earth metals are preferable) Can be mentioned. Examples of salts of these barbituric acids include sodium 5-butyl barbiturate, sodium 1,3,5-trimethyl barbiturate, sodium 1-cyclohexyl-5-ethyl barbiturate and the like.

  As a triazine compound, for example, 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 and the like.

  As a vanadium compound, a vanadium compound of IV valence and / or V valence is preferable. Examples of the vanadium compound having a valence of 4 and / or a valence of 5 include vanadium dioxide tetrabasic (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 the curability of the curable composition in the presence of the alicyclic (meth) acrylic compound (A).

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

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

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

  As the halogen compound, for example, dilauryldimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, benzyl trimethyl ammonium chloride, tetramethyl ammonium chloride, benzyl dimethyl cetyl ammonium chloride, dilauryl dimethyl ammonium bromide and the like are suitably used.

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

  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- (4) Ethyl N, N-dimethylamino) benzoate, 4,4-dimethyl-2-imidazolidinethione, vanadyl acetylacetonate (IV), copper acetylacetonate, and copper (II) acetate are most preferably used as the polymerization accelerator (D) .

  The content of the polymerization accelerator (D) in the curable composition of the present invention is not particularly limited, but from the viewpoint of the curability of the curable composition to be obtained, 100 parts by mass of the total of the polymerizable monomers Preferably, the polymerization accelerator (D) is contained in an amount of 0.001 to 30 parts by mass. When the content of the polymerization accelerator (D) is 0.001 parts by mass or more, the polymerization sufficiently proceeds, and a decrease in adhesiveness can be prevented. The content of the polymerization accelerator (D) is more preferably 0.05 parts by mass or more, and further preferably 0.1 parts by mass or more. On the other hand, even when the polymerization performance of the polymerization initiator (C) used is low because the content of the polymerization accelerator (D) is 30 parts by mass or less, the polymerization initiator (C) from the curable composition (C) ) Can be prevented. 20 mass parts or less are more preferable, and, as for content of a polymerization accelerator (D), 10 mass parts or less are more preferable.

  In the present invention, the chemical polymerization initiator (C-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 (C-2) and the polymerization accelerator (D) may each be stored in separate containers. In this case, the curable composition is provided by including at least a first material containing a chemical polymerization initiator (C-2) and a second material containing a polymerization accelerator (D). In one embodiment, the curable composition is preferably provided as a kit to be used in the form of a two-material type consisting of the first material and the second material. In this case, the curable composition is more preferably provided as a kit to be used in the form of a two-material type in which both the first and second materials are liquid or paste-like. When the curable composition is provided as a kit in the form of a two-part or two-paste form, each liquid or paste is stored with the liquids or pastes separated from one another and the two liquids or pastes immediately before use It is mixed and chemical polymerization proceeds. When a photopolymerization initiator (C-1) is further contained in the curable composition, it is preferable to proceed with photopolymerization in addition to chemical polymerization to cure the curable composition.

[(Meth) Acrylate (E) Other than Compound (A) and Compound (B)]
The curable composition of the present invention is other than the alicyclic (meth) acrylic compound (A) and the acidic group-containing (meth) acrylic compound (B) for the purpose of improving the operability or adjusting the physical properties of the cured product. It is preferable to further contain (meth) acrylate (E). That is, (meth) acrylate (E) does not contain an acidic group. Examples of the (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 a methacrylate. (Meth) acrylate (E) may be used individually by 1 type, and may use 2 or more types together.

  Examples of monofunctional (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6 -(Meth) acrylates having a hydroxyl group such as hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate and erythritol mono (meth) acrylate; Meta) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-b Alkyl (meth) acrylates such as decyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate; cyclohexyl (meth) acrylate Alicyclic (meth) acrylates such as isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isosorbide mono (meth) acrylate, isomannide mono (meth) acrylate, isoidid mono (meth) acrylate; benzyl (meth) Aromatic group-containing (meth) acrylates such as acrylates; 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- ( And silyl group-containing (meth) acrylates such as acryloyloxyundecyl trimethoxysilane. One of these may be used alone, or two or more may be used in combination. Among these, from the viewpoint of hydrophilicity, (meth) acrylates containing monofunctional hydroxyl groups are preferable.

