WO2016042770A1 - 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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- WO2016042770A1 WO2016042770A1 PCT/JP2015/004741 JP2015004741W WO2016042770A1 WO 2016042770 A1 WO2016042770 A1 WO 2016042770A1 JP 2015004741 W JP2015004741 W JP 2015004741W WO 2016042770 A1 WO2016042770 A1 WO 2016042770A1
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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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives thereof
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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
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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
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
- A61K6/61—Cationic, anionic or redox initiators
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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
- A61K6/62—Photochemical radical initiators
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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
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/76—Fillers comprising silicon-containing compounds
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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
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/77—Glass
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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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
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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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
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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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
Definitions
- the present invention relates to a dental polymerizable composition.
- Adhesive materials and filling materials are used for repairing teeth and bones.
- dental polymerizable compositions comprising a polymerizable monomer, a polymerization initiator, a filler, and the like are used.
- the dental polymerizable composition is used as a cured product by polymerizing a polymerizable monomer after shaping into a desired shape, specifically, a tooth fixed material, a denture base lining material, Uses such as dental cement and dental self-adhesive composite resin are listed.
- the swaying tooth fixing material is a material for fixing the wobbled tooth (swaying tooth) to the surrounding healthy tooth.
- a denture base lining material is a material for the purpose of improving the feeling of use in the use of dentures.
- Dental cement is a material used for adhesion of artificial materials (inlays, crowns, bridges, dentures, implants, etc.) used for a defect site. In the case where these artificial objects are allowed to function in the oral cavity for a certain period and checked for problems, temporary dental cement that can be removed from the defect after completion of the check is used.
- a dental self-adhesive composite resin is a material that fills a tooth defect site.
- the dental polymerizable composition is required to be easily shaped from a container, specifically, to have a small ejection force required for ejection and to be shaped into a desired shape after ejection.
- the cured product obtained from the shaped dental polymerizable composition is required to have surface gloss and color resistance.
- the rocking tooth fixing material is required to have an impact absorption property of the cured product and an adhesion property to the enamel when an external force is applied.
- the bending elastic modulus of the cured product needs to be in an appropriate range.
- a cured product of a denture base lining material is required to have low surface hardness and strain durability.
- the dental self-adhesive composite resin is required to suppress polymerization shrinkage stress accompanying curing from the viewpoint of adhesion to a tooth defect site.
- Patent Document 1 reports a dental polymerizable composition containing an acrylic block copolymer composed of polymethacrylic acid ester and polyacrylic acid ester.
- Patent Document 1 reports a dental polymerizable composition containing an acrylic block copolymer composed of polymethacrylic acid ester and polyacrylic acid ester.
- the present invention has an object to provide a dental polymerizable composition in which ejection force is suppressed, shaping is easy, polymerization shrinkage stress accompanying curing is low, and coloring resistance and surface gloss after curing are excellent.
- the present invention provides a swinging tooth that has low ejection force, is easy to shape, has low polymerization shrinkage stress upon curing, and has excellent resistance to coloring, impact absorption, surface gloss and adhesion to enamel after curing.
- the purpose is to provide a fixing material.
- the present invention provides a denture having a suppressed ejection force, easy shaping, low polymerization shrinkage stress accompanying curing, and excellent color resistance, flexibility, strain durability, color resistance and surface gloss after curing.
- the present invention provides a dental cement that has a suppressed ejection force, is easy to shape, has a low polymerization shrinkage stress associated with curing, and is excellent in coloring resistance, impact absorption and surface gloss after curing. Objective. Furthermore, the present invention has a suppressed ejection force, is easy to shape, has a low polymerization shrinkage stress upon curing, and further has resistance to coloring, surface gloss and adhesion to dentin (enamel and dentin) after curing. It is an object of the present invention to provide a dental self-adhesive composite resin that is excellent in resistance.
- the object is [1] A (meth) acrylic polymer block (a) having a curable functional group containing a partial structure represented by the following general formula (1) (hereinafter referred to as “partial structure (1)”) (hereinafter simply referred to as “ (Meth) acrylic polymer block (a) ”) and (meth) acrylic polymer block (b) having no curable functional group (hereinafter simply referred to as“ (meth) acrylic polymer block (b) ”.
- partial structure (1) hereinafter simply referred to as “ (Meth) acrylic polymer block (a)”
- (meth) acrylic polymer block (b) having no curable functional group hereinafter simply referred to as“ (meth) acrylic polymer block (b) ”.
- the dental polymerizable composition of the present invention has a suppressed ejection force, is easy to shape, has a low polymerization shrinkage stress accompanying curing, and is excellent in coloration resistance and surface gloss after curing.
- the rocking tooth fixing material of the present invention has low ejection force, easy shaping, low polymerization shrinkage stress accompanying curing, color resistance after curing, impact absorption, surface gloss and adhesion to enamel Excellent in properties.
- the denture base lining material of the present invention has a low ejection force, is easy to shape, has a low polymerization shrinkage stress associated with curing, and is flexible in flexibility, strain durability, color resistance and surface gloss. Excellent.
- the dental cement of the present invention has a low ejection force, is easy to shape, has a low polymerization shrinkage stress accompanying curing, and is excellent in coloration resistance, impact absorption and surface gloss after curing.
- the dental self-adhesive composite resin of the present invention has a low ejection force, is easy to shape, has a low polymerization shrinkage stress upon curing, and further has a resistance to coloration, surface gloss and dental properties (enamel after curing). Quality and dentin).
- the dental polymerizable composition of the present invention contains a (meth) acrylic block copolymer (A).
- (meth) acryl means a generic name of “methacryl” and “acryl”
- (meth) acryloyl” described later means a generic name of “methacryloyl” and “acryloyl”.
- (Meth) acrylate”, which will be described later, is a generic term for “methacrylate” and “acrylate”.
- the content of the (meth) acrylic block copolymer (A) in the dental polymerizable composition of the present invention is preferably from 0.5 to 90% by mass from the viewpoints of flexibility and ejection force. More preferably, it is more preferably 10% by mass to 80% by mass.
- the content of the (meth) acrylic block copolymer (A) in the dental polymerizable composition is 2 to 80. % By mass is preferable, 5 to 70% by mass is more preferable, and 10 to 70% by mass is further preferable.
- the content of the (meth) acrylic block copolymer (A) in the dental polymerizable composition is 3 to 90. % By weight is preferred, 10 to 80% by weight is more preferred, and 45 to 80% by weight is even more preferred.
- the content of the (meth) acrylic block copolymer (A) in the dental polymerizable composition is 0.5 to 80% by mass. 1 to 60% by mass is more preferable, and 5 to 50% by mass is more preferable.
- the content of the (meth) acrylic block copolymer (A) in the dental polymerizable composition is preferably 5 to 80% by mass, and preferably 10 to 70%. More preferably, it is more preferably 10% to 55% by weight.
- the content of the (meth) acrylic block copolymer (A) in the dental polymerizable composition is 1 to 65. % By weight is preferred, 2 to 40% by weight is more preferred, and 3 to 35% by weight is even more preferred.
- (Meth) acrylic block copolymer (A) has a (meth) acrylic polymer block (a).
- the (meth) acrylic polymer block (a) has a curable functional group containing the partial structure (1).
- the partial structure (1) is represented by the following general formula (1). (Wherein R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)
- examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 1 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group.
- the partial structure (1) of the (meth) acrylic polymer block (a) in the (meth) acrylic block copolymer (A) is provided.
- the curable functional group to be contained is preferably represented by the following general formula (2) (hereinafter, the curable functional group represented by the following general formula (2) is referred to as “curable functional group (2)”).
- R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
- R 2 and R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms
- X represents O , S, or N
- R 6 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms
- n represents an integer of 1 to 20
- hydrocarbon group having 1 to 20 carbon atoms represented by R 1 in the general formula (2) include the same hydrocarbon groups as those for R 1 in the general formula (1).
- R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and a monomer containing di (meth) acrylate (3) described later. From the viewpoint of easy and direct introduction, a hydrocarbon group having 1 to 6 carbon atoms is preferable.
- hydrocarbon groups examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl, 3-methylbutyl, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group, neopentyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group
- An alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; and an aryl group such as a phenyl group.
- a methyl group and an ethyl group are preferable from the viewpoint of the curing rate of the dental polymerizable composition of the present invention.
- X represents O, S or N (R 6 ) (R 6 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms).
- R 6 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
- examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R 6 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec-butyl group, t-butyl group, 2-methylbutyl group, 3-methylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group And alkyl groups such as neopentyl group, n-hexyl group, 2-methylpentyl group and 3-methylpentyl group; cycloal
- the integer of 1 to 20 represented by n is preferably 2 to 5 from the viewpoint of increasing the curing rate of the dental polymerizable composition of the present invention.
- X is selected from the group consisting of O, S, and N (R 5 ) (R 5 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms) and is easy to control polymerization. To O are preferred.
- examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R 5 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec-butyl group, t-butyl group, 2-methylbutyl group, 3-methylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-pentyl group And alkyl groups such as neopentyl group, n-hexyl group, 2-methylpentyl group and 3-methylpentyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; phenyl group and the like.
- the content of the partial structure (1) with respect to all monomer units forming the (meth) acrylic polymer block (a) is preferably in the range of 0.2 to 100 mol%, more preferably in the range of 10 to 90 mol%. The range of 25 to 80 mol% is more preferable.
- the (meth) acrylic polymer block (a) includes a monomer unit formed by polymerizing a monomer containing a (meth) acrylic acid ester.
- a monofunctional (meth) acrylic acid ester having one (meth) acryloyl group and a polyfunctional (meth) acrylic acid ester having two or more (meth) acryloyl groups are used. be able to.
- Examples of the monofunctional (meth) acrylic acid ester capable of forming the (meth) acrylic polymer block (a) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, Isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, (meth ) Dodecyl acrylate, 2-methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3- (trimethoxysilyl) propyl (meth) acrylate, ( 2-Aminoethyl (meth) acrylate, 2-
- alkyl methacrylates having an alkyl group having 5 or less carbon atoms such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, Most preferred is methyl methacrylate.
- polyfunctional (meth) acrylic acid ester which can form a (meth) acrylic-type polymer block (a)
- following General formula (3) wherein R 2 ′ and R 3 ′ each independently represents a hydrocarbon group having 1 to 6 carbon atoms, R 4 and R 5 each independently represents a hydrogen atom or a methyl group, and n represents 1 to Represents an integer of 20.
- the bifunctional (meth) acrylic acid ester represented by (hereinafter referred to as “di (meth) acrylate (3)”) one (meth) acryloyloxy is obtained by living anion polymerization under the conditions described later.
- a group (a (meth) acryloyloxy group represented by “CH 2 ⁇ C (R 5 ) C (O) O” in the general formula (3)) is selectively polymerized, and in the formula (2), R 1 There is a R 4 of formula (3), R 2 is 'a, R 3 is R 3 of formula (3)' R 2 of formula (3) is curable functional group X is O (2 ) Having a (meth) acrylic polymer block (a).
- examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R 2 ′ and R 3 ′ include the same hydrocarbon groups as R 2 and R 3 in the general formula (2). It is done.
- R 4 is preferably a methyl group. Further, from the viewpoint of productivity of the di (meth) acrylate (3), it is preferred that R 4 and R 5 are the same. From the above viewpoints, it is most preferable that R 4 and R 5 are both methyl groups.
