Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/50—Preparations specially adapted for dental root treatment
  • A61K6/54—Filling; Sealing
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
  • A61K6/61—Cationic, anionic or redox initiators
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
  • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/106—Esters of polycondensation macromers
  • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1535—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
  • A61K6/62—Photochemical radical initiators

Definitions

• the present disclosure relates to a curable composition preparation kit, a curable composition, a cured product, and a dental material.
• cement is used as a tooth substitute for repairing large tooth defects.
• the scope of use of cement has expanded.
• Porcelain has come to be used as a dental prosthesis from the viewpoint of aesthetics, and adhesiveness is required not only to the tooth structure but also to the porcelain.
• a photopolymerization initiator, a chemical polymerization initiator, and the like may be used for polymerization of a curable composition for dental materials such as cement.
• a chemical polymerization initiator system is a redox type polymerization initiator that combines an oxidizing agent and a reducing agent.
• a redox type polymerization initiator for example, a polymerization initiator system using an organic peroxide as an oxidizing agent and an aromatic amine compound as a reducing agent is known.
• Patent Document 1 describes a first agent containing a polymerizable monomer (a) having an acidic group, a polymerizable monomer (b) not having an acidic group, a polymerization initiator (c), and a filler (d). and at least one filler (e) selected from the group consisting of a polymerizable monomer (b) having no acidic group, a basic glass filler and alumina, a polymerization accelerator (f), and a specific structure.
• a two-paste dental curable composition is disclosed, which comprises a second component containing a silane coupling agent (g).
• Patent Document 1 International Publication No. 2019/004391
• the adhesiveness of the obtained cured product to ceramics such as porcelain can be improved, but the adhesiveness to dentin may be reduced.
• various polymerization initiators that improve adhesion to dentin tend to reduce adhesion to ceramics. That is, it is difficult to achieve both adhesion to ceramics and adhesion to dentin, and there is a need for a cement that achieves both.
• the problem to be solved by an embodiment of the present disclosure is a kit for preparing a curable composition, a curable composition, and a cured product that can obtain a cured product with excellent adhesion to ceramics and dentin. and to provide dental materials.
• a kit for preparing a curable composition each independently comprising a compound A containing at least one of the groups.
• the compound A is at least one selected from the group consisting of an organosilane containing a polymerizable group and an alkoxy group or a hydroxyl group, and an organosiloxane containing a polymerizable group, an alkoxy group or a hydroxyl group, and a siloxane bond.
• R 1 to R 6 are each independently a monovalent organic group having a polymerizable group, a monovalent organic group not having a polymerizable group, or a hydroxyl group
• m is 0 or 1
• L is a monovalent organic group having a polymerizable group, a monovalent organic group not having a polymerizable group, or a hydroxyl group
• L is an oxygen atom or a structure represented by the following general formula (Y).
• at least one of L and R 4 to R 6 in general formula (X) is a monovalent organic group having a polymerizable group, and at least one is an alkoxy group or It is a hydroxyl group.
• at least one of R 1 to R 8 in general formula (X) and general formula (Y) is a monovalent organic group having a polymerizable group, and at least one is an alkoxy group or hydroxyl group.
• R 7 to R 8 are each independently a monovalent organic group having a polymerizable group, a monovalent organic group not having a polymerizable group, a hydroxyl group, or an OSi chain, and n is an integer greater than or equal to 1, and * is the bonding position.
• the OSi chain is a monovalent organic group having an -O-Si group that forms a siloxane bond with the adjacent Si in general formula (Y).
• ⁇ 5> The curable composition according to any one of ⁇ 1> to ⁇ 4>, wherein at least one of the first agent and the second agent independently contains a transition metal compound and an organic peroxide.
• ⁇ 6> The kit for preparing a curable composition according to ⁇ 5>, wherein the first agent includes the transition metal compound and the organic peroxide, and the second agent includes the ascorbic acids and the compound A. . ⁇ 7>
• At least one of the first agent and the second agent contains at least one polymerization accelerator (1) selected from the group consisting of phosphonite compounds, phosphite compounds, and sulfite compounds ⁇ 1>
• At least one of the first agent and the second agent is a polymerization accelerator other than at least one polymerization accelerator (1) selected from the group consisting of phosphonite compounds, phosphite compounds, and sulfite compounds.
• the kit for preparing a curable composition according to any one of ⁇ 1> to ⁇ 9> which includes a certain polymerization accelerator (2).
• ⁇ 11> The kit for preparing a curable composition according to any one of ⁇ 1> to ⁇ 10>, wherein at least one of the first agent and the second agent contains a silanol condensing agent.
• ⁇ 12> The kit for preparing a curable composition according to any one of ⁇ 1> to ⁇ 11>, which is used for dental materials.
• ⁇ 14> A cured product of the curable composition according to ⁇ 13>.
• ⁇ 15> A dental material comprising the cured product according to ⁇ 14>.
• a curable composition preparation kit a curable composition, a cured product, and a dental material capable of obtaining a cured product with excellent adhesion to ceramics and dentin are provided. can be provided.
• a numerical range indicated using “ ⁇ ” means a range that includes the numerical values listed before and after " ⁇ " as the minimum and maximum values, respectively.
• the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step.
• the upper limit or lower limit described in a certain numerical range may be replaced with the value shown in the Examples.
• a combination of two or more preferred embodiments is a more preferred embodiment.
• the amount of each component means the total amount of the multiple types of substances, unless otherwise specified.
• "(meth)acrylic” means acrylic and methacryl
• “(meth)acryloyl” means acryloyl and methacryloyl.
• the curable composition preparation kit of the present disclosure includes a first agent containing a first monomer and a second agent containing a second monomer, and at least one of the first agent and the second agent contains ascorbic acids. , and a compound A containing at least one of an alkoxysilyl group and a hydroxysilyl group.
• a compound A containing at least one of an alkoxysilyl group and a hydroxysilyl group means that the first agent and the second agent This means that at least one of the first and second agents contains the compound A, and at least one of the first and second agents contains ascorbic acids.
• compound A contained in both the first agent and the second agent compound A contained in the first agent and compound A contained in the second agent may be the same or different. The same applies to ascorbic acids.
• the adhesiveness of the obtained cured product to ceramics such as porcelain can be improved, but the adhesiveness to dentin may be reduced. The extent of this can often be such that it does not adhere to the dentin at all.
• various polymerization initiators that improve adhesion to dentin tend to reduce adhesion to ceramics.
• the curable composition preparation kit of the present disclosure at least one of the first agent and the second agent contains Compound A, which is a specific silane coupling agent, and the kit can be used to prepare ceramics without impairing adhesion to dentin. can improve adhesion to.
• Ascorbic acids in the present disclosure can function as a polymerization initiator.
• the curable composition preparation kit of the present disclosure at least one of the first agent and the second agent each independently contains an ascorbic acid and a compound A containing at least one of an alkoxysilyl group and a hydroxysilyl group, Furthermore, the other configurations described above are also included. As a result, the curable composition preparation kit of the present disclosure can obtain a cured product with excellent adhesion to ceramics and dentin.
• At least one of the first agent and the second agent contains ascorbic acids.
• ascorbic acids mean ascorbic acid, ascorbic acid derivatives, or salts thereof.
• the ascorbic acid derivative or its salt in the present disclosure has a structure in which at least one of the four hydroxyl groups contained in ascorbic acid is replaced with an ether bond bonded to a carbon atom, and a structure in which at least one of the hydroxyl groups contained in ascorbic acid is replaced with an ether bond bonded to a carbon atom. It may also contain a substituted structure in the ester bond bonded to.
• the ascorbic acids of the present disclosure may be additives used in polymerization initiators (additives for polymerization initiators), and can be used in combination with other components (for example, transition metal compounds, organic peroxides, etc.) to initiate polymerization. It may also be used as an agent.
