WO2014156077A1 - 硬化性組成物 - Google Patents
硬化性組成物 Download PDFInfo
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- WO2014156077A1 WO2014156077A1 PCT/JP2014/001594 JP2014001594W WO2014156077A1 WO 2014156077 A1 WO2014156077 A1 WO 2014156077A1 JP 2014001594 W JP2014001594 W JP 2014001594W WO 2014156077 A1 WO2014156077 A1 WO 2014156077A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/10—Esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/36—Amides or imides
- C08F22/38—Amides
Definitions
- the present invention relates to a curable composition that initiates polymerization by reacting an oxidizing agent and a reducing agent. Specifically, the present invention relates to a curable composition having excellent adhesiveness, appropriate curability, and excellent long-term storage stability, and particularly suitable for dental use.
- Curable compositions containing a polymerizable monomer and a radical polymerization initiator are widely used in various applications such as paints, printing materials, adhesives, model materials, sealing materials, and dental materials.
- a radical polymerization initiator such as paints, printing materials, adhesives, model materials, sealing materials, and dental materials.
- those using (meth) acrylate polymerizable monomers and (meth) acrylamide polymerizable monomers as polymerizable monomers are used for dental cements, dental adhesives, It has been put to practical use in dental composite resins and dental room temperature polymerization resins.
- One of the common radical polymerization initiators is a polymerization initiator that combines an oxidizing agent and a reducing agent.
- a so-called redox reaction occurs to generate radicals, and the generated radicals initiate a polymerization reaction, so that the composition proceeds.
- oxidizing agent is benzoyl peroxide
- reducing agent is an amine compound.
- benzoyl peroxide has poor storage stability because of its low thermal stability, and has disadvantages in handling such as refrigeration is essential.
- amine compounds are easily changed to colored substances due to chemical changes, there are drawbacks such as difficulty in use where aesthetics are required, such as for dental materials, due to the ease of coloring. is doing.
- Patent Documents 1 and 2 propose a combination of a hydroperoxide and an acyclic thiourea compound as a radical polymerization initiator that improves the above-mentioned drawbacks.
- Patent Document 3 proposes a combination of a hydroperoxide and a cyclic thiourea compound having a cyclic structure having no substituent as a radical polymerization initiator. Hydroperoxide has higher thermal stability than benzoyl peroxide and the like, and is advantageous in storage stability. A thiourea compound is not easily colored like an amine compound.
- the adhesive strength to the dentine and the dental restorative material is excellent, and in particular, the adhesive strength to the dentin is excellent. It is desired.
- dental materials have practically appropriate curability, that is, a moderately large curing speed and a moderately long operation margin. Furthermore, it is desired to have storage stability that does not change the curability even when stored for a long time.
- the present invention is a composition in which a radically polymerizable monomer is polymerized by reacting hydroperoxide and a thiourea compound, and has excellent adhesiveness, appropriate curability, and long-term storage stability.
- An object of the present invention is to provide a novel curable composition having excellent resistance.
- the present inventors have found that radically polymerizable monomers, hydroperoxides as oxidants that are polymerization initiators, and thiourea compounds as reducing agents that are polymerization initiators.
- radically polymerizable monomers hydroperoxides as oxidants that are polymerization initiators
- thiourea compounds as reducing agents that are polymerization initiators.
- the present invention relates to a radical polymerizable monomer (a1) having no acidic group, a hydroperoxide compound (a2), a substituted ethylenethiourea compound (a3-1), a substituted propylenethiourea compound (a3-2). And a curable composition (A) containing at least one cyclic thiourea compound (a3) selected from the group consisting of a substituted butylene thiourea compound (a3-3),
- the substituted ethylenethiourea compound (a3-1) has the formula (I):
- R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent.
- a ring that may have a ring), and a structure represented by The substituted propylene thiourea compound (a3-2) has the formula (II):
- R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are each independently a hydrogen atom, an alkyl group that may have a substituent, A cycloalkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, a substituent
- An alkenyl group which may have a group, an aralkyl group which may have a substituent, or a monovalent heterocyclic ring which may have a substituent, including an oxygen atom, a sulfur atom or a nitrogen atom
- R 9 and R 11 , and R 9 and R 13 may be combined with the carbon atom to which they are bonded to
- R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 each independently have a hydrogen atom or a substituent.
- the curable composition (A) further contains a filler (a4).
- the radical polymerizable monomer (a1) having no acidic group is a (meth) acrylate polymerizable monomer and / or a (meth) acrylamide polymerizable monomer. Is the body.
- the curable composition (A) further contains an acidic group-containing radical polymerizable monomer (a5).
- the curable composition (A) further contains a vanadium compound (a6) and / or a copper compound (a7).
- the cyclic thiourea compound (a3) comprises 4-methyl-2-imidazolidinethione, 4,4-dimethyl-2-imidazolidinethione, 4-ethyl-2-imidazolidinethione, and 4,4-diethyl.
- -2-At least one selected from the group consisting of imidazolidinethiones.
- the curable composition of the present invention is suitable for dental use.
- the present invention also contains an acidic group-containing radical polymerizable monomer (b1), a polymerization accelerator (b2), a solvent (b3), and a hydrophilic radical polymerizable monomer (b4) having no acidic group. It is related with the adhesion
- the polymerization accelerator (b2) is a vanadium compound (b2-1) and / or a copper compound (b2-2).
- the adhesive kit of the present invention is suitable for dental use.
- the curable composition of the present invention has excellent adhesiveness, suitable curability, and excellent long-term storage stability while using a hydroperoxide and a thiourea compound as a radical polymerization initiator.
- the present invention contains a radically polymerizable monomer (a1) having no acidic group, contains a hydroperoxide compound (a2) as an oxidant that is a polymerization initiator, and is a polymerization initiator.
- the substituted ethylenethiourea compound (a3-1) used in the present invention has a structure represented by the following formula (I).
- R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent.
- the substituted propylenethiourea compound (a3-2) used in the present invention has a structure represented by the following formula (II).
- R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are each independently a hydrogen atom, an alkyl group that may have a substituent, A cycloalkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, a substituent
- An alkenyl group which may have a group, an aralkyl group which may have a substituent, or a monovalent heterocyclic ring which may have a substituent, including an oxygen atom, a sulfur atom or a nitrogen atom
- R 9 and R 11 , and R 9 and R 13 may be combined with the carbon atom to which they are bonded to
- the substituted butylene thiourea compound (a3-3) used in the present invention has a structure represented by the following formula (III).
- R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 each independently have a hydrogen atom or a substituent.
- Represents a good monovalent heterocyclic group (provided that R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are all hydrogen atoms) except), R 17 and R 19, R 17 and R 21, R 17 and R 23, and R 19 and R 21 together with the carbon atoms to which they are attached It may form a ring which may have a substituent.)
- the cyclic thiourea compound (a3) having these structures has a planar structure, the reaction activity with hydroperoxide can be increased, and as a result, the adhesive property of the curable composition is high. And appropriate curability.
- the cyclic thiourea compound (a3) has at least one substituent in the cyclic structure portion, and surprisingly at room temperature or higher by introducing a substituent into the cyclic structure portion of the cyclic thiourea compound. Even if it preserve
- radical polymerizable monomer (a1) having no acidic group, hydroperoxide compound (a2), and cyclic thiourea compound having the above specific structure, which are essential components of the curable composition (A) of the present invention (A3) will be described.
- radical polymerizable monomer (a1) having no acidic group without having an acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group
- it is a radically polymerizable monomer which has a polymeric group
- Preferable examples of such compounds include those having an acryloyl group or a methacryloyl group, that is, (meth) acrylate polymerizable monomers and (meth) acrylamide polymerizable monomers.
- (meth) acryl is a general term for methacryl and acryl.
- aliphatic monofunctional ones such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate (commonly referred to as “HEMA”), 3-hydroxypropyl (meth) acrylate, 3 -Chloro-2-hydroxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acryloylmorpholine, diethyl (meth) acrylamide and the like.
