WO2006016649A1 - 歯科用重合性組成物 - Google Patents
歯科用重合性組成物 Download PDFInfo
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- WO2006016649A1 WO2006016649A1 PCT/JP2005/014744 JP2005014744W WO2006016649A1 WO 2006016649 A1 WO2006016649 A1 WO 2006016649A1 JP 2005014744 W JP2005014744 W JP 2005014744W WO 2006016649 A1 WO2006016649 A1 WO 2006016649A1
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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
- A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
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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
- A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
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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
Definitions
- the present invention relates to a dental polymerizable composition.
- a dental polymerizable composition for more details, as various filling materials, repair materials, denture base materials, dental crown materials, bonding materials, adhesives, coating agents, plaque formation inhibitors, hypersensitivity inhibitors, etc. in the dental materials field
- the present invention relates to a dental composite composition that can be suitably used.
- a dental polymerizable composition comprising a polymerizable monomer and a polymerization initiator is currently widely used clinically.
- a dental polymerizable composition can be used to bond dental restoration materials called composite resins, such as dental fractures and dental caries cavity filling, and dental restorations such as composite resins and inlay Z crowns to teeth. It is used for dental adhesives and cements, artificial teeth, denture base materials, and coating agents.
- a coating agent for example, a silicone oligomer containing fluoroalkyl groups at both ends of the main chain
- a coating agent for example, a silicone oligomer containing fluoroalkyl groups at both ends of the main chain
- denture base lining material containing fluorine-containing (meth) acrylate as part of the monomer coating composition for example, see Patent Documents 3 to 4
- having polar groups such as acrylic acid Coating composition containing a fluorine-containing polymer obtained by copolymerizing a monomer and a monomer containing a fluorine atom
- Dental materials using fluorine-based materials have been proposed.
- Patent Document 1 Japanese Unexamined Patent Publication No. 2003-48842
- Patent Document 2 JP-A-5-155730
- Patent Document 3 Japanese Patent Laid-Open No. 2000-312689
- Patent Document 4 Japanese Patent Laid-Open No. 2003-95838
- Patent Document 5 Japanese Patent Publication No. 10-510531
- Patent Document 6 Japanese Patent Laid-Open No. 5-255032
- Patent Document 7 Japanese Patent Laid-Open No. 10-7731
- Patent Document 8 JP-A-10-251348
- Patent Document 9 Japanese Patent Laid-Open No. 2003-253022
- Patent Document 10 JP-A-10-245419
- Patent Document 2 The coating agent described in Patent Document 2 is fluorinated when it is worn by a toothbrush or the like.
- the compound silicon oligomer
- There are drawbacks such as very difficult to peel off.
- the alcohol residue is a fluoroalkyl group as a fluorinated compound (fluorinated (meth) acrylate) (meta )
- the power at which attalate is used The (meth) acrylate with this structure has a remarkable effect unless it is incorporated in a denture base lining material or coating composition in a certain proportion (usually 50% or more). Cannot be obtained, which is disadvantageous in terms of cost.
- Patent Document 5 describes a force that describes that a polymerizable composition comprising a fluorine-containing polymer and a monomer suppresses adhesion of black particles. Specifically described fluorine-containing polymer. Is only a random copolymer of a fluorine-containing monomer and a polar group-containing monomer, and a high antifouling effect was not recognized as long as the inventors studied.
- the dental composition described in Patent Document 6 is a cement composition by ionic crosslinking, and is different from a polymer composition, so it is used for applications that are exposed on the surface of a tooth or restorative material. V, there is a fault that can not be.
- Patent Documents 7 to 9 improve the antifouling property of a substrate by adsorbing a fluorine compound (polymer) excellent in antifouling property to a substrate such as fiber, paper, plastic, or metal.
- a fluorine compound polymer
- the anti-fouling property does not last because the fluorine compound easily peels off the surface of the substrate, and these documents are polymerized with fluorinated compounds. This suggests that it is used in combination with a sex monomer.
- the photopolymerizable coating agent described in Patent Document 10 is for the purpose of surface modification of general industrial products, and these industrial products have a complete environment at the time of application and after application. It does not give any suggestion for use as a coating agent for different natural teeth or dental restorative materials. In other words, other physical properties are required for dental applications, not just for preventing contamination. For example, in tooth surface coating agents and dental composites, discoloration in the oral cavity, abrasion resistance, resistance to discoloration of the cured product itself, prevention of plaque and biofilm accumulation, and durability against adhesion to tooth surfaces. This is because the basic performance is required as a matter of course.
- the surface can be imparted with antifouling property and plaque adhesion inhibiting property by a simple method, and is excellent in abrasion resistance, discoloration resistance and adhesion to the tooth surface of the cured product, and is a coating agent.
- a dental polymerizable composition useful as a dental composite resin is desired.
- the object of the present invention is to provide excellent resistance to contamination of the surface of the cured product, prevention of plaque adhesion, wear resistance, discoloration resistance of the cured product itself, aesthetics, and adhesion to the tooth surface in the oral cavity.
- Another object of the present invention is to provide a dental polymerizable composition.
- the present invention provides:
- Fluorine compound comprising a chain polymer having a main chain containing a monomer unit having a hydrophilic group and having terminal groups each having a fluoroalkyl group at both ends of the main chain [ (Hereinafter referred to as fluorine compound (a)),
- polymerizable monomer (b) a polymerizable monomer (hereinafter referred to as polymerizable monomer (b)), and
- polymerization initiator (c) Polymerization initiator (hereinafter referred to as polymerization initiator (c))
- the dental polymerizable composition is applied to the surface of a tooth or a dental restorative material, the solvent contained in the dental polymerizable composition is evaporated, and then cured, whereby the tooth or dental composition is cured.
- a method for curing a dental polymerizable composition comprising forming a layer of a fluorine compound on the surface of a dental restorative material
- the surface of the cured product obtained by polymerizing the polymerizable composition of the present invention has a hydrophilic group in addition to the difficulty of soiling due to the water and oil repellency of fluorine. It exhibits excellent antifouling properties such that oil-based stains are difficult to attach.
- the polymerizable composition of the present invention contributes to prevention of root caries and periodontal disease.
- the cured product of the polymerizable composition of the present invention has excellent wear resistance and gloss. Since it is maintained for a long period of time and the discoloration of the cured product itself is small, there is an effect that it is excellent in aesthetics.
- the fluorine compound (a) comprises a chain polymer having a main chain containing a monomer unit having a hydrophilic group and having terminal groups each having a fluoroalkyl group at both ends of the main chain.
- the fluorine compound (a) includes a chain polymer having a main chain containing a monomer unit having a hydrophilic group and having terminal groups each having a fluoroalkyl group at both ends of the main chain.
- the hydrophilic group include, for example, a hydroxyl group, an amide group, an amino group, an alkylamino group, a polyoxyalkylene group, a morpholyl group, a cyano group; a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, and the like.
- Acid groups or salts thereof include quaternary ammonium salt groups such as trimethylammonium chloride, pyridinium chloride, pyridinum bromide, etc .; alkylbetaine, carboxybetaine, sulfobetaine, phospho Zwitterionic groups such as betaine groups; cyclic ether groups such as epoxy groups, oxetal groups, and tetrahydrofurfuryl groups; acetyl groups, Such as Boniru group, and the like.
- acidic groups such as carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, and phosphoric acid groups or salts thereof; trimethylammonium chloride groups, pyridini Quaternary ammonium salts such as um chloride and pyridinium bromide; zwitterionic groups such as alkylbetaine, carboxybetaine, sulfobetaine and phosphobetaine are preferred! /.