- di (meth) acrylate (3) examples include, for example, 1,1-dimethylpropane-1,3-diol di (meth) acrylate, 1,1-dimethylbutane-1,4-diol di (meth) acrylate, 1,1-dimethylpentane-1,5-diol di (meth) acrylate, 1,1-dimethylhexane-1,6-diol di (meth) acrylate, 1,1-diethylpropane-1,3-diol di (meth) acrylate 1,1-diethylbutane-1,4-diol di (meth) acrylate, 1,1-diethylpentane-1,5-diol di (meth) acrylate, 1,1-diethylhexane-1,6-diol di (meth) Acrylates, etc., such as 1,1-dimethylpropane-1,3-diol di (
- acrylic acid esters may be used alone or in combination of two or more.
- the content of the monomer unit formed from the (meth) acrylic acid ester in the (meth) acrylic polymer block (a) is the total monomer forming the (meth) acrylic polymer block (a).
- the range is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and may be 100 mol% with respect to the unit.
- the (meth) acrylic polymer block (a) contains a monomer unit formed from di (meth) acrylate (3), a single unit formed from di (meth) acrylate (3) is used.
- the content of the monomer unit is preferably in the range of 0.2 to 100 mol%, preferably in the range of 10 to 90 mol%, based on all monomer units forming the (meth) acrylic polymer block (a).
- a range of 25 to 80 mol% is more preferable.
- the (meth) acrylic polymer block (a) contains a monomer unit formed from methyl methacrylate and a monomer unit formed from di (meth) acrylate (3)
- the sum of the content of monomer units formed from methyl methacrylate and the content of monomer units formed from di (meth) acrylate (3) is formed from (meth) acrylic ester.
- the range is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, still more preferably 95 to 100 mol%, and may be 100 mol% with respect to all monomer units.
- the (meth) acrylic polymer block (a) may have a monomer unit formed from a monomer other than the (meth) acrylic acid ester.
- the other monomers include ⁇ -alkoxy acrylates such as methyl ⁇ -methoxyacrylate and methyl ⁇ -ethoxyacrylate; crotonates such as methyl crotonate and ethyl crotonate; 3-methoxyacrylic acid 3-alkoxy acrylate esters such as esters; N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like ( (Meth) acrylamide; methyl 2-phenylacrylate, ethyl 2-phenylacrylate, n-butyl 2-bromoacrylate, methyl 2-bromomethylacrylate, ethyl 2-bromomethylacrylate, methyl
- the content of the monomer units formed from the other monomers in the (meth) acrylic polymer block (a) is the total monomer forming the (meth) acrylic polymer block (a).
- the amount is preferably 10 mol% or less, more preferably 5 mol% or less, based on the unit.
- the number average molecular weight (Mn) of the (meth) acrylic polymer block (a) is not particularly limited, but from the viewpoint of handleability of the (meth) acrylic block copolymer (A), 500 to 1,000,000. Is preferable, and the range of 1,000 to 300,000 is more preferable.
- Mn and the molecular weight distribution mentioned later mean the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.
- (Meth) acrylic block copolymer (A) has a (meth) acrylic polymer block (b).
- the (meth) acrylic polymer block (b) is composed of monomer units formed by polymerizing a monomer containing a (meth) acrylic acid ester and has no curable functional group. It is a united block.
- the curable functional group means a functional group exhibiting polymerizability.
- the curable functional group include ethylenic double bonds such as (meth) acryloyl group, (meth) acryloyloxy group, vinyl group, allyl group, vinyl ether group, vinyloxy group, 1,3-dienyl group, and styryl group.
- Examples of the (meth) acrylic acid ester that can form the (meth) acrylic polymer block (b) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth ) Isopropyl acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylic Dodecyl acid, 3- (trimethoxysilyl) propyl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2- (N, N-diethylamino) ethyl (meth) acrylate , 2-methoxyethyl (meth) acrylate,
- These (meth) acrylic acid esters may be used alone or in combination of two or more.
- the monofunctional (meth) acrylic acid ester used for the formation of the (meth) acrylic polymer block (b) is a monofunctional (meth) acrylic acid ester used for the formation of the (meth) acrylic polymer block (a). May be the same as or different from each other, but are preferably different.
- the content of the monomer unit formed by the (meth) acrylic ester in the (meth) acrylic polymer block (b) is the total monomer forming the (meth) acrylic polymer block (b).
- the amount is preferably 90 mol% or more, more preferably 95 mol% or more, based on the unit.
- (Meth) acrylic polymer block (b) may have a monomer unit formed from a monomer other than (meth) acrylic acid ester.
- the other monomers include ⁇ -alkoxy acrylates such as methyl ⁇ -methoxyacrylate and methyl ⁇ -ethoxyacrylate; crotonates such as methyl crotonate and ethyl crotonate; 3-methoxyacrylic acid 3-alkoxy acrylate esters such as esters; N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like ( (Meth) acrylamide; methyl vinyl ketone, ethyl vinyl ketone, methyl isopropenyl ketone, ethyl isopropenyl ketone and the like.
- These other monomers may be used alone or in combination of
- the content of the monomer unit formed by the other monomer in the (meth) acrylic polymer block (b) is the total monomer forming the (meth) acrylic polymer block (b).
- the total content is preferably 10 mol% or less, more preferably 5 mol% or less, based on the unit.
- the Mn of the (meth) acrylic polymer block (b) is not particularly limited, but is from 3,000 to 2,000,000 from the viewpoint of the handleability and mechanical properties of the (meth) acrylic block copolymer (A).
- the range of 000 is preferable, and the range of 5,000 to 1,000,000 is more preferable.
- the molecular weight distribution of the (meth) acrylic block copolymer (A), that is, the weight average molecular weight / number average molecular weight (Mw / Mn) is preferably in the range of 1.02 to 2.00, preferably 1.05 to 1.80. The range is more preferable, and the range of 1.10 to 1.50 is more preferable.
- the (meth) acrylic block copolymer (A) is a block copolymer in which at least one (meth) acrylic polymer block (a) and at least one (meth) acrylic polymer block (b) are bonded to each other.
- the (meth) acrylic polymer block (a) is a (meth) acrylic block copolymer (A) from the viewpoint of photocurability. It is preferable to form at least one terminal, more preferably a linear polymer from the viewpoint of ease of production of the (meth) acrylic block copolymer (A).
- the polymer block (a) :( meth) acrylic polymer block (b)] is not particularly limited, but is preferably 90:10 to 5:95, and 80:20 to 7:93. Is more preferably 75:25 to 10:90.
- the ratio of the mass of the (meth) acrylic polymer block (a) to the total mass of the (meth) acrylic polymer block (a) and the (meth) acrylic polymer block (b) is 5% or more.
- the dental polymerizable composition of the present invention has a high curing rate, and if it is 90% or less, the cured product obtained from the dental polymerizable composition of the present invention tends to be flexible.
- the content of the monomer unit formed from the methacrylic acid ester is preferably 5 to 85% by mass, and preferably 7 to 80% by mass. More preferred is 10 to 75% by mass.
- the content of the monomer unit formed from the acrylate ester is preferably 15 to 95% by mass, and preferably 20 to 93% by mass. More preferably, the content is 25 to 90% by mass.
- the Mn of the (meth) acrylic block copolymer (A) is not particularly limited, but is preferably in the range of 4,000 to 3,000,000 from the viewpoint of handleability, mechanical properties, etc., and 7,000 to 2, The range of 1,000,000 is more preferable, and the range of 10,000 to 1,000,000 is more preferable.
- the molecular weight distribution of the (meth) acrylic block copolymer (A), that is, the weight average molecular weight / number average molecular weight (Mw / Mn) is preferably in the range of 1.02 to 2.00, preferably 1.05 to 1.80. The range is more preferable, and the range of 1.10 to 1.50 is more preferable.
- Mw means the weight average molecular weight of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.
- the content of the partial structure (1) in the (meth) acrylic block copolymer (A) is from 0.1 to the total monomer units forming the (meth) acrylic block copolymer (A).
- the range is preferably 30 mol%, more preferably 1 to 20 mol%, and still more preferably 3 to 15 mol%.
- the number of partial structures (1) contained in the (meth) acrylic block copolymer (A) is preferably 4 or more and more than 8 per polymer molecule. Is more preferable.
- the (meth) acrylic block copolymer (A) can be obtained by forming the (meth) acrylic polymer block (a) and the (meth) acrylic polymer block (b) in a desired order.
- the method for producing the (meth) acrylic block copolymer (A) is not particularly limited, but an anionic polymerization method and a radical polymerization method are preferable, and a living anion polymerization method or a living radical polymerization method is more preferable from the viewpoint of polymerization control. An anionic polymerization method is more preferable.
- the monomer used for the production of the (meth) acrylic block copolymer (A) is preferably dried in advance under an inert gas atmosphere from the viewpoint of allowing the polymerization to proceed smoothly. In the drying treatment, a dehydrating agent or a drying agent such as calcium hydride, molecular sieves, activated alumina or the like is preferably used.
- Living radical polymerization methods include polymerization methods using chain transfer agents such as polysulfides, polymerization methods using cobalt porphyrin complexes, polymerization methods using nitroxides (see International Publication No. 2004/014926), and high-cycle heterocycles such as organic tellurium compounds.
- Polymerization method using elemental compounds see Japanese Patent No. 3839829
- RAFT reversible addition / elimination chain transfer polymerization method
- ATRP atom transfer radical polymerization method
- Japanese Patent No. 3040172 International Publication No. 2004/013192
- the atom transfer radical polymerization method is preferable, and an organic halide or a sulfonyl halide compound is used as an initiator, and at least one selected from the group consisting of Fe, Ru, Ni, and Cu is a central metal.
- An atom transfer radical polymerization method using a metal complex as a catalyst is more preferable.
- Living anionic polymerization includes living polymerization using an organic rare earth metal complex as a polymerization initiator (see JP 06-93060 A), an alkali metal or alkaline earth metal salt using an organic alkali metal compound as a polymerization initiator, etc.
- a living anion polymerization in the presence of a mineral salt see Japanese Patent Publication No. 05-507737
- a living anion polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound Japanese Patent Laid-open No. Hei 05 (1994)
- living anionic polymerizations living anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound is possible because the (meth) acrylic polymer block (a) can be directly and efficiently formed. And a living anion polymerization using an organolithium compound as a polymerization initiator in the presence of an organoaluminum compound and a Lewis base is more preferred.
- Step [I] in which an anionic polymerization is carried out in the presence of a Lewis base and a monofunctional (meth) acrylic acid ester is added after the step [I] A step [II] of polymerization, and, if necessary, a step [III] of anionic polymerization by adding a (meth) acrylic acid ester containing di (meth) acrylate (3) after the step [II]. Furthermore, the manufacturing method containing is mentioned. Moreover, the method including process [IV] which stops a polymerization reaction using a polymerization terminator is preferable.
- step [I] the (meth) acrylic polymer block (a) is formed by anionic polymerization.
- organolithium compound examples include t-butyllithium, 1,1-dimethylpropyllithium, 1,1-diphenylhexyllithium, 1,1-diphenyl-3-methylpentyllithium, ethyl ⁇ -lithioisobutyrate, butyl ⁇ -lithioisobutyrate, methyl ⁇ -lithioisobutyrate, isopropyl lithium, sec-butyl lithium, 1-methylbutyl lithium, 2-ethylpropyl lithium, 1-methylpentyl lithium, cyclohexyl lithium, diphenylmethyl lithium, ⁇ - Examples thereof include methylbenzyl lithium, methyl lithium, n-propyl lithium, n-butyl lithium, n-pentyl lithium and the like.