- HEMA 2-hydroxyethyl (meth) acrylate
- HEMA 3-
- 2,2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl] propane (commonly referred to as “Bis-GMA”), 2,2-bis [4- (4 -(Meth) acryloyloxy) -3-hydroxybut Cyphenyl] propane, 2,2-bis [4- (4- (meth) acryloyloxy) -2-hydroxybutoxyphenyl] propane, 2,2-bis [4- (5- (meth) acryloyloxy) -4- Hydroxypentoxyphenyl] propane, 2,2-bis ((meth) acryloyloxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meta ) Acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytrieth
- the hydroperoxide compound (a2) is a component that serves as an oxidizing agent for the redox polymerization initiator.
- hydroperoxide compound (a2) known compounds can be used without any limitation, but those having one or more hydroperoxide groups (—OOH groups) in the molecule are preferable. More preferred is a hydroperoxide having an —OOH group bonded to a tertiary carbon atom.
- Specific examples include 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, t-amyl hydroperoxide, p-menthane hydroperoxide, p-isopropyl group.
- Mill hydroperoxide, diisopropylbenzene hydroperoxide, diisopropylbenzene dihydroperoxide and the like can be mentioned, and these can be used alone or in combination of two or more. Among them, it is preferable to use cumene hydroperoxide and / or 1,1,3,3-tetramethylbutyl hydroperoxide.
- the blending amount of the hydroperoxide compound (a2) in the curable composition (A) is preferably 0.01 to 20% by weight of the entire curable composition (A), more preferably 0.05. ⁇ 10% by weight.
- the blending amount is less than 0.01% by weight, the function as a redox polymerization initiator may be insufficient.
- the blending amount exceeds 20% by weight, the radically polymerizable monomer in the curable composition (A). Tends to polymerize, and the storage stability of the curable composition (A) may be reduced.
- the cyclic thiourea compound (a3) is a component that serves as a reducing agent for the redox polymerization initiator.
- the cyclic thiourea compound (a3) is at least one selected from the group consisting of a substituted ethylenethiourea compound (a3-1), a substituted propylenethiourea compound (a3-2), and a substituted butylenethiourea compound (a3-3). Is used.
- any compound having a structure represented by the following formula (I) can be used without any limitation.
- R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent.
- any compound having a structure represented by the following formula (II) can be used without any limitation.
- R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , and R 14 are each independently a hydrogen atom, an alkyl group that may have a substituent, A cycloalkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, a substituent
- An alkenyl group which may have a group, an aralkyl group which may have a substituent, or a monovalent heterocyclic ring which may have a substituent, including an oxygen atom, a sulfur atom or a nitrogen atom
- R 9 and R 11 , and R 9 and R 13 may be combined with the carbon atom to which they are bonded to
- any compound having a structure represented by the following formula (III): can be used without any limitation.
- R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 each independently have a hydrogen atom or a substituent.
- Represents a good monovalent heterocyclic group (provided that R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are all hydrogen atoms) except), R 17 and R 19, R 17 and R 21, R 17 and R 23, and R 19 and R 21 together with the carbon atoms to which they are attached It may form a ring which may have a substituent.)
- the alkyl group represented by R 1 to R 24 may be linear or branched, and preferably has 1 to 12 carbon atoms. Examples thereof include a methyl group, an ethyl group, and n- Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, n- Examples include heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
- cycloalkyl group represented by R 1 to R 24 those having 3 to 10 carbon atoms are preferable, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptanyl group, a cyclooctanyl group, and a cyclononanyl group. Groups and the like.
- the alkoxyl group represented by R 1 to R 24 is preferably an alkoxyl group having 3 to 8 carbon atoms. Examples thereof include a propoxy group, an isopropoxy group, an n-butoxy group, a t-butoxy group, a pentyloxy group, and a hexyloxy group. Groups and the like.
- the aryl group represented by R 1 to R 24 is preferably an aryl group having 6 to 16 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.
- the acyl group represented by R 1 to R 24 is preferably one having 1 to 10 carbon atoms, and examples include formyl group, acetyl group, propanoyl group, butanoyl group, benzoyl group and the like.
- the alkenyl group represented by R 1 to R 24 may be linear or branched, and preferably has 2 to 8 carbon atoms, and is a vinyl group, allyl group, methylvinyl group, propenyl group. , Butenyl group, pentenyl group, hexenyl group and the like.
- the aralkyl group represented by R 1 to R 24 is preferably one having 7 to 16 carbon atoms, and examples thereof include an aryl group substituted with a lower alkyl group (particularly an alkyl group having 1 to 6 carbon atoms). Specific examples include a methylphenyl group, an ethylphenyl group, a butylphenyl group, a dimethylphenyl group, a dibutylphenyl group, and a methylnaphthyl group.
- the monovalent heterocyclic group containing an oxygen atom, sulfur atom or nitrogen atom represented by R 1 to R 24 is preferably one having 4 to 10 carbon atoms, for example, pyridyl group, imidazolyl group, piperidyl group, thienyl group. Thiopyranyl group, furyl group, pyranyl group and the like.
- alkyl group, cycloalkyl group, alkoxyl group, acyl group, and alkenyl group may have include a halogen atom (eg, chlorine atom, bromine atom), an aryl group (eg, phenyl group, naphthyl). Group), monovalent heterocyclic groups (eg, pyridyl group, imidazolyl group, etc.), etc., among which a halogen atom and an aryl group are preferable.
- the number of substituents is preferably 1 to 2.
- Examples of the substituent that the aryl group, aralkyl group, and monovalent heterocyclic group may have include a halogen atom (eg, chlorine atom, bromine atom), and an alkyl group (eg, methyl group, ethyl group). , Alkoxyl groups (eg, methoxy group, ethoxy group, etc.), aryl groups (eg, phenyl group, naphthyl group, etc.), monovalent heterocyclic groups (eg, pyridyl group, imidazolyl group, etc.), etc.
- a halogen atom and an alkyl group are preferred.
- the number of substituents is preferably 1 to 4, more preferably 1 to 2.
- R 4 and R 5 , R 9 and R 11 , R 9 and R 13 , R 17 and R 19 , R 17 and R 21 , R 17 and R 23 , and R 19 and R 21 are carbon atoms to which they are bonded. And may form a ring which may have a substituent, and a ring having 4 to 10 carbon atoms is preferable. Examples of such a ring include a cyclobutyl ring, a cyclopentyl ring, a cyclohexyl ring, a cycloheptanyl ring, a cyclooctanyl ring, a cyclononanyl ring, and the like.
- substituents that the ring may have include, for example, a halogen atom (eg, chlorine atom, bromine atom, etc.), an aryl group (eg, phenyl group, naphthyl group, etc.), and a monovalent heterocyclic group (eg, Pyridyl group, imidazolyl group and the like).
- a halogen atom eg, chlorine atom, bromine atom, etc.
- an aryl group eg, phenyl group, naphthyl group, etc.
- a monovalent heterocyclic group eg, Pyridyl group, imidazolyl group and the like.
- R 1 , R 2 , R 7 , R 8 , R 15 , and R 16 are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or aralkyl from the viewpoints of curability, adhesiveness, and availability.
- Group is preferable, a hydrogen atom, an alkyl group, and a cycloalkyl group are more preferable, and a hydrogen atom is more preferable.
- R 3 to R 6 are aryls optionally substituted with a hydrogen atom, an alkyl group, a cycloalkyl group, or a halogen atom from the viewpoints of curability, adhesiveness, availability, and solubility in a radical polymerizable monomer Group, alkenyl group and aralkyl group are preferable, hydrogen atom, alkyl group and cycloalkyl group are more preferable.
- an alkyl group having 1 or more hydrogen atoms and having 1 to 5 carbon atoms Is more preferably 3 or less, and most preferably 2 hydrogen atoms and 2 alkyl groups having 1 to 2 carbon atoms.
- R 9 to R 14 are aryl optionally substituted with a hydrogen atom, an alkyl group, a cycloalkyl group, or a halogen atom from the viewpoints of curability, adhesiveness, availability, and solubility in a radical polymerizable monomer Group, alkenyl group and aralkyl group are preferable, hydrogen atom, alkyl group and cycloalkyl group are more preferable.