- Examples of the polymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 10-hydroxy decyl (meth) acrylate, glycerol mono (Meth) acrylate, N-methylol (meth) acrylamide, N-2-hydroxychetyl (meth) acrylamide and the like.
- (meta) acrylate” means both “attalate” and “metatalate”.
- Examples of the polymerizable monomer having an amide group include N-methylol (meth) acrylamide, N-bul-2-pyrrolidone, N-bull-2-piperidone, (meth) acrylamide, N, N-dimethyl (meth) acrylamide and the like.
- (meth) acrylamide means both “acrylamide” and “methacrylamide”.
- Examples of the polymerizable monomer having an amino group-aminoamino group include 2-aminoethyl (meth) acrylate and N, N-dimethylaminoethyl (meth) acrylate.
- Examples of the polymerizable monomer having a polyoxyalkylene group include polyethylene dallicol mono (meth) acrylate.
- Examples of the polymerizable monomer having a morpholyl group include (meth) atalyloylmorpholine.
- (meth) atalyloylmorpholine means both “acryloylmorpholine” and “methacryloylmorpholine”.
- Examples of the polymerizable monomer having an zwitterion include 2- (meth) acrylamide-2-methylpropanesulfonic acid.
- Examples of the polymerizable monomer having a cyclic ether group include tetrahydrofurfuryl (meth) acrylate and glycidyl (meth) acrylate.
- Examples of the polymerizable monomer having a quaternary ammonium base include 2- (meth) atalyloyloxychetyltrimethylammonium chloride, 12- (meth) atalylooxide chloride.
- (meth) atalyloyl means both “attalyloyl” and “methacryloyl”.
- the polymerizable monomer having a phosphoric acid group or a salt thereof and the polymerizable monomer having a phosphonic acid group or a salt thereof for example, 2- (meth) taroloyloxetyl dinoide mouth Genphosphate, 4 (Meth) Atalyloxybutyl dihydrogen phosphate, 6— (Meth) Atalyloxyhexyl dihydrogen phosphate, 9— (Meth) Atalyloxyloxyno-dihydrogen phosphate, 10— (Metal ) Ataliloyloxydecyl di-nodrogen phosphate, 11 (meth) atalyleunoxenodecinoresinoidophosphate phosphate, 12 (meth) atari oral inoleoxide decinoresidue hydrogen phosphate, 16 — (meta ) Atalyloxyhexadecyl dihydrogen phosphate, 2— (meth) atta
- Examples of the polymerizable monomer having a carboxylic acid group or a salt thereof include maleic acid, itaconic acid, fumaric acid, (meth) acrylic acid, 4 (meth) acryloyloxyethoxycarbol phthalate.
- Examples of the polymerizable monomer having a sulfonic acid group or a salt thereof include 2 (meth) arylamide-2-methylpropane sulfonic acid, styrene sulfonic acid, 2-sulfoethyl (meth) acrylate, 10 sulfodecyl ( Examples include (meth) acrylate, 6-sulfohexyl (meth) acrylate, alkali metal salts, alkaline earth metal salts, and ammonium salts thereof.
- polymerizable monomers having a hydrophilic group monomers having a carboxylic acid group such as (meth) acrylic acid and 4 (meth) acryloyloxyethoxycarbophthalic acid; ) Polymerizable monomers having a phosphate group such as acryloyloxychetyl dihydrogen phosphate, 10- (meth) attayloxy decyl dihydrogen phosphate; Phosphonic acids such as vinyl phosphonic acid A polymerizable monomer having a group; and styrene sulfonic acid, etc.
- carboxylic acid group such as (meth) acrylic acid and 4 (meth) acryloyloxyethoxycarbophthalic acid
- Polymerizable monomers having a phosphate group such as acryloyloxychetyl dihydrogen phosphate, 10- (meth) attayloxy decyl dihydrogen phosphate
- Phosphonic acids such as vinyl phosphonic acid A poly
- Polymerizable monomer having a sulfonic acid group polymerizable monomer having an amphoteric ion such as 2 (meth) acrylamide 2-methylpropane sulfonic acid, 2- (meth) atallylooxychetyl trimethyl ammonium-
- Polymeric monomers having a quaternary ammonium base such as um chloride and 12- (meth) attaroyloxide decyl pyridi-mud are preferred.
- the chain polymer having a monomer unit having a hydrophilic group is a chain obtained by polymerizing one or more of the polymerizable monomers having a hydrophilic group. And the like polymer.
- Examples of the chain polymer having a monomer unit having a hydrophilic group include, for example, 2 hydroxychetyl (meth) acrylate, 3 hydroxypropyl (meth) acrylate, 10 hydroxydecyl (meth) acrylate.
- Glycerin mono (meth) acrylate ethylene glycol mono (meth) acrylate, N-methylol (meth) acrylamide, N-2-hydroxyethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-bule — 2-pyrrolidone, N bulle— 2-piperidone, (meth) acrylamide, N, N dimethyl (meth) acrylamide, 2-— (meth) acrylamido-2-methylpropanesulfonic acid, tetrahydrofurfuryl (meth) acrylate, Glycidyl (meth) atalylate, (meth) atalyloylmorpholine, N, N dimethylaminoethyl (Meth) Athalylate, 2-Aminoethyl (Meth) Atalylate, 2— (Meth) Atalyloyloxy dihydrogen phosphate, 4— (Meth) Atalyloxybutyl dihydr
- the polymerizable monomer having a hydrophilic group may be copolymerized with the polymerizable monomer having no hydrophilic group as long as the object of the present invention is not impaired. !
- the polymerizable monomer includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) Examples include attalylate, lauryl (meth) acrylate, 3- (meth) allyloyloxypropyltrimethoxysilane, butyltrioxysilane, and styrene.
- the amount of the polymerizable monomer having no hydrophilic group is usually polymerized from the viewpoint that the hydrophilicity of the entire fluorine compound (a) is not significantly impaired.
- Both ends of the chain polymer having a polymer unit of a polymerizable monomer having a hydrophilic group have a hydrophilic group using, for example, a polymerizable monomer having a fluoroalkyl group in the side chain.
- Chemical Reviews No. 96 (1 996), No. 5, pp. 1779-1808 [This is described!] It can be protected with a terminal group containing a fluoroalkyl group by, for example, a method in which a polymerizable monomer having a hydrophilic group is superposed.
- fluoroalkyl group examples include a linear, branched or cyclic fluoroalkyl group having 1 to 12 carbon atoms.
- fluoroalkyl groups include those of the formula: (CF) F (m represents an integer of 1 to 12
- a fluoroalkyl group, a perfluorocycloalkyl group, and the like are fluoroalkyl group, a perfluorocycloalkyl group, and the like. Among these, —CF group, —C F group, —C F group, —C F group and perfluoro
- Chlohexyl group is preferred.
- the number average molecular weight of the fluorine compound (a) is also preferred from the viewpoints of solubility in the polymerizable monomer (b) and the solvent (d) and antifouling properties.
- Preferable examples of the fluorine compound (a) include several groups having a main chain containing a monomer unit having a hydrophilic group and having terminal groups each containing a fluoroalkyl group at both ends of the main chain.
- Moyo V and fluorine compounds are examples having a main chain containing a monomer unit having a hydrophilic group and having terminal groups each containing a fluoroalkyl group at both ends of the main chain.
- fluorine compound (a) include compounds of the formula (I):
- each Rf independently represents a fluoroalkyl group or a fluoroalkyl group.
- R 1 and R 2 are each independently a hydrocarbon group having 1 to 6 carbon atoms which may have a hydrogen atom or a halogen atom,
- X is a hydrophilic group or a hydrophilic group A monovalent organic group having a group, Z represents a hydrogen atom or a monovalent organic group other than X;
- X and y each independently represent a degree of polymerization determined based on the number average molecular weight, and ⁇ / (x + y) is 0 to 0.5.