- organolithium compound having 3 to 40 carbon atoms and having a chemical structure having a carbon atom as an anion center is preferred, and sec-butyllithium is particularly preferred.
- organolithium compounds may be used alone or in combination of two or more.
- the amount of the organolithium compound used can be determined by the ratio to the amount of the monomer used depending on the Mn of the target (meth) acrylic block copolymer (A).
- organoaluminum compound it is suitable according to the kind etc. of the monomer (namely, di (meth) acrylate (3) and optional mono (meth) acrylate and the above-mentioned other monomers) to be used. From the viewpoint of polymerization rate, polymerization initiation efficiency, stability of polymerization terminal anion, and the like.
- AlR 7 (R 8 ) (R 9 ) (4-1) (Wherein R 7 represents a monovalent saturated hydrocarbon group, a monovalent aromatic hydrocarbon group, an alkoxy group, an aryloxy group or an N, N-disubstituted amino group, and R 8 and R 9 are each independently An aryloxy group, or R 8 and R 9 are bonded to each other to form an arylenedioxy group.)
- examples of the aryloxy group in which R 7 , R 8 , R 9 and R 10 each independently represent include a phenoxy group, a 2-methylphenoxy group, 4-methylphenoxy group, 2,6-dimethylphenoxy group, 2,4-di-t-butylphenoxy group, 2,6-di-t-butylphenoxy group, 2,6-di-t-butyl-4- Methylphenoxy group, 2,6-di-t-butyl-4-ethylphenoxy group, 2,6-diphenylphenoxy group, 1-naphthoxy group, 2-naphthoxy group, 9-phenanthryloxy group, 1-pyrenyloxy group 7-methoxy-2-naphthoxy group and the like.
- examples of the aryleneoxy group formed by combining R 8 and R 9 with each other include 2,2′-biphenol, 2,2′-methylenebisphenol, 2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), (R)-(+)-1,1'-bi-2-naphthol, (S)-(-)-1,1'-bi-2 -A functional group obtained by removing a hydrogen atom of the two phenolic hydroxyl groups in a compound having two phenolic hydroxyl groups such as naphthol.
- one or more hydrogen atoms contained in the above aryloxy group and aryleneoxy group may be substituted with a substituent.
- substituents include alkoxy groups such as methoxy group, ethoxy group, isopropoxy group and t-butoxy group; halogen atoms such as chlorine and bromine.
- examples of the monovalent saturated hydrocarbon group independently represented by R 7 , R 11, and R 12 include a methyl group, an ethyl group, and n- Alkyl groups such as propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, 2-methylbutyl group, 3-methylbutyl group, n-octyl group, 2-ethylhexyl group; cyclohexyl group And the like, and the like.
- n- Alkyl groups such as propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, 2-methylbutyl group, 3-methylbutyl group, n-octyl group, 2-ethylhexyl group; cyclohexyl group And the like, and the like.
- Examples of the monovalent aromatic hydrocarbon group each independently represented by R 7 , R 11 and R 12 include an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; Examples of the alkoxy group independently represented by R 7 , R 11 and R 12 include a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group and the like.
- N, N-disubstituted amino group each independently represented by R 7 , R 11 and R 12 examples include a dialkylamino group such as a dimethylamino group, a diethylamino group and a diisopropylamino group; a bis (trimethylsilyl) amino group, etc. Is mentioned.
- One or more hydrogen atoms contained in the above-mentioned monovalent saturated hydrocarbon group, monovalent aromatic hydrocarbon group, alkoxy group and N, N-disubstituted amino group may be substituted with a substituent.
- the substituent include alkoxy groups such as methoxy group, ethoxy group, isopropoxy group and t-butoxy group; halogen atoms such as chlorine and bromine.
- organoaluminum compound (4-1) examples include ethylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, ethylbis (2,6-di-t-butylphenoxy) aluminum, ethyl [ 2,2'-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, isobutylbis (2,6-di-) t-butylphenoxy) aluminum, isobutyl [2,2′-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum, n-octylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum N-octylbis (2,6-di-t-butylphenoxy) aluminum, n-octyl [2, '-Methylenebis (4-methyl-6-t-butylphenoxy)]
- isobutyl bis (2,6-di-t-butyl-4-methylphenoxy) aluminum, isobutyl bis (2,6 -Di-t-butylphenoxy) aluminum, isobutyl [2,2'-methylenebis (4-methyl-6-t-butylphenoxy)] aluminum and the like are preferable.
- organoaluminum compound (4-2) examples include diethyl (2,6-di-t-butyl-4-methylphenoxy) aluminum, diethyl (2,6-di-t-butylphenoxy) aluminum, diisobutyl ( 2,6-di-t-butyl-4-methylphenoxy) aluminum, diisobutyl (2,6-di-t-butylphenoxy) aluminum, di-n-octyl (2,6-di-t-butyl-4-methyl) And phenoxy) aluminum and di-n-octyl (2,6-di-t-butylphenoxy) aluminum.
- organoaluminum compounds may be used alone or in combination of two or more.
- the amount of the organoaluminum compound used can be appropriately selected according to the type of solvent and other various polymerization conditions, but is usually 1.0 to 10 with respect to 1 mole of the organolithium compound from the viewpoint of the polymerization rate. It is preferably used in the range of 0.0 mol, more preferably in the range of 1.1 to 5.0 mol, and still more preferably in the range of 1.2 to 4.0 mol. If the amount of the organoaluminum compound used exceeds 10.0 mol with respect to 1 mol of the organolithium compound, it tends to be disadvantageous in terms of economy, and if it is less than 1.0 mol, the polymerization initiation efficiency tends to decrease.
- Lewis base examples include compounds having an ether bond and / or a tertiary amine structure in the molecule.
- Examples of the compound having an ether bond in the molecule used as the Lewis base include ether.
- the ether is a cyclic ether having two or more ether bonds in the molecule or an acyclic ether having one or more ether bonds in the molecule from the viewpoint of high polymerization initiation efficiency and living property of the polymerization terminal anion. Is preferred.
- Examples of the cyclic ether having two or more ether bonds in the molecule include crown ethers such as 12-crown-4, 15-crown-5, and 18-crown-6.
- acyclic ether having one or more ether bonds in the molecule examples include acyclic monoethers such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, and anisole; 1,2-dimethoxyethane, 1,2-diethyl Ethoxyethane, 1,2-diisopropoxyethane, 1,2-dibutoxyethane, 1,2-diphenoxyethane, 1,2-dimethoxypropane, 1,2-diethoxypropane, 1,2-diisopropoxy Propane, 1,2-dibutoxypropane, 1,2-diphenoxypropane, 1,3-dimethoxypropane, 1,3-diethoxypropane, 1,3-diisopropoxypropane, 1,3-dibutoxypropane, 1,3-diphenoxypropane, 1,4-dimethoxybutane, 1,4-diethoxybutane
- Acyclic diethers such as 1,4-di
- a compound having a tertiary amine structure in the molecule includes tertiary polyamine.
- a tertiary polyamine means a compound having two or more tertiary amine structures in the molecule. Examples of the tertiary polyamine include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, N, N, N ′, N ′′, N ′′ -penta.
- Chain polyamines such as methyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetraamine, tris [2- (dimethylamino) ethyl] amine; 1,3,5-trimethylhexahydro-1 , 3,5-triazine, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,4,7,10,13,16-hexamethyl-1,4,7,10,13, Non-aromatic heterocyclic compounds such as 16-hexaazacyclooctadecane; aromatic heterocyclic compounds such as 2,2′-bipyridyl and 2,2 ′: 6 ′, 2 ′′ -terpyridine That.
- Lewis bases may be used alone or in combination of two or more.
- the amount of Lewis base used is preferably in the range of 0.3 to 5.0 moles with respect to 1 mole of the organolithium compound from the viewpoints of polymerization initiation efficiency, stability of the polymerization terminal anion, and the like.
- the range of 3.0 mol is more preferable, and the range of 1.0 to 2.0 mol is more preferable.
- the amount of the Lewis base used exceeds 5.0 mol with respect to 1 mol of the organolithium compound, it tends to be disadvantageous in terms of economy, and when it is less than 0.3 mol, the polymerization initiation efficiency tends to decrease.
- the amount of the Lewis base used is preferably in the range of 0.2 to 1.2 mol, more preferably in the range of 0.3 to 1.0 mol, with respect to 1 mol of the organoaluminum compound. .
- the living anionic polymerization is preferably carried out in the presence of an organic solvent from the viewpoint of controlling the temperature and making the system uniform so that the polymerization proceeds smoothly.
- Organic solvents include hydrocarbons such as toluene, xylene, cyclohexane, and methylcyclohexane from the viewpoints of safety, separation from water in washing of the reaction solution after polymerization, ease of recovery / reuse, etc .; chloroform, chloride Halogenated hydrocarbons such as methylene and carbon tetrachloride; esters such as dimethyl phthalate are preferred.
- These organic solvents may be used alone or in combination of two or more.
- additives may be present in the reaction system as necessary.
- the other additives include inorganic salts such as lithium chloride; metal alkoxides such as lithium methoxyethoxy ethoxide and potassium t-butoxide; tetraethylammonium chloride and tetraethylphosphonium bromide.
- the living anionic polymerization is preferably performed at ⁇ 30 to 25 ° C.
- the temperature is lower than ⁇ 30 ° C., the polymerization rate decreases and the productivity tends to decrease.
- the temperature is higher than 25 ° C., it tends to be difficult to perform polymerization with good living property.
- the living anionic polymerization is preferably performed in an atmosphere of an inert gas such as nitrogen, argon or helium. Moreover, it is preferable to carry out on sufficient stirring conditions so that a reaction system may become uniform. Moreover, it is preferable that the monomer to be used is previously dried in an inert gas atmosphere from the viewpoint of allowing living anion polymerization to proceed smoothly. In the drying treatment, a dehydrating agent or a drying agent such as calcium hydride, molecular sieves, activated alumina or the like is preferably used.
- the organic lithium compound, organoaluminum compound, Lewis base and monomer can be added to the reaction system of the anionic polymerization by contacting the Lewis base with the organoaluminum compound before contacting with the organolithium compound. It is preferable to add so as to.
- the organoaluminum compound may be added to the anionic polymerization reaction system prior to the monomer or simultaneously. When the organoaluminum compound is added to the anionic polymerization reaction system simultaneously with the monomer, the organoaluminum compound may be added after separately mixing with the monomer.
- the polymerization initiation efficiency (F1) in the step [I] is preferably 85% or more because it is excellent in the dischargeability and shapeability, stain resistance and flexibility of the resulting dental polymerizable composition. % Or more is more preferable, and it is further more preferable that it is 95% or more.
- the calculation method of the polymerization initiation efficiency (F1) is as described in Examples described later.
- step [II] a monofunctional (meth) acrylic acid ester is added, and a (meth) acrylic polymer block (b) is formed by living anionic polymerization.
- an organoaluminum compound, a Lewis base, and an organic solvent are used in a living anionic polymerization reaction system. You may add to.