- an alkyl group having 3 or more hydrogen atoms and having 1 to 5 carbon atoms Is more preferably 3 or less, most preferably 4 hydrogen atoms and 2 alkyl groups having 1 to 2 carbon atoms.
- R 17 to R 24 are aryls optionally substituted with a hydrogen atom, an alkyl group, a cycloalkyl group, or a halogen atom from the viewpoints of curability, adhesiveness, availability, and solubility in a radical polymerizable monomer Group, alkenyl group and aralkyl group are preferred, hydrogen atom, alkyl group and cycloalkyl group are more preferred.
- an alkyl group having 5 or more hydrogen atoms and having 1 to 5 carbon atoms Is more preferably 3 or less, most preferably 6 hydrogen atoms and 2 alkyl groups having 1 to 2 carbon atoms.
- the cyclic thiourea compound (a3) described above preferably has a solubility in triethylene glycol dimethacrylate of 1.0 wt% or more, and more preferably has a solubility in triethylene glycol dimethacrylate of 5.0 wt% or more. preferable.
- 4-methyl-2-imidazolidinethione is used from the viewpoint of improvement in adhesive strength, improvement in curability, availability, and solubility in radical polymerizable monomers.
- the blending amount of the cyclic thiourea compound (a3) is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, based on the entire curable composition (A). If the blending amount is less than 0.01% by weight, the function as a redox polymerization initiator may be insufficient, and if it exceeds 20% by weight, the curing start time may be shortened and an appropriate operation margin may not be obtained. is there.
- the curable composition (A) may contain a filler (a4) in order to prepare dental materials such as cement and composite resin.
- a filler used for dental use is preferably used.
- Fillers used for dental use are generally roughly classified into organic fillers, inorganic fillers, and organic-inorganic composite fillers.
- the organic filler material include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyamide, polyvinyl chloride, and polystyrene.
- the shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used. From the viewpoint of handling properties of the resulting curable composition and mechanical strength of the cured product, the average particle diameter of the organic filler is preferably 0.001 to 50 ⁇ m, and preferably 0.001 to 10 ⁇ m. More preferred.
- the average particle diameter of inorganic particles means the average particle diameter (average primary particle diameter) of primary particles of inorganic particles.
- the average particle diameter of inorganic particles can be determined by a laser diffraction scattering method or observation of particles by an electron microscope. Specifically, laser diffraction scattering is convenient for measuring the particle diameter of particles having a size of 0.1 ⁇ m or more, and observation with an electron microscope is simple for measuring the particle system of ultrafine particles having a size of 0.1 ⁇ m or less.
- the laser diffraction scattering method can be measured with a laser diffraction particle size distribution analyzer (SALD-2100: manufactured by Shimadzu Corporation) using a 0.2% aqueous solution of sodium hexametaphosphate as a dispersion medium.
- SALD-2100 manufactured by Shimadzu Corporation
- a transmission electron microscope (Hitachi, H-800NA type) photograph of particles is taken, and the particle diameter of particles (200 or more) observed within the unit field of view of the photograph It can obtain
- the particle diameter of the particles is obtained as an arithmetic average value of the longest length and the shortest length of the particles, and the average primary particle diameter is calculated from the number of particles and the particle diameter.
- Inorganic filler materials include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, and glass ceramic. , Aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, etc. .
- the shape of the inorganic filler is not particularly limited, and the particle diameter of the filler can be appropriately selected and used. From the viewpoint of handling properties of the resulting curable composition and mechanical strength of the cured product, the average particle diameter of the inorganic filler is preferably 0.001 to 50 ⁇ m, more preferably 0.001 to 10 ⁇ m. preferable.
- the shape of the inorganic filler includes an amorphous filler and a spherical filler. From the viewpoint of improving the mechanical strength of the cured product of the resulting curable composition, it is preferable to use a spherical filler as the inorganic filler.
- the spherical filler is a particle diameter in a direction perpendicular to the maximum diameter, in which a photograph of the filler is taken with a scanning electron microscope (hereinafter abbreviated as SEM), and the particles observed in the unit field of view are rounded. Is a filler having an average homogeneity of 0.6 or more divided by its maximum diameter.
- the average particle diameter of the spherical filler is preferably 0.1 to 5 ⁇ m.
- the filling rate of the spherical filler of the curable composition (A) is lowered, and the mechanical strength of the obtained cured product may be lowered.
- the average particle diameter exceeds 5 ⁇ m, the surface area of the spherical filler is reduced, and a cured product having high mechanical strength may not be obtained.
- the inorganic filler may be used after a surface treatment with a known surface treatment agent such as a silane coupling agent as necessary.
- a known surface treatment agent such as a silane coupling agent
- the surface treatment agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri ( ⁇ -methoxyethoxy) silane, ⁇ -methacryloyloxypropyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane.
- the organic-inorganic composite filler is obtained by previously adding a monomer compound to the above-described inorganic filler, forming a paste, polymerizing, and pulverizing.
- TMPT filler trimethylolpropane methacrylate and silica filler mixed and polymerized and then pulverized
- the shape of the organic-inorganic composite filler is not particularly limited, and the particle diameter of the filler can be appropriately selected and used. From the viewpoint of handling properties of the resulting curable composition and mechanical strength of the cured product, the average particle size of the organic-inorganic composite filler is preferably 0.001 to 50 ⁇ m, preferably 0.001 to 10 ⁇ m. More preferably.
- fluoroaluminosilicate glass When it is desired to impart a sustained release of fluorine to the curable composition (A), as the filler (a4), fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass and strontium calcium fluoro It is preferable to use at least one selected from the group consisting of aluminosilicate glasses, and it is more preferable to use fluoroaluminosilicate glass and / or barium fluoroaluminosilicate glass.
- the filler (a4) barium glass, strontium glass, barium boroaluminosilicate glass, strontiumboroaluminosilicate glass, strontium fluoroaluminosilicate glass It is preferable to use at least one selected from the group consisting of barium fluoroaluminosilicate glass, and it is more preferable to use barium glass and / or barium fluoroaluminosilicate glass.
- the blending amount of the filler (a4) in the curable composition (A) is preferably 0.5 to 85% by weight.
- the filler content is less than 0.5% by weight, it is not possible to obtain the filler blending effect of adjusting the viscosity of the curable composition (A) and improving the mechanical strength of the curable composition (A) after curing. There is a fear.
- the curable composition (A) of the present invention is preferably used for dental bonding materials, dental composite resins, dental cements and the like.
- the blending amount of the filler (a4) in the adhesive composition (A) is preferably 45 to 85% by weight, and more preferably 47 to 80% by weight.
- the curable composition (A) may contain an acidic group-containing radically polymerizable monomer (a5) in order to improve adhesion to a tooth or a prosthesis.
- Examples of the acidic group-containing radical polymerizable monomer (a5) used in the present invention include acidic groups such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a carboxylic acid group, and a sulfonic acid group.
- Examples thereof include polymerizable monomers having at least one and having at least one radical polymerizable group such as acryloyl group, methacryloyl group, vinyl group and styrene group.
- the acidic group-containing radical polymerizable monomer (a5) preferably has a (meth) acryloyl group from the viewpoint of radical polymerizability and safety.
- a (meth) acrylate polymerizable monomer and a (meth) acrylamide polymerizable monomer are preferable.
- the acidic group-containing radically polymerizable monomer (a5) can be used alone or in appropriate combination of two or more. Specific examples of the acidic group-containing radical polymerizable monomer (a5) will be described below.
- Phosphoric acid group-containing radical polymerizable monomers include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyloxybutyl dihydrogen Phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) acryloyloxyoctyldi Hydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) a Liloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloy
- Pyrophosphate group-containing radical polymerizable monomers include bis [2- (meth) acryloyloxyethyl pyrophosphate], bis [4- (meth) acryloyloxybutyl pyrophosphate], bis [6- (meth) pyrophosphate Examples include acryloyloxyhexyl], bis [8- (meth) acryloyloxyoctyl] pyrophosphate, bis [10- (meth) acryloyloxydecyl] pyrophosphate, and acid chlorides, alkali metal salts and amine salts thereof.