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

  Examples of aliphatic compound difunctional (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- Candiol di (meth) acrylate, 1,2-bis (3- (meth) acryloyloxy-2-hydroxypropoxy) ethane, 2,2,4-trimethylhexamethylene bis (2-carbamoyloxyethyl) dimethacrylate (common name) UDMA) and the like. One of these may be used alone, or two or more may be used in combination.

  Examples of aromatic compound-based difunctional (meth) acrylates 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) Addition mole number is 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- (4- (meth) acryloyloxydiethoxyphenyl) propane Meta) 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 and the like It is below.

  Examples of trifunctional or higher (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, penta 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 Be Among these, trimethylolpropane tri (meth) acrylate is preferable in that it is excellent in the miscibility with the alicyclic (meth) acrylic compound (A) and the strength of the cured product of the curable composition.

  The total content of (meth) acrylate (E) in the curable composition of the present invention is 1 to 10% of the total amount of polymerizable monomers from the viewpoint of the strength of the cured product of the curable composition of the present invention. The content is preferably 80% by mass, more preferably 2.5 to 60% by mass, and still more preferably 5 to 40% by mass. In one embodiment, it is preferable to contain a (meth) acrylate having a monofunctional hydroxyl group as the (meth) acrylate (E). In one embodiment, it is preferable to contain an aliphatic compound-based difunctional (meth) acrylate as the (meth) acrylate (E). Furthermore, in another embodiment, as the (meth) acrylate (E), it is preferable to contain a monofunctional (meth) acrylate having a hydroxyl group and a difunctional (meth) acrylate based on an aliphatic compound.

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

  Examples of (meth) acrylamides (F) include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N-isopropyl (N) Meta) acrylamide, N, N-di-n-butyl (meth) acrylamide, N, N-di-n-hexyl (meth) acrylamide, N, N-di-n-octyl (meth) acrylamide, N, N- Di-2-ethylhexyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N- (dihydroxyethyl) (meth) acrylamide, N- (meth) acryloyl morpholine, N, N-dimethylamino Ethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-di Ropylaminoethyl (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' '- (Meth) acryloyl diethylenetriamine, N, N ', N' ', N' '' - such as tetra (meth) acryloyl triethylenetetramine. One of these may be used alone, or two or more may be used in combination.

  Among these, N, N-dimethyl (meth) acrylamide, N, N-from the viewpoint of good compatibility with the alicyclic (meth) acrylic compound (A) and excellent strength of the cured product of the curable composition. Diethyl (meth) acrylamide, N, N-di-n-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide, N- (2-hydroxyethyl) (Meth) acrylamide, N- (meth) acryloyl morpholine, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dimethylaminobutyl (meth) acrylic N, N-diethylaminobutyl (meth) acrylamide, N- (meth) acryloyloxyethyl (meth) acrylamide, N- (meth) acryloyloxypropyl (meth) acrylamide, N, N ', N' '-tri ( Meta) acryloyl diethylene triamine, N, N ', N' ', N' ''-tetra (meth) acryloyl tri ethylene tetramine is preferred, N, N- dimethyl (meth) acrylamide, N, N- diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (meth) acryloyl morpholine, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) Acrylamide, N, N-dimethylamime Propyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N- (meth) acryloyloxyethyl (meth) acrylamide, N- (meth) acryloyloxypropyl (meth) acrylamide, N, N ', N' '-Tri (meth) acryloyl diethylene triamine, N, N', N '', N '' '-tetra (meth) acryloyl triethylene tetramine is more preferable, N, N- dimethyl acrylamide, N, N- diethyl acrylamide, N -Isopropylacrylamide, N- (2-hydroxyethyl) acrylamide, N-acryloyl morpholine, N, N-dimethylaminoethyl acrylamide, N, N-diethylaminoethyl acrylamide, N, N-dimethylaminopropyl acrylamide, N, N-diethylaminopropyl acrylamide, N- (meth) acryloyloxyethyl (meth) acrylamide, N- (meth) acryloyloxypropyl (meth) acrylamide, N, N ', N' '-tri (meth) acryloyldiethylene triamine, N, N ′, N ′ ′, N ′ ′ ′-tetra (meth) acryloyl triethylene tetramine is more preferable, and N, N-dimethyl acrylamide, N, N-diethyl acrylamide, N-acryloyl morpholine, N, N-dimethyl acrylamide Aminopropyl acrylamide, N- (meth) acryloyloxyethyl (meth) acrylamide, N- (meth) acryloyloxypropyl (meth) acrylamide, N, N ', N' '-tri (meth) acryloyldiethylene triamine, 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 of the total amount of polymerizable monomers from the viewpoint of the strength of the cured product of the curable composition of the present invention % Is preferable, 2.5 to 60% by mass is more preferable, and 5 to 40% by mass is more preferable.