- the organoaluminum compound, Lewis base, and organic solvent include the organoaluminum compound, Lewis base, and organic solvent that can be used in the above step [I].
- the amount of these organoaluminum compounds, Lewis base and organic solvent used can be appropriately selected according to the type of solvent and other various polymerization conditions.
- the conditions which can be used by process [I] can be used for the conditions of living anion polymerization.
- the rate at which the monofunctional (meth) acrylic acid ester is added may be 5 to 30 ml / min, or 7 to 20 ml. / Min.
- the block efficiency (F2) from the end of the step [I] to the end of the step [II] improves the elastomer performance, keeps the molecular weight distribution within a predetermined range, and improves the dischargeability and the reinforceability of the resulting dental polymerizable composition. Since it is excellent in formability, stain resistance and flexibility, it is preferably 50% or more, more preferably 70% or more, and further preferably 90% or more.
- the calculation method of the block efficiency (F2) is as described in the examples described later.
- step [III] In step [III], after step [II], in the same manner as in step [I], a (meth) acrylic acid ester containing di (meth) acrylate (3) is obtained in step [II].
- the (meth) acrylic polymer block (a) is formed by adding to the liquid and living anionic polymerization.
- heating may be performed as necessary.
- the block efficiency can be increased by heating. Although heating temperature is not specifically limited, 50 degrees C or less is preferable and 40 degrees C or less is more preferable.
- the living anionic polymerization can be stopped by adding a polymerization terminator such as methanol; acetic acid or hydrochloric acid in methanol; a protic compound such as aqueous solution of acetic acid or hydrochloric acid to the reaction solution.
- a polymerization terminator such as methanol; acetic acid or hydrochloric acid in methanol; a protic compound such as aqueous solution of acetic acid or hydrochloric acid
- the amount of the polymerization terminator used is usually preferably in the range of 1 to 100 mol per 1 mol of the organic lithium compound used.
- the reaction solution is poured into a poor solvent of the (meth) acrylic block copolymer (A) to precipitate the (meth) acrylic block copolymer (A), and the organic solvent is distilled off from the reaction solution.
- Examples thereof include a method for obtaining a (meth) acrylic block copolymer (A).
- the metal component derived from the organolithium compound and the organoaluminum compound remains in the separately obtained (meth) acrylic block copolymer (A), the (meth) acrylic block copolymer (A)
- the physical properties may be degraded. Therefore, it is preferable to remove the metal component derived from the organolithium compound and the organoaluminum compound after the anionic polymerization is stopped.
- As a method for removing the metal component it is effective to perform a washing treatment using an acidic aqueous solution, an adsorption treatment using an adsorbent such as an ion exchange resin, celite, activated carbon or the like.
- acidic aqueous solution hydrochloric acid, sulfuric acid aqueous solution, nitric acid aqueous solution, acetic acid aqueous solution, propionic acid aqueous solution, citric acid aqueous solution etc. can be used, for example.
- a monomer containing the di (meth) acrylate (3) described above is used.
- a polymer containing a partial structure serving as a precursor of the partial structure (1)
- a method of converting the precursor structure into the partial structure (1) after forming the block is also mentioned.
- a polymer block containing a precursor structure is obtained by polymerizing a monomer containing a polymerizable functional group and a compound containing a precursor structure.
- Examples of the polymerizable functional group include a styryl group, a 1,3-dienyl group, a vinyloxy group, a (meth) acryloyl group and the like, and a (meth) acryloyl group is preferable.
- the precursor structure includes a hydroxyl group protected by a hydroxyl group and a protecting group (silyloxy group, acyloxy group, alkoxy group, etc.), an amino group, an amino group protected by a protecting group, a thiol group, and a thiol group protected by a protecting group.
- isocyanate groups As well as isocyanate groups.
- a polymer block containing a hydroxyl group as a precursor structure is reacted with a compound having a partial structure (1) and a partial structure (carboxyl group, ester, carbonyl halide, etc.) capable of reacting with a hydroxyl group, thereby forming a (meth) acrylic polymer.
- Block (a) can be formed.
- a polymer block containing a hydroxyl group protected by a protecting group as a precursor structure can form a (meth) acrylic polymer block (a) after removing the protecting group to form a hydroxyl group.
- the polymer block containing an amino group as a precursor structure has a partial structure (1) and a partial structure that can react with the amino group (carboxyl group, carboxylic acid anhydride, ester, carbonyl halide, aldehyde group, isocyanate group, etc.).
- the (meth) acrylic polymer block (a) can be formed by reacting with a compound.
- a polymer block containing an amino group protected by a protecting group as a precursor structure can form a (meth) acrylic polymer block (a) in the same manner after removing the protecting group to form an amino group.
- a polymer block containing a thiol group as a precursor structure includes a partial structure (1) and a partial structure capable of reacting with a thiol group (carboxyl group, carboxylic anhydride, ester, carbonyl halide, isocyanate group, carbon-carbon double bond) Etc.) can be reacted with a compound having (meth) acrylic polymer block (a).
- a polymer block containing a thiol group protected by a protective group as a precursor structure can form a (meth) acrylic polymer block (a) in the same manner after removing the protective group to form a thiol group.
- the polymer block containing an isocyanate group as a precursor structure is reacted with a compound having a partial structure (1) and a partial structure (hydroxyl group, amino group, etc.) capable of reacting with the isocyanate group, to form a (meth) acrylic polymer block.
- (A) can be formed.
- the dental polymerizable composition of the present invention contains a polymerizable monomer (B).
- Radical polymerizable monomers are preferably used, for example, esters such as ⁇ -cyanoacrylic acid, (meth) acrylic acid, ⁇ -halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, itaconic acid, etc. (Meth) acrylamide; vinyl ester; vinyl ether; styrene derivative and the like. Of these, (meth) acrylic acid esters are preferred from the viewpoint of miscibility with the (meth) acrylic block copolymer (A).
- the polymerizable monomer (B) may be monofunctional, bifunctional, or trifunctional or higher.
- Examples of the monofunctional polymerizable monomer (B) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) N-butyl acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid 2,3-dibromopropyl, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxy (meth) acrylate Ethyl, 2-ethoxyethyl (me
- methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid n-- are preferable in terms of excellent miscibility with the (meth) acrylic block copolymer (A) and flexibility of the cured product.
- butyl, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate From the viewpoint of the toughness of the resulting cured product, methyl (meth) acrylate, t-butyl (meth) acrylate and isobornyl (meth) acrylate are more preferred.
- bifunctional polymerizable monomer (B) examples include 2,2-bis ((meth) acryloyloxyphenyl) propane and 2,2-bis [4- (3-acryloyloxy-2-hydroxypropoxy). ) Phenyl] propane, 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane (commonly referred to as “Bis-GMA”), 2,2-bis (4- (meth) acryloyloxyethoxy) Phenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (Meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypenta) Toxiphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxy
- Examples of the trifunctional or higher polymerizable monomer (B) include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, N, N- (2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol ], Tetramethacrylate, 1,7-diaacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, and the like.
- trimethylolpropane tri (meth) acrylate is preferable because it is excellent in miscibility with the (meth) acrylic block copolymer (A).
- polymerizable monomer (B) a polyfunctional (that is, bifunctional or trifunctional or higher) polymerizable monomer and a monofunctional polymerizable monomer may be used in combination.
- the content of the polyfunctional polymerizable monomer is 10 to 100% by mass with respect to the total amount of the polymerizable monomer (B). It is preferably 20 to 100% by mass, more preferably 40 to 100% by mass.
- the blending amount of the polyfunctional polymerizable monomer is 10% by mass or more, the toughness of the cured product of the dental polymerizable composition becomes high and is hardly broken.
- the content of the polyfunctional polymerizable monomer increases the toughness of the cured product and is not easily destroyed. Therefore, the amount is preferably 10 to 100% by mass, more preferably 50 to 99% by mass, and 60 to 98.5% by mass with respect to the total amount of the polymerizable monomer (B). Is more preferably 65 to 97.5% by mass.
- the content of the polyfunctional polymerizable monomer is from 1 to the total amount of the polymerizable monomer (B). It is preferably 75% by mass, more preferably 2.5 to 50% by mass, and further preferably 5 to 25% by mass. When the blending amount of the polyfunctional polymerizable monomer is 75% by mass or less, the flexibility of the cured product of the dental polymerizable composition is increased.
- total amount of polymerizable monomer (B) means the total amount of polymerizable monomer (B) contained in the entire dental polymerizable composition, for example, When the dental polymerizable composition of the present invention is a two-component type described later, it means the total mass of the polymerizable monomer (B) contained in each composition.
- the dental polymerizable composition of the present invention when used as a rocking tooth fixing material and a self-adhesive composite resin, is a polymerizable monomer (from the viewpoint of imparting adhesive strength to teeth, bones, metals, etc.
- a polymerizable monomer 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, or a carboxylic acid group, and a (meth) acrylic block
- 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, or a carboxylic acid group
- a (meth) acrylic block From the viewpoint of excellent miscibility with the copolymer (A), it is more preferable to use a polymerizable monomer having a phosphate group or a phosphonic acid group, and it is preferable to use a polymerizable monomer having a phosphate group. Further preferred.
- the dental polymerizable composition of the present invention is used as a dental cement and a denture base lining material
- Examples of the polymerizable monomer having a phosphate group that can be used as the polymerizable monomer (B) include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl diester.
- Hydrogen phosphate 4- (meth) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxy Heptyl dihydrogen phosphate, 8- (meth) acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl Hydrogen phosphate, 11- (meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxyhexadecyl dihydrogen phosphate, 20- (meth) Acryloyloxyeicosyl dihydrogen phosphat
- the content of the polymerizable monomer (B) having these acidic groups is not particularly limited, but is preferably 1 to 50% by mass with respect to the total amount of the polymerizable monomer (B). It is more preferably from 40 to 40% by mass, further preferably from 2.5 to 35% by mass, particularly preferably from 5 to 33% by mass.
- the dental polymerizable composition of the present invention has good adhesive strength, and when it is 50% by mass or less, the dental polymerizable composition of the present invention is miscible. Excellent in properties.
- the polymerizable monomer (B) for example, 2,2,2-trifluoroethyl (meth) acrylate, (Meth) acrylic acid 2,2,3,3,3-pentafluoropropyl, (meth) acrylic acid 2- (perfluorobutyl) ethyl, (meth) acrylic acid 3- (perfluorobutyl) -2-hydroxypropyl 2- (perfluorohexyl) ethyl (meth) acrylate, 3- (perfluorohexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxy (meth) acrylate Propyl, (meth) acrylic acid 1H, 1H, 3H-tetrafluoropropyl, (meth) acrylic acid 1H, 1H, 5H-octafluoropenty (
- the content of the (meth) acrylic acid ester having a fluorine atom is not particularly limited, but it is 20 to 100% by mass with respect to the total amount of the polymerizable monomer (B) from the viewpoint of coloring resistance. It is preferably 30 to 100% by mass, more preferably 40 to 100% by mass, and particularly preferably 40 to 95% by mass.
- the content of the polymerizable monomer (B) in the dental polymerizable composition of the present invention is preferably 10 to 95% by mass, and preferably 15 to 90% by mass from the viewpoints of flexibility and ejection force. More preferably, it is more preferably 15 to 80% by mass.
- the content of the polymerizable monomer (B) in the dental polymerizable composition is preferably 15 to 95% by mass, The content is more preferably 25 to 90% by mass, and further preferably 25 to 85% by mass.