- thiophosphate-containing radical polymerizable monomers examples include 2- (meth) acryloyloxyethyl dihydrogenthiophosphate, 3- (meth) acryloyloxypropyl dihydrogenthiophosphate, 4- (meth) acryloyloxybutyldi Hydrogenthiophosphate, 5- (meth) acryloyloxypentyl dihydrogenthiophosphate, 6- (meth) acryloyloxyhexyl dihydrogenthiophosphate, 7- (meth) acryloyloxyheptyl dihydrogenthiophosphate, 8- ( (Meth) acryloyloxyoctyl dihydrogen thiophosphate, 9- (meth) acryloyloxynonyl dihydrogen thiophosphate, 10- (meth) acryloyloxydecyl dihydro Enthiophosphate, 11- (meth) acryloyloxyundecyl dihydrogenthiophosphate
- Examples of phosphonic acid group-containing radical polymerizable monomers include 2- (meth) acryloyloxyethyl phenyl phosphonate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate, and 6- (meth) acryloyloxy. Hexyl-3-phosphonopropionate, 10- (meth) acryloyloxydecyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl-3-phosphonoacetate, 10- (meth) acryloyloxydecyl -3-Phosphonoacetate and acid chlorides, alkali metal salts and ammonium salts thereof are exemplified.
- Carboxylic acid group-containing radical polymerizable monomers include monofunctional radical polymerizable monomers having one carboxyl group or acid anhydride group in the molecule, and a plurality of carboxyl groups or acid anhydrides in the molecule. And monofunctional radically polymerizable monomers having a physical group.
- Examples of monofunctional radically polymerizable monomers having one carboxyl group or acid anhydride group in the molecule include (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloyl Aspartic acid, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxyethyl hydrogen maleate, O- (meth) acryloyl tyrosine, N- (Meth) acryloyl tyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2- (meta ) Acryloyloxybenzoic acid, 3- (meth)
- Examples of monofunctional radically polymerizable monomers having a plurality of carboxyl groups or acid anhydride groups in the molecule include, for example, 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid, 9- ( (Meth) acryloyloxynonane-1,1-dicarboxylic acid, 10- (meth) acryloyloxydecane-1,1-dicarboxylic acid, 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 12- (meth) Acryloyl oxide decane-1,1-dicarboxylic acid, 13- (meth) acryloyloxytridecane-1,1-dicarboxylic acid, 4- (meth) acryloyloxyethyl trimellitate, 4- (meth) acryloyloxyethyl trimellitate Tate anhydride, 4- (meth) acryloyloxybutyl trimell
- sulfonic acid group-containing radical polymerizable monomer examples include 2- (meth) acrylamide-2-methylpropane sulfonic acid, styrene sulfonic acid, and 2-sulfoethyl (meth) acrylate.
- the acidic group-containing radical polymerizable monomer (a5) is preferably 1 to 40 parts by weight in 100 parts by weight of the radical polymerizable monomer contained in the curable composition (A). Part by weight is more preferable, and 5 to 20 parts by weight is further preferable.
- the curable composition (A) may contain a vanadium compound (a6) and / or a copper compound (a7) as a polymerization accelerator for redox polymerization.
- a vanadium compound (a6) and / or a copper compound (a7) as a polymerization accelerator for redox polymerization.
- vanadium compound (a6) a compound soluble in a radical polymerizable monomer is preferable.
- a compound soluble in a radical polymerizable monomer includes vanadium acetylacetonate, vanadyl acetylacetonate, vanadyl stearate, vanadium naphthenate, vanadium benzoylacetonate, vanadyl oxalate, bis (maltolate) oxovanadium (IV), oxobis (1-phenyl-1) , 3-butanedionate) vanadium (IV), vanadium (V) oxytriisopropoxide, ammonium metavanadate (V), sodium metavanadate (V), vanadium pentoxide (V), divanadium tetroxide (IV) And vanadyl sulfate (IV), among others, vanadium acetylacetonate, vanadyl acetylacetonate, bis
- the compounding amount of the vanadium compound (a6) is preferably 0.005 to 0.30 parts by weight with respect to 100 parts by weight of the radical polymerizable monomer contained in the curable composition (A), and 0.008 to 0.15 parts by weight is more preferable, and 0.01 to 0.10 parts by weight is further preferable.
- the copper compound (a7) is preferably a compound soluble in a radical polymerizable monomer. Specific examples thereof include copper acetate, copper isobutyrate, copper gluconate, copper citrate, copper phthalate, copper tartrate, copper oleate, copper octylate, copper octenoate, copper naphthenate, methacrylate Acid copper, 4-cyclohexyl butyrate copper; ⁇ -diketone copper: acetylacetone copper, trifluoroacetylacetone copper, hexafluoroacetylacetone copper, 2,2,6,6-tetramethyl-3,5-heptanedionate copper, benzoylacetone copper; ⁇ -ketoester copper as copper acetoacetate; copper alkoxide as copper methoxide, copper ethoxide, copper isopropoxide, copper 2- (2-butoxyethoxy) ethoxide, copper 2- (2-methoxyethoxy) ethoxide; di
- copper carboxylate, ⁇ -diketone copper, and ⁇ -ketoester copper are preferable, and copper acetate and acetylacetone copper are particularly preferable.
- the compounding amount of the copper compound (a7) is preferably 0.0001 to 0.01 parts by weight with respect to 100 parts by weight of the radical polymerizable monomer contained in the curable composition (A), and 0.0002 More preferred is 0.005 parts by weight, and further more preferred is 0.0003 to 0.003 parts by weight.
- the curable composition (A) may further contain a photopolymerization initiator in order to configure it as a dual cure material.
- Photopolymerization initiators include (bis) acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, ⁇ -diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, ⁇ -amino ketones System compounds and the like.
- you may further contain chemical polymerization initiators other than said (a2) and (a3).
- the curable composition (A) may further contain a photopolymerization initiator and a polymerization accelerator other than the above (a2) and (a3).
- a photopolymerization initiator and a polymerization accelerator other than the above (a2) and (a3).
- the polymerization accelerator include amines, sulfinic acid and salts thereof, borate compounds, barbituric acid derivatives, triazine compounds, tin compounds, halogen compounds, aldehydes, thiol compounds, sulfites, and bisulfites.
- the curable composition (A) contains a pH adjuster, a polymerization inhibitor, a UV absorber, a thickener, a colorant, an antibacterial agent, a fragrance and the like as long as the effects of the present invention are not impaired. Also good.
- the curable composition (A) may have a form in which the hydroperoxide compound (a2) and the cyclic thiourea compound (a3) are packaged in separate agents from the viewpoint of storage stability.
- the agent containing the hydroperoxide compound (a2) is the agent A
- the agent containing the cyclic thiourea compound (a3) is the agent B
- curable composition (A) contains a filler (a4), you may mix
- the curable composition (A) contains the acidic group-containing radical polymerizable monomer (a5), the acidic group-containing radical polymerizable monomer (a5) is contained only in the agent A. It is preferable. Further, when the curable composition (A) contains the vanadium compound (a6) or the copper compound (a7), the vanadium compound (a6) and the copper compound (a7) are contained only in the B agent. Is preferred.
- the vanadium compound (a6) is blended with the B agent of the curable composition (A), the blending amount is 0.003 to 0.15% by weight with respect to the total weight of the components of the B agent. Preferably, the content is 0.005 to 0.1% by weight.
- the blending amount may be 0.00005 to 0.02% by weight based on the total weight of the components of the B agent.
- the content is 0.0001 to 0.002% by weight.
- the curable composition (A) of the present invention in which a hydroperoxide compound and a specific cyclic thiourea compound are blended with a radical polymerizable monomer as a redox polymerization initiator has high adhesiveness, particularly adhesiveness to teeth.
- the curable composition (A) of the present invention has appropriate curability, and when the curable composition (A) is packaged, the curable composition (A) is mixed and prepared. While providing a sufficient operating margin while having a sufficiently high curing rate.