[Water, water-soluble organic solvent (G)]
The curable composition of the present invention more preferably contains water and / or a water-soluble organic solvent (G) for the purpose of improving adhesion. Examples of such water-soluble organic solvents include ethanol, isopropyl alcohol, tert-butanol, isobutyl alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and the like. One of these may be used alone, or two or more may be used in combination.

  The total content of water and / or water-soluble organic solvent (G) is 10 to 1000 parts by mass with respect to 100 parts by mass of the total amount of polymerizable monomers from the viewpoint of the adhesiveness of the curable composition of the present invention The content is preferably 20 to 500 parts by mass, more preferably 50 to 200 parts by mass. In one embodiment, from the viewpoint of hydrophilicity, the content of water is preferably 0.5 to 60% by mass, more preferably 1.0 to 50% by mass, with respect to the entire curable composition. -40 mass% is further more preferable. In another embodiment, from the viewpoint of hydrophilicity, the content of the water-soluble organic solvent is preferably 0.5 to 60% by mass, and more preferably 1.0 to 50% by mass, based on the entire curable composition. And 5 to 40% by mass are more preferable. Furthermore, in another embodiment, from the viewpoint of hydrophilicity, the total content of water and the water-soluble organic solvent (G) is preferably 0.5 to 70% by mass with respect to the entire curable composition, 0 to 60% by mass is more preferable, and 5 to 55% by mass is more preferable.

[Inorganic particles]
The curable composition of the present invention can contain inorganic particles for the purpose of adjusting viscosity, suppressing sedimentation of a pigment, imparting X-ray contrast properties, and the like.

  Examples of the material of the inorganic particles 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 fluoroaluminosilicate glass And ytterbium fluoride. These can be used singly or in combination of two or more. The shape of the inorganic particles is not particularly limited, and amorphous inorganic particles, spherical inorganic particles and the like can be appropriately selected and used.

  The inorganic particles are composed of an alicyclic (meth) acrylic compound (A), an acidic group-containing (meth) acrylic compound (B), an alicyclic (meth) acrylic compound (A) and an acidic group-containing (meth) acrylic compound In order to adjust the compatibility with polymerizable monomers other than B), you may use what was surface-treated beforehand with surface treating agents, such as a silane coupling agent, as needed. As such a surface treatment agent, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, 3-methacryloyloxypropyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like.

  As a method of surface treatment, a known method can be used. For example, a method of spray addition of the above-mentioned surface treatment agent while vigorously stirring inorganic particles; dispersion of inorganic particles and the above-mentioned surface treatment agent in a suitable solvent After dissolving, the solvent is removed; the alkoxy group of the surface treatment agent is hydrolyzed with an acid catalyst in an aqueous solution to convert it into a silanol group, and after adhering to the surface of inorganic particles in the aqueous solution, water is added The removal method etc. are mentioned. In any of the above-described methods, the surface treatment can be carried out by completing the reaction between the surface of the inorganic particles and the surface treatment agent by heating generally in the range of 50 to 150 ° C. In addition, the usage-amount in particular of a surface treatment agent is not restrict | limited, For example, 1 to 10 mass parts of surface treatment agents can be used with respect to 100 mass parts of inorganic particles before a treatment.

  The average particle size of the inorganic particles is 0.001 to 10 μm and 0.005 to 5.0 μm from the viewpoint of the handleability of the resulting curable composition and the mechanical properties and aesthetics of the cured product, etc. Is preferable, and 0.01 to 1.0 μm is more preferable.

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

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

  Electron microscope observation takes, for example, a scanning electron microscope (S-4000, manufactured by Hitachi, Ltd.) photograph of particles, and the particle diameter of particles (200 or more) observed in the unit field of the photograph is It can obtain | require by measuring using image analysis type particle size distribution measurement software (Macview (Muntech Inc.)). At this time, the particle diameter of the particles is obtained as an arithmetic mean value of the longest and shortest lengths of the particles, and the average primary particle diameter is calculated from the number of particles and the particle diameter thereof.