• Examples of the salts of ascorbic acid derivatives in the present disclosure include alkali metal salts of ascorbic acid derivatives, alkaline earth metal salts of ascorbic acid derivatives, and the like. More specific examples include sodium salts, potassium salts, magnesium salts, calcium salts, etc. of ascorbic acid derivatives. Among these, calcium salts are preferred from the viewpoint of balance between polymerizability and adhesiveness.
• the ascorbic acid derivative or its salt in the present disclosure has a structure in which at least one of the four hydroxyl groups contained in ascorbic acid is replaced with an ether bond bonded to a carbon atom (hereinafter also referred to as "ether derivative of ascorbic acid"). , or a structure in which at least one of the four hydroxyl groups contained in ascorbic acid is substituted with an ester bond bonded to a carbon atom (hereinafter also referred to as "ester derivative of ascorbic acid”), and ascorbic acid It is preferable to include an ether derivative of.
• ester derivatives of ascorbic acid include those containing a structure in which at least one of the four hydroxyl groups contained in ascorbic acid is formed by reaction with a carboxylic acid (for example, a carboxylic acid having 2 to 30 carbon atoms).
• carboxylic acids having 2 to 30 carbon atoms include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, and palmitoleic acid.
• Examples include fatty acids such as sapienoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolelaidic acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid.
• fatty acids such as sapienoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolelaidic acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid.
• Examples of the ether derivative of ascorbic acid include those containing a structure in which at least one of the four hydroxyl groups contained in ascorbic acid is formed by reaction with an alkyl halide.
• Examples of the alkyl halide include alkyl chloride having 1 to 30 carbon atoms, alkyl bromide having 1 to 30 carbon atoms, and the like.
• an ether derivative of ascorbic acid is one containing a structure in which at least two of the four hydroxyl groups contained in ascorbic acid each form an ether bond to the same carbon atom (i.e., an acetal structure).
• An ether derivative of ascorbic acid containing an acetal structure can be obtained, for example, by reacting ascorbic acid with an aldehyde.
• the ether derivative of ascorbic acid of the present disclosure preferably includes a structure represented by the following general formula (A).
• * indicates the bonding position with the carbon atom.
• Two * in the general formula (A) may be bonded to the same carbon atom to form a 1,3-dioxolane skeleton.
• the ascorbic acid derivative in the present disclosure preferably includes a compound represented by the following general formula (B).
• R 1B and R 2B are each independently a hydrogen atom or a monovalent organic group. At least one of R 1B and R 2B is preferably a monovalent organic group.
• the monovalent organic group in R 1B and R 2B is preferably an organic group having 1 to 12 carbon atoms, more preferably an organic group having 1 to 10 carbon atoms, and an organic group having 3 to 10 carbon atoms. It is more preferable that
• one of R 1B or R 2B may be a hydrogen atom, and the other of R 1B or R 2B may be a monovalent organic group having 1 to 10 carbon atoms.
• the monovalent organic group in R 1B and R 2B may be an organic group containing an oxygen atom, a nitrogen atom, a sulfur atom, etc., or a hydrocarbon group to which an oxygen atom, a nitrogen atom, a sulfur atom, etc. are bonded. It may also be a hydrocarbon group.
• the salt of the ascorbic acid derivative in the present disclosure may be a salt of a compound represented by the general formula (B), or an alkali metal salt or an alkaline earth metal salt of the compound represented by the general formula (B). From the viewpoint of balance between polymerizability and adhesive properties, a calcium salt of a compound represented by general formula (B) is preferred.
• R 1B and R 2B are preferably each independently a hydrogen atom or a monovalent organic group. Further, one of R 1B or R 2B is a hydrogen atom, and the other of R 1B or R 2B is a monovalent organic group having 1 to 10 carbon atoms, or R 1B and R 2B are each independently It is preferably a monovalent organic group having 1 to 10 carbon atoms.
• R 1B or R 2B When one of R 1B or R 2B is a hydrogen atom, and the other of R 1B or R 2B is a monovalent organic group having 1 to 10 carbon atoms, the other of R 1B or R 2B is a monovalent organic group having 1 to 10 carbon atoms. It is preferably a monovalent organic group having 5 carbon atoms, more preferably a monovalent organic group having 1 to 3 carbon atoms, and even more preferably a methyl group, ethyl group, propyl group or isopropyl group, and isopropyl group. A group is particularly preferred.
• R 1B and R 2B are each independently a monovalent organic group having 1 to 10 carbon atoms
• R 1B and R 2B are each independently a monovalent organic group having 1 to 5 carbon atoms. It is preferably a monovalent organic group having 1 to 3 carbon atoms, more preferably a methyl group, ethyl group, propyl group or isopropyl group, and particularly preferably a methyl group.
• ascorbic acid represented by the following general formula (C) and an aldehyde represented by the following general formula (D) are subjected to an acetalization reaction (see broken line).
• R represents, for example, a carbonate group or a hydroxyl group.
• R is the same as R 1B or R 2B in general formula (B) above.
• aldehyde represented by the above general formula (D) examples include butanal, isobutanal, hexanal, octanal, dodecanal, and the like. These can be used alone or in combination of two or more.
• the temperature is, for example, 40°C or higher, preferably 50°C or higher, more preferably 60°C or higher, and, for example, 90°C or lower, preferably 80°C or lower, more preferably 70°C. It is as follows.
• the reaction time of the acetalization reaction is, for example, 5 hours or more, preferably 10 hours or more, more preferably 20 hours or more, and, for example, 100 hours or less, preferably 80 hours or less, more preferably 60 hours or less. be.
• a solvent, an acetalization catalyst, etc. can be added if necessary.
• solvent examples include amides (eg, dimethylacetamide, dimethylformamide, etc.). These solvents can be used alone or in combination of two or more.
• the blending ratio of the solvent is not particularly limited, and is appropriately set depending on the purpose and use.
• acetalization catalyst examples include known acetalization catalysts such as p-toluenesulfonic acid. These acetalization catalysts can be used alone or in combination of two or more.
• the addition ratio of the esterification catalyst is appropriately set depending on the purpose and use.
• an ascorbic acid derivative represented by the following general formula (B) and an alkali metal salt or alkaline earth metal salt represented by the following general formula (E) are reacted.
• X represents an alkali metal or alkaline earth metal
• R represents, for example, a carbonate group or a hydroxyl group.
• alkali metal salt or alkaline earth metal salt represented by the above general formula (E) include sodium hydroxide, sodium hydrogen carbonate, sodium carbonate, calcium hydroxide, and calcium carbonate. These can be used alone or in combination of two or more.
• the temperature is, for example, -10°C or higher, preferably -5°C or higher, more preferably 0°C or higher, for example, 100°C or lower, preferably 90°C or lower. , more preferably 80°C or lower.
• reaction time of the alkali metalation or alkaline earth metalation reaction is, for example, 0.1 hour or more, preferably 0.5 hour or more, more preferably 1 hour or more, and, for example, 10 hours or less, preferably is 8 hours or less, more preferably 6 hours.
• a solvent or the like may be added if necessary.
• solvent examples include alcohols (eg, methanol, ethanol, 2-propanol, butanol, hexanol, etc.), furans (tetrahydrofuran), and ketones (acetone, methyl ethyl ketone, etc.). These solvents can be used alone or in combination of two or more.
• alcohols eg, methanol, ethanol, 2-propanol, butanol, hexanol, etc.
• furans tetrahydrofuran
• ketones acetone, methyl ethyl ketone, etc.
• the blending ratio of the solvent is not particularly limited, and is appropriately set depending on the purpose and use.
• At least one of the first agent and the second agent contains a compound A containing at least one of an alkoxysilyl group and a hydroxysilyl group.
• Compound A contains at least one of an alkoxysilyl group and a hydroxysilyl group, the adhesiveness of the cured product can be improved.
