JP2005289961A - Microcapsule-containing curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a curable composition prevented from change with years even if a plurality of components having been impossible to be present together in an identical system are made to coexist stably in the identical system, essentially needing no kneading operation in use, and manifesting excellent curability by initiating a reaction with external energy as desired when its curing is needed in significantly improved operability and also because of essentially including no air bubbles attributable to kneading. <P>SOLUTION: This curable composition is obtained by separately encapsulating a plurality of components having been impossible to be present together in the identical system with microcapsules to stably include the respective components in a noncontact condition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a curable composition containing microcapsules such as microcapsules or nanocapsules. Specifically, in the prior art, a plurality of sets such as a set of acid-base reaction components and a set of redox polymerization initiator components that could not coexist in the same system such as the same paste or the same liquid. The present invention relates to a curable composition in which the above components are separately microencapsulated and each component is brought into a non-contact state and coexisted in the same system.
In particular, the present invention relates to a radical polymerization type or acid-base reaction type one-component curable composition and a two-partially curable composition containing microcapsules.

  In the material design in the dental field, unlike the general industry, material characteristics that can be used in a special environment in the oral cavity are required. That is, in the oral cavity, there is complete infiltration by saliva, breathing, or pulpal fluid, high acidity and protein adhesion due to bacterial metabolism, and rapid temperature changes due to food and drink intake. The cured product is required to have excellent physical properties that can withstand severe biting force and material properties that can exhibit mechanical and durable adhesion.

In dental practice, dental cement is routinely used to attach an abutment tooth, such as a crown that makes up the missing part of the crown and a crown bridge to make up the missing part with a prosthesis. ing. Typical materials are adhesive resin cements and glass ionomer cements.
For these materials, the prosthetic materials such as crowns are diversified into precious metals, non-precious metals, ceramics, etc., and the abutment teeth adhere to natural enamel, dentin, metal core, composite core, glass ionomer core, etc. Thus, it is required to have adhesive strength and physical characteristics that can sufficiently cope with a severe environment in the oral cavity such as temperature change and masticatory force.
In particular, the storage stability of these materials is so important that it can affect the clinical course.

  Furthermore, in addition to the above material characteristics, in complicated dental treatment, the operability of the material is extremely important in terms of whether or not the material characteristics are sufficiently exhibited in the oral cavity.

In dentistry clinics, because of the advantage that the kneading operation is unnecessary and the treatment or treatment time can be shortened, one solution that is a preservation and repair treatment or treatment that photopolymerizes a one-component photopolymerizable composite resin or bonding agent, or a prosthetic restoration material. Clinical procedures, such as making photopolymerizable crown-bridge composite resins, are routinely performed.
Up to now, α-diketone such as D, L-camphorquinone and N, N-dimethylaminoethyl methacrylate (Japanese Examined Patent Publication No. 54-10986) or α-diketone and N, N-dimethylaminobenzoic acid ethyl ester (Japanese Examined Publication) JP-A-60-26002) discloses a photopolymerization initiator effective for visible light polymerization passing through an exciplex by an α-diketone excited by so-called light irradiation and a photoreductive agent as a hydrogen donor.
However, these photopolymerization initiators have a problem that photocurability is lowered when an adhesive monomer having an acidic group coexists or when the initiator concentration is extremely low.

  Adhesive resin cements include composite resin types made of dental monomers and inorganic fillers, and PMMA type resin cements made of polymethyl methacrylate (PMMA) and methyl methacrylate.

Both types of resin cements contain adhesive monomers with acidic groups such as phosphate groups and carboxyl groups in the molecule, and the polymerization initiation system starts redox polymerization of a combination of benzoyl peroxide and aromatic tertiary amine. Agents and partially oxidized tributylborane are used. These adhesive resin cements have been widely used in prosthetic clinics because of their excellent adhesiveness to teeth, metals, ceramics and the like.
However, when the acidic group of the adhesive monomer comes into contact with the aromatic tertiary amine, there is a problem that a charge transfer complex is formed and the curability and adhesiveness are lowered. In addition, these resin cements have a drawback that the fluorine sustained release performance is greatly inferior to that of (resin modified) glass ionomer cement described later.

Since 1973, Wilson and Kent's invention (British Patent No. 1,316,129, 1973), glass ionomer (glass polyalkenoate) cement has high biocompatibility and good tooth adhesion, Due to its excellent ability to release fluorine, it has a high clinical expectation such as the possibility of preventing dental caries and has been used routinely in dental clinics to date.
In glass ionomer cements, the glass ionomer reaction layer, which is a hydrogel salt formed by the reaction of basic calcium aluminofluorosilicate glass with an acidic polyelectrolyte (polyalkenoic acid), which is a homopolymer or copolymer of an unsaturated carboxylic acid, is important. It has been clinically evaluated for its high ability to release and recharge fluorine.

  However, since glass ionomer cement has a slow curing reaction between glass and polyalkenoic acid, there is a problem that it takes time to obtain the hardness required for polishing after the repair treatment. Furthermore, there is a problem that the cured surface of the glass ionomer is sensitive to water and deteriorates due to water in the oral cavity.

Recently, resin-modified glass ionomer cement containing a resin component has been spreading. Japanese Patent Publication No. 2869078 proposes the effect of grafted polyalkenoic acid in which an unsaturated double bond group is introduced into the side chain.
These cements are accompanied by chemical polymerization and photopolymerization of the resin, so that the curing speed is increased and the problem of water sensitivity is also improved. However, these cements need to be accurately metered in powders and liquids in order to maintain physical properties in the powder / liquid type. That is, a measurement error causes lifting or dropping when a prosthesis such as a metal crown or an inlay is bonded.

  In order to solve these problems, capsule-type glass ionomer cements have been developed in which powders and liquids are weighed in advance and supplied to a capsule container separated by a membrane and mixed by mechanical vibration such as a mixer. The cement supplied to the plant still has the disadvantage that it begins to harden quickly when the components are mixed.

  Japanese Patent Application Laid-Open No. 11-228327 discloses a paste-paste type resin modified glass ionomer cement technique. This type of cement has a powder-to-liquid ratio that is controlled in advance at the time of manufacture, so there is no mistake in measuring powder and liquid, the above problems have been solved, operability has been improved, and water sensitivity has been improved. There is.

  As described above, the glass ionomer cement using acid-base reaction and the resin cement using redox polymerization are divided and packaged into two or more. Therefore, it is still necessary to knead when used. There is a problem that physical strength is not sufficient by enclosing air bubbles in the cured product.

  In order to solve this problem, Japanese Patent No. 3497508 and US Pat. No. 5,883,153 disclose a xerogel obtained by pre-reacting acid-reactive glass with polyalkenoic acid and freeze-drying the resulting hydrogel salt. A one-pack type photocurable dental cement containing a preformed glass ionomer filler produced by finely pulverizing a powder is proposed. This one-pack type paste (one-paste) composition has an excellent characteristic that it has high physical characteristics because it does not require kneading operation and essentially does not contain bubbles in the cured product. It is evaluated as a new category “Giomer” as a dental restorative material having sustained release of fluorine.

  However, the sustained release of fluorine is lower than that of the conventional (resin modified) glass ionomer cement, and the self-adhesiveness is inferior because the polycarboxylic acid is consumed.

  In this way, in the dental clinic, since the photopolymerization initiation system can be packaged in a single solution since the introduction of photopolymerization technology, one-paste dental composite resins have become widespread, but glass ionomers have their fluorine sustained release. However, it cannot be said that it is widespread while paying attention to safety and high biological safety. The technical factor is that a technology capable of packaging with one liquid has not been established.

In other words, in current dental practice, glass ionomers and resin cements are still supplied in two-part packaging, and they require a kneading operation at the time of use, whether they are powder / liquid type or paste / paste. Problems such as entrapment of bubbles inside and insufficient physical properties have not been fundamentally solved.
These materials are very important in dental preservation and prosthetic clinics, and there is a strong demand for the development of one-component or one-paste glass ionomers and resin cements that can be easily and fully operated.

Furthermore, although the effect is greatly expected with highly active catalysts, it is not practical because it is too catalytically active and has a significant problem in life, or it is supplied in strict packaging There are various products that are complicated to use. For example, partially oxidized tributylborane is supplied in a special glass container because it ignites when contacted with water, and sodium sulfinic acid salt is attracted by sodium when contacted with an adhesive monomer having an acidic group. It is pulled out and supplied in two-part packaging to generate sulfinic acid radicals and initiate polymerization.
However, the present situation is that sufficient storage stability cannot be ensured just by packaging in two parts.

  These materials are very important in dentistry preservation and prosthetic clinics and can be easily and fully manipulated, and these products have also been improved to be easily and fully manipulated clinically, improving storage stability. It is strongly desired to be done. It is expected that advanced treatment technology can be established by establishing a technology and product form that can package these polymerization catalysts in a single solution.

  Overcome technical issues by coexisting or non-contacting redox polymerization initiators such as acid-base reaction components and benzoyl peroxide amines, which were impossible to coexist in the same system with conventional technology Thus, there is a demand for material development that enables coexistence in the same system, even if it is two-part packaging, and enables the supply of products with good storage stability.

  In other words, non-coexistent materials such as acid-base reaction components, redox polymerization initiators and polymerization accelerators, and partially oxidized tributylborane can coexist because of their high catalytic activity and catalytic reaction like sodium sulfinic acid sodium salt. No technology has been proposed for stabilizing the product life by bringing the missing substances into a non-contact state.

  In addition, in recent dental clinics, due to polymerization initiators, there is a problem that photopolymer composite resins and bonding agents cannot be used for various light irradiators such as halogen lamps, light emitting diodes (LEDs), xenon lamps, etc. is there.

  Substances that have been supplied in two-part packaging are supplied in one pack or in a single solution, and a composition that is photocured in response to various light irradiators is expected.

Japanese Patent Publication No.54-10986 Japanese Patent Publication No. 60-26002 British Patent No. 1,316,129 Japanese Patent Publication No. 2869078 JP 11-228327 A Japanese Patent No. 3497508 US Pat. No. 5,883,153

Non-coexisting substances such as acid-base reaction components where polyalkenoic acid and acid-reactive glass react to form glass ionomers, redox polymerization reaction components such as benzoyl peroxide amines, partially oxidized tributylborane In the same paste or in the same liquid, such as a substance that has a high catalytic activity such as sodium sulfinate and aromatic sodium sulfinate, and that has been contact-reacted and has been supplied in two-part packaging, or that deteriorates when contacted by two people Multiple components that cannot be co-existed with each other are supplied in two or more divided packages. Especially when radically polymerizable monomers having acidic groups coexist, physical properties such as curing time, operability, and adhesiveness There was a problem that the characteristics changed over time and had an effect on the product life.
In addition, since it is packaged in two, it is kneaded when used, so that the operation is complicated, and it is hardened by kneading, so that there are problems that air bubbles are involved and physical properties and adhesiveness are lowered.

  Therefore, in view of the above problems, the present inventors can prevent a secular change even if a plurality of components that were impossible to coexist in the same system stably coexist in the same system, When using, essentially no kneading operation is required, and when curing is required, the reaction is initiated with external energy as desired. The present inventors have eagerly sought to provide a curable composition that exhibits excellent curability because it is not encapsulated.

That is, the present invention provides a curable composition containing microcapsules such as microcapsules or nanocapsules.
According to the present invention, the microcapsules can separately encapsulate a plurality of components that were conventionally impossible to coexist in the same system, and keep each component in a non-contact state in the composition. Therefore, the product life stability can be remarkably improved. In addition, since the curing time of the composition can be arbitrarily adjusted, handling in dentistry clinics becomes very simple, and thereby the quality of treatment can be greatly improved. The curable composition of the present invention can be used for medical and dental purposes.

  In the present specification, the term “microcapsule” refers to a microcapsule having a particle size of microsize, for example, several micrometers to several hundreds of micrometers, and “nanocapsule” refers to a nanoparticle having a particle diameter of nanosize, for example, A microcapsule having a size of several tens to hundreds of nanometers and less than a micro size. These microcapsules and nanocapsules are collectively referred to as microcapsules.

  In a first aspect, the present invention provides a one-part curable composition containing microcapsules such as microcapsules or nanocapsules.

The one-component curable composition of the present invention comprises a microcapsule, a core substance encapsulated in the microcapsule, and a substance enclosing the microcapsule. Here, the substance that encloses the microcapsules refers to a substance that becomes a base material of the curable composition.
That is, in the one-component curable composition of the present invention, a component that could not be allowed to coexist in the same system as the core material is encapsulated in the microcapsule, and the substance encapsulating the microcapsule that is the base material The microcapsules are dispersed.
Further, since the core substance is isolated by the wall material constituting the microcapsule, the core substance is stably present in the base material without reacting with each other in a non-contact state. Therefore, it is necessary that the wall material is a compound that is not affected by the core material in contact with the wall material and the material encapsulating the microcapsules.

  In the one-component curable composition of the present invention, the core substance encapsulated in the microcapsule includes a radical polymerizable monomer, a polymerization initiator, a polymerization accelerator, an electrolyte polymer, an electrolyte polymer aqueous solution, a hydroxycarboxylic acid, and a hydroxycarboxylic acid. It is a substance selected from the group consisting of an acid aqueous solution, an acid reactive filler and an acid inert filler, or a combination of two or more substances which can coexist.

  In the one-component curable composition of the present invention, the substance encapsulating the microcapsules includes a radical polymerizable monomer, a polymerization initiator, a polymerization accelerator, an electrolyte polymer, an electrolyte polymer aqueous solution, a hydroxycarboxylic acid, and a hydroxycarboxylic acid. It is a substance selected from the group consisting of an aqueous solution, an acid-reactive filler, and an acid-inert filler, or a combination of two or more substances that can coexist.

  The one-component curable composition of the present invention is characterized in that the wall material of the microcapsule is an organic compound, an inorganic compound, or an organic / inorganic composite compound.

  In the one-component curable composition of the present invention, preferably, the organic compound of the microcapsule wall material is an organic polymer compound, the inorganic compound is an inorganic polymer compound, and the organic / inorganic composite compound is an organic high compound. It is a composite material of a molecular compound and an inorganic compound having a basic skeleton such as silicon oxide and aluminum oxide.

The one-component curable composition of the present invention is characterized in that when an external force is applied, the microcapsules are disintegrated to release the core substance contained therein.
According to the present invention, the composition can be cured by initiating the curing reaction only by destroying the microcapsules in the composition by external energy.

  The curable composition containing the microcapsules according to the present invention may be cured by applying an external force to any of the conventional curing methods in which a paste divided into two or more parts is reacted by mixing the divided parts when used. You can select and use. For example, curing methods such as acid-base reaction, chemical polymerization, dual curing, photopolymerization, addition polymerization, ring-opening polymerization, and polycondensation can be arbitrarily selected and used depending on the embodiment.

  In the present invention, the external force that collapses the microcapsule includes, for example, electromagnetic waves such as visible light, magnetic fields, ultrasonic waves, pressures such as occlusal pressure, heat, stirring such as reciprocating vibration, or a combination of two or more thereof.

  Furthermore, the one-component curable composition of the present invention is characterized in that the curing reaction starts after the microcapsules are disintegrated by an external force. In particular, any one of a chemical reaction step in which a microcapsule is chemically reacted after being broken by an external force; a photocuring reaction step in which a photocuring reaction is performed by light irradiation; or a chemical photocuring reaction step in which a photocuring reaction is performed by light irradiation following the chemical reaction step. It is characterized by going through. According to the present invention, the composition may be cured by a method in which the composition is cured by initiating a curing reaction only by destroying the microcapsules by external energy, and a method of curing by photocuring in addition to this method.

  In the present invention, a photopolymerization initiator excellent in photocurability in the visible and near ultraviolet region can be added for photocuring. As such a photoinitiator, (bis) acylphosphine oxides or salts thereof, α-diketones, or coumarin compounds can be used in combination, which are halogen lamps commonly used for dentistry, Excellent light curability is exhibited by light irradiation of either a light emitting diode (LED) or a xenon lamp.

  In a second aspect, the present invention provides a bipartite curable composition containing microcapsules such as microcapsules or nanocapsules. In this specification, the bipartition curable composition packaged in two is mainly described. However, the technique of the present invention can be applied to a curable composition that is divided into three or more packages. .

The bipartite curable composition of the present invention comprises a microcapsule, a core substance encapsulated in the microcapsule, and a substance encapsulating the microcapsule, and a plurality of components to be contained in the composition are appropriately divided into two parts. It is divided. Here, the substance that encloses the microcapsules refers to a substance that becomes a base material of the curable composition.
That is, in the bipartite curable composition of the present invention, a component that could not be coexisted in the same system as a core substance or a highly active and unstable component was encapsulated in a microcapsule, The microcapsules are dispersed in a substance that encloses the microcapsules.
Further, since the core substance is isolated by the wall material constituting the microcapsule, the core substance is stably present in the base material without reacting with each other in a non-contact state. Therefore, it is necessary that the wall material is a compound that is not affected by the core material in contact with the wall material and the material encapsulating the microcapsules. However, the wall material of the microcapsule contained in one of the divided parts can be swelled or dissolved by a component in the substance enclosing the microcapsule contained in the other divided part.

  As one specific example of this aspect, the present invention provides a radical polymerization type bipartitionable curable composition.

  In the radical polymerization type bistable curable composition according to the present invention, the core substance contained in the microcapsule is composed of a radical polymerizable monomer, a polymerization initiator, a polymerization accelerator, an acid reactive filler and an acid inert filler. It is characterized in that it is a substance selected from the group or a combination of two or more substances that can coexist.

  Further, the radical polymerization type bistable curable composition according to the present invention has a material encapsulating a microcapsule in which a radical polymerizable monomer, a polymerization initiator, a polymerization accelerator, an organic polymer compound, an acid-reactive filler, or an acid-reactive filler. It is a substance selected from the group consisting of active fillers or a combination of two or more substances that can coexist.

  The radical polymerization type bistable curable composition according to the present invention is characterized in that the wall material of the microcapsule is an organic compound, an inorganic compound, or an organic / inorganic composite compound.

  As another specific example of this aspect, the present invention provides an acid-base reaction type bisecting curable composition.

  The acid-base reaction-type bistable curable composition according to the present invention includes an electrolyte polymer, an electrolyte polymer aqueous solution, a hydroxycarboxylic acid, a hydroxycarboxylic acid aqueous solution, and an acid-reactive filler. And a substance selected from the group consisting of acid-inert fillers or a combination of two or more of them which can coexist.

  Furthermore, in the acid-base reaction type bisecting curable composition according to the present invention, the substance encapsulating the microcapsule is composed of an electrolyte polymer, an electrolyte polymer aqueous solution, a hydroxycarboxylic acid, a hydroxycarboxylic acid aqueous solution, an acid-reactive filler, and It is a substance selected from the group consisting of acid inert fillers or a combination of two or more of them that can coexist.

  In addition, the acid-base reaction type bistable curable composition according to the present invention is characterized in that the wall material of the microcapsule is an organic compound, an inorganic compound, or an organic / inorganic composite compound.

  The acid-base reaction type bistable curable composition according to the present invention further comprises a core material encapsulated in a microcapsule or a substance encapsulating the microcapsule, and further comprises a radical polymerizable monomer, a polymerization initiator and a polymerization accelerator. A substance selected from the group is blended.

  The curable composition containing the microcapsules of the present invention is characterized in that the microcapsules are disintegrated to release the core material contained therein.

  In the present invention, the microcapsules can be collapsed by applying an external force. The external force includes, for example, electromagnetic waves such as visible light, magnetic fields, ultrasonic waves, pressure such as occlusal pressure, heat, stirring such as reciprocating vibration, or a combination of two or more thereof.