- Each group may be arranged randomly or in blocks.
- the fluorine compound represented by the formula (I) is preferable from the viewpoint of ease of synthesis and imparting excellent antifouling properties.
- a fluoroalkyloxy group having 1 to 12 carbon atoms is located at the terminal, an organic group having 2 to 30 carbon atoms, and a fluorine group having 1 to 12 carbon atoms.
- Examples include oloalkyloxy groups.
- the fluoroalkyloxy group and the fluoroalkyl group may be linear or branched.
- Rf fluorine represented by the formula: (CF) F (p represents an integer of 1 to 12).
- Rf group represented by (representing an elementary atom or a fluorine atom) is also preferred. Among them, a group represented by the formula: COO 2 -CH CF, a group represented by the formula: COO—CH (CF) H, a formula: COO
- a group represented by COO-CH (CF) H represented by the formula: —COO— (CH) (CF) H
- R 1 and R 2 may each independently have a hydrogen atom or a halogen atom.
- ⁇ Indicates a hydrocarbon group having 1 to 6 carbon atoms. Examples of the hydrocarbon group having a halogen atom! /, May! /, And having 1 to 6 carbon atoms include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, which may have a halogen atom, Examples include hexyl group, cyclohexyl group, and phenol group.
- R 1 and R 2 are preferably a hydrogen atom, a methyl group, a phenyl group, or a trifluoromethyl group.
- X represents a hydrophilic group or a monovalent organic group having a hydrophilic group.
- the hydrophilic group include acids such as hydroxyl group, amide group, amino group, alkylamino group, polyoxyalkylene group, morpholyl group, cyano group, carboxylic acid group, sulfonic acid group, phosphonic acid group and phosphoric acid group.
- Quaternary ammonium bases such as trimethylammonium chloride group, pyridinium chloride group, pyridinium bromide group, sulfonium base, pyrylium base, phosphonium base, ododonium base, alkyl
- zwitterionic groups such as betaine, carboxybetaine, sulfobetaine, and phosphobetaine groups
- cyclic ether groups such as epoxy groups, oxetal groups, and tetrahydrofurfuryl groups, acetyl groups, and acetocarbo groups.
- acidic groups such as carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, and phosphoric acid groups or salts thereof
- quaternary ammonia such as trimethyl ammonium chloride, pyridinium chloride, and pyridyl chloride.
- zwitterionic groups such as alkylbetaine groups, carboxybetaine groups, sulfobetaine groups, phosphobetaine groups and the like are preferred.
- the monovalent organic group having a hydrophilic group has a hydrophilic group among the side chain structures of a chain polymer obtained by polymerizing a polymerizable monomer having a hydrophilic group. It means the part corresponding to the side chain structure. For example, taking 2-hydroxyethyl methacrylate as an example of a polymerizable monomer having a hydrophilic group, the structure other than the bull bond, which is not a methyl group, that is, COO—CH 2 CH—OH. The group corresponds to X.
- CONH— (CH 2) —Y (a represents an integer of 1 to 6) is preferable.
- Y represents a hydrophilic group, and examples thereof include a hydroxyl group, an amide group, an amino group, an alkylamino group, a polyoxyalkylene group, a morpholyl group, a cyano group, a carboxylic acid group, and a sulfonic acid.
- Groups phosphonic acid groups, acidic groups such as phosphoric acid groups or salts thereof, quaternary ammonium bases such as trimethylammonium chloride group, pyridinium chloride group, pyridinium bromide group, sulfonium base, pyrylium base, phosphonium base, Zodine bases, zwitterionic groups such as alkylbetaine, carboxybetaine, sulfobetaine, phosphobetaine groups, cyclic ether groups such as epoxy groups, oxetanyl groups, tetrahydrofurfuryl groups, acetyl groups, and acetocarbon groups. Can be mentioned.
- acidic groups such as carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, phosphoric acid groups or salts thereof; quaternary ammonia such as trimethyl ammonium chloride group, pyridinium chloride group, pyridinium bromide group, etc.
- a zwitterionic group such as an alkyl betaine group, a carboxybetaine group, a sulfobetaine group, or a phosphobetaine group is preferred.
- the fluorine compound represented by the formula (I) is, for example, a compound represented by the formula:
- the solubility of the polymerizable monomer (f) having a hydrophilic group in water at 15 ° C is 10% by weight or more, preferably 20% by weight or more.
- Representative examples of the polymerizable monomer (f) having a hydrophilic group include a polymerizable monomer having a hydroxyl group, a polymerizable monomer having an amide group, and a polymerizable monomer having an amino group and an aminoalkyl group.
- Monomer polymerizable monomer having polyoxyalkylene group, polymerizable monomer having morpholyl group, polymerizable monomer having cyclic ether group, carboxylic acid group, phosphoric acid group, phosphonic acid group, sulfone Examples thereof include a polymerizable monomer having an acidic group such as an acid group, a polymerizable monomer having a quaternary ammonium base, and a polymerizable monomer having an amphoteric ion.
- Examples of the polymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 10-hydroxy decyl (meth) acrylate, glycerol mono (Meth) acrylate, N-methylol (meth) acrylamide, N-2-hydroxychetyl (meth) acrylamide and the like.
- Examples of polymerizable monomers having an amide group include N-methylol (meth) acrylamide.
- N-Bul-2-pyrrolidone N-Bul-2-piperidone, (meth) acrylamide, N, N-dimethyl (meth) acrylamide and the like.
- Examples of the polymerizable monomer having an amino group and an aminoamino group include 2-aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and the like.
- Examples of the polymerizable monomer having a polyoxyalkylene group include polyethylene dallicol mono (meth) acrylate.
- Examples of the polymerizable monomer having a morpholyl group include (meth) atalyloylmorpholine.
- Examples of the polymerizable monomer having a cyclic ether group include tetrahydrofurfuryl (meth) acrylate and glycidyl (meth) acrylate.
- polymerizable monomer having a carboxylic acid group examples include maleic acid, itaconic acid, fumaric acid, (meth) acrylic acid, 4 (meth) acryloyloxyethoxycarbophthalic acid, 4 (Meth) Ataryloxybutyloxycarboxylphthalic acid, 4 (Meth) Ataryloxyhexyloxycarboxylphthalic acid, 4 (Meth) Ataryloxyoxyloxycarboxylphthalic acid, 4 (Metal ) Ataloyloxydecyloxycarbophthalic acid, 5 (meth) atallyloylaminopentylcarboxylic acid, 6 (meth) atallyloyloxy— 1, 1— hexanedicarboxylic acid, 8 (meth) atalyloylo 1,1-octanedicarboxylic acid, 10- (meth) atallyloyloxy-1,1-decanedicarboxylic acid
- Group, pyrophosphate group (one P ( 0) (OH)
- polymerizable monomer having a phosphoric acid group and the polymerizable monomer having a phosphonic acid group include 2 (meth) attaroyloxychetyl dihydrogen phosphate, 3 (meth) attaly Royloxypropyl dihydrogen phosphate, 4-— (meth) attayloxy butyl dihydrogen phosphate, 6— (meth) attayloxy hexyl dihydride Gen phosphate, 8-— (meth) attaroyloxyoctyl Dihydrogen phosphate, 9 (meth) ataryl oxyxino-dihydrogen phosphate, 10 (meth) taloyl oxydecyl dihydrogen phosphate, 11-(meth) atta yloxy decyl nolesinoid acid phosphate, 12— (Meth) Atari Mouth Inoleoxide Decinoresinoidoid Roger Phosphate, 16 (meth)
- 3 is a polymerizable monomer having an OSO H group.