  The content of the inorganic particles in the curable composition of the present invention is 0.1 to 0.1 parts by mass relative to the total amount of 100 parts by mass of the polymerizable monomer from the viscosity of the strength of the cured product of the curable composition of the present invention The amount is preferably 50 parts by mass, more preferably 0.5 to 40 parts by mass, and still more preferably 1 to 30 parts by mass.

  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, water and / or organic solvents other than the water-soluble organic solvent (G), thickeners and the like.

  As a polymerization inhibitor, for example, hydroquinone, dibutyl hydroquinone, hydroquinone monomethyl ether, dibutyl hydroquinone monomethyl ether, t-butyl catechol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl phenol, Phenols such as 3,5-di-t-butyl-4-hydroxytoluene; quinones such as p-benzoquinone, 2,5-diphenyl-p-benzoquinone, p-toluquinone, p-xyloquinone and the like. The content of the polymerization inhibitor is preferably 0.001 to 1.0 parts by mass with respect to 100 parts by mass of the total of the polymerizable monomers.

[Use]
The curable composition of the present invention can give a cured product having excellent mechanical properties and is excellent in adhesion. Accordingly, the curable composition of the present invention is preferably used for dental use, and more preferably used for dental adhesives such as teeth and bones.

  An example of a suitable embodiment of a dental adhesive is shown. Examples of suitable dental adhesives include alicyclic (meth) acrylic compounds (A), acidic group-containing (meth) acrylic compounds (B), photopolymerization initiators (C-1), polymerization accelerators (C) D) A curable composition containing (meth) acrylate (E) and / or (meth) acrylamide (F) as an optional component is mentioned. In the adhesive for dental use, 10 to 99% by mass of the alicyclic (meth) acrylic compound (A) and 1.0 to 0.5 to the acidic group-containing (meth) acrylic compound (B) in the total amount of polymerizable monomers 50% by mass, containing 0 to 80% by mass of (meth) acrylate (E) and / or (meth) acrylamide (F), with respect to 100 parts by mass of the total amount of polymerizable monomers, a photopolymerization initiator (C- It is preferable to contain 0.001 to 30 parts by mass of 1) and 0.001 to 30 parts by mass of the polymerization accelerator (D), and in the total amount of the polymerizable monomers, the alicyclic (meth) acrylic compound ( 20 to 95 mass% of A), 2.5 to 40 mass% of an acidic group-containing (meth) acrylic compound (B), 2.5 of (meth) acrylate (E) and / or (meth) acrylamide (F) Relative to 100 mass parts of the total of polymerizable monomers, containing It is more preferable to contain 0.05 to 20 parts by mass of the polymerization initiator (C-1) and 0.05 to 20 parts by mass of the polymerization accelerator (D), and among the total of the polymerizable monomers, alicyclic 30 to 90 mass% of the formula (meth) acrylic compound (A), 5.0 to 30 mass% of the acidic group-containing (meth) acrylic compound (B), (meth) acrylate (E) and / or (meth) acrylamide (F) is contained in an amount of 5 to 40% by mass, and 0.1 to 10 parts by mass of a photopolymerization initiator (C-1) and a polymerization accelerator (D) with respect to 100 parts by mass of the total amount of polymerizable monomers It is further preferable to contain 0.1 to 10 parts by mass.

  In any of the preferred embodiments of the dental adhesive described above, the amount of each component can be appropriately changed based on the above description, the type of each component can be appropriately selected, and addition, deletion, etc. of any component. You can change it.

[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, and for example, methods such as light irradiation and heating, and when the curable composition of the present invention is a two-material type including at least a first material and a second material, the first material and the second Mixing with wood etc. may be mentioned.

  The present invention includes embodiments in which the above-described configurations are variously combined within the technical scope of the present invention as long as the effects of the present invention can be obtained.

  EXAMPLES The present invention will next be described in more detail by way of examples, which should not be construed as limiting the present invention in any way, and many modifications may be made within the technical scope of the present invention. It is possible by the person of ordinary knowledge. In the examples, parts are parts by mass unless otherwise specified.