  In particular, in the case of a two-part curable composition, the microcapsule can be disintegrated by dissolving the wall material of the microcapsule when the two divided parts are mixed.

  The bipartite curable composition according to the present invention is characterized by being a powder / liquid type, a powder / paste type, a paste / paste type, a liquid / liquid type, or a paste / liquid type.

  The curable composition according to the present invention contains a compound selected from the group consisting of a solvent, a coupling agent, a modifier, a thickener, a dye, a pigment, a polymerization preparation agent, and a polymerization inhibitor, or a combination of two or more thereof. Can be blended. For example, a solvent such as water, acetone, ethanol, isopropyl alcohol and / or a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, butylated hydroxytoluene may be added.

  The curable composition according to the present invention has a core / shell type (core material / wall material type), core / core dispersed shell type (core material / core material solid solution wall material type) or core material. It is a solid solution material type.

In the “core / shell type structure”, the core (core material) is either solid, liquid, or suspension, and the shell does not contain any of those components and causes a reaction with the core (core material). There is no wall material.
In the “core / core dispersed shell type structure”, the core (core material) is any of solid, liquid, and suspension, and the shell (wall material) contains those components. The core (core material) component exists in a concentration gradient from the center of the shell toward the outer shell, and the presence of these components in the outermost shell of the shell can be ignored, and has a function as a capsule. This function refers to isolating the core (core material) components so that they do not interact with the material encapsulating the microcapsules. In particular, when the core material is a solid such as an organic crystal, the concentration of the core material in the capsule center is substantially 100%, and the concentration decreases as it moves to the outer shell. The concentration is substantially 0%.
In the “core material solid solution material type structure”, the wall material is present in the entire microcapsule, and the core material is uniformly dissolved therein, but the core material is not present only in the outermost shell. Unlike the core / core dispersed shell structure, there is no concentration gradient of the core material in the wall material.

  The effective composition according to the present invention can be used for medical and dental purposes.

  Since the one-component curable composition of the present invention does not require kneading, the operability is remarkably improved. Furthermore, since it essentially does not enclose bubbles by kneading and expresses excellent curability, it can be used not only in the dental field but also in the field of medicine, particularly orthopedic bone cement and substitute bones.

  Since the two-parting curable composition of the present invention reacts with each other and encapsulates a plurality of components that could not coexist in the same system, the product life is significantly improved. To do.

  Specific examples of the one-part curable composition according to the present invention are, in particular, one-paste dental cement and one-part dental adhesive. More specifically, the composition of the present invention comprises a one paste glass ionomer cement, a one paste resin cement, and a one-part dental bonding agent, a one paste adhesive composite resin, and a one paste resin cement. It can be applied to embodiments such as paste dental impression materials, and is characterized by markedly improving the operability of dental treatment and the properties and adhesiveness of cured products.

  In the one-part curable composition according to the present invention, the core substance encapsulated in the microcapsule and the substance encapsulating the microcapsule are, for example, a radical polymerizable monomer, a polymerization initiator, a polymerization accelerator, an electrolyte polymer, and an electrolyte polymer. It is a substance selected from the group consisting of an aqueous solution, hydroxycarboxylic acid, hydroxycarboxylic acid aqueous solution, acid-reactive filler, and acid-inert filler, or a combination of two or more substances that can coexist.

The bipartite curable composition of the present invention can be used in the form of powder / liquid type, powder / paste type, paste / paste type, liquid / liquid type, and paste / liquid type.
Specifically, denture base resin, dental immediate (room temperature) polymerization resin, magnet mounting adhesive resin, polymethyl methacrylate (PMMA) type adhesive resin cement (polymer powder / monomer liquid type adhesive resin cement), dual Cure type adhesive resin cement, Chemical polymerization type composite resin, Dual cure type composite resin, Adhesive composite resin, Composite resin for abutment construction, Composite resin for front crown, Crown / Bridge composite resin, Compomer, Resin core material, Two Can be applied to liquid bonding agents, two-part fisher sealants, two-part orthodontic adhesives, two-part tooth coatings, dental impression materials, etc. Because of its manifestation of adhesiveness and adhesiveness, Can be used in the field of in particular, such as orthopedic bone cement and alternative bone of the medical field is not limited to.

  Further, the acid-base reaction type curable composition includes dental two-paste or powder / liquid type fitting / filling / building abutment glass ionomer cement, resin-modified glass ionomer cement, carboxylate cement. Can be used for orthodontic adhesives, pusher sealants, root canal filling materials, back layer materials, etc.

  In the radical polymerization type bistable curable composition according to the present invention, the core substance encapsulated in the microcapsule and the substance encapsulating the microcapsule are a radical polymerizable monomer, a polymerization initiator, a polymerization accelerator, an acid-reactive filler, and It is a substance selected from the group consisting of acid inert fillers or a combination of two or more substances that can coexist.

  In the acid-base reaction type splittable curable composition according to the present invention, the core material encapsulated in the microcapsule and the material encapsulating the microcapsule are electrolyte polymer, electrolyte polymer aqueous solution, hydroxycarboxylic acid, hydroxycarboxylic acid It is a substance selected from the group consisting of an aqueous solution, an acid-reactive filler and an acid-inert filler, or a combination of two or more of them that can coexist.

  In the acid-base reaction-type bistable curable composition according to the present invention, the core material encapsulated in the microcapsule or the material encapsulating the microcapsule further includes a radical polymerizable monomer, a polymerization initiator, and a polymerization accelerator. A substance selected from the group consisting of:

The radical polymerizable monomer that can be used in the curable composition according to the present invention is selected from monomers, oligomers, prepolymers, and the like having radical polymerizable unsaturated double bonds used in the dental field and general industry. The
In particular, the radical polymerizable monomer that can be used in the present invention includes a radical polymerizable monomer containing an acidic group in the molecule, a radical polymerizable monomer not containing an acidic group, a polymerizable monomer having a sulfur atom in the molecule, Si It is selected from a polymerizable monomer having an atom in the molecule, a polymerizable monomer having a fluoroalkyl group in the molecule, a polymerizable monomer having a fluorine ion releasing ability, and the like.

One or more radically polymerizable monomers of the present invention can be arbitrarily selected and added depending on the embodiment for which the curable composition of the present invention is intended. For example, in the adhesive composition, examples of adherends to be bonded in dental clinic include dental enamel and dentin, non-noble metals, noble metals, ceramic materials and dental porcelain. Such as radically polymerizable monomers containing acidic groups in adhesives to dentin and non-noble metals, polymerizable monomers having sulfur atoms in the molecules for adhesives to noble metals, and ceramic materials and dental porcelain A polymerizable monomer having Si atoms in the molecule can be appropriately added to the adhesive.
Of course, in designing adhesives that adhere to all of these adherends, radical polymerizable monomers containing acidic groups, polymerizable monomers having sulfur atoms in the molecule, polymerizable monomers having Si atoms in the molecule are used. What is necessary is just to manufacture the adhesive agent containing all. Furthermore, in combinations where polymerizable monomers containing these functional groups, polymerization initiators and polymerization accelerators cannot coexist or contact and degrade shelf life, these are used as core materials to encapsulate the adhesive in a non-contact state. It can be manufactured to implement the present invention. On the other hand, when aiming at a curable composition that does not particularly require adhesion, a radically polymerizable monomer that does not contain these functional groups may be selected and used.

  As the radical polymerizable monomer containing an acidic group that can be used in the present invention, all monomers conventionally used as dental adhesive monomers can be used, and in particular, carboxyl groups and phosphate ester groups in the molecule. , Selected from radically polymerizable monomers having a phosphonic acid group, a pyrophosphoric acid group, a sulfonic acid group, and the like.

In the present invention, among radical polymerizable monomers containing an acidic group, examples of the monomer containing a carboxyl group in the molecule include methacrylic acid, 4- (meth) acryloxyethyl trimellitic acid, 4- (meth) acryloyl. Oxyethoxycarbonylphthalic acid, 4- (meth) acryloyloxybutyloxycarbonylphthalic acid, 4- (meth) acryloyloxyhexyloxycarbonylphthalic acid, 4- (meth) acryloyloxyoctyloxycarbonylphthalic acid, 4- (meth) Acryloyloxydecyloxycarbonylphthalic acid, maleic acid, and anhydrides thereof, 5- (meth) acryloylaminopentylcarboxylic acid, 6- (meth) acryloyloxy-1,1-hexanedicarboxylic acid, 7- (meth) Acryloyloxy -1,1-heptanedicarboxylic acid, 8- (meth) acryloyloxy-1,1-octanedicarboxylic acid, 10- (meth) acryloyloxy-1,1-decanedicarboxylic acid, 11- (meth) acryloyloxy-1 , 1-undecanedicarboxylic acid and the like. Furthermore, these acid chlorides, alkali metal salts, alkaline earth metal salts, ammonium salts, and the like are also included.
In the present specification, for example, methyl (meth) acrylate means methyl methacrylate or methyl acrylate.

  In the present invention, among radically polymerizable monomers containing an acidic group, as a monomer containing a phosphate group, phosphonic acid group, or pyrophosphoric acid group in the molecule, for example, 3- (meth) acryloxypropyl-3 -Phosphonopropionate, 3- (meth) acryloxypropyl-3-phosphonoacetate, 4- (meth) acryloxybutyl-3-phosphonopropionate, 4- (meth) acryloxybutylphosphonoacetate 5- (meth) acryloxypentylphos 3-phonopropionate, 5- (meth) acryloxypentyl-3-phosphonoacetate, 6- (meth) acryloxyhexyl-3-phosphonopropionate, 6 -(Meth) acryloxyhexyl-3-phosphonoacetate, 10- (meth) acryloxydecyl-3-phos Nopropionate, 10- (meth) acryloxydecyl-3-phosphonoacetate, bis [2- (meth) acryloxyethyl] phosphate, 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxy Propyl dihydrogen phosphate, 4- (meth) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) Acryloyloxyheptyl dihydrogen phosphate, 8- (meth) acryloyloxyoctyl dihydrogen phosphate-9- (meth) acryloyloxynonyl dihydrogen phosphate 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxyhexadecyl di Hydrogen phosphate, 20- (meth) acryloyloxyeicosyl dihydrogen phosphate, di [2- (meth) acryloyloxyethyl] hydrogen phosphate, di [4- (meth) acryloyloxybutyl] hydrogen phosphate, di [ 6- (Meth) acryloyloxyhexyl] hydrogen phosphate, di [8- (meth) acryloyloxyoctyl] hydrogen phosphate, di [9- (meth) acryloyl Ruoxynonyl] hydrogen phosphate, di [10- (meth) acryloyloxydecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl-2-dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydro Gen phosphate, 2- (meth) acryloyloxyethyl 2-bromoethyl hydrogen phosphate, 2- (meth) acryloyloxyethyl phenylphosphonate, 10- (meth) acryloyloxydecylphosphonic acid, vinylphosphonic acid, p-vinylbenzyl Phosphonic acid, 2-methacryloyloxyethyl (4-methoxyphenyl) hydrogen phosphate described in JP-A-62-281885, 2-methacryloylo Xylpropyl (4-methoxyphenyl) hydrogen phosphate, di [2- (meth) acryloyloxyethyl pyrophosphate], di [4- (meth) acryloyloxybutyl pyrophosphate], di [6- (meth) acryloyloxy pyrophosphate Hexyl], di [8- (meth) acryloyloxyoctyl pyrophosphate], and polymerizable monomers such as di [10- (meth) acryloyloxydecyl pyrophosphate]. Furthermore, these acid chlorides, alkali metal salts, alkaline earth metal salts, ammonium salts, and the like are also included.

  In the present invention, among radically polymerizable monomers containing acidic groups, examples of monomers containing sulfonic acid groups in the molecule include styrene sulfonic acid, 2-sulfoethyl (meth) acrylate, and 6-sulfohexyl (meth) acrylate. Examples include 10-sulfodecyl (meth) acrylate and 2- (meth) acrylamide-2-methylpropanesulfonic acid. Furthermore, these acid chlorides, alkali metal salts, alkaline earth metal salts, ammonium salts, and the like are also included.

  The radically polymerizable monomer containing no acidic group that can be used in the present invention is selected from a monofunctional monomer, a bifunctional crosslinkable monomer, a trifunctional crosslinkable monomer, etc., corresponding to the number of olefinic double bonds. Can be used. For example, (meth) acrylic acid ester derivatives, alkylene glycol di (meth) acrylates, alkyl di (meth) acrylates, epoxy di (meth) acrylates, bisphenol A-alkyl di (meth) acrylates, urethane di (meth) acrylates, Examples thereof include urethane tri (meth) acrylates, urethane tetra (meth) acrylates, hydroxyalkyl (meth) acrylates, (meth) acrylates having a Si group and a Ti group, and styrene derivatives.

  In the present invention, among the radical polymerizable monomers that do not contain an acidic group, for example, styrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, Butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxy Sidecyl (meth) acrylate, 1,3-dihydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, 1,2-dihydroxypropyl (meth) ) Acrylate, 2-hydroxy-2-methylpropyl (meth) acrylate, 3- (meth) acryloyloxypropylpentamethyldisiloxane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxy Silane, 6- (meth) acryloyloxyhexyltrimethoxysilane, 6- (meth) acryloyloxyhexyltriethoxysilane, 10- (meth) acryloyloxydecyltrimethoxysilane, 10- (meta Acryloyloxydecyl triethoxysilane, 11- (meth) acryloyloxy undecyl trimethoxysilane, 11- (meth) acryloyloxy undecyl triethoxysilane and the like.

  In the present invention, among the radical polymerizable monomers not containing an acidic group, examples of the bifunctional crosslinkable monomer include 2,2-bis {4- (meth) acryloxypropoxyphenyl} propane; bisphenol A-diglycidyl (meth). Acrylate; Bis-GMA, [2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl)] di (meth) acrylate; UDMA, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Dipentaerythritol di (meth) acrylate, polyethylene glycol di (meth) acrylate (number of oxyethylene groups 9, 14, and 23), propylene glycol di (meth) acrylate, glycerol di (meth) acrylate, neopentylglyco Rudi (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,6-hexanedi (meth) acrylate, 1,10-decandiol di (meth) acrylate, 2,2-bis [4- (meta ) Acryloyloxypolyethoxyphenyl] propane, 2,2-bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2,2-bis [4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl Propane, pentaerythritol di (meth) acrylate, 1,2-bis [3- (meth) acryloyloxy-2-hydroxypropoxy] ethane, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, 1,3-di (meth) acrylolyloxy-2-hydroxypropane, di (meth) Acryloxy Castanopsis isophorone diurethane, di (meth) acryloxyethyl -2,2,4 trimethylhexamethylene diurethane, glycerol di (meth) acrylate, isopropyl dimethacryloyl Louis isostearoyl titanate, and the like.

  In the present invention, among the radical polymerizable monomers that do not contain an acidic group, examples of monomers having trifunctional crosslinkability or more include, for example, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meta) ) Acrylate, tetramethylol methane tri (meth) acrylate, 1,7-diaacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, N, N ′-(2,2,4- And trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate.

  Particularly suitable monomers are ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, 1,6-hexanedi (meth) acrylate, 2,2-bis {4 -(Meth) acryloxypropoxyphenyl} propane = bisphenol A-diglycidyl (meth) acrylate, di (meth) acryloxyethyl-2,2,4-trimethylhexamethylene diurethane, di (meth) acryloxyisophorone diurethane, Examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol di (meth) acrylate, and γ- (meth) acryloxypropyltrimethoxysilane.

  Examples of the radical polymerizable monomer having a sulfur atom in the molecule that can be used in the curable composition according to the present invention include a mercapto group, a disulfide group, a polysulfide group, a cyclic disulfide group, a hydropolysulfide group, a sulfide group, a thioketone group, Thioaldehyde group, thioacetal group, thiocarboxylic acid group, thiocarboxylic acid anhydride group, thiocarboxylic acid ester group, thiophenecarboxylic acid group, thiouracil group, triazine dithione group, mercaptothiadiazole group, triazine monothione group, thiirane group, thiophosphate group And a polymerizable monomer having one or more thiophosphate groups, thiopyrrolate groups, thiopyrrolate groups, and thiophosphate halide groups. In addition, alkali metal salts, alkaline earth metal salts, ammonium salts and the like of these sulfur atom-containing polymerizable monomers can also be suitably used.

  Specifically, 2- (meth) acryloyloxyethyl 6,8-dithioctanoate, 6- (meth) acryloyloxyhexyl 6,8-dithioctanoate, 10- esterification reaction product of thioctic acid and hydroxyalkyl (meth) acrylate (Meth) acryloyloxydecyl 6,8-dithiooctanate, a compound described in JP-A-2003-105272:

などが挙げられる。

Etc.

  In the present invention, as a polymerizable monomer containing a Si atom in the molecule, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane, 3- ( (Meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane, 6- (meth) acryloyloxyhexyltriethoxysilane, 10- (meth) Acryloyloxydecyltrimethoxysilane, 10- (meth) acryloyloxydecyltriethoxysilane, 11- (meth) acryloyloxyundecyltrimethoxysilane, 11- (meth) acryloyloxyun Silanes such as siltriethoxysilane, 3- (meth) acryloyloxypropylpentamethyldisiloxane, 3-chloropropyltrimethoxysilane, mercaptopropyltrimethoxysilane, hexamethyldisilazane γ- (meth) acryloxypropyltrimethoxysilane Examples include coupling agents.

  The radically polymerizable monomer having a fluoroalkyl group in the molecule that can be used in the curable composition according to the present invention contains one or more polymerizable groups such as a methacryloyl group, an acryloyl group, a vinyl group, or a vinylbenzyl group ( A meth) acrylate compound can be used. For example, the compound 2,2,2-trifluoroethyl (meth) acrylate described in JP2003-095838A, 2,2,3,3,3- Pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, etc. or 2003 Compounds described in Japanese Patent No. 105272:

などが挙げられる。

Etc.

Examples of the radical polymerizable monomer having fluorine ion releasing ability that can be used in the curable composition according to the present invention include cyclic phosphazene compounds described in JP-A No. 2003-342112. Specifically, a 6-membered ring of P ₃ N ₃ (F) _n [O (CH ₂ ) ₂ OOC (CH ₃ ) C═CH ₂ ] _6-n (n is an integer of 1 to 5) A compound or an 8-membered ring compound of P ₄ N ₄ (F) _m [O (CH ₂ ) ₂ OOC (CH ₃ ) C═CH ₂ ] _8-m (where m is an integer from 1 to 7), etc. Can be mentioned.

  These radically polymerizable monomers are used alone or in appropriate combination. Among them, 4- (meth) acryloxyethyl trimellitic acid, 4- (meth) acryloxyethyl trimellitic anhydride, 6- Radical polymerization having acidic groups such as (meth) acryloxyhexyl-3-phosphonopropionate, 6- (meth) acryloxyhexyl-3-phosphonoacetate, 10- (meth) acryloxydecyl dihydrogen phosphate Monomers; and styrene, methyl (meth) acrylate, 2-hydroxyethyl methacrylate, 2,3-dihydroxypropyl methacrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, hexamethylene glycol di (meth) Acrylate, 2,2-bis {4- (meth) acryloxypropoxyphenyl} propane; bisphenol A-diglycidyl (meth) acrylate, di (meth) acryloxyethyl-2,2,4-trimethylhexamethylenediurethane, glycerol di ( A combination with a radical polymerizable monomer not containing an acidic group such as (meth) acrylate, 6- (meth) acryloyloxyhexyl 6,8-dithioctanate, 10- (meth) acryloyloxydecyl 6,8-dithioctanate is preferable.