- the curable composition (A) of the present invention is excellent in storage stability with almost no change in curability even after long-term storage at room temperature or higher.
- the cured product of the curable composition (A) of the present invention has high transparency. Therefore, the curable composition (A) of the present invention is suitable for dental use.
- the curable composition (A) is preferably configured as a dental bonding material, a dental composite resin, a dental cement, or the like, and more preferably configured as a dental cement.
- the acidic group-containing radical polymerizable monomer (b1), the polymerization accelerator (b2), the solvent (b3), and the hydrophilic radical polymerizable monomer having no acidic group You may comprise as the adhesion
- the acidic group-containing radical polymerizable monomer (b1) is the same as the acidic group-containing radical polymerizable monomer (a5) contained in the curable composition (A).
- 10- (meth) acryloyloxydecyl dihydrogen phosphate, 4- (meth) acryloyloxyethyl trimellitate anhydride, 4- (meth) acryloyloxyethyl trimellitate, 11- (meth) Acryloyloxyundecane-1,1-dicarboxylic acid and 2- (meth) acrylamido-2-methylpropanesulfonic acid are preferred.
- the blending amount of the acidic group-containing radically polymerizable monomer (b1) in the pretreatment material (B) is preferably 3 to 35% by weight, more preferably 5 to 30% by weight. More preferably, it is 25% by weight.
- the blending amount of (b1) 3% by weight or more the decalcification of the tooth by the pretreatment material (B) is further promoted, which contributes to the improvement of the adhesion of the tooth.
- the blending amount of (b1) is 35% by weight or less, it becomes easier to make the pretreatment material (A) a uniform solution, which leads to improvement in handling properties and tooth adhesion.
- the polymerization accelerator (b2) amines, sulfinic acid and its salts, borate compounds, barbituric acid derivatives, triazine compounds, vanadium compounds, copper compounds, tin compounds, halogen compounds, aldehydes, thiol compounds , Sulfites, hydrogen sulfites, thiourea compounds, etc., and vanadium compounds (b2-1) and / or copper compounds (b2-2) are preferred.
- the same compound as the vanadium compound (a6) or the copper compound (a7) contained in the curable composition (A) can be used.
- the amount of the vanadium compound (b2-1) in the pretreatment material (B) is preferably 0.1 to 1% by weight, more preferably 0.2 to 0.7% by weight. More preferably, the content is 0.3 to 0.6% by weight.
- the blending amount of the copper compound (b2-2) in the pretreatment material (B) is preferably 0.02 to 0.2% by weight, and preferably 0.04 to 0.15% by weight. More preferred.
- the solvent (b3) used in the present invention improves the compatibility of the components of the pretreatment material and improves the permeability of the components of the pretreatment material into the tooth.
- water and a water-soluble organic solvent can be preferably used.
- the water-soluble organic solvent the boiling point under normal pressure is usually 150 ° C. or lower, and the solubility in water at 25 ° C. is 5% by weight or more, more preferably 30% by weight or more, and most preferably in any proportion.
- Soluble organic solvents are used. Among them, a water-soluble organic solvent having a boiling point of 100 ° C.
- a solvent (b3) can be used individually by 1 type or in combination of 2 or more types. When the solvent (b3) contains water, excessive evaporation of the solvent can be prevented and adhesion to dentin can be improved. Accordingly, the solvent (b3) preferably contains water.
- the content of water in the solvent (b3) is preferably 60% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, and most preferably 100% by weight.
- the amount of the solvent (b3) in the pretreatment material (B) is preferably 10 to 60% by weight, more preferably 25 to 50% by weight, and further preferably 30 to 45% by weight. preferable.
- the pretreatment material (B) has a more appropriate tooth demineralization ability, which contributes to the improvement of tooth adhesion.
- the blending amount is 60% by weight or less, the transpiration of the solvent (b3) after the pretreatment material (B) is applied to the adherend becomes easier, and the variation due to the procedure for each operator is reduced. There is an advantage that more stable adhesiveness can be obtained.
- the hydrophilic radical polymerizable monomer (b4) having no acidic group used in the present invention penetrates into the inside of the tooth, improves the degree of polymerization of the cured product, and improves the adhesive force.
- the hydrophilic radical polymerizable monomer (b4) having no acidic group means a hydrophilic radical polymerizable monomer having no acidic group having a solubility in water at 25 ° C. of 5% by weight or more. Further, those having the same solubility of 10% by weight or more are more preferable, and those having the same solubility of 30% by weight or more are more preferable.
- hydrophilic radical polymerizable monomer (b4) having no acidic group for example, it has solubility in water as described above, and has an acidic group (phosphate group, pyrophosphate group, thiophosphate group, phosphone). And those having at least one radical polymerizable group (acryloyl group, methacryloyl group, vinyl group, styrene group, etc.).
- the hydrophilic radically polymerizable monomer (b4) having no acidic group preferably has a (meth) acryloyl group from the viewpoint of radical polymerizability and safety.
- the hydrophilic radical polymerizable monomer (b4) having no acidic group is any of monofunctional (b4-1), bifunctional (b4-2), and trifunctional or higher (b4-3). There may be.
- the monofunctional hydrophilic radical polymerizable monomer (b4-1) having no acidic group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl ( (Meth) acrylate, 1,3-dihydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, Erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N- (dihydroxyethyl) (meth) acrylamide, methoxypolyethylene glycol (meth) acrylate, And (meth) acryloylmorpholine, diethyl (meth) acrylamide and the like.
- 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) are used from the viewpoint of improving the penetration of dentin into the collagen layer.
- Preferred are acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, (meth) acryloylmorpholine, and diethyl (meth) acrylamide, and particularly preferred is 2-hydroxyethyl methacrylate.
- bifunctional hydrophilic radical polymerizable monomer (b4-2) having no acidic group examples include erythritol di (meth) acrylate, sorbitol di (meth) acrylate, mannitol di (meth) acrylate, pentaerythritol di (Meth) acrylate, dipentaerythritol di (meth) acrylate, glycerol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropyloxy) ethane, ethylene bis (meth) acrylamide, propylene bis ( (Meth) acrylamide, butylenebis (meth) acrylamide, N, N ′-(dimethyl) ethylenebis (meth) acrylamide, N, N′-diethyl-1,3-propylenebis (meth) acrylamide, bis [2- (2- Methyl- (meth) acrylic Mino) ethoxycarbonyl]
- 1,2-bis (3-methacryloyloxy-2-hydroxypropyloxy) ethane, propylene bis (meth) acrylamide, N, N ′-(dimethyl) ethylenebis (meth) acrylamide and N , N′-diethyl-1,3-propylenebis (meth) acrylamide is preferred, and 1,2-bis (3-methacryloyloxy-2-hydroxypropyloxy) ethane is more preferred.
- Examples of the trifunctional or higher hydrophilic radical polymerizable monomer (b4-3) having no acidic group include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) ) Acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc.
- dipentaerythritol tetra (meth) from the viewpoint of the balance between penetrability and crosslinkability to teeth. Acrylate and dipentaerythritol penta (meth) acrylate are more preferable.
- the blending amount of the hydrophilic radical polymerizable monomer (b4) having no acidic group in the pretreatment material (B) is preferably 35 to 85% by weight, more preferably 37 to 75% by weight. Preferably, it is 40 to 65% by weight.
- the blending amount of (b4) is 35% by weight or more, the blending effect of (b4) that is an improvement in adhesiveness can be more remarkably exhibited.
- the blending amount of (b4) is 85% by weight or less, the decalcification ability of the tooth of the pretreatment material (B) can be expressed at a high level without impairing the blending effect of (b4). .
- the hydrophilic radical polymerizable monomer (b4) having no acidic group includes a bifunctional hydrophilic radical polymerizable monomer (b4-2) having no acidic group.
- the adhesiveness with a tooth substance, especially the adhesiveness with dentin becomes higher.
- the hydrophilic radical polymerizable monomer (b4) having no acidic group is a bifunctional hydrophilic radical polymerizable monomer (b4-2) and a monofunctional hydrophilic radical polymerizable monomer. Any of the mer (b4-1) is included.