• Compound A can be used as a so-called silane coupling agent.
• any compound containing at least one of an alkoxysilyl group and a hydroxysilyl group can be used without particular limitation.
• Compound A may contain at least one member selected from the group consisting of an organosilane containing a polymerizable group and an alkoxy group or a hydroxyl group, and an organosiloxane containing a polymerizable group, an alkoxy group or a hydroxyl group, and a siloxane bond. preferable.
• the organosilane in the present disclosure preferably has a polymerizable group and an alkoxy group or a hydroxyl group.
• the four bonds possessed by the silicon atom in organosilane are each independently bonded to a monovalent organic group having a polymerizable group, a monovalent organic group not having a polymerizable group, or a hydroxyl group, and at least one It is preferable that the two bonds are bonded to a monovalent organic group having a polymerizable group, and at least one bond is bonded to an alkoxy group or a hydroxyl group.
• examples of the polymerizable group include a (meth)acryloyl group, an epoxy group, an allyl group, and the like. Among the above, it is preferable that the polymerizable group includes a (meth)acryloyl group.
• the monovalent organic group having a polymerizable group in the organosilane of the present disclosure preferably has 3 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, and preferably 5 to 15 carbon atoms. More preferred.
• the monovalent organic group having a polymerizable group in the organosilane of the present disclosure may be a simple hydrocarbon group, and may include a urethane bond, an ester bond, an ether bond, etc.
• Examples of the monovalent organic group without a polymerizable group in the organosilane of the present disclosure include an optionally substituted alkyl group, an alkoxy group, and the like, with an alkoxy group being preferred.
• examples of the substituent include a hydroxyl group and an amino group.
• the monovalent organic group not having a polymerizable group in the organosilane of the present disclosure preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and has 1 to 4 carbon atoms. It is even more preferable.
• the organosiloxane in the present disclosure preferably has a polymerizable group, an alkoxy group or a hydroxyl group, and a siloxane bond (Si-O-Si).
• the remaining six bonds that do not form the above-mentioned siloxane bond, which are held by two silicon atoms in one siloxane bond in organosiloxane, are each independently an -O-Si group or a monovalent organic group having a polymerizable group.
• All the -O-Si groups contained in the organosiloxane have at least one of the four bonds of the Si bonded to the oxygen atom (-O-) that is bonded to the adjacent Si (that is, the siloxane ), and the remaining three bonds are each independently an -O-Si group, a monovalent organic group having a polymerizable group, a monovalent organic group not having a polymerizable group, or Preferably, it is bonded to a hydroxyl group.
• the remaining three bonds in the -O-Si group are bonded to the -O-Si group. are each independently bonded to an --O--Si group, a monovalent organic group having a polymerizable group, a monovalent organic group not having a polymerizable group, or a hydroxyl group.
• the organosiloxane of the present disclosure has a monovalent organic group having at least one polymerizable group and an alkoxy group or a hydroxyl group; , are bonded to the remaining three bonds of Si in the -O-Si group contained in the organosiloxane, and may be bonded to Si in the same -O-Si group, or different -O-Si groups are bonded to each other. It may be bonded to Si in the -Si group.
• the organosiloxane in the present disclosure has at least one siloxane bond, but may include an -O-Si group in addition to the one siloxane bond.
• an -O-Si group in addition to the one siloxane bond, it may contain up to 10 -O-Si groups.
• Specific embodiments and preferred embodiments of the monovalent organic group having a polymerizable group and the monovalent organic group not having a polymerizable group in the organosiloxane in the present disclosure include the monovalent organic group having a polymerizable group in the organosiloxane. The same as the specific embodiments and preferred embodiments of the monovalent organic group and the monovalent organic group having no polymerizable group.
• compound A contains a compound represented by the following general formula (X).
• R 1 to R 6 are each independently a monovalent organic group having a polymerizable group, a monovalent organic group not having a polymerizable group, or a hydroxyl group
• m is 0 or 1
• L is a monovalent organic group having a polymerizable group, a monovalent organic group not having a polymerizable group, or a hydroxyl group
• L is an oxygen atom or a structure represented by the following general formula (Y).
• at least one of L and R 4 to R 6 in general formula (X) is a monovalent organic group having a polymerizable group, and at least one is an alkoxy group or It is a hydroxyl group.
• at least one of R 1 to R 8 in general formula (X) and general formula (Y) is a monovalent organic group having a polymerizable group, and at least one is an alkoxy group or hydroxyl group.
• R 7 to R 8 are each independently a monovalent organic group having a polymerizable group, a monovalent organic group not having a polymerizable group, a hydroxyl group, or an OSi chain, and n is an integer greater than or equal to 1, and * is the bonding position.
• the OSi chain is a monovalent organic group having an -O-Si group that forms a siloxane bond with the adjacent Si in general formula (Y).
• At least one of R 1 to R 3 and at least one of R 4 to R 6 are preferably monovalent organic groups having a polymerizable group. In general formula (X), at least one of R 1 to R 3 and at least one of R 4 to R 6 are preferably an alkoxy group or a hydroxyl group.
• examples of the polymerizable group include a (meth)acryloyl group, an epoxy group, an allyl group, and the like. Among the above, it is preferable that the polymerizable group includes a (meth)acryloyl group.
• the monovalent organic group having a polymerizable group in L and R 1 to R 6 of general formula (X) preferably has 3 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, and More preferably, the number is 5 to 15.
• the monovalent organic group having a polymerizable group in L and R 1 to R 6 of general formula (X) may be a simple hydrocarbon group, but may also contain a urethane bond, an ester bond, an ether bond, etc. good.
• Examples of the monovalent organic group not having a polymerizable group in L and R 1 to R 6 of the general formula (X) include an optionally substituted alkyl group and an alkoxy group, with an alkoxy group being preferred.
• examples of the substituent include a hydroxyl group and an amino group.
• the monovalent organic group having no polymerizable group in L and R 1 to R 6 of general formula (X) preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms. , more preferably has 1 to 4 carbon atoms.
• Specific embodiments and preferred embodiments of the monovalent organic group having a polymerizable group in R 7 to R 8 of the general formula (Y) are specific to the monovalent organic group having a polymerizable group in the general formula (X). This is the same as the preferred embodiment, preferred embodiment, etc.
• Specific embodiments and preferred embodiments of the monovalent organic group not having a polymerizable group in R 7 to R 8 of the general formula (Y) are as follows: The same is true for specific embodiments, preferred embodiments, etc. of the organic group.
• n is preferably an integer of 1 to 8, more preferably an integer of 1 to 6, and even more preferably an integer of 1 to 3.
• the OSi chain is an -O-Si group (hereinafter referred to as "general formula ( It is a monovalent organic group having an -O-Si group bonded to Si in Y).
• the OSi chain may contain an -O-Si group in addition to the -O-Si group bonded to Si in general formula (Y). That is, the OSi chain is a chain structure containing one or more -O-Si groups.
• the chain structure of the OSi chain contains one or more -O-Si groups, preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
• the OSi chain may include a structure in which siloxane bonds (ie, -Si-O-Si-) are repeated in series.
• Examples of cases in which the chain structure is linear include cases in which the siloxane bonds are continuous in a linear chain.
• examples of the case where the chain structure is a branched chain include, for example, a case where the siloxane bond is a branched chain in the middle.
• the OSi chain is an oxygen atom ( -O-), and the remaining three bonds each independently form an -O-Si group (i.e., a group forming a siloxane bond), a monovalent organic group having a polymerizable group, and a polymerizable group. It is preferable that it is bonded to a monovalent organic group or a hydroxyl group that does not have a functional group. All -O-Si groups (including the -O-Si group bonded to Si in general formula (Y)) contained in the OSi chain have at least one adjacent bond among the four bonds of the Si.