- the content of the polymerizable monomer (B) in the dental polymerizable composition is preferably 10 to 90% by mass.
- the content is more preferably 15 to 80% by mass, and further preferably 15 to 50% by mass.
- the content of the polymerizable monomer (B) in the dental polymerizable composition is preferably 10 to 95% by mass, 15 It is more preferably from 90 to 90% by mass, and further preferably from 20 to 60% by mass.
- the content of the polymerizable monomer (B) in the dental polymerizable composition is preferably 10 to 80% by mass, and 15 to 70% by mass. More preferably, it is more preferably 20 to 50% by mass.
- the content of the polymerizable monomer (B) in the dental polymerizable composition is 12 to 85% by mass. It is preferably 17 to 60% by mass, more preferably 17 to 50% by mass.
- the content of the (meth) acrylic block copolymer (A) is polymerizable from the viewpoint of flexibility and ejection force.
- the amount is preferably 5 to 500 parts by mass and more preferably 10 to 250 parts by mass with respect to 100 parts by mass of the total amount of the body (B).
- the content of the (meth) acrylic block copolymer (A) is a polymerizable monomer from the viewpoint of flexibility and discharge force.
- the amount of (B) is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass with respect to 100 parts by mass.
- the content of the (meth) acrylic block copolymer (A) is selected from the viewpoints of flexibility and discharge force.
- the content of the (meth) acrylic block copolymer (A) is 100 in terms of the total amount of the polymerizable monomer (B) from the viewpoints of flexibility and discharge force.
- the amount is preferably 20 to 500 parts by mass, more preferably 40 to 400 parts by mass with respect to parts by mass.
- the content of the (meth) acrylic block copolymer (A) is polymerizable from the viewpoint of polymerization shrinkage stress and discharge force.
- the amount of the monomer (B) is preferably 2.5 to 250 parts by mass, more preferably 5 to 100 parts by mass with respect to the total amount of 100 parts by mass.
- a (meth) acrylic block copolymer other than the (meth) acrylic block copolymer (A) may be included as long as the effects of the present invention are not hindered.
- the content of other (meth) acrylic block copolymers is preferably less than 5.0% by mass, and more preferably less than 2.0% by mass.
- Examples of the polymerization initiator (C) contained in the dental polymerizable composition of the present invention include a photopolymerization initiator and a chemical polymerization initiator.
- the dental polymerizable composition of the present invention when used as a rocking tooth fixing material or a dental self-adhesive composite resin, it preferably contains a photopolymerization initiator.
- the dental polymerizable composition of the present invention when used as a denture base lining material or dental cement, it is preferable to contain a chemical polymerization initiator.
- Photopolymerization initiators include (bis) acylphosphine oxides and salts thereof, ⁇ -diketones, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, coumarins, anthraquinones, benzoin alkyl ether compounds, Examples include ⁇ -aminoketone compounds, and (bis) acylphosphine oxides and salts thereof, and ⁇ -diketones are preferable from the viewpoint of curability.
- Examples of (bis) acylphosphine oxides that can be used as the photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 2,6-dichlorobenzoyldiphenylphosphine.
- JP 2000-159621 A the compounds described in JP 2000-159621 A can also be mentioned.
- 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyl Phenylphosphine oxide sodium salt is particularly preferred.
- Examples of ⁇ -diketones that can be used as a photopolymerization initiator include diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4 ′. -Oxybenzyl, acenaphthenequinone and the like.
- camphorquinone is particularly preferable from the viewpoint of having a maximum absorption wavelength in the visible light region.
- the dental polymerizable composition of the present invention contains a photopolymerization initiator
- the partial structure (1) exhibits polymerizability by irradiation with light
- the dental polymerizable composition of the present invention is cured and cured.
- light rays include visible light rays, far ultraviolet rays, ultraviolet rays (UV), near ultraviolet rays, infrared rays, and the like. From the viewpoints of safety to living bodies, curing speed, availability of irradiation devices, prices, and the like. Visible light is preferred.
- Examples of the chemical polymerization initiator include organic peroxides such as ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, peroxyester, and peroxydicarbonate.
- ketone peroxide examples include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide.
- hydroperoxides examples include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, 1 1,3,3-tetramethylbutyl hydroperoxide and the like.
- Diacyl peroxides that can be used as chemical polymerization initiators include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichloro Examples include benzoyl peroxide and lauroyl peroxide.
- Diacyl peroxides that can be used as chemical polymerization initiators include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichloro Examples include benzoyl peroxide and lauroyl peroxide.
- Peroxyketals that can be used as a chemical polymerization initiator include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane. 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, n-butyl 4,4-bis (t-butylperoxy) valerate and the like.
- Peroxyesters that can be used as a chemical polymerization initiator include ⁇ -cumyl peroxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethyl.
- Pentylperoxy-2-ethylhexanoate Pentylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t -Butylperoxyhexahydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate and the like.
- hydroperoxide is preferable from the balance of safety, storage stability, and polymerization initiating ability, cumene hydroperoxide, t-butyl hydroperoxide, 1,1,3,3-tetra Methylbutyl hydroperoxide is more preferred.
- the content of the polymerization initiator (C) is preferably 0.01 to 15% by mass and more preferably 0.05 to 8% by mass with respect to the whole dental polymerizable composition of the present invention. .
- the content of the polymerization initiator (C) is preferably 0.001 to 30 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomers (B) from the viewpoint of curability of the resulting composition. 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass.
- content of a polymerization initiator (C) is less than 0.001 mass part, superposition
- polymerization may not fully advance, and when it exceeds 30 mass parts, it may precipitate from a composition.
- the dental polymerizable composition of the present invention preferably contains a polymerization accelerator (D).
- the polymerization accelerator (D) include amines, sulfinic acids and salts thereof, sulfites, bisulfites, aldehydes, thiourea compounds, organophosphorus compounds, vanadium compounds, copper compounds, borate compounds, barbituric acid derivatives, triazines. Examples thereof include compounds, tin compounds, halogen compounds, and thiol compounds.
- Examples of amines that can be used as the polymerization accelerator (D) include primary aliphatic amines such as n-butylamine, n-hexylamine, and n-octylamine; diisopropylamine, dibutylamine, and N-methylethanol.
- Secondary aliphatic amines such as amines; N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-dodecyldiethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N- Ethyl diethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine Tertiary aliphatic amines such as N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di (2-hydroxyethyl) -p-toluidine, N, N N-bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N
- tertiary aliphatic amines are preferable from the viewpoint of curing speed, and N-methyldiethanolamine, triethanolamine, N, N-di (2-hydroxyethyl) -p-toluidine, 4- (N, N-dimethylamino) are preferred.
- Ethyl benzoate, n-butoxyethyl N, N-dimethylaminobenzoate, and 4-N, N-dimethylaminobenzophenone are more preferable, and N-methyldiethanolamine and triethanolamine are more preferable from the viewpoint of storage stability. .
- Examples of the sulfinic acid and its salt that can be used as the polymerization accelerator (D) include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, p- Calcium toluenesulfinate, benzenesulfinate, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinate, 2,4,6-trimethylbenzenesulfinate Sodium, potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-to Ethylbenzenesulfinic acid, sodium 2,4,6-triethylbenzenesulf
- Examples of the sulfite and bisulfite that can be used as the polymerization accelerator (D) include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium bisulfite, and potassium bisulfite. From the viewpoint, sodium sulfite is preferable.
- aldehyde that can be used as the polymerization accelerator (D) include terephthalaldehyde; benzaldehyde derivatives such as dimethylaminobenzaldehyde, p-methyloxybenzaldehyde, p-ethyloxybenzaldehyde, and pn-octyloxybenzaldehyde. . Among these, pn-octyloxybenzaldehyde is preferable from the viewpoint of curability.
- Examples of the thiourea compound that can be used as the polymerization accelerator (D) include 1- (2-pyridyl) -2-thiourea, thiourea, methylthiourea, ethylthiourea, N, N′-dimethylthiourea, N , N′-diethylthiourea, N, N′-di-n-propylthiourea, N, N′-dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthio
- Examples include urea, tetraethylthiourea, tetra-n-propylthiourea, tetracyclohexylthiourea, 3,3-dimethylethylenethiourea, 4,4-dimethyl-2-imidazolinethione and the like
- Examples of the organic phosphorus compound that can be used as the polymerization accelerator (D) include triphenylphosphine, 2-methyltriphenylphosphine, 4-methyltriphenylphosphine, 2-methoxytriphenylphosphine, 4-methoxytriphenylphosphine, -N-butylphosphine, triisobutylphosphine, tri-t-butylphosphine and the like. Of these, triphenylphosphine and 2-methyltriphenylphosphine are preferable from the viewpoint of curability.
- the vanadium compounds that can be used as the polymerization accelerator (D) are preferably IV and / or V vanadium compounds.
- IV-valent and / or V-valent vanadium compounds include divanadium tetroxide (IV), vanadyl acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl), and the like.
- 1,3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), ammonium metavanadate (V) and the like are preferably used. .
- Examples of the copper compound that can be used as the polymerization accelerator (D) include acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like.
- the content of the polymerization accelerator (D) is preferably 0.01 to 15% by mass, more preferably 0.05 to 8% by mass, based on the whole dental polymerizable composition of the present invention. .
- the content of the polymerization accelerator (D) is preferably 0.001 to 30 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomers (B) from the viewpoint of curability of the resulting composition. 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass.
- the blending amount of the polymerization accelerator (D) is less than 0.001 part by mass, the polymerization may not proceed sufficiently, and when it exceeds 30 parts by mass, it may be precipitated from the composition.
- a chemical polymerization initiator and a polymerization accelerator (D) may be combined to form a redox polymerization initiator.
- the chemical polymerization initiator and the polymerization accelerator (D) are preferably stored in separate containers and mixed immediately before use. Therefore, the dental polymerizable composition is preferably a two-component type of a first agent containing a chemical polymerization initiator and a second agent containing a polymerization accelerator (D). It is more preferable that the two agents are both pasty.
- the dental polymerizable composition of the present invention may further contain a filler (E) in order to adjust the ejection force or increase the mechanical strength of the obtained cured product.
- a filler E
- examples of such fillers include organic fillers, inorganic fillers, and organic-inorganic composite fillers.
- organic filler examples include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, polyester, polyamide, polycarbonate, polyphenylene ether.
- the combination etc. are mentioned, These may be used individually by 1 type, or may use 2 or more types together.
- the shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used.
- Examples of the inorganic filler include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, Examples include aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate glass. These may be used alone or in combination of two or more.
- the shape of the inorganic filler is not particularly limited, and an amorphous filler and a spherical filler can be appropriately selected and used.
- the inorganic filler may be used after being surface-treated with a known surface treating agent such as a silane coupling agent as necessary.
- a known surface treating agent such as a silane coupling agent
- surface treating agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri ( ⁇ -methoxyethoxy) silane, 3-methacryloyloxypropyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and the like.
- the method of surface treatment is not particularly limited, for example, a method of spray-adding the surface treatment agent while vigorously stirring the inorganic filler, a solvent after dispersing or dissolving the inorganic filler and the surface treatment agent in an appropriate solvent Or a method of removing water after hydrolyzing the alkoxy group of the surface treatment agent in an aqueous solution with an acid catalyst to convert it to a silanol group and attaching it to the surface of the inorganic filler in the aqueous solution.