- the blending amount of the bifunctional hydrophilic radical polymerizable monomer (b4-2) having no acidic group is 1 in 100 parts by weight of the total amount of the radical polymerizable monomer contained in the pretreatment material (B). It is preferably ⁇ 20 parts by weight, more preferably 2 to 15 parts by weight, still more preferably 5 to 12 parts by weight.
- (b4) includes both of the bifunctional hydrophilic radical polymerizable monomer (b4-2) and the monofunctional hydrophilic radical polymerizable monomer (b4-1). preferable.
- the blending amount of (b4-2) is preferably 1 to 35 parts by weight, more preferably 100 parts by weight of the total amount of radical polymerizable monomers contained in the pretreatment material (B).
- the amount is 2 to 15 parts by weight, more preferably 5 to 12 parts by weight.
- the blending amount of (b4-1) is preferably 20 to 85 parts by weight, more preferably 40 parts in 100 parts by weight of the total amount of the radical polymerizable monomers contained in the pretreatment material (B). 72 parts by weight, more preferably 45-69 parts by weight.
- the pretreatment material (B) may further contain a polymerization inhibitor (b5) from the viewpoint of storage stability.
- a polymerization inhibitor include 3,5-di-t-butyl-4-hydroxytoluene, hydroquinone, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, 2,6-t-butylphenol, 4-methoxyphenol, and the like. One or more of these may be blended.
- the blending amount of the polymerization inhibitor in the pretreatment material (B) is preferably 0.2 to 5% by weight, more preferably 0.4 to 5% by weight, still more preferably 0.7 to 3% by weight. 2% by weight is even more preferred.
- the blending amount of the polymerization inhibitor (b5) in the pretreatment material (B) is less than 0.4% by weight, the storage stability of the pretreatment material is not sufficient and the color may be changed.
- the polymerization inhibitor may not be dissolved in the pretreatment material composition, and the polymerization inhibitor may precipitate during storage or composition preparation.
- the pretreatment material (B) may further contain a filler.
- a filler the thing similar to the filler (a4) contained in the above-mentioned curable composition (A) can be used.
- the pretreatment material (B) may be blended with a pH adjuster, an ultraviolet absorber, a thickener, a colorant, an antibacterial agent, a fragrance and the like as long as the effects of the present invention are not impaired.
- the packaging form of the pretreatment material (B) may be determined for convenience in consideration of storage stability, and is not particularly limited.
- the polymerization catalyst may be divided and mixed immediately before use. However, in consideration of operability, it is preferably one liquid.
- the adhesive kit of the present invention is excellent in adhesiveness, particularly adhesiveness to the tooth, and has an appropriate curability, and is excellent in operation margin time after contact between the pretreatment material and the adhesive material. Furthermore, it is excellent in storage stability.
- the cured product of the curable composition (A) has high transparency. Therefore, it is suitable for dental use.
- the pretreatment material (B) is used as a dental primer
- the curable composition (A) is used as a dental bonding material, a dental composite resin, a dental cement, or the like.
- the pretreatment material (B) is a dental primer
- the curable composition (A) is a dental cement kit having a dental cement.
- the A paste and B paste obtained as described above were filled in a paste container of “Clear Fill (registered trademark) Esthetic Cement” (manufactured by Kuraeno Noritake Dental Co., Ltd.) which is an automix syringe.
- a mixing chip (“Clear Fill (registered trademark) Esthetic Cement Mixing Chip, manufactured by Kurarenorita Dental Co., Ltd.) is attached to the tip of the paste container. Then, using the mixing chip, A paste and B paste were mixed in an equal volume ratio of 1: 1 to obtain a composition.
- Preparation of pretreatment agent (B) Each component shown in Tables 2 to 4 was mixed at a normal weight ratio shown in the table at room temperature to prepare a primer composition as a pretreatment agent (B). The obtained pretreatment agent (B) was used by filling a container of “Clearfill (registered trademark) Megabond (registered trademark) primer” (manufactured by Kurarenorita Dental Co., Ltd.).
- a composition obtained by kneading A paste and B paste of the curable composition (A) at a volume ratio of 1: 1 using a mixing chip as described above is placed on the obtained bovine tooth surface.
- the film was covered with a release film (trade name “EVAL”, manufactured by Kuraray Co., Ltd.), and allowed to stand at room temperature for 1 hour to be cured.
- EVAL a release film
- one of the stainless steel cylindrical rods (diameter 7 mm, length 2.5 cm) was used by using a dental resin cement (trade name “Panavia 21” manufactured by Kuraray Noritake Dental Co., Ltd.).
- the end face (circular cross section) was bonded and allowed to stand for 30 minutes.
- the prepared pretreatment material (B) is applied in the round hole with a brush, left for 20 seconds, and then air-blowed on the surface to apply the pretreatment material (B).
- the solution was dried until the fluidity was lost. Obtained by kneading the paste A and B paste of the curable composition (A) on a coated surface of the obtained pretreatment material (B) at a volume ratio of 1: 1 using a mixing chip as described above.
- the composition was placed and covered with a release film (trade name “EVAL” manufactured by Kuraray Co., Ltd.), and then allowed to stand at room temperature for 1 hour to be cured.
- one of the stainless steel cylindrical rods (diameter 7 mm, length 2.5 cm) was used by using a dental resin cement (trade name “Panavia 21” manufactured by Kuraray Noritake Dental Co., Ltd.).
- the end face (circular cross section) was bonded and allowed to stand for 30 minutes.
- the test sample immersed in distilled water was allowed to stand for 24 hours in a thermostatic chamber maintained at 37 ° C. to obtain a test piece. A total of five samples for adhesion test were prepared.
- Tensile bond strengths of the above five adhesion test samples were measured with a universal testing machine (manufactured by Shimadzu Corporation) with the crosshead speed set to 2 mm / min. did.
- the polymerized cured product was immersed in distilled water at 37 ° C. for 24 hours and stored, and then subjected to a bending test.
- the bending strength and the flexural modulus were measured by performing a three-point bending test with a universal testing machine at a span of 20 mm and a crosshead speed of 1 mm / min. The average values of the bending strength and the bending elastic modulus for the five samples were taken as the bending strength and bending elastic modulus of the sample.
- a disk-shaped sample (diameter: about 2 cm and thickness: 1 mm) was prepared as follows. That is, a cover glass was placed on a slide glass, and two plate-like stainless steel spacers having a thickness of 1 mm were placed on the slide glass at positions separated from each other by 2.5 cm or more. Between the two spacers, the composition obtained by kneading the paste A and B paste of the curable composition (A) at a volume ratio of 1: 1 using a mixing chip is placed in a hemisphere, The composition was covered with another cover glass and slide glass from above.
- the composition was sandwiched between two glass slides and pressed into a disk shape, and the pressed composition was allowed to stand in a thermostat at 37 ° C. for 1 hour to be completely cured. Since the value in the test largely fluctuates depending on the thickness of the sample, the thickness of the sample was regulated within the range of 0.99 to 1.00 mm (maximum thickness portion 1.00 mm, minimum thickness portion 0.99 mm).
- the lip surface of the bovine mandibular anterior teeth was polished with silicon carbide paper (Nihon Kenshi Co., Ltd.) under running water (# 80) to obtain a sample in which the flat surface of dentin was exposed.
- the flat surface was sized so that a bottom surface of a cylinder having a diameter of 9 mm was sufficiently placed thereon.
- the obtained flat surface was further polished with # 1000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) and then immersed in distilled water.
- a circular cross section of a cylindrical SUS chip (diameter 9 mm and height about 7 mm) was polished with # 1000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.).
- # 1000 silicon carbide paper manufactured by Nihon Kenshi Co., Ltd.
- the bovine teeth soaked in distilled water and the polished SUS chip obtained as described above were allowed to stand in an open chamber set at 35 ° C. for 2 hours and then used for the test.
- the bovine teeth After drying the bovine teeth after standing in an open chamber by air blowing the surface water, it is fixed on the glass slide using utility wax (manufactured by GC Corporation) so that the smooth surface is on top. did.