• an -O-Si group that is, a group that forms a siloxane bond
• a polymerizable group It is preferable that it is bonded to a monovalent organic group, a monovalent organic group not having a polymerizable group, or a hydroxyl group. That is, for example, an -O-Si group (i.e., a group forming a siloxane bond) is bonded to the four bonds of Si in the -O-Si group bonded to Si in general formula (Y).
• -O-Si group at least one of the four bonds of Si is bonded to the oxygen atom (-O-) that is bonded to the adjacent Si, and the remaining three bonds are are each independently bonded to an -O-Si structure (that is, a group forming a siloxane bond), a monovalent organic group having a polymerizable group, a monovalent organic group not having a polymerizable group, or a hydroxyl group.
• monovalent organic groups having a polymerizable group bonded to Si include the monovalent organic group having a polymerizable group and the monovalent organic group having no polymerizable group in general formula (X). It is the same as each specific aspect, preferable aspect, etc.
• the content of compound A is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more, based on the total amount of ascorbic acids and compound A. preferable.
• the content of Compound A may be 95% by mass or less, or 90% by mass or less, based on the total amount of ascorbic acids and Compound A.
• the content of compound A is more preferably 1.0% by mass or more, and even more preferably 1.5% by mass or more, based on the total mass of the curable composition to be prepared.
• the content of compound A is more preferably 12.0% by mass or less, even more preferably 9.0% by mass or more, and 6.0% by mass or less, based on the total mass of the curable composition to be prepared. It is particularly preferable that it is less than % by mass.
• Compound A preferably has a molecular weight of 100 or more, more preferably 150 or more, and even more preferably 200 or more.
• Compound A preferably has a molecular weight of 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.
• Compound A may have a molecular weight of 200 to 1000.
• compound A may be an organosiloxane.
• the method for producing compound A in the present disclosure includes a method using organosilane.
• organosilane include 3-acryloxypropylmethoxysilane or 3-methacryloxypropyl, from the viewpoint that the obtained compound A copolymerizes with a polymerizable monomer and hardens, and from the viewpoint of improving adhesion to ceramic materials.
• it contains methoxysilane.
• Polymerization by hydrolysis and condensation of organosilane may be carried out by known methods. For example, although it is generally carried out without a solvent, it may be carried out in the presence of an organic solvent that dissolves the organosilane used in the reaction.
• Polymerization by hydrolysis and condensation is carried out by adding water and an acid or base that serves as a catalyst for the hydrolysis reaction to the above-mentioned organosilane liquid (including a mixed liquid of multiple types of organosilanes) or the solution. You can.
• Compound A in the present disclosure may be synthesized by appropriately setting conditions depending on the target compound A. For example, 0.01 mol to 0.2 mol of hydrochloric acid is added dropwise to 1 mol of organosilane at room temperature under stirring, the temperature is raised to about 50°C to 80°C, and the temperature is increased for a predetermined period of time (for example, 2 hours to 72 hours). hydrolytic condensation at a certain degree). Compound A can be obtained by heating this to 60° C. to 120° C., distilling off the by-product alcohol under normal pressure and concentrating it, and then filtering it. The degree of polymerization may be adjusted by, for example, heating temperature, heating time, amount of hydrolytic condensation catalyst (acid or base), and the like.
• the obtained compound A can be confirmed by molecular weight analysis using LC/MS (liquid chromatography mass spectrometry), gel filtration chromatography, or the like.
• LC/MS liquid chromatography mass spectrometry
• gel filtration chromatography or the like.
• a commercially available product can also be used as the compound A in the present disclosure.
• compounds having epoxy groups such as KR-517 (manufactured by Shin-Etsu Chemical Co., Ltd.), X-24-9590 (manufactured by Shin-Etsu Chemical Co., Ltd.), and KR-516 (manufactured by Shin-Etsu Chemical Co., Ltd.); KR-511 Compounds with a vinyl group such as (manufactured by Shin-Etsu Chemical Co., Ltd.); Compounds with a methacrylic group such as KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.); Examples include compounds having an acrylic group.
• At least one of the first agent and the second agent each independently contain a transition metal compound and an organic peroxide.
• At least one of the first agent and the second agent independently contains a transition metal compound and an organic peroxide means that at least one of the first agent and the second agent contains a transition metal compound, This also means that at least one of the first agent and the second agent contains an organic peroxide.
• the transition metal compound contained in the first part and the transition metal compound contained in the second part may be the same or different. . The same applies to organic peroxides.
• the first part contains a transition metal compound and an organic peroxide
• the second part contains ascorbic acids and Compound A.
• the transition metal compound is preferably a compound that is soluble in the monomer component in the curable composition preparation kit described below.
• transition metal compound examples include copper compounds, vanadium compounds, molybdenum compounds, scandium compounds, titanium compounds, chromium compounds, manganese compounds, iron compounds, cobalt compounds, and nickel compounds.
• the transition metal compound contains at least one of a copper compound and a vanadium compound, and more preferably a copper compound.
• Copper compounds include copper acetate, copper isobutyrate, copper gluconate, copper citrate, copper phthalate, copper tartrate, copper oleate, copper octylate, copper octenoate, copper naphthenate, and methacrylic acid.
• Copper copper 4-cyclohexylbutyrate; ⁇ -diketone copper, copper acetylacetone, copper trifluoroacetylacetone, copper hexafluoroacetylacetone, copper 2,2,6,6-tetramethyl-3,5-heptanedionato, copper benzoylacetone; - As copper ketoester, copper ethyl acetoacetate; as copper alkoxide, copper methoxide, copper ethoxide, copper isopropoxide, copper 2-(2-butoxyethoxy) ethoxide, copper 2-(2-methoxyethoxy) ethoxide; copper dithiocarbamate
• the salt include copper dimethyldithiocarbamate; examples of the salt of copper and an inorganic acid include copper nitrate; and copper chloride.
• copper carboxylate, copper ⁇ -diketone, and copper ⁇ -ketoester are preferred, and copper acetate and copper acetylacetone are more preferred, from the viewpoint of solubility and reactivity with monomers.
• Vanadium compounds include vanadyl acetylacetonate, vanadium (III) naphthenate, vanadyl stearate, vanadium benzoylacetonate, bis(maltolate)oxovanadium(IV), oxobis(1-phenyl-1,3-butanedioate) Examples include vanadium (IV).
• the content of the transition metal compound is 0.00005 parts by mass to 0.1 parts by mass with respect to the total of 100 parts by mass of the first part and the second part.
• the amount is preferably 0.0001 part by mass to 0.05 part by mass, and even more preferably 0.001 part to 0.03 part by mass.
• Organic peroxides can be used without particular limitations. Typical organic peroxides include hydroperoxide, peroxyester, ketone peroxide, peroxyketal, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, and the like. Among these, hydroperoxide is preferable because even if the curable composition is provided in a packaged form and stored for a long period of time, there is little variation in the operable time.
• One type of organic peroxide may be used alone, or a plurality of types may be used in combination.
• the hydroperoxides include cumene hydroperoxide, t-butyl hydroperoxide, t-hexyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3, Examples include 3-tetramethylbutyl hydroperoxide and t-amyl hydroperoxide.
• any one containing an acyl group on one side of the peroxy group (-OO- group) and a hydrocarbon group (or a group similar thereto) on the other side can be used without any restrictions.
• Specific examples include ⁇ , ⁇ -bis(neodecanoylperoxy)diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl- 1-Methyl ethyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, 1,1 , 3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-eth)
• ketone peroxide examples include methyl ethyl ketone peroxide, cyclohexanoperoxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide.
• Peroxyketals include 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butyl peroxy) 3,3,5-trimethylcyclohexanone, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclodecane, 2,2-bis(t-butylperoxy)cyclohexane, oxy)butane, n-butyl 4,4-bis(t-butylperoxy)valerate, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, and the like.
• dialkyl peroxides examples include ⁇ , ⁇ -bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, and t-butylcumylbenzene.