- polymerizable monomer having a sulfonic acid group examples include 2 (meth) acrylamide-2 methylpropane sulfonic acid, styrene sulfonic acid, 2-sulfoethyl (meth) atrelate, 10-sulfodecyl (meth)
- acid chlorides, alkali metal salts, alkaline earth metal salts and ammonium salts, such as acrylate, 6-sulfohexyl (meth) acrylate, etc. Can be mentioned.
- polymerizable monomer having a quaternary ammonium base examples include 2 (meth) attayl oxychetyl trimethyl ammonium chloride, 12- (meth) attaroyloxide decyl pyridi -Umbromide, 2 (meth) atalylooxychetyl dimethyloctylan mo-um chloride, and the like.
- polymerizable monomer having an zwitterionic group examples include 2 (meth) acrylamide
- Examples thereof include 2-methylpropanesulfonic acid.
- the fluorine compound (a) is a carboxylic acid group or a sulfonic acid as a hydrophilic group of the polymerizable monomer ⁇ from the viewpoint of providing higher antifouling properties and an effect of suppressing the adhesion of plaque to the surface of the cured product.
- Groups, acidic groups such as phosphonic acid groups and phosphoric acid groups or salts thereof; quaternary ammonium bases such as trimethyl chloride group, pyridinium chloride group, pyridinium bromide group; alkyl betaine group, carboxybetaine It preferably has a zwitterionic group such as a group, a sulfobetaine group or a phosphobetaine group.
- the fluorine compound (a) having the hydrophilic group can be easily obtained by using the polymerizable monomer having the hydrophilic group.
- the polymerizable monomer (f) having a hydrophilic group may be used alone or in combination of two or more kinds.
- a polymerizable monomer having two or more acidic groups is used as a polymerizable monomer having a hydrophilic group
- at least one polymerizable monomer having a carboxylic acid group is used. It is desirable.
- (meth) acrylic acid is particularly preferred as the polymerizable monomer having a carboxylic acid group.
- the value of the molar ratio of (meth) acrylic acid to the other polymerizable monomer having an acidic group [(meth) acrylic acid Z other polymerizable monomer] is 0.5 to 100, preferably 1 to 50, more preferably 2 to 10.
- the polymerizable monomer (f) is a polymerizable monomer having no hydrophilic group within a range that does not impair the antifouling property, such as methyl (meth) acrylate, butyl (meta It may be used with hydrophobic monomers such as) acrylate, (meth) attayloxypropyltrimethoxysilane, vinyltrimethoxysilane.
- the amount of the hydrophobic monomer is usually preferably not more than 50 mol%, preferably not more than 20 mol%, based on the total amount of polymerizable monomers used for polymerization. More preferred to be.
- the peroxyacid compound (e) is used as a polymerization initiator.
- the peroxide (e) include peroxides represented by the formula: 1 «—00-0 to 0-1 « (where 1 «is the same as above).
- a fluorine compound represented by the formula (I) is obtained by polymerizing the polymerizable monomer (f) using a peracid fluoroalkane as the peracid compound (e).
- a peracid fluoroalkane as the peracid compound (e).
- a normal polymerization method using a peroxide as a polymerization initiator can be applied. More specifically, for example, in the presence of a peroxyfluoroalkanoyl, in an inert solution such as a halogenated aliphatic hydrocarbon, the polymerizable monomer is at a temperature of 0 to 150 ° C. at normal pressure.
- the fluorine compound represented by the formula (I) can be produced by polymerizing the monomer (f) and, if necessary, a hydrophobic monomer.
- fluorine compound (a) for example, a fluorine monomer having a perfluoroalkyl group in the side chain is used, and the polymerizable monomer (f) or the polymerizable monomer is used.
- examples thereof include a block copolymerization method with a monomer mixture of the monomer (f) and a hydrophobic monomer.
- fluorine monomer examples include 1H, 1H, 2H, 2H-norfluo-mouth hexyl (meth) acrylate, 1H, 1H, 2H, 2H-tridecafluorooctyl (meta ) Atrelate, 1H, 1H, 2H, 3H, 3H— 2-Hydroxymonotridecafluoronorol (meth) acrylate, 1H, 1H, 2H, 2H—Unde force fluoro-5-methylhexyl (meth) Atalylate, 1H, 1H, 5H—octafluoropentyl (meth) atalylate, 1H, 1H, 6H—decafluorohexyl (meth) atarylate, 1H, 1H, 7H—dodecafluoroheptyl (meth) atari 1H, 1H, 9H—Hexadecafluoronorol (meth)
- the amount of the fluorine compound (a) is 0 with respect to 100 parts by weight of the polymerizable monomer (b) from the viewpoints of antifouling property, plaque adhesion-inhibiting effect, strength of the cured product and wear resistance. 001-30 parts by weight, preferably 0.01-10 parts by weight.
- Types of the polymerizable monomer (b) and the polymerization initiator (c) used in the present invention are not particularly limited.
- a force capable of using a commonly used one is generally a combination of a radical polymerizable monomer and a radical polymerization initiator (radical polymerizable composition), and a cationic polymerizable monomer and a cationic polymerization initiator. (Cationic polymerizable composition) and the like.
- radical polymerizable monomer in the polymerizable monomer (b) include a-cyanoacrylic acid, (meth) acrylic acid, OC halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, Examples thereof include esters derived from unsaturated carboxylic acids such as maleic acid and itaconic acid, (meth) acrylamides, (meth) acrylamide derivatives, butyl esters, butyl ethers, mono N vinyl derivatives, styrene derivatives and the like. Of these, (meth) acrylic acid esters are preferred.
- Tetramethylol methanetri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol hex (meth) acrylate, (N, N '-(2, 2, 4 trimethylhexa methylene) bis (2 (Aminocarbo-loxy) propane 1,3 diol]] tetramethacrylate, 1,7 diacryloyloxy 2,2,6,6-tetraatyloxyoxymethyl 4-oxaheptane, and the like.
- the polymerizable monomer (b) can be used either alone or as a mixture of two or more of V and deviation.
- the polymerizable composition of the present invention is polymerized with a functional monomer that imparts adhesion to these substrates. It may be preferable to contain it as a part of the monomer (b).
- the functional monomer for example, 2 (meth) atalylooxychetyl dihydrogen phosphate, 10— (meth) allyloyloxydecyl dihydrogen phosphate, 2— (meth) attaroyloxyxhe Monomers having a phosphoric acid group, such as thiol hydrogen phosphate, and 11— (meth) atallyloyloxy 1,1-undecane dicarboxylic acid, 4 (meth) ataryloxyethoxycarbophthalate
- a monomer having a carboxylic acid group such as an acid is preferable because it exhibits excellent adhesion to a tooth and a base metal.
- the functional monomer for example, 10-mercaptodecyl (meth) atalylate, 6- [3- (4 benzylbenzyl) propylamino]-1, 3, 5 triazine-2, 4 dithione, JP-A-10-1473
- the thiouracil derivatives described in Japanese Patent Publication No. 11-92461 The compounds having sulfur elements listed above are preferred because they exhibit excellent adhesion to precious metals.
- a silane coupling agent such as 3-methacryloyloxypropyltrimethoxysilane is effective for adhesion to ceramics, porcelain, and dental composite resins.
- the amount of the functional monomer may be 0.1 to 80 parts by weight with respect to 100 parts by weight of the total polymerizable monomer (b) from the viewpoint of adhesive strength to the substrate and adhesion durability. preferable.