[Analysis of alicyclic (meth) acrylic compound (A)]
In the following production examples, the alicyclic (meth) acrylic compound (A) was identified by ¹ H-NMR measurement. The purity of the alicyclic (meth) acrylic compound (A) was measured by UPLC (Ultra-Performance Liquid Chromatography). ^The apparatus and conditions which were used for < ¹ > H-NMR and UPLC measurement are as follows.

[Device and condition of ¹ H-NMR measurement]
Device: Nuclear magnetic resonance device “JNM-LA400” (manufactured by Nippon Denshi Co., Ltd.)
Heavy solvent: deuterated chloroform

[Analysis of purity by UPLC]
Device: ACQUITY UPLC (made by Nippon Waters Co., Ltd.)
Column: ACQUITY UPLC BEH C18 1.7μm (made 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

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

[Alicyclic (meth) acrylic compound (A)]
Production Example 1 Synthesis of isosorbide dimethacrylate In a 2 L four-necked flask, 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. The mixture was cooled to 5 ° C. in an ice bath, and 202 g (2.0 mol) of triethylamine was slowly dropped using a dropping funnel while confirming the heat of reaction. After completion of the dropwise addition, stirring was continued for 5 hours under ice cooling. Thereafter, the temperature was returned to room temperature and stirring was further performed for 3 hours to complete the reaction.

  After completion of the reaction, the reaction product 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 obtained ¹ H-NMR measurement and UPLC analysis were performed using the obtained liquid, it was found to be isosorbide dimethacrylate (yield 90.4% based on the raw material isosorbide). In the following 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。

The isosorbide dimethacrylate represented by these was used as alicyclic (meth) acryl compound (A) -I-1.

Production Example 2 Synthesis of a Compound (Alicyclic (Meth) Acrylic Compound (A) -I-2) Represented by the Following Formula

  In a 2 L four-necked flask, 146 g (1 mol) of isosorbide is dissolved in 670 g of 50% by mass aqueous potassium hydroxide solution, 19.3 g (0.06 mol) of tetrabutylammonium bromide as a phase transfer catalyst, and 726 g (6.0 mol) of allyl bromide The reaction mixture was heated under reflux for 7 hours and 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 is dissolved in 500 mL of methylene chloride, 79.8 g (1.1 mol) of m-chloroperbenzoic acid is added, and the mixture is stirred at room temperature for 24 hours and then with an aqueous potassium carbonate solution Washing, filtration and drying gave 117 g (yield 90%) of isosorbide diglycidyl ether.

  Add 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, and stir at 75 ° C. for 1 hour under a nitrogen atmosphere. Then, after stirring at 100 ° C. for 3 hours, it was dissolved in 400 mL of methylene chloride, washed with an aqueous potassium carbonate solution, filtered and dried to obtain 101.6 g (yield 90%) of a viscous liquid.

The obtained liquid was used for ¹ H-NMR measurement and UPLC analysis described above to find that it was a compound represented by the above formula (yield: 78% based on the raw material isosorbide). Hereinafter, the compound represented by the said Formula was used as alicyclic (meth) acrylic compound (A) -I-2 in the Example.

Production Example 3 Synthesis of a Compound (Alicyclic (Meth) Acryl Compound (A) -II-1) Represented by the Following Formula

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

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

When the obtained ¹ H-NMR measurement and UPLC analysis were performed using the obtained liquid, it was found to be a compound represented by the above formula (yield 92.3% based on the raw material isosorbide). Hereinafter, the compound represented by the said Formula was used as alicyclic (meth) acryl compound (A) -II-1 in the Example.

Preparation 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), 50 mL of 1,2-dichloroethane, and 5.0 g (50 mmol) of triethylamine were added, and the mixture was stirred with a stirrer chip at 25 ° C. in the atmosphere. 20 g (224 mmol) of methacrylic acid was added, the temperature was raised with an oil bath, and the mixture was stirred at 80 to 85 ° C. for 5 hours. As a result of sampling a part of the reaction product and performing UPLC measurement, disappearance of 1,3-bis (4-glycidyloxyphenyl) adamantane was confirmed.

The reaction mixture was washed sequentially with saturated aqueous NaHCO ₃ (100 mL × 2), 1N HCl (100 mL × 1), 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 dried in vacuo to give 1,3-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] adamantane (36.8 g, yield 88%). This was used as Comparative Example 4 and 5 as the alicyclic (meth) acrylic compound 1.