- Known methods can be applied.
- the surface treatment can be performed by heating in the range of 50 to 150 ° C. to complete the reaction between the surface of the inorganic filler and the surface treatment agent.
- organic-inorganic composite filler those obtained by adding a monomer compound to the above-mentioned inorganic filler in advance, forming a paste, polymerizing and pulverizing, for example, TMPT filler (trimethylolpropane methacrylate) are used. And a 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.
- the average particle diameter of the filler (E) is preferably 0.001 to 50 ⁇ m, and preferably 0.001 to 10 ⁇ m from the viewpoints of the handleability of the resulting dental polymerizable composition and the mechanical strength of the cured product. It is more preferable that In the present specification, the average particle diameter of the filler can be measured by any method known to those skilled in the art. For example, a laser diffraction particle size distribution measuring apparatus (SALD-2100: manufactured by Shimadzu Corporation) described in the following examples ) Can be easily measured.
- SALD-2100 manufactured by Shimadzu Corporation
- 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.
- 0.1 ⁇ m is a value measured by a laser diffraction scattering method.
- the laser diffraction scattering method can be measured using a 0.2% sodium hexametaphosphate aqueous solution as a dispersion medium with a laser diffraction particle size distribution analyzer (SALD-2100: manufactured by Shimadzu Corporation).
- SALD-2100 manufactured by Shimadzu Corporation
- the electron microscope observation is, for example, taking a picture of a scanning electron microscope (S-4000, manufactured by Hitachi, Ltd.) of particles, and measuring the particle diameter of particles (200 or more) observed in the unit field of view of the photograph. It can be determined by measuring using image analysis type particle size distribution measurement software (Macview (Mounttech Co., Ltd.)).
- 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.
- the content of the filler (E) in the dental polymerizable composition of the present invention is preferably 0 to 85% by mass and more preferably 0 to 80% by mass from the viewpoints of flexibility and ejection force. Preferably, it is 1 to 79% by mass.
- the filler (E) content in the dental polymerizable composition is 0 to 70% by mass.
- the content is preferably 0 to 45% by mass, and more preferably 0 to 18% by mass.
- the filler (E) contains ultrafine particles having an average particle diameter of 0.1 ⁇ m or less.
- the content of the filler (E) in the dental polymerizable composition is preferably 0 to 80% by mass, and 0 to 75% by mass. More preferably, it is more preferably 20 to 70% by mass.
- the filler (E) includes a filler having an average particle diameter exceeding 1 ⁇ m.
- the content of the filler (E) in the dental polymerizable composition is preferably 15 to 85% by mass, 35 It is more preferably from ⁇ 80% by mass, and further preferably from 46 to 79% by mass.
- the filler (E) contains a filler having an average particle diameter exceeding 1 ⁇ m.
- the filler (E) content is such that when the dental polymerizable composition of the present invention is a rocking tooth fixing material or a denture base lining material, the handleability of the resulting dental polymerizable composition and its cured product From the viewpoint of mechanical strength, 0 to 250 parts by mass of filler (E) with respect to 100 parts by mass of the total amount of the polymerizable components ((meth) acrylic block copolymer (A) and polymerizable monomer (B)). Is preferable, and 0 to 100 parts by mass is more preferable.
- the total amount of the polymerizable components ((meth) acrylic block copolymer (A) and polymerizable monomer (B)) is 100 parts by mass.
- the filler (E) is preferably 0 to 400 parts by mass, more preferably 0 to 300 parts by mass.
- the total amount of polymerizable components ((meth) acrylic block copolymer (A) and polymerizable monomer (B)) is 100.
- the filler (E) is preferably 50 to 500 parts by weight, more preferably 100 to 400 parts by weight with respect to parts by weight.
- the dental polymerizable composition of the present invention includes other polymers such as natural rubber, synthetic polyisoprene rubber, liquid for the purpose of modifying flexibility, ejection force and the like within the range not impairing the gist of the present invention.
- Polyisoprene rubber and hydrogenated product thereof polybutadiene rubber, liquid polybutadiene rubber and hydrogenated product thereof, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, acrylic rubber, isoprene-isobutylene rubber, acrylonitrile-butadiene rubber, styrenic elastomer
- polystyrene-polyisoprene-polystyrene block copolymer polystyrene-polybutadiene-polystyrene block copolymer, poly ( ⁇ -methylstyrene) -polybutadiene-poly ( ⁇ -methylstyrene) block
- the dental polymerizable composition of the present invention can contain a softener as necessary.
- the softener include petroleum softeners such as paraffinic, naphthenic, and aromatic process oils, and vegetable oil softeners such as paraffin, peanut oil, and rosin. These may be used alone or in combination of two or more.
- the content of the softening agent is not particularly limited as long as the gist of the present invention is not impaired.
- the total amount of the (meth) acrylic block copolymer (A) and the polymerizable monomer (B) is 100 parts by mass. Is 300 parts by mass or less, preferably 100 parts by mass or less.
- a known additive can be blended with the dental polymerizable composition of the present invention within a range where the performance is not deteriorated.
- additives include polymerization inhibitors, antioxidants, pigments, dyes, ultraviolet absorbers, thickeners and the like.
- polymerization inhibitor examples include hydroquinone, hydroquinone monomethyl ether, dibutyl hydroquinone, dibutyl hydroquinone monomethyl ether, t-butylcatechol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butylphenol, 3,5-di-t-butyl-4-hydroxytoluene and the like.
- the content of the polymerization inhibitor is 0.001 to 1.0 mass with respect to 100 mass parts of the total amount of the polymerizable components ((meth) acrylic block copolymer (A) and polymerizable monomer (B)). Part is preferred.
- the dental polymerizable composition of the present invention has a low ejection force and is easily shaped.
- the cured product has flexibility and excellent shock absorption, low polymerization shrinkage stress accompanying curing, excellent adhesion, and excellent surface gloss and color resistance.
- the dental polymerizable composition of the present invention is most suitable for a rocking tooth fixing material, a denture base lining material and a dental cement, and is excellent in relaxation of polymerization shrinkage stress. It is also suitable for resins.
- the denture base lining material comprises 10 to 1000 parts by weight of a (meth) acrylic block copolymer (A) and a polymerization initiator (C) with respect to 100 parts by weight of the total amount of the polymerizable monomer (B).
- 0.05 to 20 parts by mass containing 0.05 to 20 parts by mass of a polymerization accelerator (D), and polymerizable components ((meth) acrylic block copolymer (A) and polymerizable monomer (B) ) Is preferably contained in an amount of 0 to 250 parts by weight based on 100 parts by weight of the total amount of (meth) acrylic block copolymer (A) based on 100 parts by weight of the polymerizable monomer (B).
- D polymerization accelerator
- the E) more preferably contains 0-100 parts by weight.
- dental cement An example of a suitable configuration of dental cement is shown.
- 5 to 500 parts by mass of the (meth) acrylic block copolymer (A) and 0.1% of the polymerization initiator (C) are added to 100 parts by mass of the polymerizable monomer (B).
- the E) more preferably contains 0 to 300 parts by weight.
- the dental self-adhesive composite resin has a polymerization initiator (2.5 to 250 parts by mass of (meth) acrylic block copolymer (A) based on 100 parts by mass of the polymerizable monomer (B)).
- the filler (E) is preferably contained in an amount of 50 to 500 parts by mass with respect to 100 parts by mass of the total amount of (B)), and the (meth) acrylic block copolymer with respect to 100 parts by mass of the polymerizable monomer (B) 5 to 100 parts by weight of (A), 0.1 to 10 parts by weight of polymerization initiator (C), 0.1 to 10 parts by weight of polymerization accelerator (D), and a polymerizable component ((meth) acrylic 100 block quality of block copolymer (A) and polymerizable monomer (B)) More preferably contains the filler (E) 100 ⁇ 400 parts by weight with respect to part.
- Conditions such as the type and content of each component in the rocking tooth fixing material, denture base lining material, dental cement, and dental self-adhesive composite resin of the preferred embodiment are the ranges described separately in this specification. Can be appropriately selected and changed.
- Visible light is preferable as the light used for curing the dental polymerizable composition of the present invention, and LED, halogen lamp, arc light and xenon lamp, and combinations thereof are used for irradiation with visible light. be able to.
- a conventional method for preparing a dental polymerizable composition can be employed, and examples thereof include a method in which each component is kneaded in a predetermined blending amount to be uniform. Further, after each component is kneaded to be uniform, vacuum defoaming treatment may be performed.
- the raw materials were dried and purified by a conventional method and degassed with nitrogen, and the transfer and supply were performed in a nitrogen atmosphere.
- step [I] The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in step [I] was 100%. Further, Mn (Mn (R-1)) of the obtained polymer was 1,340, and Mw / Mn was 1.16. Furthermore, the polymerization initiation efficiency (F1) in step [I] was 99%.
- step [I] The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in step [I] was 100%. Further, Mn (Mn (R-1)) of the obtained polymer was 7,860, and Mw / Mn was 1.23. Furthermore, the polymerization initiation efficiency (F1) in step [I] was 99%.
- step [I] The consumption rate of 1,1-dimethylpropane-1,3-diol dimethacrylate and methyl methacrylate in step [I] was 100%. Further, Mn (Mn (R-1)) of the obtained polymer was 1,250, and Mw / Mn was 1.18. Furthermore, the polymerization initiation efficiency (F1) in step [I] was 99%.
- n-butyl acrylate in the step [II] was 100%. Further, Mn (Mn (R-2)) of the obtained polymer was 19,200 and Mw / Mn was 1.19. Furthermore, the block efficiency (F2) from step [I] to step [II] was 100%.
- the white precipitate thus obtained is a triblock copolymer composed of PMMA-PnBA-PMMA (hereinafter referred to as “(meth) acrylic block copolymer 1”), and the total Mw thereof is 85,000, Mw / Mn is 1.13, and the ratio of each polymer block is PMMA (10% by mass) -PnBA (80% by mass) -PMMA (10% by mass) (a total of 20 masses of PMMA) %)There was found.
- Sample 1 is PMMA, whose Mw is 7,300, and Mw / Mn is 1.06;
- Sample 2 is a PMMA-PnBA diblock copolymer, and its Mw is 77,000. , Mw / Mn was 1.16.
- CQ camphorquinone
- BAPO bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide
- Filler (E) -1 Colloidal silica powder (“Aerosil 380” manufactured by Nippon Aerosil Co., Ltd., average particle diameter: 7 nm)
- Filler (E) -2 3-methacryloyloxypropyltrimethoxysilane-treated silica powder 100 g of silica powder obtained by grinding silica (“Aerosil 130” manufactured by Nippon Aerosil Co., Ltd.) with a vibration ball mill, 3-methacryloyloxypropyltrimethoxysilane 0.5 g and 200 ml of toluene were placed in a 500 ml eggplant flask and stirred at room temperature for 2 hours. Subsequently, toluene was distilled off under reduced pressure, followed by vacuum drying at 40 ° C. for 16 hours and then at 90 ° C.
- filler (E) -2 3-methacryloyloxypropyltrimethoxysilane-treated silica powder (filler (E) -2). It was.
- the average particle size of the filler (E) -2 was measured using a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, model “SALD-2100”, dispersion medium: 0.2% sodium hexametaphosphate aqueous solution). 0.02 ⁇ m.