  The compounding amount of these radically polymerizable monomers is used in a wide range corresponding to the embodiment of the present invention, and is 1% by weight to 99% by weight with respect to the total amount of the curable composition of the present invention. Yes, preferably 30% to 95% by weight, particularly preferably 50% to 93% by weight. If it is less than 1% by weight or more than 99% by weight, the curability of the curable composition becomes insufficient, and the effect of adding filler tends to decrease, whereby the adhesiveness or physical properties tend to be lowered.

  The polymerization initiator used in the curable composition according to the present invention can be selected from polymerization initiators used in the dental field and general industry. In particular, polymerization initiators or water-soluble polymerization initiators for photopolymerization and chemical polymerization can be used singly or in appropriate combination of two or more.

  Photopolymerization initiators that can be used in the present invention include (bis) acylphosphine oxides, water-soluble acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, α-diketones, and coumarins. , Anthraquinones, benzoin alkyl ether compounds, α-amino ketone compounds and the like.

  In the present invention, as the acylphosphine oxides, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6- Examples include trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, and benzoyldi- (2,6-dimethylphenyl) phosphonate. .

  In the present invention, examples of bisacylphosphine oxides include bis (2,6-dichlorobenzoyl) phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis (2,6 -Dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, (2,5 , 6-tri Chirubenzoiru) -2,4,4-trimethyl pentyl phosphine oxide, bis (2,4,6-trimethylbenzoyl) acyl phosphine oxide.

  In the present invention, as the water-soluble acylphosphine oxides, for example, metal salts of polymerization initiators such as metal salts and quaternary ammonium salts of acylphosphine oxides, metal salts of sulfinic acids, and quaternary ammonium salts of thioxanthones. Salts and / or quaternary ammonium salts.

  Examples of the metal salts and quaternary ammonium salts of acylphosphine oxides include those having an alkali metal ion, alkaline earth metal ion, pyridinium ion or ammonium ion in the acylphosphine oxide molecule. For example, the general formula (1):

［式中、ＲａはＲ２基または−ＯＲ２基であり、Ｅは酸素原子またはイオウ原子であり、Ｒｍは−Ｏ⁻Ｍ^＋または−ＮＲ_ｙＲ_ｚであり、Ｍ^＋は水素イオン、アルカリ金属イオン、アルカリ土類金属イオン（２分子のアシルホスフィンオキサイドに対して１つのアルカリ土類金属イオン）、ピリジニウムイオン（芳香環が有機基で置換されていても良い）、または、ＨＮ^＋Ｒ３Ｒ４Ｒ５（式中、Ｒ３、Ｒ４、Ｒ５は、同一または異なる有機基または水素原子）で示されるアンモニウムイオンで示されるなど医療的に受容できるカチオンであり、Ｒ１およびＲ２は同じか異なっていてもよく、それぞれ水素原子、アルキル、アルケニル、アルキニルまたはアリール；１つまたは２以上のハロゲン、アルコキシ、ニトロ、アルキル、−ＣＦ_３、ニトリルまたはカルボン酸または塩、エステルまたはアミドによって置換されたアルキル、アルケニル、アルキニルまたはアリールのそれぞれ全てであり、およびＲ_ｙおよびＲ_ｚは、同じか異なっていてもよく、それぞれ水素原子、アルキルまたは医療的に受容できる誘導体のそれぞれ全てである。］
で表される水溶性アシルホスフィンオキサイド類を欧州特許第０００９３４８号または特開昭５７−１９７２８６号に開示されている方法により合成して、使用することができる。

[In the formula, Ra is an R 2 group or —OR 2 group, E is an oxygen atom or a sulfur atom, R m is —O ⁻ M ⁺ or —NR _y R _z , and M ⁺ is a hydrogen ion or an alkali metal ion] , Alkaline earth metal ions (one alkaline earth metal ion for two molecules of acylphosphine oxide), pyridinium ions (the aromatic ring may be substituted with an organic group), or HN ⁺ R3R4R5 (wherein , R3, R4, and R5 are medically acceptable cations such as those represented by ammonium ions represented by the same or different organic groups or hydrogen atoms, and R1 and R2 may be the same or different and each represents a hydrogen atom , Alkyl, alkenyl, alkynyl or aryl; one or more halogens, alkoxy, nitro, alkyl, —CF ₃ Each of alkyl, alkenyl, alkynyl or aryl substituted with a nitrile or carboxylic acid or salt, ester or amide, and R _y and R _z may be the same or different and each represents a hydrogen atom, alkyl or All of the medically acceptable derivatives. ]
The water-soluble acylphosphine oxides represented by the formula (1) can be synthesized by the method disclosed in European Patent No. 0009348 or Japanese Patent Application Laid-Open No. 57-197286 and used.

  Examples of such water-soluble acylphosphine oxides include monomethylacetylphosphonate / sodium, monomethyl (1-oxopropyl) phosphonate / sodium, monomethylbenzoylphosphonate / sodium, monomethyl (1-oxobutyl) phosphonate / sodium, monomethyl (2- Methyl-1-oxopropyl) phosphonate sodium, acetylphosphonate sodium, monomethylacetylphosphonate sodium, acetylmethylphosphonate sodium, methyl 4- (hydroxymethoxyphosphinyl) -4-oxobutanoate sodium salt, methyl 4-oxo-phosphonobutanoate monosodium salt, acetylphenylphosphinate sodium salt, (1-oxopropyl) pe Tylphosphinate sodium, methyl 4- (hydroxypentylphosphinyl) -4-oxobutanoate sodium salt, acetylpentylphosphinate sodium, acetylethylphosphinate sodium, methyl (1,1-dimethyl) methyl Phosphinate sodium, (1,1-Ditoxyethyl) methyl phosphinate sodium, (1,1-Ditoxyethyl) methyl phosphinate sodium, methyl 4- (hydroxymethylphosphinyl) -4-oxobutanoate lithium Salt, 4- (hydroxymethylphosphinyl) -4-oxobutanoic acid dilithium salt, methyl (2-methyl-1,3-dioxolan-2-yl) phosphinate sodium salt, methyl (2-methyl- 1,3-thiazolidine-2 -Yl) phosphonite sodium salt, (2-methylperhydro-1,3-diazin-2-yl) phosphonite sodium salt, acetylphosphinate sodium salt, (1,1-diethoxyethyl) phosphonite sodium salt (1,1-diethoxyethyl) methylphosphonite sodium salt, methyl (2-methyloxathiolan-2-yl) phosphinate sodium salt, methyl (2,4,5-trimethyl-1,3-dioxolane) -2-yl) phosphinate sodium salt, methyl (1,1-propoxyethyl) phosphinate sodium salt, (1-methoxyvinyl) methylphosphinate sodium salt, (1-ethylthiovinyl) methylphosphinate sodium salt Methyl (2-methylperhydro-1,3-diazin-2-y ) Phosphinate sodium salt, methyl (2-methylperhydro-1,3-thiazin-2-yl) phosphinate sodium salt, methyl (2-methyl-1,3-diazolidin-2-yl) phosphinate sodium salt, Methyl (2-methyl-1,3-thiazolidin-2-yl) phosphinate sodium salt, (2,2-dicyano-1-methylethynyl) phosphinate sodium salt, acetylmethylphosphinate oxime sodium salt, acetylmethylphosphine Fine O-benzyl oxime sodium salt, 1-[(N-ethoxyimino) ethyl] methyl phosphinate sodium salt, methyl (1-phenyliminoethyl) phosphinate sodium salt, methyl (1-phenyl hydrazone ethyl) phosphinate・ Natriu Salt, [1- (2,4-dinitrophenylhydrazono) ethyl] methyl phosphinate sodium salt, acetyl methyl phosphinate semicarbazone sodium salt, (1-cyano-1-hydroxyethyl) methyl phosphinate Sodium salt, (dimethoxymethyl) methylphosphinate sodium salt, formylmethylphosphinate sodium salt, (1,1-dimethoxypropyl) methylphosphinate sodium salt, methyl (1-oxopropyl) phosphinate sodium salt, ( 1,1-dimethoxypropyl) methylphosphinate / dodecylguanidine salt, (1,1-dimethoxypropyl) methylphosphinate / isopropylamine salt, acetylmethylphosphinate thiosemicarbazone sodium salt, 1,3,5-tri Butyl-4-methylamino-1,2,4-triazolium (1,1-dimethoxyethyl) -methylphosphinate, 1-butyl-4-butylaminomethylamino-3,5-dipropyl-1,2,4- Triazolium (1,1-dimethoxyethyl) -methylphosphinate, 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide potassium salt, 2,4,6-trimethylbenzoyl Examples thereof include ammonium salts of phenylphosphine oxide. Furthermore, the compounds described in JP 2000-159621 A:

も挙げられる。

Also mentioned.

  These (bis) acylphosphine oxides and water-soluble acylphosphine oxides are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,4,6- Trimethylbenzoyl) acylphosphine oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are particularly preferred.

  The blending amount of these (bis) acylphosphine oxides and water-soluble acylphosphine oxides is used in a wide range corresponding to the embodiment of the present invention, but is based on the total amount of the curable composition of the present invention. It is 0.001% to 15% by weight, preferably 0.01% to 10% by weight, and particularly preferably 0.1% to 5% by weight.

  In the present invention, thioxanthones or quaternary ammonium salts of thioxanthones include, for example, thioxanthone, 2-chlorothioxanthen-9-one, 2-hydroxy-3- (9-oxy-9H-thioxanthene-4- Yloxy) -N, N, N-trimethyl-propaneaminium chloride, 2-hydroxy-3- (1-methyl-9-oxy-9H-thioxanthen-4-yloxy) -N, N, N-trimethyl-propane Aminium chloride, 2-hydroxy-3- (9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-propaneaminium chloride, 2-hydroxy-3- (3,4-dimethyl) -9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium Rholide, 2-hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride, 2-hydroxy-3- (1,3 , 4-trimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propaneaminium chloride and the like.

  A particularly preferred thioxanthone is 2-chlorothioxanthen-9-one, and the quaternary ammonium salt of thioxanthone is 2-hydroxy-3- (3,4-dimethyl-9H-thioxanthene-2- (Iloxy) -N, N, N-trimethyl-1-propaneaminium chloride.

  In the present invention, examples of ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

  In the present invention, α-diketones include, for example, diacetyl, dibenzyl, D, L-camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′-oxy. Examples include benzyl and acenaphthenequinone.

In the present invention, examples of the coumarin compound include 3,3′-carbonylbis (7-diethylaminocoumarin), 3- (4-methoxybenzoyl) coumarin, 3-chenoylcoumarin, and 3-benzoyl-5,7-dimethoxycoumarin. 3-benzoyl-7-methoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3- (p-nitrobenzoyl) coumarin, 3- ( p-nitrobenzoyl) coumarin, 3-benzoyl-8-methoxycoumarin, 3,5-carbonylbis (7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3′-carbonylbiscoumarin, 3-benzoyl -7-dimethylaminomarine, 3-benzoylbenzo [f] coumarin, 3 Carboxycoumarin, 3-carboxy-7-methoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo [f] coumarin, 7-methoxy-3- (p- Nitrobenzoyl) coumarin, 3- (p-nitrobenzoyl) coumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoyl-6-nitrocoumarin, 3-benzoyl-7-diethylaminomarine, 7-dimethylamino-3- ( 4-iobenzoyl) coumarin, 7-diethylamino-3- (4-iobenzoyl) coumarin, 7-diethylamino-3- (4-diethylamino) coumarin, 7-methoxy-3- (4-methoxybenzoyl) coumarin, 3- (4-nitrobenzoyl) benzo [f] coumarin, 3- 4-ethoxycinnamoyl) -7-methoxycoumarin, 3- (4-dimethylaminocinnamoyl) coumarin, 3- (4-diphenylaminocinnamoyl) coumarin, 3-[(3-dimethylbenzothiazol-2-ylidene) Acetyl] coumarin, 3-[(1-methylnaphtho [1,2-d] thiazol-2-ylidene) acetyl] coumarin, 3,3′-carbonylbis (6-methoxycoumarin), 3,3′-carbonylbis (7 -Acetoxycoumarin), 3,3′-carbonylbis (7-dimethylaminocoumarin), 3- (2-benzothiazoyl) -7- (diethylamino) coumarin, 3- (2-benzothiazoyl) -7- ( Dibutylamino) coumarin, 3- (2-benzimidazolyl) -7- (diethylamino) coumarin, 3- (2-benzothiazoyl) ) -7- (Dioctylamino) coumarin, 3-cabetoxy-7- (dimethylamino) coumarin, 3,3′-carbonylbis (7-dibutylaminocoumarin), 3,3′-carbonyl-7-diethylaminocoumarin-7 ′ -Bis (butoxyethyl) aminocoumarin, 10- [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3,6,7-1,1,7,7-tetra Methyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one, 10- (2-benzothiazoyl) -2,3,6,7-tetrahydro-1,1, 7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidin-11-one and the like are described in JP-A-9-3109 and JP-A-10-245525. Compound
In particular, 3,3′-carbonylbis (7-diethylaminocoumarin) and 3,3′-carbonylbis (7-dibutylaminocoumarin) are suitable.

  In the present invention, examples of anthraquinones include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1-hydroxyanthraquinone, and the like. Can be mentioned.

  In the present invention, examples of benzoin alkyl ethers include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  In the present invention, examples of α-aminoketones include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one.

  The chemical polymerization initiator that can be used in the present invention includes an organic peroxide, an acidic polymerization catalyst, a sulfinic acid (salt), a borate compound and the like.

In the present invention, examples of the organic peroxide include diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, and hydroperoxides.
Specific examples of diacyl peroxides include benzoyl peroxide, m-toluoyl peroxide, 2,4-dichlorobenzoyl peroxide, and the like.
As peroxyesters, t-butylperoxybenzoate, bis-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy-2-ethyl Examples include hexanoate, t-butyl peroxymaleic acid, and t-butyl peroxyisopropyl carbonate.
Examples of dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, and the like.
Examples of peroxyketals include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane.
Examples of ketone peroxides include cyclohexanone peroxide, methyl ethyl ketone peroxide, and methyl acetoacetate peroxide.
Examples of hydroperoxides include t-butyl hydroperoxide, p-diisopropylbenzene peroxide, cumene hydroperoxide, and the like.

  In the present invention, examples of the acidic polymerization catalyst include ascorbic acids and barbituric acids described later.

  In the present invention, as the sulfinic acid or a salt thereof, for example, p-position toluenesulfinic acid, sodium toluenesulfinate, potassium toluenesulfinate, lithium toluenesulfinate, calcium toluenesulfinate, benzenesulfinate, sodium benzenesulfinate, Potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinate, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate, Lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinate, 2,4,6-triethylbenze Sodium sulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-isopropylbenzenesulfinate Sodium 2,4,6-isopropylbenzenesulfinate, potassium 2,4,6-isopropylbenzenesulfinate, lithium 2,4,6-isopropylbenzenesulfinate, calcium 2,4,6-isopropylbenzenesulfinate, etc. And sodium benzenesulfinate and sodium p-toluenesulfinate are particularly preferable.

In the present invention, examples of the aryl borate compound include a borate compound having 1 to 4 aryl groups in one molecule.
Specifically, as a borate compound having one aryl group in one molecule, trialkylphenyl boron, trialkyl (p-chlorophenyl) boron, trialkyl (p-fluorophenyl) boron, trialkyl (3.5) -Bistrifluoromethyl) 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-butyl) Oxyphenyl) boron, trialkyl (p-octyloxyphenyl) boron, trialkyl Sodium salt of lithium (m-octyloxyphenyl) boron (alkyl group is n-butyl group, n-octyl group, n-dodecyl group, etc.), lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium Examples thereof include salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts.

  Further, as borate compounds having two aryl groups in one molecule, dialkyldiphenyl boron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, dialkyldi (3,5-bistrifluoromethyl) phenylboron 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-octyloxyphenyl) boron , Dialkyldi (m -Octyloxyphenyl) boron (alkyl group is the same as above) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butyl Examples thereof include pyridinium salt, methylquinolinium salt, ethylquinolinium salt, and butylquinolinium salt.

  Further, as borate compounds having three aryl groups in one molecule, monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, monoalkyltri (3, 5-bistrifluoromethyl) 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, monoalkyltri (p -Octyloxyphenyl) boron, monoalkyltri (m-octyloxyphenyl) boron (alkyl group is the same as above) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethyl Ammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt and the like can be mentioned.

  Furthermore, as a borate compound having four aryl groups in one molecule, tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl) 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-octyloxyphenyl) boron Tetrakis (m-octyloxyphenyl) phospho Boron, (p-fluorophenyl) triphenylboron, (3,5-bistrifluoromethyl) phenyltriphenylboron, (p-nitrophenyl) triphenylboron, (m-butyloxyphenyl) triphenylboron, (p -Butyloxyphenyl) triphenylboron, (m-octyloxyphenyl) triphenylboron, (p-octyloxyphenyl) triphenylboron, sodium salt of alkyl group as described above, lithium salt, potassium salt, magnesium Examples thereof include salts, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, and butylquinolinium salt.

  Among these aryl borate compounds, it is more preferable to use a borate compound having 3 or 4 aryl groups in one molecule from the viewpoint of storage stability.

  These aryl borate compounds can be used alone or in combination.

  Preferably, the polymerization initiator is t-butyl hydroperoxide, potassium benzoyl persulfate, ascorbic acid, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine oxide. Sodium salt, D, L-camphorquinone, 2-hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride, benzene Sodium sulfinate and sodium p-toluenesulfinate.

  These chemical polymerization and photopolymerization radical polymerization initiators and water-soluble polymerization initiators may be used alone or in combination of two or more compounds. The blending amount of these polymerization initiators is 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the total amount of radically polymerizable monomers of the curable composition of the present invention. % By weight, particularly preferably 0.1% by weight to 3% by weight.

The curable composition according to the present invention may contain a polymerization accelerator together with a polymerization initiator.
The polymerization accelerator used in the curable composition according to the present invention can be selected from compounds conventionally used as a photopolymerization accelerator or a room temperature polymerization accelerator. In particular, barbituric acid derivatives, aromatic amines, aliphatic amines, tin compounds, aldehydes and compounds having a thiol group, halomethyl group-substituted s-triazine derivatives, diphenyliodonium salt compounds, IV values and V-valent vanadium compounds are preferred.

  In the present invention, the barbituric acid derivative that can be used as a polymerization accelerator is represented by the following general formula (2):

［式中、Ｒ１、Ｒ２およびＲ３は、同一もしくは異なっていてもよく、それぞれハロゲン原子、アルキル基、アルコキシ基、アリル基またはシクロヘキシル基等の置換基を有してもよい脂肪族、芳香族、脂環式または複素環式残基もしくは水素元素を表す。］で表される化合物を含む。

[Wherein R1, R2 and R3 may be the same or different and each may have a substituent such as a halogen atom, an alkyl group, an alkoxy group, an allyl group or a cyclohexyl group, an aliphatic, an aromatic, Represents an alicyclic or heterocyclic residue or a hydrogen element. ] The compound represented by this is included.

  Specifically, for example, barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-ethylbarbituric acid Acid, 5-isopropyl barbituric acid, 5-cyclohexyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-n-butylbarbi Tool acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid, 1,3-dimethyl-5-cyclohexylbarbituric acid 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid Turic acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1, 3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5 Hexyl barbituric acid, 5-butyl-1-cyclohexyl barbituric acid, 1-benzyl-5-phenylbarbituric acid and thiobarbituric acids, and salts thereof (especially preferred are alkali metals or alkaline earth metals), For example, sodium 5-butylbarbiturate, 1,3,5-trimethylbarbitur Sodium and 1-cyclohexyl-5-ethyl barbituric sodium tool acid.

  Particularly preferred barbituric acid derivatives are 5-butyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, and 1-benzyl-5-phenylbarbituric acid and These are the sodium salts of barbituric acids.