[Acid group-containing (meth) acrylic compound (B)]
(B) -1 MDP: 10-methacryloyloxydecyl dihydrogen phosphate (B) -2 4-META: 4-methacryloyloxyethyl trimellitate anhydride

[Photoinitiator (C-1)]
(C-1) -1 CQ: camphor quinone

[Polymerization accelerator (D)]
(D) -1 PDE: ethyl 4- (N, N-dimethylamino) benzoate

[(Meth) Acrylate (E) Other than Compound (A) and Compound (B)]
(E) -1 HEMA: 2-hydroxyethyl methacrylate (E) -2 # 801: 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane

[(Meth) acrylamide (F)]
(F) -1 DEAA: N, N-diethylacrylamide

[Water, water-soluble organic solvent (G)]
Water: Purified water (Japanese Pharmacopoeia)
Ethanol: Wako Pure Chemical Industries, Ltd. (special grade)

[Inorganic particles]
Inorganic particles 1: Dichlorodimethylsilane surface-treated silica fine particle powder Nippon Aerosil Co., Ltd. "Aerosil (registered trademark) R972", average particle diameter 16 nm

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

Examples 1 to 9 and Comparative Examples 1 to 5
The raw materials shown in Tables 1 and 2 are mixed at normal temperature (23 ° C.) in the dark to prepare curable compositions, and these curable compositions are characterized according to the methods of Test Examples 1 and 2 below. The The results are shown in Tables 1 and 2.

Test Example 1 Evaluation of Flexural Properties The strength was evaluated by a bending test in accordance with ISO 4049: 2009. Specifically, it is as follows. The air and water-soluble organic solvent of the curable compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 5 are air-blown and dried, and then the mold made of SUS (2 mm long × 25 mm wide × 2 mm thick) is used. It filled up, and the upper and lower sides (surface of 2 mm x 25 mm) of the curable composition (paste) were pressure-contacted with the slide glass. Next, with a visible light irradiator for dental use (Pencure 2000, manufactured by Morita Co., Ltd.), the surface of the paste was irradiated with light at five points on one side for 10 seconds each over the slide glass to cure the curable composition. 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-100 kNI, manufactured by Shimadzu Corporation) to measure the bending strength and the bending elastic modulus. . The results are shown in Tables 1 and 2. In this measurement, the higher the bending strength and the bending elastic modulus, the better the strength of the cured product. When the bending strength is 100 MPa or more and the bending elastic modulus is 3.0 GPa or more, the cured product is excellent in strength.

Test Example 2: Measurement of tensile bond strength The labial surface of the bovine lower incisor was abraded in flowing water with # 80 silicon carbide paper (manufactured by Nippon Ken Paper Co., Ltd.), and then # 1000 silicon carbide paper (Nihon Ken Paper Co., Ltd.) The surface water was removed with a dental air syringe to obtain a bovine tooth having a flat surface of enamel. Similarly, a bovine tooth having a flat surface of dentin was obtained.

  An adhesive tape having a thickness of about 150 μm having a round hole of 3 mm in diameter was attached to the flat surface of the obtained bovine tooth having a flat surface of the above-mentioned enamel. Next, the curable compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 5 assuming dental adhesives are applied in the above-mentioned round holes, air-blown after 10 seconds, and water and water-soluble organic compounds are obtained. The solvent was distilled off. Next, light was irradiated for 10 seconds with a dental visible light irradiator (Pencure 2000, manufactured by Morita Co., Ltd.). Subsequently, a dental composite resin "CLEARFIL (registered trademark) Majesty (registered trademark) ES-2" (manufactured by KURARENORI TAKE Dental Co., Ltd.) is filled in the round hole, and the surplus portion overflowing from the round hole is surfaced with a razor. After removing so as to be smooth, light was irradiated for 10 seconds with a dental visible light irradiator (Pencure 2000, manufactured by Morita Co., Ltd.). Next, the end face of the stainless steel cylindrical rod (diameter 7 mm, length 2.5 cm) coated with a commercially available dental resin cement ("Panabia (registered trademark) 21" manufactured by Kurare Noritake Dental Co., Ltd.) on the end face is the above-mentioned end face Bond to cover the surface filled with dental composite resin, let stand for 30 minutes at room temperature, then immerse in distilled water, stand for 24 hours in a 37 ° C thermostat, test sample (n = 5) I got