- a known radical polymerization initiator such as a heat polymerization initiator, a room temperature polymerization initiator, or a photopolymerization initiator is used. ! /
- heat polymerization initiator examples include polymerization initiators such as peroxide compounds and azo compounds having a use temperature range of 40 to 100 ° C.
- heat polymerization initiators include organic peroxides such as disilver oxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, and hydrogen peroxides. There is a bowl.
- disilver oxides examples include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide, and the like.
- peroxyesters examples include t-butyl peroxybenzoate, bis-t-butyl peroxyisophthalate, 2,5 dimethyl-2,5-bis (benzoylperoxy) hexane, and t-butylperoxy 2-ethyl.
- dialkyl peroxides examples include dicumyl peroxide, dibutyl butyl peroxide, lauroyl peroxide, and the like.
- peroxyketals examples include 1,1bis (t-butylperoxy) 3,3,5-trimethylcyclohexane.
- ketone peroxides include methyl ethyl ketone peroxide. Can be mentioned.
- hydride mouth peroxides examples include t-butyl hydride mouth peroxide.
- the room temperature polymerization initiator for example, a redox polymerization initiator system composed of an oxidizing agent (polymerization initiator) and a reducing agent (accelerator) can be suitably used.
- a redox polymerization initiator system composed of an oxidizing agent (polymerization initiator) and a reducing agent (accelerator)
- oxidizing agent polymerization initiator
- reducing agent reducing agent
- benzoyl peroxide can be used as a polymerization initiator
- aromatic tertiary amine such as diethanoltoluidine or aromatic sulfinate can be used as an accelerator.
- the polymerizable composition of the present invention preferably takes a packaging form of two or more parts.
- the oxidant in the redox polymerization initiator system include the disilver oxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, and hydoxyperoxides. Prefer organic peracids.
- reducing agent for example, aromatic tertiary amine, aliphatic tertiary amine and sulfinic acid or a salt thereof are preferable.
- aromatic tertiary amines include N, N dimethylamine, N, N dimethyl-p toluidine, N, N dimethyl-m-toluidine, N, N-jetyl 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-tert-butylaniline, N, N bis (2-hydroxyethyl) —3,5-dimethylaniline, N, N—di (2 hydroxyethylenole) -p-tonoleidine N, N bis (2 hydroxyethyl) 3, 4 —dimethylaline, N, N bis (2 hydroxyethyl) 4 ethylline, N, N bis (2 hydroxy
- Examples of the aliphatic tertiary amine include trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyljetanolamine, Nn-butyljetanolamine, N-lauryldiethanolamine.
- sulfinic acid or a salt thereof examples include benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, calcium benzenesulfinate, lithium benzenesulfinate, toluenesulfinate, sodium toluenesulfinate, toluenesulfin.
- the photopolymerization initiator As the photopolymerization initiator, a special light irradiation device (for example, an ultraviolet irradiation device) is not required, and a light irradiation device in the visible light region, which has been widely used in the past, can be used.
- a photopolymerization initiator excited by light having a wavelength of 350 to 700 nm is preferred.
- Examples of the photopolymerization initiator excited by light having a wavelength of 350 to 700 nm include a-diketones, ketals, thixanthones, acyl acylphosphine oxides, coumarins, and halomethyl group-substituted s-triazines. Derivatives and the like.
- ⁇ -diketones examples include camphorquinone, benzyl, and 2,3 pentanedi. ON etc. are mentioned.
- ketals examples include benzyl dimethyl ketal and benzyl jetyl ketal.
- thixanthones examples include 2-chlorothixanthone, 2,4 jetylthioxanthone, and the like.
- acyl phosphine oxides examples include 2, 4, 6 trimethyl benzoyl diphosphine phosphine oxide, 2, 6 dimethoxy benzoyl diphosphine phosphine oxide, 2, 6 diclonal benzoyl diphenol.
- water-soluble acyl phosphine oxide compounds disclosed in JP-B-3-57916 examples include 2, 4, 6 trimethyl benzoyl diphosphine phosphine oxide, 2, 6 dimethoxy benzoyl diphosphine phosphine oxide, 2, 6 diclonal benzoyl diphenol.
- Examples of the above-mentioned coumarins include JP-A-10-245525 such as 3, 3, 1-carborubis (7 jetylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, and 3 thienoyl coumarin. Examples include compounds described in the publication.
- halomethyl group-substituted s-triazine derivatives examples include 2, 4, 6 tris (trichloromethyl) s triazine, 2, 4, 6 tris (tribromomethyl) monos-triazine, 2-methyl 4, 6 bis (trichloromethyl) -s-triazine and the like described in JP-A-10-245525.
- Each of the photopolymerization initiators can be used alone or in admixture of two or more.
- the amount of the radical polymerization initiator is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 100 parts by weight of the polymerizable monomer (b). Is preferably 0.1 to 3 parts by weight.
- a photopolymerization initiator When a photopolymerization initiator is used, it is preferable to use a photopolymerization initiator and a reducing agent in combination in order to promote photocurability.
- Examples of the reducing agent mainly include tertiary amines, aldehydes, compounds having a thiol group, and these may be used alone or in combination of two or more. May be.
- tertiary amines examples include 2 dimethylaminoethyl (meth) acrylate, N, N bis [(meth) attayllooxychetyl]-N-methylamine, 4-dimethylaminobenzoate Butyl 4-dimethylaminobenzoate, butoxychetyl 4-dimethylaminobenzoate, N-methyljetanolamine, 4-dimethylaminobenzophenone, and the like.
- aldehydes include dimethylaminobenzaldehyde and terephthalaldehyde.
- Examples of the compound having a thiol group include 2 mercaptobenzoxazole, decane thiol, 3-mercaptopropyltrimethoxysilane, and thiobenzoic acid.
- the amount of the reducing agent is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 100 parts by weight of the polymerizable monomer (b). Desirably, it is ⁇ 3 parts by weight.
- polymerizable composition of the present invention in addition to the radical polymerizable composition containing the radical polymerizable monomer and the radical polymerization initiator as described above, as the polymerizable monomer (b), cationic polymerizable monomer
- a cationically polymerizable composition containing a cationic polymerization initiator as a monomer or a polymerization initiator (c) can also be used.
- strong cationic polymerizable monomers include cationic polymerizable vinyl compounds, ratatones, and cyclic ethers.
- Examples of the cationically polymerizable bur compound include ethylene glycol dibutene ethere, glyceronole trivinino reetenole, trimethylololepropane trivinino reetenole, vinyl ethers such as 4 vinyl ether styrene and allyl vinyl ether. Derivatives.
- latatones examples include cyclic latatones such as ⁇ -propiolatatones and ⁇ -force prolatatanes.
- cyclic ethers examples include alicyclic epoxy compounds, oxetane compounds, spiro orthoesters, bicycloorthoesters, and cyclic carbonates. Of these, alicyclic epoxy compounds and oxetane compounds are preferred.
- Examples of alicyclic epoxy compounds include 3, 4 epoxycyclohexylmethyl-3 ', 4, Mono-epoxycyclohexanecarboxylate (manufactured by Union Carbide, trade name: U VR6105 (low viscosity product) and UVR6110 (low viscosity product), Daicel Chemical Industries, trade name: CELLOXIDE2021, etc.), screw (3, 4 Epoxycyclohexenolemethinole) Adipate (manufactured by Nion Carbide, trade name: UVR6128), bullcyclohexene monoepoxide [trade name: CELOXIDE2000, made by Daicel Chemical Industries, Ltd.], ⁇ -force prolatathon Modified 3, 4—Epoxycyclohexenoremethinole 3 ′, 4 ′ Epoxycyclohexane strength norevoxilate (manufactured by Daicel Chemical Co., Ltd., trade name: CELOXIDE2081), 1 methyl
- oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, 1, 4
- a photopower thione polymerization initiator is suitable.