  Examples of the aromatic amine that can be used as a polymerization accelerator in the present invention include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di (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-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-isopropylaniline, N, N- Bis (2-hydroxyethyl) -3,5-di-t-butylaniline, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N- Diethyl -P-toluidine, N, N-dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4- Isopropylaniline, N, N-dimethyl-4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylaminobenzoic acid methyl ester, N, N-dimethylaminobenzoic acid n-butoxyethyl ester, 4-N, N-dimethylaminobenzoic acid 2- (methacryloyloxy) ethyl ester, 4-N, N-dimethylamino Includes benzophenone, butyl 4-dimethylaminobenzoate, and the like.

Examples of the aliphatic amine that can be used as a polymerization accelerator in the present invention include 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 and the like.
Particularly preferred amines are N, N-di (2-hydroxyethyl) -p-toluidine, 4-N, N-dimethylaminobenzoic acid ethyl ester.

  The tin compound that can be used as a polymerization accelerator in the present invention is di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, di-n-butyltin dilaurate, or a mixture thereof. including. Particularly suitable tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate.

Among aldehydes and compounds having a thiol group that can be used as a polymerization accelerator in the present invention, aldehydes include terephthalaldehyde, dimethylaminobenzaldehyde, and the like.
Examples of the compound having a thiol group include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

  The halomethyl group-substituted s-triazine derivative that can be used as a polymerization accelerator in the present invention is:

で表される化合物や２,４,６−トリス（トリクロロメチル）−ｓ−トリアジン、２,４,６−トリス（トリブロモメチル）−ｓ−トリアジン、２−メチル−４,６−ビス（トリクロロメチル）−ｓ−トリアジン等の特開平１０−２４５５２５号公報に記載されている化合物を含む。

Or 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (trichloro) And compounds described in JP-A-10-245525 such as methyl) -s-triazine.

  Examples of diphenyliodonium salt compounds that can be used as a polymerization accelerator in the present invention include bromides such as diphenyliodonium and p-octyloxyphenyliodonium, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, trifluoromethanesulfonate salt, and the like. Including compounds described in JP-A-9-3109.

  The IV and / or V vanadium compounds that can be used as a polymerization accelerator in the present invention include divanadium tetroxide (IV), vanadium acetylacetonate (IV), vanadyl oxalate (IV), and vanadyl sulfate. (IV), oxobis (1-phenyl-1,3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), ammon metavanadate (V), etc. The compound etc. which are described in Unexamined-Japanese-Patent No. 2003-96122, such as vanadium compounds, etc. are included.

  Examples of the polymerization accelerator of the curable composition of the present invention include potassium persulfate and sodium persulfate, which are useful as a redox polymerization initiation system used in combination with an acidic polymerization catalyst such as ascorbic acid.

  These polymerization accelerators may be used alone or in combination of two or more compounds.

  In particular, as a polymerization initiator of the curable composition of the present invention, coumarin as a photopolymerization initiator, a borate compound as a chemical polymerization initiator, and a halomethyl group-substituted s-triazine derivative or diphenyliodonium salt as a polymerization accelerator. A ternary polymerization initiator mixed with compounds, a halomethyl group-substituted s-triazine derivative or a diphenyliodonium salt compound, a ternary polymerization initiator of IV and / or V valent vanadium compounds should be combined. Can be suitably used.

  In the one-component curable composition according to the present invention, these polymerization accelerators may be used alone or in combination of two or more compounds. The blending amount of these polymerization accelerators is 0.01 to 15% by weight, preferably 0.1 to 5% by weight, based on the total amount of the curable composition of the present invention. Particularly preferred is 0.5 to 3% by weight.

  Moreover, in the bisecting curable composition according to the present invention, the blending amount of these polymerization accelerators is 0.001% by weight to 15% by weight with respect to the total amount of the curable composition of the present invention, It is preferably 0.01% to 5% by weight, and particularly preferably 0.1% to 3% by weight.

  The electrolyte polymer and the electrolyte polymer aqueous solution that can be used in the curable composition according to the present invention can be selected from electrolyte polymers and electrolyte polymer aqueous solutions that are used in the dental field and general industry.

The electrolyte polymer that can be used in the present invention includes, for example, polyalkenoic acids, and the electrolyte polymer aqueous solution that can be used in the present invention includes, for example, an aqueous solution of polyalkenoic acids.
Polyalkenoic acids react with acid-reactive glasses to form glass ionomers, with side groups containing repeating units such as carboxyl groups, phosphoric acid groups, sulfonic acid groups, organic groups by amide bonds, and grafted unsaturated double bond groups. A homopolymer or copolymer of an unsaturated compound having one or more.

  In particular, homopolymers and copolymers of unsaturated mono-, di- and tricarboxylic acids having a carboxyl group in the side chain are preferred, specifically acrylic acid, maleic acid, crotonic acid, cinnamic acid, 3- Examples include polymers or copolymers containing repeating units derived from butene-1,2,3-tricarboxylic acid, tricarballylic acid, 2-hydroxyethyl methacrylate, or itaconic acid.

  In addition, polyalkenoic acids that are used in photocurable glass ionomer cements and have a conventionally known unsaturated group in the side chain are also preferably used. Furthermore, a polyalkenoic acid having an organic group by a carboxyl group and an amide bond, and a compound capable of binding to calcium of tooth is also preferably used.

  The molecular weight of the polyalkenoic acid used in the present invention is, for example, 1500-150,000, preferably 3000-70000, more preferably 3000-30000 in the case of polyacrylic acid. If the molecular weight of the polyalkenoic acid is too large, thickening due to gelation occurs rapidly during the reaction with the fluorine-containing glass, and the reaction is difficult to proceed.

  The hydroxycarboxylic acid and the hydroxycarboxylic acid aqueous solution used in the curable composition according to the present invention can be selected from hydroxycarboxylic acids and hydroxycarboxylic acid aqueous solutions used in the dental field and general industry.

  The hydroxycarboxylic acid that can be used in the present invention includes, for example, a compound containing a hydroxyl group and a carboxyl group in the molecule such as tartaric acid and malic acid, and the hydroxycarboxylic acid aqueous solution that can be used in the present invention includes the above compound. Aqueous solution.

  The acid-reactive filler used in the curable composition according to the present invention is selected from acid-reactive fillers used in the dental field and general industry, and a basic glass powder such as fluoroaluminosilicate is preferred.

Examples of the acid-reactive filler and basic glass powder of the curable composition of the present invention include fluorine-containing glass.
Here, the glass is a supercooled mixture of oxides and is usually a glass containing silica in combination with alumina.

The fluoride ion sustained release property which is a characteristic of the curable composition of the present invention is greatly influenced by the composition of the glass used as a raw material. As the fluorine-containing glass, specifically, those conventionally used as a glass ionomer cement are used. A typical composition of the fluorine-containing glass is as follows:
SiO ₂ -Al ₂ O ₃ -CaF _{2
SiO 2 -Al 2 O 3 -CaF 2} -AlPO 4
_{SiO 2 -Al 2 O 3 -CaF 2} -AlPO 4 -Na 3 AlF 6
The Al ₂ O ₃ / SiO ₂ molar ratio of the glass is preferably 1: 1 or less. This ratio provides a filler with optimal properties.

The glass can be prepared from a mixture of alumina, silica, aluminum fluoride and calcium fluoride, and optionally aluminum phosphate and cryolite (sodium aluminum fluoride). Preferred mixtures have the following composition:
Calcium oxide (CaO) 5-40 mol%
Silica _(SiO 2) 15 to 70 mol%
Alumina (Al ₂ O ₃ ) 10-50 mol%
Sodium oxide _(NaO 2) 0 to 7 mol%
Phosphorus pentoxide _{(P 2} O 5) _0~7 mole%
The amount of fluorine contained in these glasses is preferably 5 to 60 mol%. In the above composition, calcium oxide is used, but any alkaline earth metal oxide can be used.

These glasses are generally known as alkaline earth metal aluminofluorosilicate glasses.
At least a part of the alkaline earth metal may be replaced with a lanthanide metal such as lanthanum, gadolinium, or ytterbium. Furthermore, some or all of the alumina in these glasses may be replaced with a Group 3 metal other than aluminum. Similarly, a part of silica in the glass may be replaced with zirconium oxide or titanium oxide.
If the glass contains strontium, lanthanum, gadolinium, ytterbium or zirconium, the glass becomes radiopaque. It is preferable that 10% by weight or more of the radiopaque material is contained in the curable composition of the present invention.

  The fluorine-containing glass used in the present invention may be prepared by any conventional method, but can be obtained by a sol-gel method or a melting method. The fluorine-containing glass used particularly preferably can be arbitrarily prepared by selecting constituent elements.

  As the sol-gel method, for example, a first solution containing a soluble aluminum compound and a soluble silicon compound is reacted with a second solution containing a group 2 metal soluble compound, and the resulting gel is heat-dried or freeze-dried. It is the method of drying and collecting by. When this method is used, a relatively low temperature can be used, avoiding the use of additives usually used in the production of glass such as a flux agent. For this reason, glass with higher transparency than before can be obtained.

Other compounds such as organometallic or inorganic salt alcohol solutions may be added at the sol stage to obtain divalent or trivalent glasses.
An acidic or basic catalyst may be added to the sol-gel reaction mixture to increase the gelation rate. After gelation, it is dried to remove the residual solvent. The gel may also be sintered at relatively low temperatures, such as 400 ° C. By this method, a refractory glass homogeneous at a relatively low temperature can be obtained.

This sol-gel method is particularly suitable for the production of glasses incorporating gadolinium and the following five-component glasses:
_{X n O m -CaO-Al 2} O 3 -SiO 2 -F
[Wherein, X _n O _m is an oxide of the radiopaque substance X. It is particularly suitable for the production of

In general, it is difficult to produce such a five-component glass. However, according to the sol-gel method, the following materials: CaO source, CaCO ₃ dissolved in HCl; Al ₂ O ₃ source, isobutyl alcohol and Aluminum secondary butoxide (Asb) in ethanol; tetraethylorthosilicate as SiO ₂ source; 40% hydrofluoric acid as F source; easily soluble Gd (NO ₃ ) ₃ as Gd ₂ O ₃ source; SrO source As described above, glass can be easily produced from ethanol-soluble Sr (NO ₃ ) ₂ ;

Asb may be replaced with an ethanol or methanol solution of Al (NO ₃ ) ₃ · 9H ₂ O. Further, calcium oxide may be replaced with anhydrous Ca (NO ₃ ) ₂ dissolved in ethanol at 50 ° C.
These solutions are mixed while stirring at 50 ° C. Thereafter, it may be refluxed at 70 ° C. After drying, the resulting material is pulverized while soft and then dried at a temperature of 400 to 500 ° C. This is further pulverized to the required size.

  These acid reactive fillers may be used alone or in combination of two or more compounds. The blending amount of these fillers is 0.1% by weight to 80% by weight, preferably 1% by weight to 50% by weight, particularly preferably based on the total amount of the curable composition of the present invention. 3% to 30% by weight. When it is less than 1% by weight or more than 80% by weight, the operability of the curable composition becomes insufficient, and the adhesiveness and physical properties tend to decrease.

  The acid inert filler used in the curable composition according to the present invention includes, for example, an inorganic filler and an organic composite filler.

The acid inert filler that can be used in the present invention is a silica filler, ultrafine colloidal silica, or a mineral based on silica such as kaolin, clay, mica, mica, based on silica, Al ₂ O ₃ , Ceramics and glasses containing B ₂ O ₃ , TiO ₂ , ZrO ₂ , BaO, La ₂ O ₃ , SrO ₂ , CaO, P ₂ O _5, etc., especially lanthanum glass, barium glass, strontium glass, soda glass, lithium It can be selected from borosilicate glass, borosilicate glass, bioglass and the like.

  Furthermore, inorganic fillers such as crystalline quartz, hydroxyapatite, alumina, titanium oxide, yttrium oxide, zirconia, calcium phosphate, barium sulfate, aluminum hydroxide, talc, quartz, alumina, aluminosilicate, silicon nitride, etc., inorganic fillers and organic fillers Polymethyl (such as pre-reacted glass ionomer filler (PRG filler) produced by pre-reacting a composite filler with filler, fluoroaluminosilicate glass and acid-reactive glass, polyalkenoic acid and water to form a gel and then drying. (Meth) acrylate, polyethyl (meth) acrylate, copolymer of methyl methacrylate and ethyl methacrylate, polystyrene, polyfunctional methacrylate polymer, polyamide, polyvinyl chloride, chloroprene rubber, nitrile rubber Styrene - may be selected from organic polymer powders, organic fillers obtained by grinding a thermosetting resin cured product or the like comprising a cured thermosetting resin or an inorganic filler such as butadiene rubber.

  Preferably, the acid inert filler is a silica filler or ultrafine colloidal silica, and the surface layer may be surface-treated with a silane coupling agent for the purpose of improving wettability.

  These acid inert fillers may be used alone or in combination of two or more compounds. The blending amount of these fillers is 0.1% to 70% by weight, preferably 1% to 40% by weight, particularly preferably based on the total amount of the curable composition of the present invention. 3% by weight to 20% by weight.

  In order to adjust the mechanical strength, operability, applicability, and fluidity of the curable composition of the present invention, surface treatment with an acid inert filler in advance with a known surface treatment agent such as a silane coupling agent, if necessary. It may be used after that.

  As these surface treating agents, known ones can be used without limitation. Specifically, in addition to the radically polymerizable monomer containing the Si group described above, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxy Silane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 6- (meth) acryloyl Oxyhexyltrimethoxysilane, 6- (meth) acryloyloxyhexyltriethoxysilane, 10- (meth) acryloyloxydecyltrimethoxysilane, 10- (meth) acryloyloxydecyl Ethoxysilane, 11- (meth) acryloyloxyundecyltrimethoxysilane, 11- (meth) acryloyloxyundecyltriethoxysilane, 3- (meth) acryloyloxypropylpentamethyldisiloxane, 3-chloropropyltrimethoxysilane, Silane coupling agents such as mercaptopropyltrimethoxysilane and hexamethyldisilazane; isopropyl triisostearoyl tyranaate, isopropyl trioctanoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl dimethacryloyl iso Titanate coupling agents such as stearoyl titanate and isopropyl tricumylphenyl titanate; acetoalkoxyal Examples include aluminum coupling agents such as minium diisopyropyrate.

  These coupling agents are used alone or in combination of two or more. These coupling agents are usually blended as they are when preparing the curable composition of the present invention. For example, in the case of a silane coupling agent or the like, it is hydrolyzed with an acid or alkali in advance and converted into a silanol group. You may mix | blend. Further, the silyl group of the silane coupling agent may be hydrolyzed with time after preparation to be partially or entirely converted into a silanol group.

  The curable composition according to the present invention is characterized in that the microcapsule wall material is an organic compound, an inorganic compound, or an organic / inorganic composite compound.

In the present invention, an organic polymer compound is used as the organic compound that can be used as the microcapsule wall material.
The organic polymer compound is particularly useful in a bipartite curable composition. That is, when the two liquids are kneaded to dissolve the wall material and the core material such as a polymerization initiator or a polymerization accelerator is released, the wall material depends on the thickness of the capsule wall material, the molecular weight of the polymer, and the crosslinking density. The dissolution rate of the composition can be adjusted to control the cure rate of the composition. For example, if a polymer having a low molecular weight or a low crosslinking density is used, the dissolution rate of the capsule can be increased.

  Examples of such organic compounds include homopolymers and copolymers of (meth) acrylates, polyfunctional (meth) acrylate polymers, polyethylene, polyvinyl chloride, styrene homopolymers and copolymers, chloroprene rubber, and nitrile rubber. , Polyolefins such as gum arabic, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetate, polyesters, polyamides, polyimides, epoxy resins, polyurethanes, polyureas, melamine resins, polyacetals, polyamides, polypyrrole , Cellulose resins such as polyether, polycarbonate, polyvinylidene chloride, thiocol, polysulfone hydroxyethyl cellulose, carboxymethyl cellulose, gelatins, and the like.

  These polymers include polystyrene, polymethyl (meth) acrylate, polyethyl (meth) acrylate, polypropyl (meth) acrylate, polybutyl (meth) acrylate, polypentyl (meth) acrylate, polyhexyl (meth) acrylate, polydecyl (meth) acrylate, Poly-2-hydroxyethyl (meth) acrylate, poly-3-hydroxypropyl (meth) acrylate, poly-4-hydroxybutyl (meth) acrylate, poly-5-hydroxypentyl (meth) acrylate, poly-6-hydroxyhexyl (Meth) acrylate, poly-10-hydroxydecyl (meth) acrylate, copolymer of methyl (meth) acrylate and ethyl (meth) acrylate, poly (3,4-ethylenedioxy pillow) ), Nylon 6 and nylon 12 copolymers, and polymethyl (meth) acrylate, polyethyl (meth) acrylate, and a copolymer of methyl (meth) acrylate and ethyl (meth) acrylate, gelatin is particularly suitable. .

  In the present invention, any inorganic oxide composition that can be synthesized by a sol-gel method can be suitably used as the inorganic compound that can be used as the wall material.

  In the present invention, the inorganic compound that can be used as the microcapsule wall material is, for example, silicon oxide, aluminum oxide, titanium oxide, calcium oxide, and a composite thereof that can be synthesized by a condensation and substitution inorganic reaction such as a sol-gel method. Specifically, it is polysiloxane.

  In the present invention, as an organic / inorganic composite compound that can be used as a wall material, an organic compound that is condensed with organosilanes based on tetraethyl silicate and can be further modified with these functional groups can be used.

  In the present invention, the organic / inorganic composite compound that can be used as the microcapsule wall material includes, for example, a crosslinked salt of a reactive polymer and a metal, a compound obtained by modifying an inorganic oxide with an organic compound, such as an organic polymer It is a composite material of a compound and an inorganic compound having a basic skeleton such as silicon oxide and aluminum oxide.

  In the curable composition according to the present invention, a solvent, a coupling agent, a modifier, a thickener, a dye, a pigment, a polymerization regulator, a polymerization inhibitor, and the like can be appropriately blended.

  Examples of the solvent include water; alcohols such as ethanol, methanol, 1-propanol, and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone, pentanone, and hexanone; esters such as ethyl acetate, methyl acetate, and ethyl propionate; Ethers such as 2-dimethoxyethane, 1,2-diethoxyethane and tetrahydrofuran; hydrocarbons such as heptane, hexane, octane and toluene; and halogenated hydrocarbons such as chloroform and dichloromethane are preferably used. . Of these, water, acetone, ethanol, isopropyl alcohol and the like are preferably used.

  These solvents may be used alone or in combination of two or more. The blending amount of these solvents is 1% to 90% by weight, preferably 10% to 60% by weight, particularly preferably 30% by weight, based on the total amount of the curable composition of the present invention. % To 50% by weight.

  A well-known thing can be used as a coupling agent without a restriction | limiting. Specifically, those described above as the surface treatment agent for the acid inert filler can be used.

  Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, butylated hydroxytoluene and the like, which are suitable for stabilizing the shelf life of the composition.

  In the curable composition according to the present invention, the method for producing the microcapsules can be selected from various production methods usually carried out in the general industry, and there are chemical, physicochemical and physical methods, You may combine them suitably.

  In the present invention, chemical methods for producing microcapsules include interfacial polymerization microencapsulation, in situ polymerization microencapsulation, and liquid-cured coating microencapsulation. The former two methods are capsule synthesis methods utilizing a polymer synthesis reaction, and the other one method is considered to be a synthesis method utilizing property changes.