- the slide glass on which the bovine teeth were placed was placed on the work surface of the open chamber, and the position of the bovine teeth was adjusted so that the work surface and the smooth surface of the bovine teeth were parallel.
- the pretreatment material (B) is applied to the above smooth surface with a brush, left for 20 seconds, and then air-blowed on the surface to dry the applied pretreatment material (B) until the fluidity disappears. did.
- Test Example 1 After placing the composition obtained by kneading A paste and B paste of the curable composition (A) at a volume ratio of 1: 1 as described above on the polished surface of the SUS chip using a mixing chip. The SUS chip was gently placed on the bovine teeth so that the surface to which the composition was applied was in contact with the smooth surface of the bovine teeth. Immediately thereafter, 150 g of a cylindrical weight (diameter 3 cm) was placed on the SUS chip for 1 second, and then the weight was removed. This time was taken as the measurement start time. After 30 seconds from the start of measurement, lightly touch with your finger to check whether the SUS tip moves, then repeat the same operation every 10 seconds, and the place where the SUS tip stops moving is the operation allowance time when the primer contacts did.
- the curable composition and adhesive kit of the present invention are suitable for dental use, and particularly suitable for dental cement and dental cement kit.
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Abstract
Description
前記置換エチレンチオ尿素化合物(a3-1)は、式(I):
前記置換プロピレンチオ尿素化合物(a3-2)は式(II):
前記置換ブチレンチオ尿素化合物(a3-3)は、式(III):
#801:1,2-ビス(3-メタクリロイルオキシ-2-ヒドロキシプロポキシ)エタン
HEMA:2-ヒドロキシエチルメタクリレート
BisGMA:2,2-ビス〔4-(3-メタクリロイルオキシ)-2-ヒドロキシプロポキシフェニル〕プロパン
D2.6E:2,2-ビス(4-メタアクリロイルオキシポリエトキシフェニル)プロパン (エトキシ基の平均付加モル数:2.6)
3G:トリエチレングリコールジメタクリレート
[酸性基含有重合性単量体]
MDP:10-メタクリロイルオキシデシルジハイドロジェンホスフェート
[ハイドロパーオキサイド化合物]
THP:1,1,3,3-テトラメチルブチルハイドロパーオキサイド
[チオ尿素誘導体]
DMETU:4,4-ジメチル-2-イミダゾリジンチオン
METU:4-メチル-2-イミダゾリジンチオン
DEETU:4,4-ジエチル-2-イミダゾリジンチオン
DMPTU:5,5-ジメチル-3,4,5,6-テトラヒドロピリミジン-2(1H)-チオン
CPPTU:5-(2-クロロフェニル)-3,4,5,6-テトラヒドロピリミジン-2(1H)-チオン
EtTU:2-イミダゾリジンチオン
PrTU:テトラヒドロ-2(1H)ピリミジンチオン
BzTU:N-ベンゾイルチオ尿素
TMTU:N,N,N’-トリメチルチオ尿素
[バナジウム化合物]
VOAA:バナジルアセチルアセトネート
BMOV:ビス(マルトラート)オキソバナジウム(IV)
[銅化合物]
CuAA2:アセチルアセトン銅(II)
Cu(OAc)2:酢酸銅(II)
[重合禁止剤]
BHT:3,5-ジ-t-ブチル-4-ヒドロキシトルエン
[紫外線吸収剤]
TN236:チヌビン236(チバ・スペシャリティ・ケミカルズ社製)
[光重合開始剤]
CQ:カンファーキノン
[フィラー]
8235:ショット(株)社製のシラン処理バリウムガラス粉、平均粒子径:2μm、シラン処理濃度:1.4%
G018-117:ショット(株)社製のシラン処理バリウムフルオロアルミノシリケートガラス粉、平均粒子径:2μm、シラン処理濃度:1.4%
Ar380:日本アエロジル(株)社製の微粒子シリカ「AEROSIL(登録商標) 380」 平均粒子径:7nm
[その他]
DMAEMA:ジメチルアミノエチルメタクリレート
JJA:4-(N,N-ジメチルアミノ)安息香酸エチル
各実施例及び比較例の硬化性組成物(A)と前処理剤(B)を以下のように調製し、その特性を評価した。結果を表2~4に示す。
表2~4に記載の各モノマー成分を、表に記載の重量比で常温で混合し、各モノマー組成物を調製した。その後、各モノマー組成物と各種フィラーを表に記載の重量比で常温で混合し、Aペースト及びBペーストを調製した。続いて、Bペーストのみ「クリアフィル(登録商標)FII」(クラレノリタケデンタル(株)製)のレジン容器に15gずつ移し、容器の蓋をして、60℃の恒温器内に24時間静置した後、常温に戻してから用いた。上述のようにして得られたAペースト及びBペーストを、オートミックスシリンジである「クリアフィル(登録商標)エステティック セメント」(クラレノリタケデンタル(株)製)のペースト容器に充填した。なお、Aペースト及びBペーストを混合して組成物を得る際は、前記ペースト容器の先端にミキシングチップ(「クリアフィル(登録商標)エステティック セメント ミキシングチップ、クラレノリタケデンタル(株)製)を装着し、当該ミキシングチップを用いてAペースト及びBペーストを体積比1:1で等量混合して組成物とした。
表2~4に記載の各成分を、表に記載の重量比で常温下で混合して前処理剤(B)であるプライマー組成物を作製した。得られた前処理剤(B)は、「クリアフィル(登録商標) メガボンド(登録商標) プライマー」(クラレノリタケデンタル(株)製)の容器に充填して用いた。
チオ尿素化合物0.030g、及び0.15gに、トリエチレングリコールジメタクリレートをそれぞれ2.97g、及び2.85gを添加した後、25℃にて1時間攪拌して目視で観察し、以下の基準に従って溶解度の評価を実施した。
ウシ下顎前歯の唇面を流水下にて(#80)シリコン・カーバイド紙(日本研紙(株)製)で研磨して、エナメル質の平坦面を露出させたサンプル及び象牙質の平坦面を露出させたサンプルをそれぞれ得た。得られたそれぞれのサンプルを流水下にて#1000のシリコン・カーバイド紙(日本研紙(株)製)でさらに研磨した。研磨終了後、表面の水をエアブローすることで乾燥した。乾燥後の平滑面に、直径3mmの丸穴を有する厚さ約150μmの粘着テープを貼着し、接着面積を規定した。
硬化性組成物(A)のAペーストとBペーストとをミキシングチップを用いて体積比1:1で混練して得た組成物を、混練して直ちにレジン収容部に静置した以外は、JIS T6611:2009の「6.4 操作時間」の記載に準じて、硬化性組成物(A)の23℃操作余裕時間(初期)を測定した。
硬化性組成物(A)を充填したオートミックスシリンジを、50℃の恒温器内で2週間保存した後、「23℃操作余裕時間(初期)」と同様の方法で操作余裕時間を測定した。
硬化性組成物(A)を充填したオートミックスシリンジを、50℃の恒温器内で4週間保存した後、「23℃操作余裕時間(初期)」と同様の方法で操作余裕時間を測定した。
硬化性組成物(A)のAペーストとBペーストとをミキシングチップを用いて体積比1:1で混練して得た組成物を、混練して直ちにレジン収容部に静置した以外は、JIS T6611:2009の「6.5 硬化時間」の記載に準じて、硬化性組成物(A)の37℃硬化時間(初期)を測定した。