  Further, an adhesive tape having a thickness of about 150 μm having a round hole of 3 mm in diameter was attached to the flat surface of the obtained bovine tooth having a flat surface of the dentin. Next, the curable compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 5 assuming dental adhesives are applied in the above-mentioned round holes, air-blown after 10 seconds, and water and water-soluble organic compounds are obtained. The solvent was distilled off. Next, light was irradiated for 10 seconds with a dental visible light irradiator (Pencure 2000, manufactured by Morita Co., Ltd.). Subsequently, the dental composite resin Clearfil (registered trademark) Majesty (registered trademark) ES flow (manufactured by Kuraray Noritake Dental Co., Ltd.) is filled in the round hole, and the surplus portion overflowing from the round hole is a razor surface. After removing so as to be smooth, light was irradiated for 10 seconds with a dental visible light irradiator (Pencure 2000, manufactured by Morita Co., Ltd.). Next, the end face of the stainless steel cylindrical rod (diameter 7 mm, length 2.5 cm) coated with a commercially available dental resin cement ("Panabia (registered trademark) 21" manufactured by Kurare Noritake Dental Co., Ltd.) on the end face is the above-mentioned end face Bond to cover the surface filled with dental composite resin, let stand for 30 minutes at room temperature, then immerse in distilled water, stand for 24 hours in a 37 ° C thermostat, test sample (n = 5) I got

  The stainless steel cylindrical rod and cow tooth of the above test sample are connected to an autograph (AG-100kNI, manufactured by Shimadzu Corporation), and a tensile test is performed at a crosshead speed of 2 mm / min. The tensile bond strengths of the compositions were each measured. Each tensile test was performed 5 times each, and the average value was taken as the tensile bond strength. The results are shown in Tables 1 and 2.

  It is excellent in adhesiveness in tensile adhesive strength being 15 Mpa or more.

  From the results of Tables 1 and 2, the cured products of Examples 1 to 9 corresponding to the curable composition of the present invention have large flexural strength and flexural modulus and are excellent in strength. It also has excellent adhesion to enamel and dentin. On the other hand, the composition of Comparative Example 1 not containing the acidic group-containing (meth) acrylic compound (B) did not have adhesiveness. In addition, the composition of Comparative Example 2 containing the aromatic (meth) acrylic compound did not obtain a uniform composition and was not sufficiently cured. The composition of Comparative Example 3 was low in strength. The composition of Comparative Example 4 containing an alicyclic (meth) acrylic compound different from the present invention did not obtain a uniform composition and did not cure sufficiently. The composition of Comparative Example 5 resulted in low strength and adhesion.

  Since the curable composition of the present invention can obtain a cured product having excellent mechanical properties and adhesiveness, it can be suitably used, for example, in dental applications such as dental adhesives.

Claims (12)

An alicyclic (meth) acrylic compound (A), an acidic group-containing (meth) acrylic compound (B), and a polymerization initiator (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) It is an integer of -30.)
(Meth) acrylic compound (A) -I represented by the formula, and 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 of them is independently an integer of 0 to 30.)
The curable composition which is at least 1 sort (s) chosen from the group which consists of an alicyclic (meth) acrylic compound (A) -II represented by these.   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 an alkylene group of 6. R ^1, R ^2, R ³ and R ⁴ are methacryloyl group, the curable composition according to any one of claims 1 to 3 wherein the alicyclic (meth) acrylic compound (A).   The curable composition according to any one of claims 1 to 4, further comprising a polymerization accelerator (D).   The method according to any one of claims 1 to 5, further comprising (meth) acrylate (E) other than the alicyclic (meth) acrylic compound (A) and the acidic group-containing (meth) acrylic compound (B). Curable composition.   7. The curable composition according to claim 6, containing a monofunctional (meth) acrylate having a hydroxyl group as the (meth) acrylate (E).   The curable composition of Claim 6 or 7 which contains the difunctional (meth) acrylate of an aliphatic compound type | system | group as said (meth) acrylate (E).   The curable composition according to any one of claims 1 to 8, further comprising (meth) acrylamide (F).   The curable composition according to any one of claims 1 to 9, further comprising water and / or a water-soluble organic solvent (G).   The curable composition according to any one of claims 1 to 10, which is a dental curable composition.   The curable composition according to claim 11, which is a dental adhesive.