The interfacial polymerization method is a method of synthesizing capsules by utilizing a polycondensation reaction at the interface in a combination of a hydrophobic monomer and a hydrophilic monomer.
Specifically, a hydrophobic monomer is contained in an organic solvent immiscible with water, and this is emulsified in an aqueous phase to prepare a stable emulsion. By adding and stirring a hydrophilic monomer to this emulsion, a polymerization reaction occurs at the water / oil interface, and a polymer film is formed and encapsulated. In this case, the hydrophobic component is included in the generated membrane.
On the other hand, in the case of a hydrous capsule, it can be prepared by reversing the water phase and the oil phase. That is, an aqueous solution containing a hydrophilic monomer is emulsified in an oil phase to prepare a stable emulsion. By adding a hydrophobic monomer to this emulsion and stirring, a polymerization reaction occurs at the oil / water interface, resulting in a polymer coating. Generated and encapsulated. In this case, the hydrophilic component is included in the generated film.

As monomers that can be used in the interfacial polymerization method, hydrophilic monomers include polyamines, glycols, and polyhydric phenols, and hydrophobic monomers include polybasic acid chlorides, bishaloformates, and isocyanates. .
Polymers produced by the combination thereof are polyester, polyamide, polyurethane, polyurea and polyurethane, and these polymer coatings can be suitably used for the microcapsules according to the present invention.
In any emulsification, emulsification in the presence of a suitable surfactant, dispersion stabilizer, dispersion stabilization aid or the like is advantageous for stabilizing the emulsion.

  In the in-situ polymerization method, unlike the above-described interfacial polymerization method mainly using a polycondensation reaction, at least one kind of monomer may be used. That is, encapsulation is possible with the use of either hydrophilic or hydrophobic monomers, and the combinations of the monomers are infinite.

  In the present invention, the radical polymerizable monomer for in-situ polymerization other than the radical polymerizable monomer described above in the present invention and the monomer used for polycondensation reaction and ring-opening polymerization are p-chlorostyrene as an example of vinyl monomer. , Vinyl naphthalene, unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene, halogens such as vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl butyrate Esters of monocarboxylic acids including vinyl halides, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloro acrylate, butyl methacrylate, and the like Vinyl esters, acrylonitrile, methacrylonitrile, vinyl ethers including vinyl methyl ether, vinyl isobutyl ether, and vinyl ethyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone, 3 1,4-ethylenedioxypyrrole, N-vinylindole and N-vinylpyrrolidene, formaldehyde and amines such as urea, melamine, dimethylolurea etc. or their precondensates or condensation products, if desired It can be modified by co-condensation of phenols such as resorcinol. Moreover, lactams, such as epsilon caprolactam, etc. can be mentioned.

As the radical polymerizable monomer for in-situ polymerization that can be used for the capsule wall of the present invention, any of the above-mentioned radical polymerizable monomers can be used as a core material encapsulated in the capsule or a substance that encapsulates the capsule.
Among them, 4- (meth) acryloxyethyl trimellitic acid, 4- (meth) acryloxyethyl trimellitic anhydride, 6- (meth) acryloxyhexyl-3-phosphonopropionate, 6- (meta ) Radical polymerizable monomer having an acidic group such as acryloxyhexyl-3-phosphonoacetate, 10- (meth) acryloxydecyl dihydrogen phosphate, and styrene, methyl (meth) acrylate, 2-hydroxyethyl methacrylate, 2 , 3-dihydroxypropyl methacrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, 2,2-bis {4- (meth) acryloxypropoxyphenyl} propane Bisfe A-diglycidyl (meth) acrylate, di (meth) acryloxyethyl-2,2,4-trimethylhexamethylene diurethane, glycerol di (meth) acrylate, 6- (meth) acryloyloxyhexyl 6,8-dithiooctanoate A radical polymerizable monomer that does not contain an acidic group, such as 10- (meth) acryloyloxydecyl 6,8-dithiooctanate, is preferable.

  These radical polymerizable monomers may be used alone as appropriate in consideration of the core substance and the use environment, or two or more compounds may be combined. In addition, for the purpose of stabilizing the composite emulsion and the like, a polymer soluble in these monomers can be suitably used.

Here, as an example, capsule synthesis by in-situ polymerization is shown.
An equivalent amount of polyacrylic acid aqueous solution is emulsified in methyl methacrylate containing 10 wt% polymethyl methacrylate and 1 wt% benzoyl peroxide in the presence of a nonionic surfactant. The obtained primary emulsion is secondarily dispersed in 10 volumes of ion-exchanged water containing a protective colloid agent, and heated to 70 ° C. with stirring to perform in-situ polymerization. The obtained capsule is thoroughly washed and then oven-dried to obtain a polyacrylic acid aqueous solution capsule using polymethyl methacrylate as a wall material.

  In the submerged cured coating method, polysaccharide polymers such as polyvinyl alcohol, gelatin, glycerol, albumin, collagen, epoxy resins, alginic acid and salts thereof, and waxes can be suitably used as the capsule wall material. That is, any wall material and curing agent that cause insolubilization in each solvent by modification or the like can be suitably used for the capsule wall of the present invention.

  In the present invention, the physicochemical methods for producing the microcapsules include a microencapsulation method by a coacervation method and an interfacial precipitation (dry in liquid) microencapsulation method.

There are two types of coacervation methods: a method using phase separation from an aqueous solution system and a method using phase separation from an organic solution system.
Furthermore, methods utilizing phase separation from aqueous solutions are classified into simple coacervation methods, complex coacervation methods and pH control methods. In addition, methods using phase separation from organic solution systems include phase separation by combining a good solvent and a poor solvent, a method of causing phase separation with a phase separation-inducing liquid polymer, and a temperature. There is a method of causing phase separation using a change in solubility of a polymer or the like, and any of these methods can be suitably used.

As an example, an encapsulation example by a pH control method using triethylenedimethacrylate (TEGDMA) gelatin is shown.
An oil / water (O / W) emulsion is prepared at 40 ° C. by emulsifying TEGDMA in a 5 wt% gelatin aqueous solution containing sodium dodecyl sulfate as a surfactant with a high-pressure homogenizer. Next, 5 wt% aqueous solution of gum arabic at the same temperature is added and mixed uniformly. Coacervation is induced by adjusting the pH of the system below the isoelectric point of this gelatin with a 2.5 wt% aqueous acetic acid solution while sufficiently stirring.
The coacervate film deposited on the TEGDMA surface layer becomes a non-moving body by cooling. Further, after adding a very small amount of a formalin aqueous solution and then increasing the pH of the system to 8.5 with a 2.5 wt% sodium carbonate aqueous solution, gelatin becomes insoluble in water and hardens. This is isolated and dried to produce a TEGDMA gelatin capsule.

  In the submerged drying method, not only hydrophilic substances but also hydrophobic substances can be encapsulated in the same manner. The core material can encapsulate not only a liquid but also a solid material such as a crystal.

When using a liquid drying method to microencapsulate a liquid as a core material, for example, a polyacrylic acid aqueous solution with a polymer, prepare a reaction vessel with a stirrer and use a copolymer of methyl methacrylate and ethyl methacrylate as a low-boiling solvent. A water / oil (W / O) emulsion obtained by emulsifying an aqueous polyacrylic acid solution in the presence of a surfactant in a dissolved polymer solution is added to distilled water containing a large amount of a surfactant, and emulsified again. / Oil) / oil [(W / O) / W] emulsion. While the emulsion is stirred, the low boiling point solvent is evaporated by gently heating and depressurizing to obtain a fine particle capsule containing an aqueous polyacrylic acid solution.
These obtained capsules are repeatedly filtered and washed with water, and then dried at normal pressure or slightly reduced pressure to obtain fine particles in which an aqueous polyacrylic acid solution is encapsulated with a copolymer as an inclusion substance.

In addition, when a solid, for example, benzoyl peroxide, is encapsulated as a core substance by a submerged drying method using a submerged drying method, it is added to a polymer solution in which a copolymer of methyl methacrylate and ethyl methacrylate is dissolved in a low boiling point solvent. A solid / oil (S / O) emulsion in which fine powder of benzoyl oxide is suspended is added and dispersed in distilled water containing a large amount of a surfactant, and (solid / oil) / oil [(S / O) / W] Emulsion is obtained. While stirring this composite emulsion, the low boiling point solvent is evaporated by gently heating and reducing the pressure to obtain fine particle capsules containing benzoyl peroxide.
These obtained capsules are repeatedly filtered and washed with water, and then dried under reduced pressure to obtain fine particles in which benzoyl peroxide is encapsulated with a copolymer as an inclusion substance.

  Similarly, an active substance such as ascorbic acid can be encapsulated. In addition, when the core substance is water-soluble and the secondary continuous phase is aqueous, it is more preferable to adjust the osmotic pressure by adding salts to the secondary continuous phase.

Furthermore, it is also possible to microencapsulate an acid-reactive filler such as fluoroaluminosilicate with a hydrophilic polymer using a submerged drying method.
That is, after a fluoroaluminosilicate powder is suspended and dispersed in an aqueous polyvinyl alcohol solution as a primary dispersion, this primary dispersion is secondarily dispersed in toluene containing a surfactant. Thereafter, a large amount of absolute ethanol is added as a dehydrating agent to precipitate polyvinyl alcohol in toluene. Thereby, fluoroaluminosilicate powder encapsulated with polyvinyl alcohol as a hydrophilic polymer can be obtained.

Similarly, an acid-reactive filler such as fluoroaluminosilicate can be microencapsulated with a hydrophobic polymer using a submerged drying method.
That is, after a fluoroaluminosilicate powder is suspended and dispersed in an ethyl acetate solution of polymethyl methacrylate as a primary dispersion, this primary dispersion is secondarily dispersed in ion-exchanged water containing a surfactant. Thereafter, the composite emulsion is heated under reduced pressure while stirring to remove ethyl acetate and dry. Thereby, a fluoroaluminosilicate powder encapsulated with polymethylmethacrylate as a hydrophobic polymer can be obtained.

  In the present invention, physical (mechanical) methods for producing microcapsules include spray drying microencapsulation, air suspension coating microencapsulation, vacuum deposition coating microencapsulation, electrostatic coalescence micro Examples include an encapsulation method, a solution dispersion cooling microencapsulation method, and an inorganic wall microencapsulation method.

  The spray drying method is generally used in the industry as a granulation method, but is also an effective method as an encapsulation method. The mother liquor that can be prepared by this method includes an aqueous solution containing a water-soluble emulsion, an organic solution containing an oil-soluble emulsion, and a suspension containing a capsule slurry. This is also an effective technique for immobilizing the final capsule of the suspension prepared by the interfacial polymerization method, in-situ polymerization method, or in-liquid drying method.

For example, ethylene glycol dimethacrylate (EGDMA) is added to a 10 wt% polyvinyl alcohol aqueous solution so as to be 20 wt%, and a solution emulsified with a rotary homogenizer is prepared. EGDMA encapsulated with polyvinyl alcohol can be obtained by drying at a feed rate of 60 mL / min, a blower air volume of 0.5 m ³ / min, and a spray pressure of 100 kPa.

[(W / O) / W], [(O / W) / O], [(S / O) / W] and [(S / W) / O] using the chemical and physicochemical methods described above. When a capsule is synthesized through an emulsion state such as the above, the size of the capsule can be arbitrarily adjusted to a desired final particle size by adjusting the energy applied during emulsification or secondary dispersion.
That is, in the case of a relatively large size, microcapsules having a size of several micrometers to several hundred micrometers can be obtained by preparing a composite emulsion by swirling flow of a low energy device such as a chemical mixer or a simple turbine.
On the other hand, when an ultrasonic generator, an ultrahigh pressure homogenizer, or the like is used, nanocapsules having a size of several tens of nanometers to several hundred nanometers can be prepared.
If a rotary homogenizer composed of a rotor and a stator is used, these intermediate size capsules can be prepared.
Furthermore, these sizes can be adjusted by the type and concentration of the surfactant.

  Examples of the one-part curable composition of the present invention include, for example, fluoroaluminosilicate glass fine powder inclusion-PVA microcapsule, polyacrylic acid aqueous solution-PVA microcapsule, radical polymerizable monomer, photopolymerization produced by the W / O emulsion method. A one-paste photopolymerizable resin-modified glass ionomer cement is produced by mixing an initiator and an accelerator, a silane-treated silica filler, an ultrafine particle filler, and a polymerization inhibitor, and the cement is filled in a plastic mini-syringe.

  When this cement is used in a dental clinic, first, dental caries are removed by a conventional method, and cavity formation and cavity cleaning are performed. The mini-syringe filled with the cement is then placed in an ultrasonic box and the capsule is broken by ultrasound to initiate the glass ionomer reaction, and the one paste cement is pushed out with a plunger to fill the cavity. Thereafter, the surface of the filling is shaped and adjusted to a tooth surface, photopolymerized, and finish-polished by a conventional method to complete the filling treatment.

  Even when the two-part curable composition of the present invention is implemented in the form of a two-paste photopolymerizable (resin-modified) glass ionomer cement, as described above, except that there is a step of mixing two parts. Can be used for dental treatment.

  The one-part curable composition of the present invention includes a one-paste glass ionomer cement, a one-paste rangen modified glass ionomer cement, a one-paste adhesive resin cement, and a one-paste. Dual Cure Adhesive Resin Cement, One Paste Chemical Polymerization Composite Resin, One Paste Dual Cure Composite Resin, One Paste Adhesive Composite Resin, One Paste Crown Bridge Front Crown Composite It can be used for resins, one-paste compomers, one-paste resin core materials, one-part dental bonding agents, fisher sealants, orthodontic adhesives, tooth coating agents, and the like.

  According to the present invention, an external force is applied to the curable composition to break the microcapsule wall material, thereby releasing the encapsulated material from protection, and mixing with the material constituting the curable composition leads to curing. The initial object is achieved according to the embodiment of the crimped invention.

The external force is not particularly limited as long as it is necessary to destroy the capsule wall material and express medically safe energy. However, visible light, near-ultraviolet rays, ultraviolet rays, X-rays and other electromagnetic waves, magnetic fields, ultrasonic waves, occlusal pressure The pressure can be selected and applied from an external force such as agitation such as pressure, heat, and reciprocating vibration.
A plurality of external forces can be selected and added. For example, the capsule wall material can be destroyed by applying visible light after applying ultrasonic waves to the curable composition.

  Specifically, as a core substance, one or both of a set of components that undergo acid-base reaction, a set of components that undergo redox reaction, or a set of components that generate radicals upon contact are separately encapsulated in advance. The paste prepared by mixing the prepared microcapsules, radical polymerizable monomer, photopolymerization initiators, filler, ultrafine particle filler and polymerization inhibitor is filled into a plastic mini-syringe, and one-paste photopolymerized resin modified glass Prepare a curable composition such as ionomer cement, photopolymerization resin cement, or one-part photopolymerization bonding agent, and destroy the outer wall material of the microcapsule in the composition with ultrasonic waves before use. The treatment of the treatment site during progression and photopolymerization by irradiation with light allows the realization of the one-component curable composition of the present invention. It can be completed.

The curable composition of the present invention can disintegrate the microcapsules by a method other than external force to release the core substance.
Specifically, as a core substance, one or both of a set of components that undergo an acid-base reaction, a set of components that undergo a redox reaction, or a set of components that generate radicals upon contact are made of an organic polymer compound in advance. Separately encapsulate to make microcapsules, mix organic polymer, radical polymerizable monomer containing acid group, radical polymerizable monomer not containing acid group, polymerization initiator, and polymerization inhibitor, There is a method in which a curable composition of a monomer liquid type resin cement is prepared, and the reaction is started by mixing and swelling and dissolving the capsule to destroy the wall material.

  Furthermore, for example, an external force such as an ultrasonic wave is applied to destroy the wall material of the capsule containing the same core substance in the composition to start a curing reaction, or a treatment site while the reaction is in progress. After the treatment, the photopolymerization is performed by light irradiation, whereby the implementation of the curable composition of the present invention can be completed.

  Next, the present invention will be specifically described with reference to examples and comparative examples. In addition, this invention is not limited to these Examples at all.

[Synthesis of microcapsules by chemical methods]
Example 1: Synthesis of microcapsule of polyacrylic acid aqueous solution Glass ionomer cement CX-Plus liquid material (manufactured by Matsukaze Co., Ltd.) as a core material, condensed ricinoleic acid hexaglycerin (Sunsoft 818SX: Taiyo Kagaku Co., Ltd.) as an organic phase added surfactant Company), toluene as organic solvent, methyl methacrylate (MMA) as monomer, benzoyl peroxide as polymerization initiator (BPO: lyophilized product manufactured by Nacalai Tesque Co., Ltd.), ion-exchanged water as outer phase water, stable dispersion in outer phase water Gelatin (manufactured by Nacalai Tesque Co., Ltd.) was used as the agent.

First, 10 g of MMA containing 2% by weight (wt%) of BPO was dissolved in 50 mL of toluene containing 0.60 g of condensed ricinoleic acid hexaglycerin. To the organic phase, 25 mL of CX-Plus liquid material which is an aqueous phase in the core substance was stirred with a Hiscotron homogenizer at 5000 rpm for 10 minutes while cooling at 10 ° C. to prepare a primary dispersed phase.
Next, under heating at 60 ° C., gelatin was stirred and dissolved in 300 mL of ion-exchanged water so as to be 3 wt% to prepare an outer aqueous phase.
Thereafter, with the outer aqueous phase heated to 40 ° C., the primary dispersed phase was added at 500 rpm with a three-one motor stirrer to obtain a composite emulsion. While maintaining the rotation of the composite emulsion, the internal temperature was raised to 80 ° C. and heating was continued for 6 hours.
Thereafter, the inside of the reaction system was kept at a slightly reduced pressure, and the solvent was removed for about 2 hours. After completion of the reaction, the microcapsules synthesized by vacuum filtration were separated. Thereafter, washing with sufficient ion-exchanged water was performed, and hot air drying was performed at 40 ° C. to obtain a light yellow polyacrylic acid aqueous solution-containing microcapsule. The yield was 89%. As a result of the particle size analysis, the average particle size was about 200 μm. As a result of SEM observation, it was found that a relatively mononuclear structure was formed.

Examples 2 to 9: Production of microcapsules of polyacrylic acid aqueous solution The reagents were the same as in Example 1, but the conditions such as concentration and stirring were changed as shown in Table 1. However, the amount of toluene as an organic solvent was fixed at 50 mL.
From the results of SEM observation, it was found that depending on the composition, a multinuclear structure was also included.
Here, the “mononuclear structure” means a structure in which a single cavity exists in the capsule and the core substance is encapsulated inside the single cavity, and the “multinuclear structure” means This means a structure in which a plurality of cavities are present in the capsule, and a core substance is encapsulated in each of the plurality of cavities.
The properties of the obtained microcapsules are shown in Table 2.

Example 10: Synthesis of microcapsules of tartaric acid aqueous solution Tartaric acid aqueous solution adjusted to various concentrations as a core substance, Neugen ET-83 (Daiichi Kogyo Seiyaku Co., Ltd.) as an organic phase-added surfactant, and triethylene glycol dimethacrylate as a monomer (TEGDMA: manufactured by Shin-Nakamura Chemical Co., Ltd.), azoisobutyronitrile (AIBN) as a polymerization initiator, ion-exchanged water as outer phase water, degree of polymerization 3500 as dispersion stabilizer in outer phase water, degree of saponification 86.0 90.0 mol% polyvinyl alcohol (PVA: Wako Pure Chemical Industries, Ltd.) was used.
First, 1.50 g of ET-83 was dissolved in 50 mL of TEGDMA. To the organic phase, 25 mL of a 10 wt% aqueous tartaric acid solution as an aqueous phase in the core substance was stirred with a Hiscotron homogenizer at 5000 rpm for 10 minutes while cooling at 10 ° C. to prepare a primary dispersed phase.
Next, under heating at 70 ° C., PVA was stirred and dissolved in 300 mL of ion-exchanged water so as to be 5 wt% to prepare an outer aqueous phase.
Thereafter, with the outer aqueous phase heated to 40 ° C., the primary dispersed phase was added at 500 rpm with a three-one motor stirrer to obtain a composite emulsion. While maintaining the rotation of the composite emulsion, the internal temperature was raised to 80 ° C. and heating was continued for 6 hours. After completion of the polymerization reaction, the microcapsules synthesized by vacuum filtration were separated. Thereafter, washing with sufficient ion-exchanged water was performed, and white tartaric acid aqueous solution-containing microcapsules were obtained by drying with hot air at 40 ° C. The yield was 92%. As a result of the particle size analysis, the average particle size was about 100 μm. As a result of SEM observation, it was found that a relatively mononuclear structure was formed.