硬化性組成物(A)を充填したオートミックスシリンジを、50℃の恒温器内で2週間保存した後、「37℃硬化時間(初期)」と同様の方法で操作余裕時間を測定した。
硬化性組成物(A)を充填したオートミックスシリンジを、50℃の恒温器内で4週間保存した後、「37℃硬化時間(初期)」と同様の方法で操作余裕時間を測定した。
スライドガラス板上にポリエステルフィルムを敷設し、その上に縦2mm×横25mm×深さ2mmのステンレス製の型枠を載置した。次いで、硬化性組成物(A)のAペーストとBペーストとをミキシングチップを用いて体積比1:1で混練して得た組成物を型枠内に充填し、型枠内の組成物の表面をポリエステルフィルムを介してスライドガラスで圧接し、2枚のスライドガラスを幅25mmのダブルクリップを用いて固定した。ダブルクリップで固定したサンプルを37℃の恒温器内で1時間静置して重合硬化させた後、サンプルを恒温器から取り出し、型枠から組成物の重合硬化物を取り外した。重合硬化物を37℃の蒸留水中に24時間浸漬して保管した後、曲げ試験を行った。曲げ強度及び曲げ弾性率は、万能試験機により、スパン20mm、クロスヘッドスピード1mm/分で3点曲げ試験を行って測定した。5個の試料についての曲げ強度及び曲げ弾性率の平均値を、その試料の曲げ強度及び曲げ弾性率とした。
硬化性組成物(A)を用いて、円盤型(直径約2cm及び厚さ1mm)のサンプルを次のようにして作製した。すなわち、スライドガラスの上にカバーガラスを載せ、さらにその上に厚さ1mmの板状のステンレス製スペーサーを2枚、互いに2.5cm以上離れた位置に置いた。それら2枚のスペーサーの間に、硬化性組成物(A)のAペーストとBペーストとをミキシングチップを用いて体積比1:1で混練して得た組成物を半球状に載置し、その組成物にもう1枚のカバーガラス及びスライドガラスを上方から被せた。2枚のスライドガラスの間に組成物を挟み込んで円盤状に圧接し、その圧接状態の組成物を37℃の恒温器内に1時間静置して、完全に硬化させた。サンプルの厚みにより試験での値が大きく変動してしまうため、サンプルの厚みを0.99~1.00mm(最大厚み部1.00mm、最小厚み部0.99mm)の範囲内に規制した。
上記作製した硬化性組成物(A)からなるペースト硬化物の円盤型(直径約2cm及び厚さ1mm)のサンプルについて、JIS-Z8729に記載の条件を満足する分光色差計(日本電色工業(株)製、商品名「SE 6000」)を用いて、D65光源、測色視野2度の条件において、試験片の背後に標準白板を置いた状態でL*、a*、b*表色系での色度を測定し、これらをL*0、a*0、b*0とした。続いて、当該サンプルをスクリュー管中に移し、蒸留水を充填した後、蓋をしっかりと締めて70℃の恒温器内に4週間静置した。静置後のサンプルについても同様の手法でL*、a*、b*表色系での色度を測定し、これらをL*1、a*1、b*1とした。得られたそれぞれの値を下式に代入し、変色の指標であるΔE*を求めた。
ΔE*={(L*1-L*0)2+(a*1-a*0)2+(b*1-b*0)2}1/2
ウシ下顎前歯の唇面を流水下にて(#80)シリコン・カーバイド紙(日本研紙(株)製)で研磨して、象牙質の平坦面を露出させたサンプルを得た。当該平坦面は、直径9mmの円柱の底面が充分に載せられる大きさとした。得られた平坦面を、#1000のシリコン・カーバイド紙(日本研紙(株)製)でさらに研磨した後、蒸留水中に浸漬した。続いて、円柱状のSUSチップ(直径9mm及び高さ約7mm)の円断面を、#1000のシリコン・カーバイド紙(日本研紙(株)製)で研磨した。以上のようにして得られた、蒸留水に浸漬した牛歯と、研磨後のSUSチップとを、35℃に設定したオープンチャンバー中に2時間静置してから試験に用いた。
前記SUSチップの研磨面に、硬化性組成物(A)のAペーストとBペーストとを、上述の通りミキシングチップを用いて体積比1:1で混練して得た組成物を載置した後、組成物を塗布した面が、牛歯の平滑面と接するように、牛歯の上にSUSチップを静かに置いた。その後、直ちに150gの円柱状の錘(直径3cm)を当該SUSチップの上に1秒間載せてから、錘を除去し、この時点を測定開始時間とした。測定開始から30秒経過後に指で軽く触れてSUSチップが動くか否かを確認し、続いて10秒毎に同じ動作を繰り返し、SUSチップが動かなくなったところをプライマー接触時の操作余裕時間とした。
Claims (10)
- 酸性基を有しないラジカル重合性単量体(a1)、ハイドロパーオキサイド化合物(a2)、並びに、置換エチレンチオ尿素化合物(a3-1)、置換プロピレンチオ尿素化合物(a3-2)、及び置換ブチレンチオ尿素化合物(a3-3)からなる群より選択される少なくとも1種の環状チオ尿素化合物(a3)を含有する硬化性組成物(A)であって、
前記置換エチレンチオ尿素化合物(a3-1)は、式(I):
前記置換プロピレンチオ尿素化合物(a3-2)は式(II):
前記置換ブチレンチオ尿素化合物(a3-3)は、式(III):
- 前記硬化性組成物(A)が、フィラー(a4)をさらに含有する請求項1に記載の硬化性組成物。
- 前記酸性基を有しないラジカル重合性単量体(a1)が、(メタ)アクリレート系重合性単量体及び/又は(メタ)アクリルアミド系重合性単量体である請求項1に記載の硬化性組成物。
- 前記硬化性組成物(A)が、酸性基含有ラジカル重合性単量体(a5)をさらに含有する請求項1に記載の硬化性組成物。
- 前記硬化性組成物(A)が、バナジウム化合物(a6)及び/又は銅化合物(a7)をさらに含有する請求項1に記載の硬化性組成物。
- 前記環状チオ尿素化合物(a3)が、4-メチル-2-イミダゾリジンチオン、4,4-ジメチル-2-イミダゾリジンチオン、4-エチル-2-イミダゾリジンチオン、及び4,4-ジエチル-2-イミダゾリジンチオンからなる群より選択される少なくとも1種である請求項1に記載の硬化性組成物。
- 歯科用である請求項1に記載の硬化性組成物。
- 酸性基含有ラジカル重合性単量体(b1)、重合促進剤(b2)、溶媒(b3)、及び酸性基を有しない親水性ラジカル重合性単量体(b4)を含有する前処理材(B)と、請求項1に記載の硬化性組成物(A)とを含む接着キット。
- 前記重合促進剤(b2)が、バナジウム化合物(b2-1)及び/又は銅化合物(b2-2)である請求項8に記載の接着キット。
- 歯科用である請求項8に記載の接着キット。
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JP2018168099A (ja) * | 2017-03-30 | 2018-11-01 | 株式会社ジーシー | 歯科用プライマー及び歯科用補綴物接着用キット |
JP2019089724A (ja) * | 2017-11-14 | 2019-06-13 | 株式会社ジーシー | 歯科用光重合性組成物及び光重合開始剤 |
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US20210393488A1 (en) * | 2018-11-28 | 2021-12-23 | Kuraray Noritake Dental Inc. | Dental adhesive material kit |
JPWO2021049335A1 (ja) * | 2019-09-10 | 2021-03-18 | ||
WO2021049335A1 (ja) * | 2019-09-10 | 2021-03-18 | 株式会社ジーシー | 歯科用重合性組成物 |
JP7233554B2 (ja) | 2019-09-10 | 2023-03-06 | 株式会社ジーシー | 歯科用重合性組成物 |
WO2021201207A1 (ja) * | 2020-04-03 | 2021-10-07 | 日本曹達株式会社 | 2液型接着性組成物 |
WO2023058773A1 (ja) | 2021-10-08 | 2023-04-13 | クラレノリタケデンタル株式会社 | 歯科用硬化性組成物及び歯科用キット |
Also Published As
Publication number | Publication date |
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US9889070B2 (en) | 2018-02-13 |
JP6248093B2 (ja) | 2017-12-13 |
ES2821820T3 (es) | 2021-04-27 |
EP2979681A1 (en) | 2016-02-03 |
EP2979681A4 (en) | 2016-09-21 |
CN105101935A (zh) | 2015-11-25 |
CN105101935B (zh) | 2018-02-23 |
JPWO2014156077A1 (ja) | 2017-02-16 |
US20160051450A1 (en) | 2016-02-25 |
EP2979681B1 (en) | 2020-09-16 |
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