- the light-power thione polymerization initiator include known sulfo-um salt and ammonium salt, as well as diaryl rhododonium salt, triarylsulfo-um salt and the like, and JP-A-6-298912. Can be used by appropriately selecting from those described in JP-A-8-143806 and JP-A-8-283320.
- the light-power thione polymerization initiator a commercially available product can be used as it is. Typical examples of commercial products are manufactured by Nippon Soda Co., Ltd., trade names: CI— 1370, CI 2064, CI 2397, CI— 2624, CI— 2639, CI— 2734, CI— 2758, CI— 2823, CI— 2855, CI-5 102, etc., Rhodia, Inc., trade name: PHOTOINITIATOR2047, etc., Union Carbite, trade names: UVI-6974, UVI-6990, etc. Is not to be done.
- the amount of the cationic polymerization initiator used depends on the type and the cationic polymerizable compound used. Although it varies depending on the type and amount ratio, use conditions, etc., from the viewpoint of improving curability and enhancing storage stability, it is usually 0.1 to 20 parts by weight with respect to 100 parts by weight of the cationically polymerizable compound. Preferably, it is 1 to: LO parts by weight, more preferably 1 to 5 parts by weight.
- composition comprising an epoxy compound and a hydroxyl group-containing compound described in JP-T-10-508067, JP-T 2001-520758, JP-T 2001-5-20759, etc.
- the present invention can also be applied to a system cured with a photopolymerization catalyst comprising a ododonium salt (polymerization initiator) and a visible light sensitizer (accelerator).
- U is more preferable as an embodiment of the polymerizable composition.
- a solvent ( d) is an added composition.
- the solvent (d) referred to in the present specification is a liquid having a boiling point within the range of 40 to 180 ° C under normal pressure, such as water, methanol, ethanol, isopropanol, n-propanol, butanol.
- Cyclohexanol and other alcohols chloroform, formaldehyde, methylene chloride, chlorine, benzene, hydrocarbons such as hexane, cyclohexane, toluene, xylene, acetone, methyl ethyl ketone, Powers including ketones such as cyclohexanone, esters such as ethyl acetate and butyl acetate, ethers, etc.
- the present invention is not limited to such examples.
- the advantage of using the solvent in this manner is that the fluorinated compound can be easily dissolved, and further, the polymerizable composition is based on the polymerizable composition.
- the fluorine compound can be localized on the surface of the polymerizable composition (vapor-liquid interface) in the process of evaporation of the solvent, and the fluorine compound layer is densely packed on the surface after curing. It is formed, and the surface has higher antifouling property.
- a solvent that is highly compatible with the fluorine compound and can be evaporated relatively easily after coating such as water, methanol, ethanol, propanol, butanol, and acetone, is preferable.
- the amount of the solvent (d) is usually 30 to: L000 parts by weight, preferably 50 to 500 parts by weight, more preferably 100 to 300 parts by weight with respect to 100 parts by weight of the polymerizable monomer (b). Part.
- composition ratios of the components (a) to (d) in the polymerizable composition of the present invention are collectively described.
- the amount of the fluorine compound (a) relative to 100 parts by weight of the polymerizable monomer (b) is 0.001 to 30 parts by weight, preferably 0.01 to 10 parts by weight of the polymerization initiator (c).
- the amount should be 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and the amount of solvent (d) should be 30 to L000 parts by weight, preferably 50 to 500 parts by weight.
- the polymerizable composition of the present invention may be reconstituted in order to increase the storage stability near room temperature. In other words, it is possible to divide and package the constituents that interact with each other and mix them before use to polymerize them.
- a redox polymerization catalyst comprising a peroxide and a reducing agent
- the peroxide and the reducing agent are packaged separately, and both are weighed before use. By mixing, it can be polymerized and cured.
- the fluorine compound (a) is more localized on the surface of the cured product.
- the polymerizable monomer (b) and the solvent (a) are selected so that the fluorine compound (a) is not dissolved and the polymerizable monomer is selected and the fluorine compound (a) is uniformly dissolved when the solvent is mixed. It is preferable to adjust each kind and amount of d).
- the fluorine compound (a) is also precipitated on the surface of the polymerizable composition, so that the surface of the cured product becomes denser. A layer of a proper fluorine compound (a) can be formed.
- the polymerizable composition of the present invention is applied to the surface of a tooth or a dental restorative material
- a method of curing the polymerizable composition after evaporating the solvent contained in the compatible composition is exemplified, and a method of curing the polymerizable composition by light irradiation is preferable from the viewpoint of easy operation.
- the polymerizable composition of the present invention includes a filler, an ultraviolet absorber, an acid inhibitor, a polymerization inhibitor, a colorant, an antibacterial agent, an X-ray contrast agent, and a thickener depending on the purpose. In addition, it can be done by adding additional fluorescent agents.
- fluoride ion sustained release filler such as fluoroaluminosilicate glass filler, calcium fluoride, sodium fluoride, sodium monofluorophosphate. Can do.
- a surfactant having antibacterial activity such as cetylpyridyl-um chloride, 12 (meth) atalyloxydecylpyridyl-um bromide, or photocatalytic acid titanium Can do.
- fine powders such as glass fillers containing heavy metal elements such as barium, ytterbium, strontium, and lanthanum (for example, noroboroboroaluminosilicate glass), ytterbium fluoride, and barium sulfate. Can be added.
- heavy metal elements such as barium, ytterbium, strontium, and lanthanum (for example, noroboroboroaluminosilicate glass), ytterbium fluoride, and barium sulfate.
- thickeners such as sodium polyacrylate, sodium alginate and gum arabic, and microfilar silica with an average particle size of 0.1 ⁇ m or less [e.g. Japan Aerosil Co., Ltd., trade name: Aerosil] can be added.
- a filler is further blended.
- Fillers are roughly classified into organic fillers and inorganic fillers.
- organic fillers examples include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate / ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, and ethylene acetate butyl copolymer.
- Polymers such as styrene-butadiene copolymer; polytetrafluoroethylene (PTFE), tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer ( FEP), poly (vinylidene fluoride) (PVDF), polytrifluoroethylene chloride (PCTFE), and other fluorine resins, etc. are used. These should be used alone or in combination of two or more. Can do.
- PTFE polytetrafluoroethylene
- FEP tetrafluoroethylene-ethylene copolymer
- FEP tetrafluoroethylene-hexafluoropropylene copolymer
- PVDF poly (vinylidene fluoride)
- PCTFE polytrifluoroethylene chloride
- inorganic fillers include various glasses (including silicon dioxide (quartz, quartz glass, silica gel, etc.), alumina, silicon as a main component, and boron and Z or aluminum together with various heavy metals) Ceramics, diatomaceous earth, kaolin, clay mineral (montmorillonite, etc.), activated clay, synthetic zeolite, my strength, calcium fluoride, ytterbium fluoride, calcium phosphate, barium sulfate, zirconium dioxide, titanium dioxide, hydroxyapatite, etc. These can be used alone or in admixture of two or more.
- an organic-inorganic composite filler obtained by adding a polymerizable monomer to these inorganic fillers, making a paste, polymerizing and curing, and pulverizing may be used.
- the amount of the filler is appropriately determined in consideration of the operability (consistency) of the paste and the mechanical strength.
- the amount of the filler is 10 to 1800 parts by weight, preferably 50 to 1500, based on 100 parts by weight of the total of the fluorine compound (a), the polymerizable monomer (b) and the polymerization initiator (c). The weight part is desirable.