- Barium glass powder treated with filler (E) -3 3-methacryloyloxypropyltrimethoxysilane 100 g of barium glass powder obtained by pulverizing barium glass (“E-3000” manufactured by ESTEC Co., Ltd.) with a vibration ball mill, 3-methacryloyloxypropyl 0.5 g of trimethoxysilane (“KBM-503” manufactured by Shin-Etsu Silicone Co., Ltd.) (0.5 part by weight with respect to 100 parts by weight of the core filler) and 200 mL of toluene were placed in a 500 mL eggplant flask and stirred at room temperature for 2 hours.
- KBM-503 trimethoxysilane
- toluene was distilled off under reduced pressure, followed by vacuum drying at 40 ° C. for 16 hours and then at 90 ° C. for 3 hours to obtain 3-methacryloyloxypropyltrimethoxysilane-treated barium glass powder [Filler (E) -3]. Obtained.
- the average particle size of filler (E) -3 was measured using a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, model “SALD-2100”, dispersion medium: 0.2% sodium hexametaphosphate aqueous solution). .4 ⁇ m.
- each component was mixed at 20 ° C. in the amounts shown in Table 2, and paste A as a dental polymerizable composition according to Examples 7 to 12 and Comparative Examples 3 to 4 (above-mentioned A B paste (corresponding to the second agent) and B paste (corresponding to the first agent) were prepared.
- each component was mixed at 20 ° C. in the amounts shown in Table 3, and paste A as a dental polymerizable composition according to Examples 13 to 18 and Comparative Examples 5 to 6 (the first paste) And B paste (corresponding to the second agent) were prepared.
- Test Example 1 Discharge force obtained in Examples 1 to 6 and Comparative Examples 1 and 2 assuming a swinging tooth fixing material, and Examples 19 to 24 and Comparative Examples 7 to 8 assuming a dental self-adhesive composite resin
- the dental polymerizable composition was stored in a container of a commercially available dental composite resin (Kurarenoritake Dental Co., Ltd., Clearfil Majesty LV, capacity 1.5 mL) equipped with a guide chip having an inner diameter of 0.5 mm at the tip. .
- the crosshead equipped with a jig for compressive strength test is lowered at 25 ° C. at 4 mm / min, so that the extruded member enters the container. Then, it was discharged from the discharge portion through the guide chip, and the maximum load was set as the discharge force.
- Tables 1 and 4 The results are shown in Tables 1 and 4.
- the crosshead equipped with the jig for compressive strength test is lowered at 25 ° C. at 4 mm / min.
- the extruded member was allowed to enter, and after the A paste and B paste were kneaded with a mixing tip, the paste was discharged, and the maximum load was the discharge force.
- the discharge force is 50 N or less, when extruding the paste from the container, it can be easily discharged with one hand, and the discharge performance is extremely good. Although ejection is possible at a pressure exceeding 50N and 80N or less, both hands may be required for ejection. If it exceeds 80 N, it is difficult to discharge with both hands.
- Test Example 2 Shapeability Examples 1 to 6 and Comparative Examples 1 to 2 and dental self-adhesiveness assuming a swinging tooth fixing material by drawing a circle with a diameter of 4 mm on dental kneaded paper 59 mm long by 83 mm wide 0.3 g of the dental polymerizable composition obtained in Examples 19 to 24 and Comparative Examples 7 to 8 assuming a composite resin was placed in a hemisphere throughout the circle, and the dental kneaded paper was kept at a constant temperature of 37 ° C.
- the dental polymerizable composition was stood vertically in a container and allowed to stand for 3 minutes, and the distance moved from the circle of the dental polymerizable composition was measured. This test was performed three times, and the average value of the three measurement values was defined as the sagging distance (mm). The larger the sagging distance, the easier the dental polymerizable composition flows. The results are shown in Tables 1 and 4.
- Test Example 3 Bending elastic modulus A cylindrical mold in which the dental polymerizable compositions obtained in Examples 1 to 6 and Comparative Examples 1 and 2 assuming a rocking tooth fixing material were placed on a slide glass ( Stainless steel, 2 mm ⁇ 25 mm (rectangular), 2 mm thick) was filled, and a slide glass was further placed on the mold. Next, the dental polymerizable composition was cured with a dental visible light irradiator (Morita Co., Ltd., PenCure 2000) by irradiating light on each of the five locations through the glass slides on the upper and lower surfaces for 10 seconds. Was made.
- a dental visible light irradiator Morita Co., Ltd., PenCure 2000
- the paste A and B which are the dental polymerizable compositions obtained in Examples 13 to 18 and Comparative Examples 5 to 6 assuming dental cement, are kneaded and placed in the above mold placed on a slide glass. And a slide glass was further placed on the mold.
- the dental polymerizable composition was cured by allowing it to stand in a 37 ° C. incubator for 30 minutes to prepare a test piece.
- the bending test of the obtained test piece was performed at a crosshead speed of 1 mm / min using an autograph (manufactured by Shimadzu Corporation, AG-100 kNI), and the flexural modulus was measured. The results are shown in Tables 1 and 3.
- the bending elastic modulus is preferably in the range of 500 to 2000 MPa from the viewpoint of impact durability.
- Test Example 4 A hardness A paste and B paste, which are dental polymerizable compositions obtained in Examples 7 to 12 and Comparative Examples 3 to 4 assuming denture base lining materials, were kneaded and placed on a slide glass. After filling the installed ring-shaped mold (made of stainless steel, inner diameter 1.5 cm, thickness 2 mm), and further placing a slide glass on the mold, it is allowed to stand in a 37 ° C. incubator for 30 minutes. It hardened and the disk-shaped test piece was produced. Based on JIS K7215, the hardness (A hardness) of the hardened
- the A hardness at 37 ° C. is 50 or less.
- Test Example 6 Surface Gloss Obtained in Examples 1 to 6 and Comparative Examples 1 and 2 assuming a swing tooth fixing material, and Examples 19 to 24 and Comparative Examples 7 to 8 assuming a dental self-adhesive composite resin
- a ring-shaped mold made of stainless steel, inner diameter 20 mm, thickness 2 mm
- a slide glass was further placed on the mold.
- the dental polymerizable composition was cured by irradiating each of the 6 spots for 10 seconds through the slide glass on both the upper and lower sides with a dental visible light irradiator (Morita Co., Ltd., PenCure 2000) to test the specimen.
- a dental visible light irradiator Morita Co., Ltd., PenCure 2000
- the dental polymerizable compositions obtained in Examples 7 to 13 and Comparative Examples 3 to 4 assuming denture base lining materials, and Examples 13 to 18 and Comparative Examples 5 to 6 assuming dental cement were used. After kneading a certain A paste and B paste, the dental moldable composition is cured by filling the mold set on the slide glass and allowing it to stand for 30 minutes in an incubator at 37 ° C. A test piece was prepared.
- ⁇ L is preferably 70 or more, and more preferably 80 or more.
- ⁇ L is preferably 40 or more and 65 or less.
- Test Example 7 Color resistance Chromaticity (L * 1, a * 1, b * ) of a test piece used in a surface gloss test using a spectrocolorimeter (manufactured by Nippon Denshoku Industries Co., Ltd., SE2000, D65 light source) 1) (Chromaticity before color resistance test) was measured.
- ⁇ E needs to be 5 or less.
- Test Example 8 Tensile bond strength The lip surface of bovine mandibular anterior teeth was polished with # 80 silicon carbide paper (Nippon Kenshi Co., Ltd.) under running water, and then # 1000 silicon carbide paper (Nihon Kenshi Co., Ltd.) Then, the surface water was removed with a dental air syringe to obtain bovine teeth having an enamel flat surface. Similarly, bovine teeth having a flat surface of dentin were obtained.
- the surface of the dental polymerizable composition was partially uncured.
- the end surface of a stainless steel cylindrical rod (diameter: 7 mm, length: 2.5 cm) coated with a commercially available dental resin cement (Kurarenoritake Dental Co., Ltd., Panavia 21) is the above-mentioned dental polymerizable composition.
- a commercially available dental resin cement Karl Fischer Dental Co., Ltd., Panavia 21
- an adhesive tape having a thickness of about 150 ⁇ m having a 3 mm diameter round hole was attached to the flat surface of the obtained bovine tooth having a flat surface of the dentin.
- the dental polymerizable compositions obtained in Examples 19 to 24 and Comparative Examples 7 to 8 assuming a dental self-adhesive composite resin were filled in the round holes. The excess portion overflowing from the round hole was removed with a razor so that the surface was smooth.
- the surface filled with the dental polymerizable composition was irradiated with light for 10 seconds with a dental visible light irradiator (manufactured by Morita, Pencure 2000). At this time, the surface of the dental polymerizable composition was partially uncured.
- test sample stainless steel rod and bovine teeth were connected to an autograph (manufactured by Shimadzu Corporation, AG-100kNI), and a tensile test was conducted at a crosshead speed of 2 mm / min.
- the adhesive strength of each composition was measured.
- Each tensile test was performed 5 times, and the average value was taken as the tensile bond strength. The results are shown in Tables 1 and 4.
- the tensile adhesive strength is 7.5 N or more, the adhesiveness is excellent.
- Test Example 9 Polymerization Shrinkage Stress Ring-shaped mold (made of stainless steel, inner diameter 5.5 mm ⁇ thickness 0.8 mm) placed on a glass plate (thickness 4.0 mm) sandblasted with alumina powder having a particle size of 50 ⁇ m
- the dental polymerizable compositions obtained in Examples 1 to 24 and Comparative Examples 1 to 8 were filled therein.
- a stainless steel jig ( ⁇ 5 mm) connected to an autograph manufactured by Shimadzu Corporation, AG-100kNI
- the polymerization shrinkage stress is preferably 100 N or less, and more preferably less than 85 N.
- the dental polymerizable compositions of Examples 1 to 6 that assumed a rocking tooth fixing material had small ejection force and sag distance, easy shaping, and low polymerization shrinkage stress due to curing. It was. Moreover, these hardened
- the dental polymerizable composition of Comparative Example 1 containing no (meth) acrylic block copolymer is inferior in formability, bending elastic modulus of cured product, and tensile adhesive strength to bovine enamel. The polymerization shrinkage stress was high.
- the dental polymerizable composition of Comparative Example 2 containing the (meth) acrylic block copolymer 1 which does not contain the (meth) acrylic block copolymer (A) and does not have a curable functional group. was inferior in discharge force and coloring resistance.
- the dental polymerizable compositions of Examples 7 to 12 assuming a denture base lining material have small ejection force and sag distance, are easy to shape, and have a polymerization shrinkage stress associated with curing. It was low. Moreover, these hardened
- the dental polymerizable composition of Comparative Example 3 containing no (meth) acrylic block copolymer is inferior in formability, has a high A hardness of the cured product, a high polymerization shrinkage stress, and a compression permanent. A strain test could not be performed.
- the dental polymerizable composition of Comparative Example 4 which does not contain the (meth) acrylic block copolymer (A) and contains the (meth) acrylic block copolymer 1 having no curable functional group. Has a large ejection force, and its cured product has a large compression set and inferior color resistance.
- the dental polymerizable compositions of Examples 13 to 18 assuming dental cement had small ejection force and sag distance, easy shaping, and low polymerization shrinkage stress due to curing. . Moreover, these hardened
- the dental polymerizable composition of Comparative Example 5 containing no (meth) acrylic block copolymer has low formability, high polymerization shrinkage stress due to curing, and the flexural modulus of the cured product is low. it was high.