• dialkyl peroxides examples include luperoxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, and the like.
• diacyl peroxide examples include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, and succinic acid peroxide. , m-toluoylbenzoyl peroxide, and benzoyl peroxides.
• peroxydicarbonate examples include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di- Examples include 2-ethylhexyl peroxydicarbonate, di-2-methoxybutyl peroxydicarbonate, and di(3-methyl-3-methoxybutyl)peroxydicarbonate.
• the content of the organic peroxide is preferably 0.01 parts by mass to 6 parts by mass, and 0.01 parts by mass to 4 parts by mass, based on a total of 100 parts by mass of the first part and the second part.
• the amount is more preferably 0.05 parts by mass to 3 parts by mass.
• the first agent contains a transition metal compound and an organic peroxide
• the second agent Preferably, the agent contains ascorbic acids.
• At least one of the first agent and the second agent may each independently contain a sulfinic acid, an amine compound, etc.
• sulfinic acids refer to sulfinic acids, sulfinic acid derivatives, and salts thereof.
• Aromatic sulfinic acids include benzenesulfinic acid, p-toluenesulfinic acid, o-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, 2,4,6-trimethylbenzenesulfinic acid, 2, Lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, calcium salts, strontium salts, iron salts, zinc salts, such as 4,6-triisopropylbenzenesulfinic acid, chlorobenzenesulfinic acid, naphthalenesulfinic acid, etc. Examples include ammonium salt, tetramethylammonium salt, and
• amine compound examples include aromatic amines, aliphatic amines, heterocyclic amines, and the like.
• aromatic amine As the aromatic amine, known aromatic secondary amines, aromatic tertiary amines, etc. may be used. Examples of aromatic secondary amines or aromatic tertiary amines include N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, diethanol-p-toluidine (DEPT), N,N- Bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-isopropylaniline, N , N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-isopropylaniline, N,N-bis(2-hydroxyethyl) -3,5-di-t-butylaniline, N,N-dimethylaniline, N,N-di
• aromatic amine means an aromatic amine that does not fall under the below-mentioned heterocyclic amine.
• aliphatic amine examples include primary aliphatic amines such as n-butylamine, n-hexylamine, and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine, and N-methylethanolamine; N-Methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2-(dimethylamino)ethyl(meth)acrylate, N-methyldiethanolamine di(meth)acrylate, N-ethyldiethanolamine di( Examples include tertiary aliphatic amines such as meth)acrylate, triethanolamine tri(meth)acrylate, triethanolamine, trimethylamine, triethylamine, and tributylamine.
• heterocyclic amine is an amine having a heterocycle.
• heterocyclic amines that can function as monodentate, bidentate, or tridentate heterocyclic electron donor ligands.
• the heterocyclic amines include furan, thiophene, pyrrole, pyridine, bipyridine, picollimine, ⁇ -pyran, ⁇ -thiopyran, phenanthroline, pyrimidine, bis-pyrimidine, pyrazine, indole, coumarin, thionaphthene, carbazole, and dibenzofuran.
• heterocyclic amines derived from unsubstituted or substituted heteroarenes such as bismidazole and bisoxazoline, or salts thereof.
• Preferred heterocyclic amines include 1H-benzotriazole (BTA), 5-methyl-1H-benzotriazole, and benzimidazole.
• the first agent contains the first monomer
• the second agent contains the second monomer.
• the first monomer and the second monomer may be the same monomer or different monomers.
• known monomers can be used as the first monomer and the second monomer.
• the first monomer and the second monomer may be monomers that do not contain acidic groups, or may be monomers that contain acidic groups (hereinafter also referred to as "acidic monomers").
• the first monomer and the second monomer include monomers that do not contain acidic groups.
• the monomer is a monomer that undergoes a radical polymerization reaction and becomes a polymer due to the action of ascorbic acids, transition metal compounds, organic peroxides, etc. of the present disclosure.
• the number of monomers constituting the monomers in the present disclosure is not limited to one type, and two or more types may be used.
• Examples of monomers that do not contain acidic groups include (meth)acrylate monomers that do not contain acidic groups.
• Examples of the (meth)acrylate monomer that does not contain an acidic group include monofunctional monomers, bifunctional monomers, and trifunctional or higher functional monomers.
• the monomer content i.e., the total amount of the first monomer and the second monomer in the curable composition to be prepared
• the monomer content is 10% by mass based on the total mass of the curable composition to be prepared. It is preferably from 90% by weight, more preferably from 20% to 75% by weight, even more preferably from 30% to 60% by weight.
• Monomer monomers include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, 2,3-dihydroxy
• An example is propyl (meth)acrylate.
• 2-hydroxyethyl methacrylate (HEMA) is preferred.
• aromatic compound-based difunctional monomers examples include 2,2-bis((meth)acryloyloxyphenyl)propane, 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, 2,2-bis(4-( meth)acryloyloxypolypropoxyphenyl)propane, and the like.
• Bis-GMA 2,2-bis[4-(3-(methacryloyloxy)-2-hydroxypropoxyphenyl)propane
• Bis-GMA 2,2-bis(4-methacryloyloxypolyethoxyphenyl) Propane
• aliphatic compound-based difunctional monomers examples include erythritol di(meth)acrylate, sorbitol di(meth)acrylate, mannitol di(meth)acrylate, pentaerythritol di(meth)acrylate, and dipentaerythritol di(meth)acrylate.
• glycerol di(meth)acrylate ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 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, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate , 1,10-decanediol di(meth)acrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (UDMA), 1,2-bis(3-methacryloyloxy-2-hydroxy) Examples include propyloxy)ethane.
• UDMA 2,2,4-trimethylhexam
• glycerol dimethacrylate triethylene glycol dimethacrylate (TEGDMA), 1,6-hexanediol dimethacrylate (HexDMA), neopentyl glycol dimethacrylate (NPG), 2,2,4-trimethylhexamethylene bis( 2-Carbamoyloxyethyl) dimethacrylate (UDMA) and 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane are preferred.
• TEGDMA triethylene glycol dimethacrylate
• HexDMA 1,6-hexanediol dimethacrylate
• NPG neopentyl glycol dimethacrylate
• UDMA 2,2,4-trimethylhexamethylene bis( 2-Carbamoyloxyethyl) dimethacrylate
• 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane are preferred.
• trifunctional or higher functional monomers examples include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate.
• acrylate dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-( Examples include aminocarboxy)propane-1,3-diol]tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, and the like.
• the above monomers may be blended singly or in combination of multiple types.
• the content of the monomer that does not contain an acidic group is preferably in the range of 10 parts by mass to 100 parts by mass, and 20 parts by mass to 100 parts by mass, based on the total 100 parts by mass of the monomer components in the curable composition preparation kit of the present disclosure.
• the range of 100 parts by weight is more preferable, and the range of 50 parts by weight to 100 parts by weight is even more preferable.
• the monomer component in the kit for preparing a curable composition of the present disclosure includes an acidic monomer described below
• the content of monomers that do not contain acidic groups is the sum of the monomer components in the kit for preparing a curable composition of the present disclosure.
• the amount is preferably 10 parts by weight to 99 parts by weight, more preferably 30 parts by weight to 97 parts by weight, and even more preferably 50 parts by weight to 95 parts by weight.
• the first monomer and the second monomer preferably contain a (meth)acrylic monomer (C) having a molecular weight of 100 to 5,000.
• the molecular weight of the (meth)acrylic monomer (C) is preferably from 120 to 3,000, even more preferably from 150 to 2,000, particularly preferably from 200 to 1,000.
• the content of the (meth)acrylic monomer (C) relative to the total content of the first monomer and the second monomer is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more. It is more preferable that
• the first monomer or the second monomer contains an acidic monomer. More specifically, in the curable composition preparation kit of the present disclosure, either the first monomer in the first agent or the second monomer in the second agent preferably contains an acidic monomer.