- dental polymerizable composition of the present invention include dental composite filler materials, dental crown materials, dental composite resins such as bonding materials, orthodontic adhesives, cavities, etc.
- Dental adhesives such as coating adhesives and tooth fissure sealants, denture base materials, denture base mucous membrane regulators, fisher sealants, coatings for tooth surfaces and dental prostheses, surface lubricants, etc.
- a solvent included as described above, a hard thin film can be formed after curing, so that it can be applied to various coating applications, such as fish sealants, tooth surfaces and dental prostheses. It can be suitably used as a dental coating agent, a surface stain, a surface lubricant, a hypersensitivity suppressant, a dental cure, and the like.
- the dental polymerizable composition of the present invention is used as a coating agent for a tooth surface or a dental restorative material
- various pretreatments can be applied in order to enhance adhesion to the surface.
- an adhesive ply that is etched with a phosphoric acid aqueous solution or that contains a functional monomer having adhesiveness to the tooth substance is also possible to apply a toner or a bonding agent.
- the substrate when the substrate is ceramic, composite resin, metal, etc., it can be subjected to a sandblasting treatment or a primer treatment containing a silane coupling agent or a phosphoric acid monomer.
- the base material when the base material is a resin such as polymethylmetatalylate (PMMA) or polycarbonate, like a denture base resin, a base material is applied by applying a strong infiltrating agent such as methylene chloride and a solvent. It is also possible to apply a treatment to swell.
- PMMA polymethylmetatalylate
- a base material is applied by applying a strong infiltrating agent such as methylene chloride and a solvent. It is also possible to apply a treatment to swell.
- a bovine enamel was used as a base material, and a coloring test using a turmeric pigment was performed.
- the contamination resistance evaluation using turmeric was performed by the Japanese Society for Prosthetic Dentistry 35th (1991) 542- 5 55 This is based on the evaluation method described on the page.
- the smooth front surface of the enamel was prepared by smooth wet polishing the front teeth of the cow with # 1000 silicon carbide paper. A 35% aqueous phosphoric acid solution was applied to the surface, allowed to stand for 30 seconds, washed with running water, and etched. After the surface of the surface is dried using an air syringe, the polymerizable composition is further applied and the volatile components are slowly evaporated, and then a dental light irradiator (Morita, trade name: JETLITE3000) is used. Then, light irradiation was performed until the unpolymerized layer on the surface disappeared, and polymerization was cured.
- a dental light irradiator Morita, trade name: JETLITE3000
- the degree of discoloration was measured by comparing the chromaticity of the specimen before immersion with the chromaticity after immersion and expressing the difference in chromaticity as ⁇ E *. The larger the value of ⁇ E *, the greater the coloring and the poorer the stain resistance.
- the photopolymerizable coating solution was applied to the glass surface with a brush and allowed to stand at room temperature for 10 minutes, and then air blowing was performed gently to evaporate the solvent ethanol. Polymerization and curing were carried out by irradiating light for 90 seconds with a dental light irradiator (trade name: UNIX, manufactured by Kurtour Co., Ltd.) to form an antifouling coating film with no unpolymerized layer remaining on the surface. Before the light irradiation, the thickness of the coating agent layer was adjusted to 200 / zm by using a spacer and a release film (EVAL).
- EVAL release film
- the obtained test plate was stored in 70 ° C water for 7 days, and the degree of discoloration was evaluated by comparing the chromaticity before and after immersion. As before, the chromaticity of the specimen before immersion and the chromaticity after immersion were compared, and the difference between the chromaticities was expressed as ⁇ E *. The larger the value of ⁇ E *! /, The more discolored the cured product is! / !.
- a toothbrush wear test was performed using the above-described bovine enamel enamel coated and cured as a test piece.
- 3 2 2 2 2 2 force ⁇ 1) in a solution (50 g), peracid-perfluoro-1,2,5-dimethyl -70 g of a solution supplemented with 3, 6 dioxanonanoyl (5 mmol, 4.9 g) was added and reacted at 45 ° C for 5 hours under a nitrogen stream.
- the obtained white powder was subjected to suction filtration, and the product was sufficiently washed with hexane for purification. Further, the obtained product was dried at 50 ° C. under vacuum for 2 days. As a result, 4.7 g of the target product, polyacrylic acid having both ends blocked with a fluoroalkyl group, was obtained. It was.
- the spectrum of the obtained product is as follows.
- a photocurable coating composition having the following composition was prepared. That is, as a polymerizable monomer, dipentaerythritol hexaatalylate (manufactured by Kyoei Chemical Co., Ltd., trade name: DPE 6A, hereinafter referred to as DPA6) 35 parts by weight, methyl metatalylate (hereinafter referred to as MMA) 15 parts by weight, 1 part by weight of 2,4,6 trimethylbenzoyldiphenylphosphine oxide (hereinafter referred to as TMDPO) was uniformly dissolved as a photopolymerization initiator.
- DPE 6A dipentaerythritol hexaatalylate
- MMA methyl metatalylate
- TMDPO 2,4,6 trimethylbenzoyldiphenylphosphine oxide
- ACA a compound having a perfluoroalkyl group at both ends of the polyacrylic acid obtained in Synthesis Example 1
- ACA a compound having a perfluoroalkyl group at both ends of the polyacrylic acid obtained in Synthesis Example 1
- Example 1 a photopolymerizable coating agent was prepared in the same manner as in Example 1 using the fluorine compounds and polymers described in Table 1 instead of ACA, and the physical properties thereof were evaluated. The result
- Comparative Example 4 is a force S having a structure in which fluoroalkyl groups are randomly introduced into the main chain of polyacrylic acid, and a polymer having fluoroalkyl groups at both ends, which has almost no effect on stain resistance in dental applications. You can see the importance of using it.
- Comparative Example 3 does not include a monomer unit containing a hydrophilic group and does not show an effect of stain resistance in dental use. Further, as compared with Comparative Example 3, the polymerizable composition obtained in each Example is excellent in wear resistance if the cured product is discolored.
- a polymerizable composition was prepared in the same manner as in Example 1 except that the amount of ACA added to the coating agent of Example 1 was changed as shown in Table 3. ) was measured. The results are shown in Table 3.
- Example 1 Using the polymerizable composition of Example 1, a test piece for stain resistance test coated in the same manner as in Example 1 was prepared. The test specimen for stain resistance test was immersed in 70% ethanol and stirred for 30 minutes to wash the coated surface.
- Example 1 Using the polymerizable composition of Example 1, coating was performed in the same manner as in Example 1 to prepare a test specimen for stain resistance test. After immersing the test specimen for contamination test in 37 ° C water for 10 days, a turmeric color test (stain resistance test) was conducted in the same manner. The surface antifouling property was not substantially impaired by immersion in water.
- Example 1 A test specimen for stain resistance prepared by coating the polymerizable composition of Example 1 in the same manner as in Example 1 was immersed in a saturated aqueous solution of calcium hydroxide and calcium carbonate at 25 ° C for 5 minutes. did. Similarly, when a coloring test (contamination resistance test) was performed using turmeric, the ⁇ ⁇ * value was 8.5, indicating excellent antifouling properties.
- Plaque test specimens were placed in an artificial oral appliance, and the amount of biofilm (plaque) adhering to the surface was quantified to evaluate plaque adhesion.