Examples 11 to 18: Synthesis of microcapsules of tartaric acid aqueous solution The reagents were the same as in Example 10, but the conditions such as concentration and stirring were changed as shown in Table 3.
The characteristics of the obtained microcapsules are shown in Table 4.

Examples 19 to 27: Synthesis of microcapsules of hydroxycarboxylic acid and polyacrylic acid aqueous solution The basic operation is the same as in Example 10, but the conditions such as monomer type / concentration, hydroxycarboxylic acid type / concentration are shown in Table 5. This was carried out with various changes. Surfactant (ET-83) was fixed at 1.50 g, and hydroxycarboxylic acid was used by dissolving in CX-Plus solution. The outer phase water was fixed to 5 wt% -300 mL of polyvinyl alcohol (PVA: Wako Pure Chemical Industries, Ltd.) having a polymerization degree of 3500 and a saponification degree of 86.0 to 90.0 mol%. The primary dispersion stirring speed and the secondary dispersion stirring speed were the same as in Example 10.
The characteristics of the obtained microcapsules are shown in Table 6.

Example 28: Synthesis of a wall capsule made of an inorganic material Ion exchange water as a core substance, Neugen ET-83 (Daiichi Kogyo Seiyaku Co., Ltd.) as an organic phase-added surfactant, and orthotetraethyl silicate (TEOS: Nacalai Tesque Co., Ltd.) as a monomer Manufactured by the company), 0.1M aqueous hydrogen chloride solution (HCl) as a polymerization initiator, ion-exchanged water as outer phase water, polyvinyl alcohol having a polymerization degree of 3500 and a saponification degree of 86.0 to 90.0 mol% as a dispersion stabilizer in the outer phase water. Alcohol (PVA) was used.
First, 1.50 g of ET-83 was dissolved in 50 mL of TEOS. To the organic phase, 25 mL of ion-exchanged water, which is an aqueous phase in the core material, was stirred with a Hiscotron homogenizer at 5000 rpm for 10 minutes while cooling at 10 ° C. to prepare a primary dispersed phase.
Next, under heating at 70 ° C., PVA was stirred and dissolved in 300 mL of ion-exchanged water so as to be 5 wt% to prepare an outer aqueous phase.
Thereafter, with the outer aqueous phase heated to 40 ° C., the primary dispersed phase was added at 500 rpm with a three-one motor stirrer to obtain a composite emulsion. Thereafter, 30 mL of HCl was added, and the internal temperature was raised to 80 ° C. while the composite emulsion was kept rotating, and heating was continued for 6 hours.
After completion of the polymerization reaction, the capsule container synthesized by filtration under reduced pressure was fractionated. Thereafter, washing with ion-exchanged water was performed, and the washing was completed when the pH of the washing water became neutral.
Then, it dried for 5 days with the freeze dryer, and obtained the comparatively bulky white capsule container. Thereafter, heat treatment was performed at 150 ° C. for 5 hours. The yield was 95%. As a result of the particle size analysis, the average particle size was about 200 μm. As a result of SEM observation, the cross section formed a mononuclear void structure.

Example 29
5.0 g of the hollow inorganic wall capsule obtained in Example 28 was dispersed in 50 mL of 1,3,5-trimethylbarbituric acid (TMBA) saturated water and shaken at 23 ° C. for 1 week in a shaker. Thereafter, the microcapsules enclosing the TMBA saturated water were separated by filtration, washed with a very small amount of ion-exchanged water, and dispersed in a solution of 1 wt% ethylcellulose / dichloromethane in 50 mL. The outer shell is instantaneously dried with a spray dryer at an inlet drying temperature of 80 ° C., a supply rate of 50 mL / min, a blower air volume of 0.5 m ³ / min, and a spray pressure of 100 kPa. Obtained a microcapsule having a silicon oxide and a core material saturated with 1,3,5-trimethylbarbituric acid.

Examples 30-34
Instead of the TMBA saturated water of Example 29, microcapsules were synthesized using saturated water of the compounds described in Table 7.

Example 35
5.0 g of the hollow inorganic wall capsule obtained in Example 28 was placed in a high vacuum state of 0.05 Torr, stirred with an electromagnetic induction stirrer, and 50 mL of triethylene glycol dimethacrylate (TEGDMA) was injected. Thereafter, the microcapsules enclosing the TEGDMA were separated by filtration, washed with a very small amount of ethanol, and dispersed in 50 mL of a 1 wt% PVA aqueous solution. The suspension is instantaneously dried with a spray dryer at an inlet drying temperature of 100 ° C., a supply rate of 50 mL / min, a blower air volume of 0.5 m ³ / min, and a spraying pressure of 100 kPa. Microcapsules having a shell of silicon oxide and a cored material of TEGDMA were obtained.

Examples 36-40
Instead of TEGDMA in Example 35, microcapsules were synthesized using the compounds described in Table 8.

Example 41: Synthesis of microcapsule of polyacrylic acid aqueous solution by submerged drying method Glass ionomer cement CX-Plus liquid material (manufactured by Matsukaze Co., Ltd.) as a core substance, condensed ricinoleate hexaglycerin (Sunsoft) as an organic phase-added surfactant 818SX: Taiyo Kagaku Co., Ltd.), polymethyl methacrylate as wall polymer (PMMA: manufactured by Mitsubishi Rayon), ethyl acetate as organic solvent, ion-exchanged water as outer phase water, gelatin as dispersion stabilizer in outer phase water (Nacalai Tesque) Used).
First, 10 g of PMMA was dissolved in 50 mL of ethyl acetate containing 0.60 g of hexaglycerin condensed ricinoleate. To the organic phase, 25 mL of CX-Plus liquid material, which is an aqueous phase in the core substance, was stirred with a Hiscotron homogenizer at 5000 rpm for 10 minutes while cooling at 10 ° C. to prepare a primary dispersed phase.
Next, under heating at 60 ° C., gelatin was stirred and dissolved in 300 mL of ion-exchanged water so as to be 3 wt% to prepare an outer aqueous phase.
Thereafter, with the outer aqueous phase heated to 40 ° C., the primary dispersed phase was added at 500 rpm with a three-one motor agitator to obtain a composite emulsion. The composite emulsion was kept heated and stirred under reduced pressure for 6 hours while maintaining the internal temperature while maintaining the rotation.
After the solvent removal, the microcapsules synthesized by vacuum filtration were separated. Thereafter, washing with sufficient ion-exchanged water was performed, and hot air drying was performed at 40 ° C. to obtain a light yellow polyacrylic acid aqueous solution-encapsulating microcapsule. The yield was 95%. As a result of the particle size analysis, the average particle size was about 150 μm. From SEM observation, it was found that a relatively multinuclear structure was formed.

Example 42: Synthesis of microcapsules of inorganic powder-dispersed monomer by in-liquid drying method Bis-GMA / TEGDMA (60/40) in which glass ionomer cement CX-Plus powder material (manufactured by Matsukaze Co., Ltd.) was dispersed as a core material by 50 wt%. , Wt%) mixed monomer suspension, polyvinyl alcohol (PVA) as the wall material polymer, castor oil as the outer phase oil phase, absolute ethanol as the dilute agglomerate, formalin as the PVA hardener, and 6M aqueous hydrogen chloride solution.
First, 25 mL of Bis-GMA / TEGDMA (60/40, wt%) mixed monomer suspension in which 50 wt% of CX-Plus powder material as a core material phase is dispersed in 50 mL of 10 wt% PVA aqueous solution is 750 rpm with a Hiscotron homogenizer. The mixture was stirred for 10 minutes under cooling at 10 ° C. to adjust the primary dispersed phase. Next, the primary dispersed phase was added to 300 mL of castor oil at 500 rpm with a three-one motor agitator while cooling at 10 ° C. to obtain a [(O / W) / O] type composite emulsion.
Next, 300 mL of absolute ethanol was added to partially dehydrate the PVA aqueous solution phase, which is a wall material precursor, and then 5 mL of 6 M hydrogen chloride aqueous solution and 15 mL of formalin were added and cured by heating at 90 ° C. for 20 minutes. Thereafter, the solution was filtered under reduced pressure, washed with a large amount of ion-exchanged water, and dried in an oven at 40 ° C. to obtain microcapsules. The yield was 85%. As a result of the particle size analysis, the average particle size was about 250 μm. The color of the capsule was slightly dull beige.

Example 43: Synthesis of microcapsules by interfacial polymerization (1)
An aqueous phase was prepared by dissolving 0.35 g of 1,6-hexanediamine (manufactured by Aldrich), 0.36 g of sodium carbonate and 0.5 g of TW-20 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in 50 g of ion-exchanged water. To this prepared aqueous phase, 25 g of triethylene glycol dimethacrylate (TEGDMA: manufactured by Shin-Nakamura Chemical Co., Ltd.) was stirred with a Hiscotron homogenizer at 700 rpm for 10 minutes under cooling at 10 ° C. to obtain an oil / water (O / W) solution. A primary dispersed phase was prepared.
Next, in a mixed organic solvent of chloroform / cyclohexane (= 1/4) containing 1 wt% of Sorgen 30 (Daiichi Kogyo Seiyaku Co., Ltd.), the primary dispersed phase is cooled at 5 ° C. under 500 rpm with a three-one motor agitator. To obtain a [(O / W) / O] type composite emulsion. While continuing stirring, 50 mL of a mixed organic solvent of chloroform / cyclohexane (= 1/4) in which 0.55 g of adipic acid chloride (manufactured by Aldrich) was dissolved was added. After stirring for about 1 hour, the microcapsules were separated by filtration and washed with cyclohexane. Microcapsules enclosing the obtained TEGDMA were obtained. The yield was 97%. As a result of the particle size analysis, the average particle size was about 710 μm. The color of the capsule was slightly white and highly transparent.

Examples 44-48
Instead of TEGDMA in Example 43, microcapsules were synthesized using the compounds described in Table 9.

Example 49: Synthesis of microcapsules by interfacial polymerization (2)
A continuous phase was prepared by dissolving 1.00 g of polyvinyl alcohol (Wako Pure Chemicals # 500) in 150 g of ion-exchanged water. To this prepared continuous phase, a homogeneous solution of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 mL of ethylene glycol dimethacrylate (EGDNA) was stirred with a histone colon homogenizer at 1000 rpm for 10 minutes at 23 ° C. An emulsion of / water (O / W) was prepared.
While stirring this emulsion at 60 ° C. with a three-one motor stirrer at 500 rpm, 20.0 g of ion-exchanged water in which 1.00 g of hexamethylenetetramine (manufactured by Kanto Chemical) was dissolved as a water-soluble monomer was added to the dropping funnel. The solution was added dropwise over 1 hour. After completion of dropping, the reaction was carried out for 10 hours while maintaining stirring and heating.
After completion of the reaction, the microcapsules were separated by filtration under reduced pressure, and washed with ion-exchanged water and n-hexane. The microcapsule which included the obtained EGDMA was obtained. The yield was 97%. As a result of the particle size analysis, the average particle size was about 75 μm. The color of the capsule was light yellow and highly transparent.

Examples 50-54
Instead of EGDMA in Example 49, microcapsules were synthesized using the compounds described in Table 10.

Example 55: Synthesis of microcapsules by interfacial polymerization (3)
A continuous phase was prepared by dissolving 1.00 g of polyvinyl alcohol (Wako Pure Chemicals # 500) in 150 g of ion-exchanged water. To this prepared continuous phase, a homogeneous solution of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 mL of ethylene glycol dimethacrylate (EGDNA) was stirred with a histone colon homogenizer at 1000 rpm for 10 minutes at 23 ° C. An emulsion of / water (O / W) was prepared.
While stirring this emulsion at 60 ° C. with a three-one motor stirrer at 500 rpm, 20.0 g of ion-exchanged water in which 1.00 g of carbodihydrazide (manufactured by Tokyo Kasei Kogyo) was dissolved as a water-soluble monomer was added to a dropping funnel. The solution was added dropwise over 1 hour. After completion of dropping, the reaction was carried out for 10 hours while maintaining stirring and heating.
After completion of the reaction, the microcapsules were separated by filtration under reduced pressure, and washed with ion-exchanged water and n-hexane. The microcapsule which included the obtained EGDMA was obtained. The yield was 97%. As a result of the particle size analysis, the average particle size was about 75 μm. The color of the capsule was light yellow and highly transparent.

Examples 56-60
Microcapsules were synthesized using the water-soluble monomers listed in Table 11 instead of the carbodihydrazide of Example 55. The amount added was fixed at 1.00 g.

Example 61: Preparation of one-paste glass ionomer 10 g of 1 wt% polyvinyl alcohol in a 100 mL polyethylene container for non-bubbling kneader NBK-2 (manufactured by Sinky), 5 g of the microcapsules synthesized in Example 1 and glass ionomer 7 g of cement CX-Plus powder material (manufactured by Matsukaze Co., Ltd.) was added and mixed at 23 ° C. for 5 minutes at a rotation speed of 200 rpm to prepare a one paste glass ionomer cement.
The prepared one paste glass ionomer cement was filled in a hermetic container and subjected to a forced test at 50 ° C., but no gelation was observed after 3 months. Further, when 1 g of this one paste glass ionomer cement was subjected to ultrasonic vibration with an output of 200 W-20 kHz for 10 seconds at 23 ° C., gelation occurred at 23 ° C. 3 minutes after the start of vibration, and completely cured after 9 minutes. did.

Examples 62 to 69: Preparation of one paste glass ionomer cement The basic composition and operation are the same as in Example 61, but the various CX-Plus liquid materials of Examples 2 to 9 are encapsulated as microcapsules to be added. One paste glass ionomer cement was prepared using 5 g of the capsule.
The prepared one-paste glass ionomer cement was filled in a hermetic container and subjected to a forced test at 50 ° C. Furthermore, the gelation and curing time was measured when 1 g of this one paste glass ionomer cement was subjected to ultrasonic vibration with an output of 200 W-20 kHz at 23 ° C. for 10 seconds. The test results are shown in Table 12.

Example 70: Preparation of one paste glass ionomer cement 10 g of 1 wt% polyvinyl alcohol in a 100 mL polyethylene container for non-bubbling kneader NBK-2 (manufactured by Sinky), 5 g of microcapsules synthesized in Example 1 1 g of the microcapsules synthesized in Example 10 and 7 g of glass ionomer CX-Plus powder material (manufactured by Matsukaze Co., Ltd.) were added and mixed at 23 ° C. for 5 minutes at a rotation speed of 200 rpm to prepare a one-paste glass ionomer cement.
The prepared one paste glass ionomer cement was filled in a hermetic container and subjected to a forced test at 50 ° C., but no gelation was observed after 3 months. Further, when 1 g of this one paste glass ionomer cement was subjected to ultrasonic vibration with an output of 200 W-20 kHz for 10 seconds at 23 ° C., gelation occurred at 23 ° C. after 3.5 minutes from the start of vibration, and after 8 minutes. Completely cured.

Examples 71 to 78: Preparation of One Paste Glass Ionomer Cement The basic composition and operation are the same as in Example 70, but the microcapsules to be added enclose various CX-Plus liquid materials of Examples 2 to 9. Capsules and tartaric acid-encapsulated capsules of Examples 11 to 18 were added in the same manner to prepare a one paste glass ionomer cement.
The prepared one-paste glass ionomer cement was filled in a hermetic container and subjected to a forced test at 50 ° C. Furthermore, the gelation and curing time was measured when 1 g of this one paste glass ionomer cement was subjected to ultrasonic vibration with an output of 200 W-20 kHz at 23 ° C. for 10 seconds. These results are shown in Table 13.

Comparative Example 1
Non-Bubbling Kneader NBK-2 (manufactured by Sinky Corporation) in a 100 mL polyethylene container 10 g of 1 wt% polyvinyl alcohol, 5 g of glass ionomer CX-Plus liquid material (manufactured by Matsukaze Co., Ltd.) and glass ionomer CX-Plus powder material (stock) 7g) and mixed at 23 ° C. for 5 minutes. During mixing, gelation occurred due to initiation of acid-base reaction.
From this result, it was found that it was impossible to prepare a one-paste glass ionomer cement without using the microcapsules as described in Example 1.

Example 79: Preparation of One Paste Resin Modified Glass Ionomer Cement 10 g of mixed monomer of Bis-GMA / TEGDMA (40/60, wt%) in a 100 mL polyethylene container for non-bubbling kneader NBK-2 (Sinky) 7 g of the microcapsules encapsulating the polyacrylic acid synthesized in Example 19, 0.5 g of the microcapsules encapsulating the catalyst (saturated aqueous solution of potassium persulfate) synthesized in Example 33, and the catalyst synthesized in Example 34 (Ascorbic acid saturated aqueous solution) 0.5 g of encapsulated microcapsules and 7 g of glass ionomer CX-Plus powder material (manufactured by Matsukaze Co., Ltd.) are added and mixed at 23 ° C. for 5 minutes at a rotation speed of 200 rpm, and one paste resin modified glass ionomer Cement was prepared.
The prepared one paste glass ionomer cement was filled in a hermetic container and subjected to a forced test at 50 ° C., but no gelation was observed after 3 months. Further, when 1 g of this one paste resin modified glass ionomer cement was subjected to ultrasonic vibration with an output of 200 W-20 kHz for 10 seconds at 23 ° C., gelation occurred at 23 ° C. after 3.5 minutes from the start of vibration. Completely cured after a minute.

Examples 80-87: Preparation of One Paste Resin Modified Glass Ionomer Cement The basic formulation and operation are the same as in Example 79, but the microcapsules added are the glass ionomers CX-Plus of Examples 20 to 27. A liquid material and a hydroxycarboxylic acid-encapsulated capsule were added to prepare a one paste resin modified glass ionomer cement.
The prepared one-paste glass ionomer cement was filled in a hermetic container and subjected to a forced test at 50 ° C. Furthermore, gelation and curing time were measured when 1 g of this one paste resin modified glass ionomer cement was subjected to ultrasonic vibration with an output of 200 W-20 kHz at 23 ° C. for 10 seconds. Table 14 shows the results.

Comparative Example 2
Mixing of 10 g of Bis-GMA / TEGDMA (40/60, wt%) mixed monomer and 1.0 g of tartaric acid / 25 ml of CX-Plus liquid material into a 100 mL polyethylene container for non-bubbling kneader NBK-2 (manufactured by Sinky) 7 g of liquid, 0.5 g of saturated aqueous potassium persulfate solution, 0.5 g of saturated aqueous ascorbic acid solution and 7 g of glass ionomer CX-Plus powder material (manufactured by Matsukaze Co., Ltd.) were added and mixed at 23 ° C. for 5 minutes at a rotation speed of 200 rpm. did. During mixing, gelation occurred due to initiation of acid-base reaction and redox polymerization reaction.
From this result, it was found that it was impossible to prepare a one paste glass ionomer cement without using the microcapsules as described in Examples 19, 33 and 34.