• the first monomer contains an acidic monomer
• the second agent contains ascorbic acids and Compound A. This can prevent the silane coupling agent from reacting under acidic conditions. That is, by mixing the first part and the second part at a desired time to obtain a curable composition, the time to react the silane coupling agent under acidic conditions can be adjusted.
• the curable composition preparation kit of the present disclosure when at least one of the first agent and the second agent contains an acidic monomer, for example, when the curable composition preparation kit of the present disclosure is used for dental purposes, good tooth quality and high resistance to dental prosthetic materials can be achieved. Adhesive properties can be imparted.
• the first monomer in the first part contains an acidic monomer
• the second part contains ascorbic acids
• the first monomer in the first agent contains an acidic monomer
• the second agent does not contain an acidic monomer and contains ascorbic acids.
• the acidic monomer has at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, a carboxylic acid group, and an acryloyl group, a methacryloyl group, a vinyl group, or a styrene group.
• Examples include monomers containing at least one polymerizable group such as a group.
• the acidic monomer has an affinity with the adherend and also has a demineralizing effect on the tooth substance.
• (meth)acryloyloxyalkyl dihydrogen phosphate such as 10-(meth)acryloyloxydecyl dihydrogen phosphate (MDP), 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)acryloyloxydecyl]hydrogen phosphate, 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl Phenyl hydrogen phosphate, 2-(meth)acryloyloxyalkyl dihydrogen phosphate
• pyrophosphate group-containing monomers include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, and their acid chlorides, alkali metal salts, and ammonium salts. be done.
• thiophosphoric acid group-containing monomers examples include 2-(meth)acryloyloxyethyldihydrogenthiophosphate, 3-(meth)acryloyloxypropyldihydrogenthiophosphate, and acid chlorides, alkali metal salts, and ammonium salts thereof. be done.
• Examples of phosphonic acid group-containing monomers include 2-(meth)acryloyloxyethyl phenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, and acid chlorides, alkali metal salts, and ammonium salts thereof. be done.
• sulfonic acid group-containing monomer examples include 2-(meth)acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, and 2-sulfoethyl (meth)acrylate.
• carboxylic acid group-containing monomers examples include monomers containing one carboxy group in the molecule and monomers containing multiple carboxy groups in the molecule.
• Monomers containing one carboxyl group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloyl aspartic acid, O-(meth)acryloyltyrosine, N-(meth)acryloyl Tyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth)acryloyloxybenzoic acid acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, 2-(meth)acryloyloxybenzoic acid, ) acryloy
• Examples of monomers containing multiple carboxyl groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, and 10-(meth)acryloyloxyhexane-1,1-dicarboxylic acid.
• 10-(meth)acryloyloxydecyl dihydrogen phosphate MDP
• 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate 2-(meth)acryloyloxyethyl dihydrogen phosphate
• 4-(meth)acryloyloxyethyl trimellitate anhydride 4-(meth)acryloyloxyethyl trimellitate
• 2-(meth)acrylamido-2-methylpropane Sulfonic acid 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid
• dihydroxyethyl methacrylate trimethylhexyldicarbamate are preferred.
• the above acidic monomers may be used alone or in combination.
• the content of the acidic monomer is preferably 1 part by mass to 50 parts by mass, and preferably 3 parts by mass to 40 parts by mass, based on 100 parts by mass of the total amount of monomer components in the curable composition preparation kit of the present disclosure. It is more preferable that the amount is 5 parts by weight to 30 parts by weight.
• the content of the acidic monomer is 1 part by mass or more, it is easy to obtain high adhesiveness to various adherends.
• the content of the acidic monomer is 50 parts by mass or less, it is easy to maintain a balance between polymerizability and adhesiveness.
• the total amount of monomer components means the total amount of the acidic monomer and the above-mentioned monomer not containing an acidic group.
• monomers described in known documents such as WO 2012/157566, WO 2015/015220, WO 2015/015221, and JP 2016-094482 are used. can be used.
• the total content of ascorbic acids contained in the first and second parts should be 0.1% by mass to 5% by mass based on the total mass of the curable composition to be prepared, from the viewpoint of adhesive properties. It is preferably 0.3% by mass to 3% by mass, and even more preferably 0.5% by mass to 2% by mass.
• At least one of the first agent and the second agent includes at least one polymerization accelerator selected from the group consisting of phosphonite compounds, phosphite compounds, and sulfite compounds. 1) may be included.
• the second agent preferably contains ascorbic acids and the polymerization accelerator (1).
• the phosphonite compound may be a trivalent organic phosphorus compound in which a carbon atom is bonded to a phosphorus atom.
• the phosphonite compound contained in the polymerization accelerator (1) of the present disclosure preferably includes a structure represented by the following general formula (I).
• * indicates the bonding position to the carbon atom.
• the three * marks are preferably bonding positions to a carbon atom contained in a hydrocarbon group, and more preferably bonding positions to a carbon atom contained in a benzene ring.
• the phosphonite compound may contain one structure represented by general formula (I), or may contain two or more structures.
• the phosphonite compound preferably contains two structures represented by the general formula (I), and the two structures represented by the general formula (I) are bonded via a divalent linking group (preferably a biphenyl structure). It is more preferable to include a structure that
• the phosphonite compound contained in the polymerization accelerator (1) of the present disclosure preferably contains a compound represented by the following general formula (II).
• R B1 is an n-valent hydrocarbon group
• R B2 and R B3 are each independently a monovalent hydrocarbon group
• n is an integer of 1 or 2.
• n-valent hydrocarbon group in R B1 examples include an n-valent aliphatic hydrocarbon group, an n-valent alicyclic hydrocarbon group, an n-valent aromatic hydrocarbon group, a combination of two or more of these, etc. It will be done.
• the monovalent hydrocarbon group in R B1 is preferably an alkyl group, a phenyl group, a biphenyl group, or the like.
• the hydrogen atom of the phenyl group or biphenyl group in R B1 may be substituted with a substituent such as an alkyl group.
• the divalent hydrocarbon group in R B1 is preferably an alkylene group, a phenylene group, a 4,4'-biphenylene group, a 4,3'-biphenylene group, a biphenylene group such as a 3,3'-biphenylene group, or the like.
• the hydrogen atom contained in the phenylene group or biphenylene group in R B1 may be substituted with a substituent such as an alkyl group.
• R B2 and R B3 each independently represent a monovalent hydrocarbon group, preferably an alkyl group, a phenyl group, or the like.
• the hydrogen atom contained in the phenyl group in R B2 and R B3 may be substituted with an alkyl group such as a tert-butyl group or n-butyl group.
• n is an integer of 1 or 2, preferably 2.
• phosphonite compound contained in the polymerization accelerator (1) of the present disclosure include, for example, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylene-di-phosphonite, tetrakis(2, 4-di-tert-butyl-5-methylphenyl)4,4'-biphenylene-di-phosphonite, tetrakis(2,4-di-tert-butylphenyl)4,3'-biphenylene-di-phosphonite, tetrakis( 2,4-di-tert-butylphenyl)3,3'-biphenylene-di-phosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene-di-phosphonite, tetrakis(2 ,6-di-tert-butylphenyl)-4,3'-biphenylene
• phosphite compounds include triphenyl phosphite, trisnonylphenyl phosphite, tricresyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono(tridecyl) phosphite, tris Examples include (2,4-di-tert-butylphenyl) phosphite.
• sulfite compounds include ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethyl methyl sulfite, methyl-n-propyl sulfite, ethyl-n-propyl sulfite, and di-n-propyl sulfite.
• examples include sulfite, diphenyl sulfite, methylphenyl sulfite, ethyl sulfite, dibenzyl sulfite, benzyl methyl sulfite, benzylethyl sulfite, and the like.