- Example 1 the coating agent used in Example 1 was applied and photocured, and the plaque adhesion was tested. That is, a commercially available hard resin for crowns [Kuraray Medical Co., Ltd., trade name : Este C & B (E1 shade)] paste into a mold with a 4mm x 4mm XI .5mm hole, pressed with a glass plate, and a dental light irradiator (Morita, product name: Photopolymerization (3 minutes) with ⁇ -light II), followed by caloric heat treatment (110 ° C, 15 minutes) with a dental heater (Kuraray Medical Co., Ltd., product number: KL100), 4 mm A sample plate with a size of X 4 mm XI .5 mm was prepared.
- a commercially available hard resin for crowns [Kuraray Medical Co., Ltd., trade name : Este C & B (E1 shade)] paste into a mold with a 4mm x 4mm XI .5mm hole,
- the surface of the sample plate was ground with silicon carbide paper (# 800), and the photopolymerizable coating agent obtained in Example 1 was applied to the surface of the ground sample plate with a micropipette 0.5.
- ZL was sampled and applied, and the solvent was slowly evaporated, followed by photopolymerization (3 minutes) with a light irradiator (Morita, product name: ⁇ Light II) to prepare the coating surface and test surface It was.
- the sample was fixed with a utility wax in a fluorocarbon resin holder in the artificial oral cavity device.
- This device keeps a temperature of 37 ° C and continuously dripping a solution containing bacteria in the oral cavity and a culture solution onto the test surface for a long period of time, giving the test surface a similar environment to the test surface, and biofilm (plaque).
- the specific test procedure is as follows.
- Saliva collected in advance was centrifuged (rotation speed: 15000 rpm), and the supernatant was filtered using a filter (0.22 ⁇ mC ⁇ ). The filtrate was placed on the test surface of the sample and allowed to rest for 30 minutes to produce a pellicle on the test surface.
- the solution dripped onto the test surface was Streptococcus mutans MT 8148 as a bacterium.
- bacterial suspension containing 1% sucrose as a carbohydrate
- PBS PBS
- test surface force of sample Plaque remaining on the surface without peeling was quantified. Specifically, the plaque-attached sample plate was treated with 0.5N sodium hydroxide solution and then centrifuged (rotation speed: 3000 rpm) to separate the precipitate and the supernatant. This precipitate is redispersed in PBS, and the turbidity (Turbidity, OD) of the precipitate is measured with a spectrophotometer to determine the amount of cells.
- a composition obtained by removing the polymerizable monomer and the polymerization catalyst from the coating agent of Example 1 50 parts by weight of ethanol and 5 parts by weight of the fluorine compound (ACA) O. 5 used in Example 1) were mixed uniformly. Dissolved) was prepared. Using this as a coating agent, it was applied to the cured surface of the base material (hard crown resin) with a brush, left at room temperature for 2 hours to remove the solvent, and the base material surface was coated with a fluorine compound. When this test piece was immersed in a turmeric suspension in the same manner as in Reference Example 5 and the stain resistance was evaluated, ⁇ * was 30.8.
- Comparative Reference Example 2 it is presumed that the effect of stain resistance was not obtained because the fluorine compound peeled off the base material.
- Reference Example 5 contains a polymerizable monomer, and it is thought that the effect of high V and contamination resistance was obtained by fixing the fluorine compound with the coating film obtained by polymerization and curing.
- the dental polymerizable composition of the present invention includes, for example, a dental composite resin such as a dental composite filling material, a crown material, and a bonding material, an orthodontic adhesive, and an adhesive for cavity application.
- dental adhesives such as tooth gap sealants, denture base materials, denture basement mucosa regulators, fisher sealants, coatings for tooth surfaces and dental prostheses, surface lubricants, etc. It can be suitably used for coating applications such as, for example, fisher sealants, coating agents for tooth surfaces and dental prostheses, surface stains and surface lubricants, hypersensitivity suppression materials, and dental cures.
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Abstract
Description
Claims
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CA002576263A CA2576263A1 (en) | 2004-08-11 | 2005-08-11 | Dental polymerizable composition |
US11/659,811 US7683103B2 (en) | 2004-08-11 | 2005-08-11 | Dental polymerizable composition |
EP05770647.5A EP1787623B1 (en) | 2004-08-11 | 2005-08-11 | Dental polymerizable composition |
JP2006531728A JP4673310B2 (ja) | 2004-08-11 | 2005-08-11 | 歯科用重合性組成物 |
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EP (1) | EP1787623B1 (ja) |
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Cited By (4)
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---|---|---|---|---|
JP2010534246A (ja) * | 2007-07-25 | 2010-11-04 | スリーエム イノベイティブ プロパティズ カンパニー | 被膜形成歯科用組成物及び関連する方法 |
JP2014009219A (ja) * | 2012-07-03 | 2014-01-20 | Tokuyama Dental Corp | 歯科用接着性組成物 |
JP2015209421A (ja) * | 2014-04-30 | 2015-11-24 | サンメディカル株式会社 | 歯科用組成物 |
WO2021132699A1 (ja) | 2019-12-25 | 2021-07-01 | クラレノリタケデンタル株式会社 | エネルギー線硬化性立体造形物用コーティング材及びそれを含むエネルギー線硬化性立体造形用材料キット並びにそれを用いた立体造形物及びその製造方法 |
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US20090286207A1 (en) * | 2008-05-16 | 2009-11-19 | Bawa Anoop K S | Dental composite stain |
US8217081B2 (en) * | 2009-04-07 | 2012-07-10 | The United States of America as represented by the Secretary of Commerce, the National Institute of Standards and Technology | Polymerizable biomedical composition |
US9642687B2 (en) | 2010-06-15 | 2017-05-09 | The Procter & Gamble Company | Methods for whitening teeth |
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US10111282B2 (en) | 2011-07-25 | 2018-10-23 | Ivoclar Vivadent Ag | Dental furnace |
EP2949311B1 (en) | 2014-05-30 | 2019-10-16 | Shofu Inc. | Dental composition containing ion sustained-release glass |
JPWO2016006637A1 (ja) | 2014-07-11 | 2017-04-27 | 三井化学株式会社 | 歯科用補綴物 |
GB201512023D0 (en) * | 2015-07-09 | 2015-08-19 | Univ London Queen Mary | Dental compositions |
EP3120827B1 (de) * | 2015-07-22 | 2019-02-06 | Ivoclar Vivadent AG | Adhäsive dentalwerkstoffe mit stark aciden haftpolymeren |
CN110072564B (zh) * | 2016-10-27 | 2022-01-07 | 生物医学键合有限公司 | 作为底涂剂用于粘合性改善的包含硫醇、烯烃和含膦酸化合物的组合物 |
CN114788786B (zh) * | 2021-08-12 | 2023-09-26 | 天津大学 | 两性离子聚合物/无定形磷酸钙纳米复合物及其制备方法和应用 |
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JP2014009219A (ja) * | 2012-07-03 | 2014-01-20 | Tokuyama Dental Corp | 歯科用接着性組成物 |
JP2015209421A (ja) * | 2014-04-30 | 2015-11-24 | サンメディカル株式会社 | 歯科用組成物 |
WO2021132699A1 (ja) | 2019-12-25 | 2021-07-01 | クラレノリタケデンタル株式会社 | エネルギー線硬化性立体造形物用コーティング材及びそれを含むエネルギー線硬化性立体造形用材料キット並びにそれを用いた立体造形物及びその製造方法 |
Also Published As
Publication number | Publication date |
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JPWO2006016649A1 (ja) | 2008-05-01 |
US7683103B2 (en) | 2010-03-23 |
JP4673310B2 (ja) | 2011-04-20 |
CA2576263A1 (en) | 2006-02-16 |
EP1787623B1 (en) | 2014-03-26 |
EP1787623A4 (en) | 2012-02-15 |
EP1787623A1 (en) | 2007-05-23 |
US20080039592A1 (en) | 2008-02-14 |
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