Example 88: Preparation and curing time of one paste resin modified glass ionomer cement 10 g of glass ionomer CX-Plus liquid material (manufactured by Matsukaze Co., Ltd.) in a 100 mL polyethylene container for non-bubbling kneader NBK-2 (manufactured by Sinky) 10 g of microcapsules encapsulating the glass ionomer CX-Plus powder material synthesized in Example 42 and monomers, and 0.5 g of microcapsules encapsulating the catalyst (saturated aqueous solution of potassium persulfate) synthesized in Example 33 One-paste resin modified glass ionomer cement was prepared by adding 0.5 g of the catalyst (ascorbic acid saturated aqueous solution) -encapsulated microcapsule synthesized in Example 34 and mixing at 23 ° C. for 5 minutes at a rotation speed of 200 rpm.
The prepared one paste glass ionomer cement was filled in a hermetic container and subjected to a forced test at 50 ° C., but no gelation was observed after 3 months. When 1 g of this one-paste resin modified glass ionomer cement was subjected to ultrasonic vibration with an output of 200 W-20 kHz for 10 seconds at 23 ° C., gelation occurred at 4.0 ° C. after the start of vibration at 23 ° C. Completely cured after a minute.

[One paste (resin modified) glass ionomer cement tooth-metal bond strength and compressive strength]
Using the one paste glass ionomer cement of Examples 62 to 78 and the one paste resin modified glass ionomer cement of Examples 79 to 88 of the one-part curable composition of the present invention, The thickness and compressive strength were measured.

[Shear adhesion test]
The tooth quality was changed to human teeth and freshly extracted bovine anterior teeth were used. The roots were removed and the pulp removed, and then embedded in epoxy resin. The lip surface enamel and dentin of the bovine teeth were polished with water-resistant polishing paper No. 80 under water pouring and then polished with water No. 600 under water pouring, and the polished tooth surfaces were dried with compressed air containing no oil. Further, an aluminum oxide powder was sprayed on the adhesion surface of the stainless steel rod (diameter 5 mm, length 12 mm) to perform sandblasting.
Subsequently, 1 g of the one paste (resin modified) glass ionomer cement of Examples 62 to 88 was subjected to ultrasonic vibration with an output of 200 W-20 kHz for 10 seconds at 23 ° C., and the pastes in which the reaction was started were interposed. A stainless steel rod was joined to the tooth surface subjected to the adhesion treatment, a load of 200 g was applied, and the paste mud protruding from the adhesion interface was removed with a blade.
Then, it left still for 1 hour in a 100% humidity wet box, and was immersed in 37 degreeC distilled water. 24 hours after adhesion, the shear adhesion test specimen was measured with a Instron universal testing machine (Instron 5567, Instron) at a crosshead speed of 1 mm / min, and the average of n = 7 The value was determined. The results are shown in Table 15.

[Measurement of compressive strength]
Using the one paste (resin modified) glass ionomer cement of Examples 62 to 88, a compression strength test specimen (diameter 3 mm, height 6 mm) was produced according to the ISO standard. The prepared specimen was immersed in distilled water at 37 ° C. for 24 hours, and then the compressive strength was measured at a crosshead speed of 1 mm / min using an Instron universal testing machine, and an average value of n = 5 was obtained. The results are shown in Table 15.

Example 89
Disperse 5.0 g of the hollow inorganic wall capsule obtained in Example 28 in 50 mL of 1-benzyl-5-phenylbarbituric acid sodium salt (BPBA-Na) saturated water and shake at 23 ° C. for 1 week with a shaker. did.
Thereafter, the microcapsules enclosing the BPBA-Na saturated water were separated by filtration, washed with a very small amount of ion-exchanged water, and dispersed in a solution of 1 wt% ethylcellulose / dichloromethane in 50 mL. The suspension was instantaneously dried with a spray drier at an inlet drying temperature of 80 ° C., a supply rate of 50 mL / min, a blower air volume of 0.5 m ³ / min, and a spray pressure of 100 kPa. Microcapsules were obtained in which the shell was silicon oxide and the core material was 1-benzyl-5-phenylbarbituric acid sodium salt saturated water.

Examples 90-98
Microcapsules were synthesized using the saturated water of the compounds described in Table 16 instead of the BPBA-Na saturated water of Example 89.

Example 99
While placing 5.0 g of the hollow inorganic wall capsule obtained in Example 28 in a high vacuum state of 0.05 Torr, stirring with an electromagnetic induction stirrer, 50 mL of 4-acryloxyethyl trimellitic acid (4-AET) saturated water was added. Injected. Thereafter, the microcapsules enclosing the TEGDMA were separated by filtration, washed with a very small amount of ethanol, and dispersed in 50 mL of a 1 wt% PVA aqueous solution. The suspension is instantaneously dried with a spray dryer at an inlet drying temperature of 100 ° C., a supply rate of 50 mL / min, a blower air volume of 0.5 m ³ / min, and a spraying pressure of 100 kPa. Microcapsules having a shell of silicon oxide and a core material of TEGDMA were obtained.

Examples 100-104
Microcapsules were synthesized using the compounds described in Table 17 instead of TEGDMA in Example 99.

Example 105: Preparation of one-paste resin cement 14 g of mixed monomer of Bis-GMA / TEGDMA (40/60, wt%), 2-hydroxyethyl in a polyethylene container for non-bubbling kneader NBK-2 (Sinky) 2 g of methacrylate, 2 g of 4-methacryloxyethyl trimellitic anhydride (4-META), 2 g of 6-methacryloxyhexylphosphonoacetate (6-MHPA), synthesized in Example 30, N, N-di 0.2 g of microcapsules encapsulating (hydroxyethyl) -p-toluidine (DEPT), 0.2 g of microcapsules encapsulating benzoyl peroxide (BPO) synthesized in Example 96, synthesized in Example 92 0.2 g of microcapsules encapsulating 1-cyclohexyl-5-ethylbarbituric acid (CEBA), butylated hydride Add 800 ppm of roxytoluene, 40 g of silane-treated silica filler (average particle size: 5 μm) and 2 g of ultrafine filler (Aerosil R-972: manufactured by Nippon Aerosil Co., Ltd.) and mix at 23 ° C. for 20 minutes at a rotation speed of 200 rpm. -A paste resin cement was prepared.
The prepared one-paste resin cement was filled into a hermetic container and subjected to a forced test at 50 ° C., but no gelation was observed after 3 months. Further, when 1 g of this one-paste resin cement was subjected to ultrasonic vibration with an output of 200 W-20 kHz for 10 seconds at 23 ° C., gelation occurred at 23 ° C. after 3.5 minutes from the start of vibration, and complete after 6 minutes. Cured.

Example 106: Preparation of One Paste Dual Cure Resin Cement The basic formulation and operation is the same as in Example 105 except that 6-methacryloxyhexylphosphonoacetate (6-MHPA) is replaced with 6-methacryloxyhexylphospho. A one-paste resin cement was prepared in the same manner as in Example 105 except that it was replaced with nopropionate (6-MHPP) and 0.1 g of 2,4,6-trimethylbenzoylphenylphosphine oxide was added.
The prepared one-paste resin cement was filled into a hermetic container and subjected to a forced test at 50 ° C., but no gelation was observed after 3 months. Further, in the dark room, 1 g of this one-paste resin cement was subjected to ultrasonic vibration with an output of 200 W-20 kHz for 10 seconds at 23 ° C., and at 23 ° C., gelation occurred 3.5 minutes after the start of vibration. Fully cured after 6 minutes.
On the other hand, 1 g of this one paste resin cement was subjected to ultrasonic vibration with an output of 200 W-20 kHz for 10 seconds at 23 ° C., and then irradiated with visible light with Matsukaze Griplight II (manufactured by Matsukaze Co., Ltd.) 2 minutes later. It was confirmed that it was a one-paste resin cement that was instantly photocured and capable of chemical and photopolymerization (dual cure).

Example 107: Preparation of One Paste Dual Cure Resin Cement The basic formulation and operation is the same as the one paste dual cure resin cement of Example 106, 0.1 g D, L-camphorquinone, and 3,3 A one-paste resin cement was prepared in the same manner as in Example 106 except that 0.001 g of '-carbonylbis (7-diethylaminocoumarin) was added.
The prepared one-paste resin cement was filled into a hermetic container and subjected to a forced test at 50 ° C., but no gelation was observed after 3 months. Further, in a dark room, 1 g of this one paste resin cement was subjected to ultrasonic vibration with an output of 200 W-20 kHz for 10 seconds at 23 ° C., and gelation occurred at 23 ° C. after 3 minutes from the start of vibration. Later it was fully cured.
On the other hand, 1 g of this one-paste resin cement was subjected to ultrasonic vibration with an output of 200 W-20 kHz for 10 seconds at 23 ° C., and then irradiated with light after 2 minutes. Here, the light irradiator is Matsukaze Grip Light II (Hal) using a halogen lamp (manufactured by Matsukaze Co., Ltd.), and a light-emitting diode (LED) irradiator Eliper Free Light 2 (LED) (manufactured by 3M Esper) Also, Xenon lamp Apollo Elite 95E (Xe) (manufactured by DMD) was used. The illuminance measurement wavelength region of these irradiators was set to 400 to 515 nm.
From the above test results, it was confirmed that this one-paste resin cement was a dual cure and was a one-paste resin cement capable of photopolymerization in a multi-wavelength region (400 to 515 nm).

[Don paste-metal bond strength and bending strength of one paste resin cement]
Using the one-paste resin cements of Examples 105 to 107 of the one-part curable composition of the present invention, the adhesive strength and bending strength between tooth and metal were measured.

[Shear adhesion test]
The tooth quality was changed to human teeth and freshly extracted bovine anterior teeth were used. The roots were removed and the pulp removed, and then embedded in epoxy resin. The lip surface enamel and dentin of the bovine teeth were polished with water-resistant polishing paper No. 80 under water pouring and then polished with water No. 600 under water pouring, and the polished tooth surfaces were dried with compressed air containing no oil.
Next, equal amounts of the primer A solution and the B solution of “Impervafluorobond” (manufactured by Matsukaze Co., Ltd.), a photopolymerization type dental bonding agent, were collected in an eye plate and mixed with a microbrush. The mixed solution was applied with a microbrush so as to be rubbed against the prescribed surface of enamel or dentin (rubbing treatment or active treatment), and after 20 seconds, volatile components were evaporated with compressed air containing no oil.

Further, an aluminum oxide powder was sprayed on the adhesion surface of the stainless steel rod (diameter 5 mm, length 12 mm) to perform sandblasting. Subsequently, ultrasonic vibration with an output of 200 W-20 kHz was applied to 1 g of the one-paste resin cement of Examples 105 to 107 at 23 ° C. for 10 seconds, and each of the pastes in which the reaction was started was interposed to complete the above-mentioned adhesion treatment. A stainless steel rod was joined to the tooth surface, a load of 200 g was applied, and the paste mud protruding from the adhesive interface was removed with a blade.
Subsequently, the adhesion interface was irradiated with light for 20 seconds from an oblique direction using a pine-style grip light II (Hal: halogen lamp). Thereafter, the shear bond strength test was performed by immersing the test specimen in 37 ° C. distilled water for 24 hours, and using an Instron universal testing machine (Instron 5567, Instron) at a crosshead speed of 1 mm / min. An average value of 7 was obtained. The results are shown in Table 18.

[Measurement of bending strength]
Using the one-paste resin cements of Examples 93 to 95, a three-point bending test was performed according to the ISO standard. Take a prototype one-paste resin cement, fill it with a plastic spatula into a bending test specimen, press it with a cover glass, and irradiate it with a pine wind grip light II (manufactured by Matsukaze Co., Ltd.) for 30 seconds to bend the specimen ( 25 × 2.0 × 2.0, mm), immersed in distilled water at 37 ° C. for 24 hours, measured with an Instron universal tester at a crosshead speed of 1 mm / min, and an average value of n = 5 Asked. The results are shown in Table 18.

Comparative Example 3
14 g of mixed monomer of Bis-GMA / TEGDMA (40/60, wt%), 2 g of 2-hydroxyethyl methacrylate, 4-methacryloxyethyl trimellit in a polyethylene container for non-bubbling kneader NBK-2 (manufactured by Sinky) 2 g of acid anhydride (4-META), 2 g of 6-methacryloxyhexylphosphonoacetate (6-MHPA), 0.2 g of N, N-di (hydroxyethyl) -p-toluidine (DEPT), peroxide 0.2 g of benzoyl (BPO), 0.2 g of 1-cyclohexyl-5-ethylbarbituric acid (CEBA), 800 ppm of butylated hydroxytoluene, 40 g of silanized silica filler (average particle size: 5 μm), ultrafine particles 2 g of filler (Aerosil R-972: manufactured by Nippon Aerosil Co., Ltd.) was added and 20 at 23 ° C. at a rotation speed of 200 rpm. It was mixed between. During mixing, gelation occurred due to initiation of redox polymerization reaction.
From this result, it was found that it was impossible to prepare a one paste glass ionomer cement without using microcapsules as described in Examples 30, 96 and 92.

Examples 108-117 and Comparative Examples 4-5
The curable composition of the present invention was examined in the form of a one-pack one-step photopolymerizable bonding agent. As microcapsules, microcapsules of sodium p-toluenesulfinate synthesized in Example 31 (capsule 31), 2,4,6-trimethylbenzoylphenylphosphine oxide sodium (TBPO-Na) synthesized in Example 97 (capsule) 97), 6- (meth) acryloxyhexyl-3-phosphonoacetate (6-MHPA), 6- (meth) acryloxyhexyl-3-phosphonopropionate (6-MHPP) as radical polymerizable monomers, 4-methacryloxyethyl trimellitic acid (4-MET), 4-methacryloxyethyl trimellitic anhydride (4-META), 2-hydroxyethyl methacrylate (HEMA), Bis-GMA / TEGDMA (= 60/40, wt%) (Bis-GSol.) as a polymerization initiator, 2,4,6-trimethylbenzoylphenylphos Dioxide (TBPO), D, L-camphorquinone (CQ), 1-benzyl-5-phenylbarbituric acid (BPBA), N, N-dimethylaminobenzoic acid (DMBE), di-n- as a polymerization accelerator Octyl tin dilaurate (Tin-Lau), acetone, and Aerosil R-972 (3 parts by weight) were mixed to prepare a one-pack one-step photopolymerizable bonding agent having the composition shown in Table 19.
Subsequently, enamel and dentin were prepared in accordance with Example 88, a photopolymerizable bonding agent was applied using water remaining on the tooth surface, and allowed to stand for 20 seconds. ”(Manufactured by Matsukaze Co., Ltd.) and photopolymerized for 30 seconds to prepare a test specimen, and after 24 hours of immersion in 37 ° C. water, a shear adhesion test was conducted according to Example 88. The results are shown in Table 19.

Examples 118-121
The curable composition of the present invention was examined in the form of a one-pack one-step photopolymerizable bonding agent.
Sodium p-toluenesulfinate microcapsules synthesized in Example 31 (3 parts by weight), 2,4,6-trimethylbenzoylphenylphosphine oxide sodium (TBPO-Na) synthesized in Example 97 (2 parts by weight) 6- (meth) acryloxyhexyl-3-phosphonoacetate (6-MHPA) (15 parts by weight), 4-methacryloxyethyl trimellitic acid (4-MET) (20 parts by weight) as radical polymerizable monomers, 2-hydroxyethyl methacrylate (HEMA) (7 parts by weight), Bis-GMA / TEGDMA (= 60/40, wt%) (28 parts by weight), 2,4,6-trimethylbenzoylphenylphosphine oxide as a polymerization initiator (TBPO) (1 part by weight), CQ (1 part by weight), 3,3′-carbonylbis (7-diethylamino) as a coumarin compound Nocoumarin) (0.005 parts by weight), acetone (30 parts by weight), and Aerosil R-972 (3 parts by weight) were mixed to prepare “Bond A”.
Only “Bond A” coumarin compound was replaced with 3,3′-carbonylbis (7-dibutylaminocoumarin) (0.005 parts by weight) to prepare “Bond B”.
The 6-MHPA of “Bond A” and “Bond B” was replaced with 6- (meth) acryloxyhexyl-3-phosphonopropionate (6-MHPP) (15 parts by weight) to obtain “Bond C” and “ Bond D "was prepared.
A shear adhesion test was conducted in accordance with Example 108 using one-component, one-step photopolymerizable bonding agent, Bonds A to D. The results are shown in Table 20.

Here, the light irradiator is a Matsukaze Grip Light II (Hal) using a halogen lamp (manufactured by Matsukaze Co., Ltd.), and a light emitting diode (LED) irradiator Eliper Free Light 2 (LED) (manufactured by 3M Esper) And Xenon lamp Apollo Elite 95E (Xe) (manufactured by DMD). Illuminance of each light irradiator was used at Matsukaze Grip Light II: 650 mW / cm ² , Eliper Free Light 2: 635 mW / cm ^2, and APPOLLOELITE 95E: 1330 mW / cm ² . The illuminance measurement wavelength region of these irradiators was set to 400 to 515 nm.

As is apparent from the results of Table 20, acylcapsule phosphine oxide and its sodium salt and p-toluenesulfinic acid sodium salt microcapsules, α-diketone, coumarin compound, and polymerization constituting the one-part curable composition of the present invention. The photopolymerizable composition containing the accelerator showed high photocurability in any light irradiation of halogen light, LED and xenon lamp, and as a result, showed high enamel adhesion and dentin adhesion.
By coexisting the visible light sensitization effect of coumarin compounds and photopolymerization initiators such as APO-Na and α-diketone encapsulated in microcapsules, three types of light irradiators can be used for a wide range of wavelengths. Even when used, it is considered that high adhesive strength was exhibited.

Example 122: Preparation of two-paste resin cement 14 g of mixed monomer of Bis-GMA / TEGDMA (40/60, wt%), 2-hydroxyethyl in a polyethylene container for non-bubbling kneader NBK-2 (Sinky Corporation) 2 g of methacrylate, 2 g of 4-methacryloxyethyl trimellitic anhydride (4-META), 2 g of 6-methacryloxyhexylphosphonoacetate (6-MHPA), benzoyl peroxide (BPO) synthesized in Example 96 0.2 g of microcapsules encapsulating 1), 0.2 g of microcapsules encapsulating 1-cyclohexyl-5-ethylbarbituric acid (CEBA) synthesized in Example 92, 800 ppm of butylated hydroxytoluene, silane treatment 40 g silica filler (average particle size: 5 μm), ultrafine filler (Aero Le R-972: were mixed at 23 ° C. at a rotational speed of 200rpm added Nippon Aerosil Co., Ltd.) 2 g 20 minutes to prepare a paste A. Similarly, 20 g of a mixed monomer of Bis-GMA / TEGDMA (40/60, wt%) and a microcapsule containing N, N-di (hydroxyethyl) -p-toluidine (DEPT) synthesized in Example 30 0.2 g, 40 g of silane-treated silica filler (average particle size: 5 μm), and 2 g of ultrafine filler (Aerosil R-972) were mixed to prepare paste B.
The prepared paste A and paste B were filled in a hermetic container and subjected to a forced test at 50 ° C., but no gelation was observed after 3 months. Moreover, when ultrasonic vibration with an output of 200 W-20 kHz was applied to 1 g of an equal amount paste of paste A and paste B for 10 seconds at 23 ° C., gelation occurred at 23 ° C. after 3.5 minutes from the start of vibration, Fully cured after 6 minutes. Further, this mixed paste remained in a mud state even after one day without applying ultrasonic vibration.