• the total content of the polymerization accelerator (1) contained in the first part and the second part is 0.1 parts by mass to 100 parts by mass of the total amount of the first part and the second part.
• the amount is preferably 5 parts by weight, and more preferably 0.2 parts to 2 parts by weight.
• At least one of the first agent and the second agent may include a polymerization accelerator (2) that is a polymerization accelerator other than the polymerization accelerator (1).
• the polymerization accelerator (2) of the present disclosure is not particularly limited, and examples thereof include inorganic salts, thiourea, and the like.
• inorganic salts include sodium sulfite, calcium sulfite, potassium sulfite, potassium nitrate, potassium chloride, potassium sulfate, and sodium chloride.
• thiourea examples include acetylthiourea, phenylthiourea, triethylthiourea, tetramethylthiourea, dimethylthiourea, diphenylthiourea, and the like.
• the total content of the polymerization accelerator (2) contained in the first part and the second part is 0.0001 parts by mass to 100 parts by mass of the total amount of the first part and the second part.
• the amount is preferably 1 part by weight, and more preferably 0.001 part to 0.3 part by weight.
• the total content of inorganic salts contained in the first part and the second part is 0.0001 part by mass to 0.1 part by mass with respect to the total amount of 100 parts by mass of the first part and the second part.
• the amount is preferably 0.001 parts by mass to 0.01 parts by mass.
• the total content of thiourea contained in the first agent and the second agent is 0.001 parts by mass to 1.0 parts by mass based on 100 parts by mass of the total amount of the first agent and the second agent.
• the amount is preferably 0.005 parts by weight to 0.5 parts by weight.
• the first part and the second part contains a silanol condensing agent.
• the first monomer includes a silanol condensing agent
• the second agent includes ascorbic acids and compound A.
• silanol condensing agent can be used without particular limitation.
• silanol condensing agents include titanium (IV) tetrabutoxide, titanium (IV) tetrapropoxide, titanium (IV) bis(ethyl acetoacetate) diisopropoxide, titanium (IV) bis(ethylhexoxy) bis(2- Organic titanium compounds such as ethyl-3-hydroxyhexoxide), titanium (IV) acetylacetonate, titanium (IV) bis(acetylacetonato) diisopropoxide; aluminum (III) acetylacetonate, aluminum trisethyl Organoaluminum compounds such as acetoacetate and diisopropoxyaluminum ethyl acetoacetate; organotin compounds such as di-n-octyltin dilaurate; phosphoric acid compounds such as phosphoric acid, polyphosphoric acid and its salts; zirconium ( IV) Zi
• At least one of the first agent and the second agent may contain a filler, and it is preferable that the first agent and the second agent contain a filler.
• a filler may be used alone, or a combination of multiple types may be used.
• the filler include inorganic fillers, organic fillers, and composite fillers of inorganic fillers and organic fillers.
• Inorganic fillers include, for example, various glasses (mainly composed of silicon dioxide, containing heavy metals, oxides such as boron and aluminum as necessary), various ceramics, diatomaceous earth, kaolin, clay minerals (montmorillonite, etc.), Activated clay, synthetic zeolite, mica, calcium fluoride, ytterbium fluoride, calcium carbonate, calcium phosphate, aluminum sulfate, barium sulfate, calcium sulfate, zirconium dioxide, titanium dioxide, aluminum oxide, boron oxide, barium oxide, lanthanum oxide, strontium oxide , zinc oxide, calcium oxide, lithium oxide, sodium oxide, bismuth oxide, yttrium oxide, calcium phosphate, hydroxyapatite, aluminum hydroxide, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, ytterbium fluoride, etc.
• glasses mainly composed of silicon dioxide, containing heavy metals, oxides such as boron
• fine powder having a primary particle size of 0.001 ⁇ m to 100 ⁇ m is preferably used.
• inorganic fillers include barium borosilicate glass fine powder (8235, GM27884 and G018-053 (manufactured by Shott), etc.), strontium boroaluminosilicate glass fine powder (G018-093 and G018-163 (manufactured by Shott), etc.).
• lanthanum glass fine powder GM31684 and G018-161 (manufactured by Shott), etc.), fine fluoroaluminosilicate glass powder (such as G018-091 and Schott G018-117 (manufactured by Shott), etc.), zirconium and/or cesium Containing boroaluminosilicate glass fine powder (G018-307, G018-308 and G018-310 (manufactured by Shott), etc.), silica fine powder (Aerosil OX50, Aerosil 50, Aerosil 200, Aerosil 380, Aerosil R972, Aerosil 130 (Evonik) (Manufactured), etc.).
• organic fillers include fine powders such as polymethyl methacrylate, polyethyl methacrylate, polyfunctional methacrylate polymers, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, and styrene-butadiene rubber.
• composite fillers of inorganic fillers and organic fillers include those in which inorganic fillers are dispersed in organic fillers, and inorganic/organic composite fillers in which inorganic fillers are coated with various polymers.
• the filler may be used after being previously surface-treated with a known surface treatment agent such as a silane coupling agent.
• Surface treatment agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri( ⁇ -methoxyethoxy)silane, ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - Examples include mercaptopropyltrimethoxysilane and ⁇ -aminopropyltriethoxysilane.
• the total content of the filler contained in the first part and the second part is preferably in the range of 10% by mass to 80% by mass, and 30% by mass to 80% by mass, based on the total mass of the curable composition to be prepared. More preferably, the range is from 50% by mass to 75% by mass.
• Non-conductive filler In the curable composition preparation kit of the present disclosure, at least one of the first agent and the second agent preferably contains a non-conductive filler.
• a non-conductive filler means a filler having a resistance value of 1.00 ⁇ 10 ⁇ 4 ⁇ m or more.
• the upper limit of the resistance value of the non-conductive filler is not particularly limited, and may be, for example, 1.00 ⁇ 10 20 ⁇ m.
• Non-conductive filler examples include, for example, organic materials such as polyethylene, polystyrene, phenol resin, epoxy resin, acrylic resin, and benzoguanamine resin; silica (dimethylsilylated silica, etc.); silicates (borosilicate glass (barium borosilicate glass, etc.)); ), aluminosilicate glasses (boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, barium aluminosilicate glass, etc.)), ceramics, and inorganic materials such as boron nitride and barium nitride.
• organic materials such as polyethylene, polystyrene, phenol resin, epoxy resin, acrylic resin, and benzoguanamine resin
• silica dimethylsilylated silica, etc.
• silicates borosilicate glass (barium borosilicate glass, etc.)
• aluminosilicate glasses
• silica and silicates are preferable, and dimethylsilylated silica and barium aluminosilicate are more preferable as materials for the non-conductive filler.
• the first part contains a non-conductive filler, and the content of the non-conductive filler relative to the total mass of the first part is preferably 10% by mass or more, more preferably 20% by mass or more, More preferably, it is 30% by mass or more.
• the second part contains a non-conductive filler
• the second part contains the non-conductive filler
• the content of the non-conductive filler with respect to the total mass of the second part is 10% by mass or more.
• the content is preferably 20% by mass or more, more preferably 30% by mass or more.
• the content of the non-conductive filler is 10% by mass or more based on the total mass of the first component, and the non-conductive filler is When a conductive filler is included in the second part, it is preferable that the content of the non-conductive filler is 10% by mass or more based on the total mass of the second part.
• At least one of the first agent and the second agent includes additives such as a photopolymerization initiator, a stabilizer (polymerization inhibitor), a colorant, a fluorescent agent, and an ultraviolet absorber.
• a photopolymerization initiator a known photopolymerization initiator can be used, and examples thereof include camphorquinone (CQ), ethyl dimethylaminobenzoate (EDB), and the like.
• antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth)acryloyloxydodecylpyridinium bromide, (meth)acryloyloxyhexadecylpyridinium chloride, (meth)acryloyloxydecyl ammonium chloride, and triclosan may be added. good.