Example 123: Preparation of a two-paste dual cure resin cement The basic formulation and operation are the same as in Example 122 except that 6-methacryloxyhexylphosphonoacetate (6-MHPA) is replaced with 6-methacryloxyhexylphospho. A two-paste resin cement was prepared in the same manner as in Example 122 except that it was replaced with nopropionate (6-MHPP) and 0.1 g of 2,4,6-trimethylbenzoylphenylphosphine oxide was further added.
The prepared two-paste resin cement paste A and paste B were filled into a hermetic container and subjected to a forced test at 50 ° C., but no gelation was observed after 3 months. Further, in the dark room, 1 g of paste A and paste B in an equal amount mixed paste was subjected to ultrasonic vibration with an output of 200 W-20 kHz for 10 seconds at 23 ° C., and after 23 minutes at 3.5 ° C. Occurred and was fully cured after 6 minutes.
On the other hand, an ultrasonic vibration with an output of 200 W-20 kHz was applied to 1 g of an equal amount paste of paste A and paste B at 23 ° C. for 10 seconds, and then 2 minutes later, a pine wind grip light II (manufactured by Matsukaze Co., Ltd.) visible light. When irradiated, it was instantly photocured and confirmed to be a two-paste resin cement capable of chemical and photopolymerization (dual cure). In addition, this mixed paste was kept in a muddy state even after one day under the shading cover without applying ultrasonic vibration.

Example 124: Preparation of a two-paste dual cure resin cement The basic formulation and operation was as follows: paste B of the two-paste dual cure resin cement of Example 123, 0.1 g of D, L-camphorquinone, and A two-paste resin cement was prepared in the same manner as in Example 123 except that 0.001 g of 3,3′-carbonylbis (7-diethylaminocoumarin) was added.
The prepared two-paste resin cement paste A and paste B were filled into a hermetic container and subjected to a forced test at 50 ° C., but no gelation was observed after 3 months. In addition, when an ultrasonic vibration with an output of 200 W-20 kHz was applied to 1 g of an equal amount mixed paste of paste A and paste B at 23 ° C. for 10 seconds in a dark room, gelation occurred at 23 ° C. after 3 minutes from the start of vibration. Produced and fully cured after 6 minutes.
On the other hand, an ultrasonic vibration having an output of 200 W-20 kHz was applied to 1 g of an equal amount paste of paste A and paste B for 10 seconds at 23 ° C., and then light-irradiated 2 minutes later. Here, the light irradiator is Matsukaze Grip Light II (Hal) using a halogen lamp (manufactured by Matsukaze Co., Ltd.), and a light-emitting diode (LED) irradiator Eliper Free Light 2 (LED) (manufactured by 3M Esper) Also, Xenon lamp Apollo Elite 95E (Xe) (manufactured by DMD) was used. The illuminance measurement wavelength region of these irradiators was set to 400 to 515 nm.
From the above test results, it was confirmed that this two-paste resin cement was a dual cure and was a two-paste resin cement capable of photopolymerization in a multi-wavelength region (400 to 515 nm).

[Tooth-resin cement tooth-metal bond strength and bending strength]
Using the two-paste resin cements of Examples 122-124 of the bipartite curable composition of the present invention, the bond strength and bending strength between tooth and metal were measured.

[Shear adhesion test]
The tooth quality was changed to human teeth and freshly extracted bovine anterior teeth were used. The roots were removed and the pulp removed, and then embedded in epoxy resin. The lip surface enamel and dentin of the bovine teeth were polished with water-resistant polishing paper No. 80 under water pouring and then polished with water No. 600 under water pouring, and the polished tooth surfaces were dried with compressed air containing no oil.
Next, equal amounts of the primer A solution and the B solution of “Impervafluorobond” (manufactured by Matsukaze Co., Ltd.), a photopolymerization type dental bonding agent, were collected in an eye plate and mixed with a microbrush. The mixed solution was applied with a microbrush so as to be rubbed against the prescribed surface of enamel or dentin (rubbing treatment or active treatment), and after 20 seconds, volatile components were evaporated with compressed air containing no oil.

Further, an aluminum oxide powder was sprayed on the adhesion surface of the stainless steel rod (diameter 5 mm, length 12 mm) to perform sandblasting. Subsequently, an ultrasonic vibration having an output of 200 W-20 kHz was applied to 1 g of an equal amount mixed paste of paste A and paste B of the two-paste resin cements of Examples 122 to 124 at 23 ° C. for 10 seconds, and each reaction started. A stainless steel rod was joined to the above-mentioned tooth surface subjected to the adhesion treatment with the mixed paste interposed therebetween, a load of 200 g was applied, and the paste mud protruding from the adhesion interface was removed with a blade.
Subsequently, the adhesion interface was irradiated with light for 20 seconds from an oblique direction using a pine-style grip light II (Hal: halogen lamp). Thereafter, the shear bond strength test was performed by immersing the test specimen in 37 ° C. distilled water for 24 hours, and using an Instron universal testing machine (Instron 5567, Instron) at a crosshead speed of 1 mm / min. An average value of 7 was obtained. The results are shown in Table 21.

[Measurement of bending strength]
Using the two-paste resin cements of Examples 122 to 124, a three-point bending test was performed according to the ISO standard. A prototype two-paste resin cement was sampled, and an ultrasonic vibration with an output of 200 W-20 kHz was applied to 1 g of an equal amount mixed paste of paste A and paste B at 23 ° C. for 10 seconds, and each paste whose reaction was started was made with a plastic spatula. Fill the mold of the bending test body, press with the cover glass, and then irradiate light with Matsukaze Griplight II (manufactured by Matsukaze Co., Ltd.) for 30 seconds to give the bending test body (25 × 2.0 × 2.0, mm) After being prepared and immersed in distilled water at 37 ° C. for 24 hours, an average value of n = 5 was obtained by measuring at an cross-head speed of 1 mm / min using an Instron universal testing machine. The results are shown in Table 21.

Examples 125-134 and Comparative Examples 6-7
The curable composition of the present invention was examined in the form of a two-component one-step photopolymerizable bonding agent. As microcapsules, PVA microcapsules of sodium p-toluenesulfinate synthesized according to Example 42 (capsule A), PVA microcapsules of 2,4,6-trimethylbenzoylphenylphosphine oxide sodium (TBPO-Na) ( Capsule B), 6- (meth) acryloxyhexyl-3-phosphonoacetate (6-MHPA), 6- (meth) acryloxyhexyl-3-phosphonopropionate (6-MHPP) as a radical polymerizable monomer 4-methacryloxyethyl trimellitic acid (4-MET), 4-methacryloxyethyl trimellitic anhydride (4-META), 2-hydroxyethyl methacrylate (HEMA), Bis-GMA / TEGDMA (= 60/40) , Wt%) (Bis-G Sol.), 2,4,6-trimethylbenzoyl as a polymerization initiator Phenylphosphine oxide (TBPO), D, L-camphorquinone (CQ), 1-benzyl-5-phenylbarbituric acid (BPBA), N, N-dimethylaminobenzoic acid (DMBE), di- n-Octyltin dilaurate (Tin-Lau), acetone, and Aerosil R-972 (3 parts by weight) were mixed to prepare a two-pack one-step photopolymerizable bonding agent having the composition shown in Table 22.
Subsequently, enamel and dentin were prepared according to Example 88, and equal amounts of the bonding agent and distilled water were mixed in the eye plate, and the mixed solution was added to the teeth without applying ultrasonic vibration. It was applied to the surface and allowed to stand for 20 seconds, then photopolymerized for 20 seconds, and further joined with a photopolymerized composite resin “Beauty Fill” (manufactured by Matsukaze Co., Ltd.) to photopolymerize for 30 seconds to prepare a test specimen. After 24 hours of immersion in water, a shear adhesion test was performed according to Example 88. The results are shown in Table 22.

Examples 135-138
The curable composition of the present invention was examined in the form of a two-component one-step photopolymerizable bonding agent.
Sodium p-toluenesulfinate microcapsules A synthesized in Example 125 (3 parts by weight), 2,4,6-trimethylbenzoylphenylphosphine oxide sodium (TBPO-Na) microcapsules B (2 parts by weight), As radical polymerizable monomers, 6- (meth) acryloxyhexyl-3-phosphonoacetate (6-MHPA) (15 parts by weight), 4-methacryloxyethyl trimellitic acid (4-MET) (20 parts by weight), 2 -Hydroxyethyl methacrylate (HEMA) (7 parts by weight), Bis-GMA / TEGDMA (= 60/40, wt%) (28 parts by weight), 2,4,6-trimethylbenzoylphenylphosphine oxide ( TBPO) (1 part by weight), CQ (1 part by weight), 3,3′-carbonylbis (7-diethyl) as a coumarin compound “Bond A” was prepared by mixing aminocoumarin) (0.005 parts by weight), acetone (30 parts by weight), and Aerosil R-972 (3 parts by weight).
Only “Bond A” coumarin compound was replaced with 3,3′-carbonylbis (7-dibutylaminocoumarin) (0.005 parts by weight) to prepare “Bond B”.
The 6-MHPA of “Bond A” and “Bond B” was replaced with 6- (meth) acryloxyhexyl-3-phosphonopropionate (6-MHPP) (15 parts by weight) to obtain “Bond C” and “ Bond D "was prepared.
A shear adhesion test was conducted in accordance with Example 125 using a two-component one-step photopolymerizable bonding agent, Bonds A to D. The results are shown in Table 23.

Here, the light irradiator is a Matsukaze Grip Light II (Hal) using a halogen lamp (manufactured by Matsukaze Co., Ltd.), and a light emitting diode (LED) irradiator Eliper Free Light 2 (LED) (manufactured by 3M Esper) And Xenon lamp Apollo Elite 95E (Xe) (manufactured by DMD). Illuminance of each light irradiator was used at Matsukaze Grip Light II: 650 mW / cm ² , Eliper Free Light 2: 635 mW / cm ^2, and APPOLLOELITE 95E: 1330 mW / cm ² . The illuminance measurement wavelength region of these irradiators was set to 400 to 515 nm.

As is apparent from the results of Table 23, acylphosphine oxide and its sodium salt and p-toluenesulfinic acid sodium salt microcapsules, α-diketone, coumarin compound, polymerization constituting the bipartite curable composition of the present invention The photopolymerizable composition containing the accelerator showed high photocurability in any light irradiation of halogen light, LED and xenon lamp, and as a result, showed high enamel adhesion and dentin adhesion.
By coexisting the visible light sensitization effect of coumarin compounds and photopolymerization initiators such as APO-Na and α-diketone encapsulated in microcapsules, three types of light irradiators can be used for a wide range of wavelengths. Even when used, it is considered that high adhesive strength was exhibited.

Examples 139 to 142 and Comparative Examples 8 to 11
Benzoyl peroxide (BPO), N, N-di (hydroxyethyl) -p-toluidine (DEPT), 1,3,5-trimethylbarbituric acid (TMBA) as the core material, and polyethyl methacrylate ( PEMA) microcapsules were synthesized. The average particle size was 30 μm. A polymer powder / monomer liquid type adhesive resin cement was examined using the synthesized microcapsules.
BPO capsule, DEPT capsule, TMBA capsule, polymethyl methacrylate powder (PMMA), copolymer powder of methyl methacrylate and ethyl methacrylate (PMMA-PEMA), polyethyl methacrylate powder (PEMA), spherical silica filler, fine particle filler (Aerosil R-972) : Nippon Aerosil Co., Ltd.), N, N-di (hydroxyethyl) -p-toluidine (DEPT), 1,3,5-trimethylbarbituric acid (TMBA), methyl methacrylate (MMA), diethylene glycol dimethacrylate (TEGDMA) , Benzoyl peroxide (BPO), butylated hydroxytoluene (BHT), 2-hydroxyethyl methacrylate (HEMA), 4-methacryloxyethyl trimellitic acid (4-MET), 4-methacryloxyethyl trimellitic anhydride ( 4-META), 4-acryloxyethyl trimellitic acid (4-AET), 4-methacryloxy Tilt trimellitic anhydride (4-META), 6-methacryloxyhexyl 3-phosphonoacetate (6-MHPA), and 10- (meth) acryloyloxydecyl 6,8-dithiooctanate (10-MDDT) are used. Then, a polymer powder / monomer liquid type adhesive resin cement having the composition shown in Table 1 was prepared according to Table 24.

[Tooth bond strength and precious metal bond strength of polymer powder / monomer liquid type adhesive resin cement]
Using the curable compositions of Examples 139 to 142 and Comparative Examples 8 to 11 of the present invention, the dentin-metal bond strength and noble metal bond strength of the dentin were measured.
[Shear adhesion test]
The adhesion test between the dentin and the stainless steel rod was conducted according to Example 124, and the dentin-metal adhesion strength was measured. For the precious metal adhesion strength, epoxy-embedded Matsukaze Super Gold Type 4 (Matsukaze Co., Ltd.) (diameter: 6 mm, length: 2 mm) of a gold alloy cast with Matsukaze Argon Caster (Matsukaze Co., Ltd.) Using. The adhesive surface of the gold alloy was polished with water-resistant polishing paper No. 600 under water pouring, then sprayed with aluminum oxide powder, sandblasted, and dried with compressed air containing no oil.
Subsequently, a noble metal adhesive primer “Metal Link” (manufactured by Matsukaze Co., Ltd.) was applied to the adhesive surface of the gold alloy and dried. Further, an aluminum oxide powder was sprayed on the adhesion surface of the stainless steel rod (diameter 5 mm, length 12 mm) to perform sandblasting.
Subsequently, using Examples 139 to 142 and Comparative Examples 8 to 11, the above-mentioned adhesive-treated adhesive polymer mud mixed with a powder / liquid ratio = 2/1 was interposed between the resin-resin mud. A stainless steel rod was joined to the tooth surface, a load of 200 g was applied, and the cement mud protruding from the adhesion interface was removed with a blade.
Thereafter, the specimen was immersed in distilled water at 37 ° C. for 24 hours. Next, the shear adhesion strength of the shear adhesion test specimen was measured at an cross head speed of 1 mm / min using an Instron universal testing machine (Instron 5567, Instron), and an average value of n = 7 was obtained. . The results are shown in Table 25.
The powder material and the liquid material were forced to stand at 40 ° C. and a humidity of 75% for 1 month, and the same adhesion test was measured. Furthermore, the curing time was measured by the thermistor method. These results are shown in Table 25.

As is clear from the results in Table 25, in Comparative Examples 8 to 11, the adhesive strength and the curing time deteriorated after 40 months and 1 month. Moreover, all the comparative examples which were left to stand at 100% humidity at 40 ° C. for 1 month had agglomerated powder material, resulting in poor fluidity and operability.
On the other hand, the adhesive strength and setting time after 40 ° C.-1 month of the adhesive resin cements of Examples 139 to 142 of the present invention in which the polymerization initiator was microencapsulated hardly changed. It became clear that the fluidity and operability of the powder were stable.

Claims (26)

  A one-part curable composition containing microcapsules.   The core substance contained in the microcapsule is a radical polymerizable monomer, a polymerization initiator, a polymerization accelerator, an electrolyte polymer, an electrolyte polymer aqueous solution, a hydroxycarboxylic acid, a hydroxycarboxylic acid aqueous solution, an acid-reactive filler, and an acid-reactive filler. The one-component curable composition according to claim 1, which is a substance selected from the group consisting of active fillers or a combination of two or more substances which can coexist.   The material encapsulating the microcapsule is a radical polymerizable monomer, a polymerization initiator, a polymerization accelerator, an electrolyte polymer, an electrolyte polymer aqueous solution, a hydroxycarboxylic acid, a hydroxycarboxylic acid aqueous solution, an acid reactive filler, and an acid inert filler. The one-component curable composition according to claim 1, wherein the one-component curable composition is a substance selected from the group consisting of two or more substances that can coexist.   The one-component curable composition according to claim 1, wherein the wall material of the microcapsule is an organic compound, an inorganic compound, or an organic / inorganic composite compound.   3. The one-component curable composition according to claim 2, wherein the microcapsule is collapsed by applying an external force to release the core substance contained therein.   The one-component curable composition according to claim 5, wherein the external force is an electromagnetic wave, a magnetic field, an ultrasonic wave, a pressure, heat, vibration, or a combination of two or more thereof.   6. The one-component curable composition according to claim 5, wherein the curing reaction starts after the core material to be included is released.   Either a chemical reaction step that chemically reacts after the core material to be included is released; a photocuring reaction step that undergoes a photocuring reaction by light irradiation; or a chemical photocuring reaction step that undergoes a photocuring reaction by light irradiation following the chemical reaction step The one-component curable composition according to claim 5, wherein   The one-component curable composition according to claim 1, comprising (bis) acylphosphine oxides or salts thereof, α-diketones, or a coumarin compound as a photopolymerization initiator.   A radical polymerization type two-parting curable composition containing microcapsules.   The core substance included in the microcapsule is a substance selected from the group consisting of radical polymerizable monomers, polymerization initiators, polymerization accelerators, acid-reactive fillers and acid-inert fillers, or two or more of these substances that can coexist. The two-parting curable composition according to claim 10, which is a combination.   The substance encapsulating the microcapsule is a substance selected from the group consisting of radically polymerizable monomers, polymerization initiators, polymerization accelerators, organic polymer compounds, acid-reactive fillers or acid-inert fillers, or two or more of them that can coexist. 11. The bipartite curable composition according to claim 10, which is a combination of substances.   11. The two-part curable composition according to claim 10, wherein the wall material of the microcapsule is an organic compound, an inorganic compound or an organic / inorganic composite compound.   An acid-base reaction type two-parting curable composition containing microcapsules.   The core substance included in the microcapsule is a substance selected from the group consisting of an electrolyte polymer, an electrolyte polymer aqueous solution, a hydroxycarboxylic acid, a hydroxycarboxylic acid aqueous solution, an acid-reactive filler, and an acid-inactive filler, or those capable of coexisting The two-parting curable composition according to claim 14, which is a combination of two or more.   The substance encapsulating the microcapsule is a substance selected from the group consisting of an electrolyte polymer, an electrolyte polymer aqueous solution, a hydroxycarboxylic acid, a hydroxycarboxylic acid aqueous solution, an acid reactive filler, and an acid inert filler, or two or more of them The two-parting curable composition according to claim 14, which is a combination.   The two-part curable composition according to claim 14, wherein the wall material of the microcapsule is an organic compound, an inorganic compound, or an organic / inorganic composite compound.   The substance selected from the group consisting of a radically polymerizable monomer, a polymerization initiator, and a polymerization accelerator is further blended in the core substance encapsulated in the microcapsule or the substance encapsulating the microcapsule. 14. The bipartite curable composition according to 14.   15. The bipartite curable composition according to claim 10 or 14, wherein the microcapsules are disintegrated to release the core material contained therein.   20. The bipartite curable composition according to claim 19, wherein the microcapsules disintegrate by applying an external force.   21. The bipartite curable composition according to claim 20, wherein the external force is an electromagnetic wave, a magnetic field, an ultrasonic wave, a pressure, heat, vibration, or a combination of two or more thereof.   20. The bipartite curable composition according to claim 19, wherein the microcapsule disintegrates by dissolving the wall material of the microcapsule when the two divided parts are mixed.   The two-parting curable composition according to claim 10 or 14, which is a powder / liquid type, a powder / paste type, a paste / paste type, a liquid / liquid type, or a paste / liquid type.   A compound selected from the group consisting of a solvent, a coupling agent, a modifier, a thickener, a dye, a pigment, a polymerization regulator, and a polymerization inhibitor, or two or more compounds thereof are blended. Item 15. The curable composition according to item 1, 10 or 14.   The structure of the microcapsule is a core / shell type (core material / wall material type), a core / core dispersion shell type (core material / core material solid solution wall material type), or a core material solid solution material type. The curable composition according to 1, 10 or 14. The curable composition according to any one of claims 1 to 25, which is used for medical and dental purposes.