• Known dyes and pigments may be added to the curable composition preparation kit of the present disclosure.
• the curable composition preparation kit of the present disclosure is preferably used for dental materials.
• dental materials include, but are not limited to, dental adhesives, dental filling materials, dental sealants (tooth fissure sealants), abutment building materials, denture base resins, and denture base lining materials. , dental crown prosthesis resins (hard resins for dental crowns), dental room temperature polymerization resins, and the like.
• the curable composition preparation kit of the present disclosure is particularly preferably used as a dental adhesive.
• dental adhesives include dental adhesive resin cement, orthodontic adhesives, adhesives for fixing loose teeth, cavity coating adhesives, and dental bonding materials. Cement is preferred.
• dental filling materials include dental composite resins (including dental self-adhesive composite resins), root canal filling materials, temporary sealants, backing materials, and the like.
• the curable composition of the present disclosure is a mixture of the first agent and the second agent in the curable composition preparation kit of the present disclosure. That is, the curable composition of the present disclosure includes the first monomer of the present disclosure, the second monomer, ascorbic acids, and compound A containing at least one of an alkoxysilyl group and a hydroxysilyl group. Further, the curable composition of the present disclosure may further contain components such as the above-mentioned transition metal compound and organic peroxide.
• the curable composition of the present disclosure since the curable composition of the present disclosure includes the above configuration, it has excellent adhesiveness to ceramics and to dentin.
• Specific examples and preferred embodiments of the monomers, ascorbic acids, compound A, transition metal compounds, and organic peroxides in the curable composition are as follows: Examples, preferred embodiments, etc. are the same.
• the curable composition of the present disclosure preferably further includes a non-conductive filler. Specific examples, preferred embodiments, etc. of the non-conductive filler in the curable composition are the same as those for the above-mentioned non-conductive filler.
• the curable composition of the present disclosure may include the aforementioned additives.
• the cured product of the present disclosure is a cured product of the curable composition of the present disclosure, or a cured product obtained using the curable composition preparation kit of the present disclosure.
• the cured product of the present disclosure can be suitably used as a dental material. That is, the dental material of the present disclosure preferably includes the cured product of the present disclosure.
• pTSS Sodium salt of p-toluenesulfinic acid (aromatic amine)
• DEPT diethanol-p-toluidine (heterocyclic amine)
• BTA 1H-benzotriazole (polymerization accelerator)
• Triphenyl Phosphite Triphenyl phosphite DitBuPhenyl-biphenyl-phosphonite: Tetrakis(2,4-di-tert-butylphenyl) [1,1'-biphenyl]-4,4'-diylbis(phosphonite)
• NaCl Sodium chloride
• ATH Acetylthiourea
• 8-MOS 8-methacryloxyoctyltrimethoxysilane, molecular weight 318.5, viscosity at 25°C 5.3 mPa ⁇ s
• 3-APSO Siloxane oligomer of 3-acryloxypropylmethoxysilane, molecular weight distribution 400-800, viscosity at 25°C 49 mPa ⁇ s
• 3-MPSO Siloxane oligomer of 3-methacryloxypropylmethoxysilane, molecular weight distribution 400-900, viscosity at 25°C 29 mPa ⁇ s
• Ascorbic acids Ascorbic Acid: L-calcium ascorbate dihydrate
• IPD Ascorbic acid 5-(2,2-dimethyl-1,3-dioxolan-4-yl)-3,4-dihydroxyfuran-2(5H)-one
• Calcium IPDAA Calcium salt of 5-(2,2-dimethyl-1,3-dioxolan-4-yl)-3,4-dihydroxyfuran-2(5H)-one
• Calcium AS6P ester Calcium salt of ascorbic acid palmitoyl ester
• Calcium C4iso AAA Calcium salt of 3,4-dihydroxy-5-(2-isopropyl-1,3-dioxolan-4-yl)furan-2(5H)-one
• Calcium C12AAA Calcium salt of 3,4-dihydroxy-5-(2-undecyl-1,3-dioxolan-4-yl)furan-2(5H)-one
• Adhesion strength was determined by applying a shear load parallel to the bovine tooth adherend and in contact with the surface at a crosshead speed of 1.0 mm/min, and the cylindrical cured material adhered to the bovine tooth adherend peeling off from the surface. It was determined from the shear load when
• Adhesive strength was over 17 MPa.
• Adhesion strength is determined by applying a shear load parallel to the ceramic adherend and in contact with the surface at a crosshead speed of 1.0 mm/min, and when the cylindrical cured object adhered to the ceramic adherend peels off from the surface. It was determined from the shear load of
• Adhesive strength was over 17 MPa.
• B Adhesive strength was 13 MPa or more and 17 MPa or less.
• C Adhesive strength was less than 13 MPa.
• Adhesive evaluation 2 A bovine mandibular anterior tooth was subjected to root cutting and pulp extraction, placed in a plastic cylindrical container with a diameter of 25 mm and a depth of 25 mm, and embedded in an acrylic resin. This will be used as a bovine tooth adherend. Immediately before use, the bovine tooth adherend was polished with waterproof emery paper (P400) to carve out the smooth surface of the bovine dentin. Adhesiveness evaluation was performed according to ISO16506 using the first and second agents in each Example listed in Table 11, which were separately prepared as test specimens used for measuring adhesive strength.
• Adhesion strength was determined by applying a shear load parallel to the bovine tooth adherend and in contact with the surface at a crosshead speed of 1.0 mm/min, and the cylindrical cured material adhered to the bovine tooth adherend peeling off from the surface. It was determined from the shear load when
• the obtained adhesive strength was evaluated according to the same evaluation criteria as in ⁇ Evaluation of Adhesiveness>, and was used as an index of adhesiveness to dentin.
• ⁇ Ceramic adhesion 2> A dental feldspathic glass ceramic (manufactured by VITA Zahnfabrik, VITA blocs Mark II) was placed in a plastic cylindrical container with a diameter of 25 mm and a depth of 25 mm, and embedded in an acrylic resin. This is used as a ceramic adherend. Immediately before use, the ceramic adherend was polished with waterproof emery paper (P600) to carve out a smooth ceramic surface. Adhesiveness evaluation was performed according to ISO16506 using the first and second agents in each Example listed in Table 11, which were separately prepared as test specimens used for measuring adhesive strength.
• the first agent and the second agent in each example listed in Table 11 were weighed so that the second agent was 1.6 equivalent to the first agent, and mixed for 20 seconds.
• an appropriate amount was applied to the adhering surface of a previously prepared cylindrical cured filler composition (Venus Diamond, manufactured by Kulzer, the adhering surface was polished with waterproof emery paper P600), and the above-mentioned method was applied. It was placed vertically onto a ceramic adherend prepared as described above. Thereafter, pressure was applied using a special jig with a force of 5N.
• Adhesion strength is determined by applying a shear load parallel to the ceramic adherend and in contact with the surface at a crosshead speed of 1.0 mm/min, and when the cylindrical cured object adhered to the ceramic adherend peels off from the surface. It was determined from the shear load of
• the obtained adhesive strength was evaluated according to the same evaluation criteria as the evaluation criteria for ⁇ ceramic adhesiveness>, and was used as an index of adhesiveness to ceramics.
• the first agent includes a first monomer and the second agent includes a second monomer, and at least one of the first agent and the second agent contains ascorbic acids, an alkoxysilyl group, and a hydroxyl group.
• a kit for preparing a curable composition each independently containing Compound A containing at least one of a silyl group, it was possible to obtain a cured product with excellent adhesion to ceramics and adhesion to dentin. did it.
• Comparative Example 1 and Comparative Example 2 which used a curable composition preparation kit that did not contain ascorbic acids, did not adhere to dentin and had poor adhesion to dentin.
• Comparative Example 3 which used a curable composition preparation kit that did not contain Compound A, had poor adhesion to ceramics.

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