- the dental polymerizable composition of Comparative Example 6 which does not contain the (meth) acrylic block copolymer (A) and contains the (meth) acrylic block copolymer 1 having no curable functional group. Had a large discharge force and was inferior in the coloration resistance of the cured product.
- the dental polymerizable compositions of Examples 19 to 24 assuming a self-adhesive composite resin have small ejection force and sag distance, are easy to shape, and have a polymerization shrinkage stress accompanying curing. It was low. These cured products were also excellent in surface gloss and color resistance. Furthermore, the adhesiveness with respect to a tooth substance was also excellent.
- the dental polymerizable composition of Comparative Example 7 containing no (meth) acrylic block copolymer is inferior in formability and inferior in tensile adhesive strength to bovine enamel and bovine dentin. The polymerization shrinkage stress was high.
- the dental polymerizable composition of Comparative Example 8 which does not contain the (meth) acrylic block copolymer (A) and contains the (meth) acrylic block copolymer 1 having no curable functional group. Had a large ejection force and was inferior in coloration resistance of the cured product.
- the dental polymerizable composition of the present invention has a suppressed ejection force, is easy to shape, has a low polymerization shrinkage stress accompanying curing, and is excellent in coloration resistance and surface gloss after curing.
- the dental polymerizable composition of the present invention is excellent in impact absorption after curing and adhesiveness to enamel, so that it can be suitably used for a rocking tooth fixing material or dental cement. it can.
- the dental polymerizable composition of the present invention is excellent in flexibility and strain durability after curing in addition to the above properties, it can be suitably used for a denture base lining material.
- the dental polymerizable composition of the present invention is excellent in adhesiveness to teeth (enamel and dentin), and therefore can be suitably used for dental self-adhesive composite resins. it can.
Abstract
Description
義歯床裏装材の硬化物には、表面硬度の低さおよび歪み耐久性が求められる。
歯科用セメント、特に仮着用の歯科用セメントには、取り外しを可能とするため、硬化物の曲げ弾性率を適当な範囲とする必要がある。
歯科用自己接着性コンポジットレジンには、歯牙の欠損部位への密着性の観点から、硬化に伴う重合収縮応力の抑制が求められる。
しかしながら、歯科用重合性組成物の吐出力の抑制、硬化に伴う重合収縮応力の抑制、ならびに硬化物の耐着色性および歪み耐久性等のさらなる改善が求められている。
[1]下記一般式(1)で示される部分構造(以下「部分構造(1)」と称する)を含む硬化性官能基を有する(メタ)アクリル系重合体ブロック(a)(以下、単に「(メタ)アクリル系重合体ブロック(a)」と称する)および硬化性官能基を有さない(メタ)アクリル系重合体ブロック(b)(以下、単に「(メタ)アクリル系重合体ブロック(b)」と称する)からなる(メタ)アクリル系ブロック共重合体(A)(以下、単に「(メタ)アクリル系ブロック共重合体(A)」と称する)、重合性単量体(B)、および重合開始剤(C)を含有する、歯科用重合性組成物;
[2]一般式(1)で示される部分構造を含む硬化性官能基が、下記一般式(2)で示される硬化性官能基である、[1]の歯科用重合性組成物;
[3]一般式(2)において、R1は水素原子またはメチル基を表し、XがOである、[2]の歯科用重合性組成物;
[4]重合促進剤(D)をさらに含有する、[1]~[3]のいずれかの歯科用重合性組成物;
[5]フィラー(E)をさらに含有する、[1]~[4]のいずれかの歯科用重合性組成物;
[6]上記[1]~[5]のいずれかの歯科用重合性組成物からなる動揺歯固定材;
[7]上記[1]~[5]のいずれかの歯科用重合性組成物からなる義歯床裏装材;
[8]上記[1]~[5]のいずれかの歯科用重合性組成物からなる歯科用セメント;ならびに
[9]上記[1]~[5]のいずれかの歯科用重合性組成物からなる歯科用自己接着性コンポジットレジン;
を提供することで達成される。
本発明の歯科用重合性組成物は(メタ)アクリル系ブロック共重合体(A)を含有する。なお、本明細書中において「(メタ)アクリル」とは「メタクリル」と「アクリル」との総称を意味し、後述する「(メタ)アクリロイル」は「メタクリロイル」と「アクリロイル」との総称を意味し、後述する「(メタ)アクリレート」は「メタクリレート」と「アクリレート」との総称を意味する。
一般式(2)中、XはO、SおよびN(R5)(R5は水素原子または炭素数1~6の炭化水素基を表す)からなる群から選択され、重合制御のしやすさからOが好ましい。XがN(R5)である場合、R5が表す炭素数1~6の炭化水素基としては、例えばメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、t-ブチル基、2-メチルブチル基、3-メチルブチル基、2-エチルブチル基、3-エチルブチル基、2,2-ジメチルブチル基、2,3-ジメチルブチル基、n-ペンチル基、ネオペンチル基、n-ヘキシル基、2-メチルペンチル基、3-メチルペンチル基等のアルキル基;シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基;フェニル基等が挙げられる。
で示される二官能(メタ)アクリル酸エステル(以下、「ジ(メタ)アクリレート(3)」と称する)を用いると、後述する条件下でリビングアニオン重合することで、一方の(メタ)アクリロイルオキシ基(上記一般式(3)中「CH2=C(R5)C(O)O」で示される(メタ)アクリロイルオキシ基)が選択的に重合して、式(2)において、R1が式(3)のR4であり、R2が式(3)のR2’であり、R3が式(3)のR3’であり、XがOである硬化性官能基(2)を有する(メタ)アクリル系重合体ブロック(a)が形成できる。
Al-O-Ar (4)
(式中、Arは芳香族環を表す。)
で示される化学構造を分子中に含む有機アルミニウム化合物、並びにルイス塩基の存在下でアニオン重合する工程[I]、前記工程[I]の後に、単官能(メタ)アクリル酸エステルを添加し、アニオン重合する工程[II]、および必要に応じて、前記工程[II]の後に、ジ(メタ)アクリレート(3)を含有する(メタ)アクリル酸エステルを添加し、アニオン重合する工程[III]をさらに含む製造方法が挙げられる。また、重合停止剤を用いて重合反応を停止させる工程[IV]を含む方法が好ましい。
工程[I]では、アニオン重合によって、(メタ)アクリル系重合体ブロック(a)を形成する。
AlR7(R8)(R9) (4-1)
(式中、R7は一価の飽和炭化水素基、一価の芳香族炭化水素基、アルコキシ基、アリールオキシ基またはN,N-二置換アミノ基を表し、R8およびR9はそれぞれ独立してアリールオキシ基を表すか、あるいはR8およびR9は互いに結合してアリーレンジオキシ基を形成している。)
で示される有機アルミニウム化合物(以下、有機アルミニウム化合物(4-1)と称する)、または下記一般式(4-2)
AlR10(R11)(R12) (4-2)
(式中、R10はアリールオキシ基を表し、R11およびR12はそれぞれ独立して一価の飽和炭化水素基、一価の芳香族炭化水素基、アルコキシ基またはN,N-二置換アミノ基を表す。)
で示される有機アルミニウム化合物(以下、有機アルミニウム化合物(4-2)と称する)が挙げられる。
工程[II]では、単官能(メタ)アクリル酸エステルを添加し、リビングアニオン重合によって、(メタ)アクリル系重合体ブロック(b)を形成する。工程[II]で用いる単量体(すなわち、単官能(メタ)アクリル酸エステルおよび任意成分である他の単量体)以外に、有機アルミニウム化合物、ルイス塩基および有機溶媒をリビングアニオン重合の反応系に添加してもよい。該有機アルミニウム化合物、ルイス塩基および有機溶媒としては、上記した工程[I]で用いることのできる有機アルミニウム化合物、ルイス塩基および有機溶媒が挙げられる。これらの有機アルミニウム化合物、ルイス塩基および有機溶媒の使用量は、溶媒の種類、その他種々の重合条件等に応じて適宜好適な量を選択できる。リビングアニオン重合の条件は、工程[I]で用いることのできる条件を使用できる。また、重合反応を調整し、得られる共重合体(A)のブロック効率を高める点から、単官能(メタ)アクリル酸エステルを添加する速度を、5~30ml/分としてもよく、7~20ml/分としてもよい。工程[I]の終了後から工程[II]の終了までのブロック効率(F2)は、エラストマー性能を高め、分子量分布を所定の範囲内とし、得られる歯科用重合性組成物の吐出性と賦形性、耐汚染性および柔軟性に優れることから、50%以上であることが好ましく、70%以上であることがより好ましく、90%以上であることがさらに好ましい。ブロック効率(F2)の算出方法は、後記する実施例に記載のとおりである。
工程[III]では、工程[II]の後に、工程[I]と同様にして、ジ(メタ)アクリレート(3)を含有する(メタ)アクリル酸エステルを、工程[II]で得られた反応液に添加して、リビングアニオン重合によって、(メタ)アクリル系重合体ブロック(a)を形成する。工程[III]では、必要に応じて、加熱してもよい。加熱によって、ブロック効率を高めることもできる。加熱温度は特に限定されないが、50℃以下が好ましく、40℃以下がより好ましい。
上記リビングアニオン重合は、メタノール;酢酸または塩酸のメタノール溶液;酢酸、塩酸の水溶液等のプロトン性化合物等の重合停止剤を反応液に添加することにより停止できる。重合停止剤の使用量は、通常、用いる有機リチウム化合物1モルに対して1~100モルの範囲が好ましい。
ラジカル重合性単量体が好適に用いられ、例えば、α-シアノアクリル酸、(メタ)アクリル酸、α-ハロゲン化アクリル酸、クロトン酸、桂皮酸、ソルビン酸、マレイン酸、イタコン酸等のエステル;(メタ)アクリルアミド;ビニルエステル;ビニルエーテル;スチレン誘導体等が挙げられる。中でも(メタ)アクリル系ブロック共重合体(A)との混和性の観点から(メタ)アクリル酸エステルが好ましい。重合性単量体(B)は、単官能性であっても、二官能性であっても、三官能性以上であってもよい。
中でも、硬化速度の観点から第3級脂肪族アミンが好ましく、N-メチルジエタノールアミン、トリエタノールアミン、N,N-ジ(2-ヒドロキシエチル)-p-トルイジン、4-(N,N-ジメチルアミノ)安息香酸エチル、N,N-ジメチルアミノ安息香酸n-ブトキシエチル、および4-N,N-ジメチルアミノベンゾフェノンがより好ましく、保存安定性の観点から、N-メチルジエタノールアミン、トリエタノールアミンがさらに好ましい。
重合後の各単量体の消費率は、重合反応液0.5mlを採取してメタノール0.5ml中に入れて混合後、該混合液から0.1mlを採取して、重クロロホルム0.5mlに溶解させて1H-NMR(JEOL製ECX400、測定温度=25℃)を測定した結果から算出した。
得られた重合体のゲルパーミュエーションクロマトグラフィー(装置:東ソー製、HLC-8220GPC、カラム:東ソー製、TSK-gel SuperMultiporeHZ-M(カラム径=4.6mm、カラム長=15cm)、測定条件:流速=0.35ml/分、温度=40℃、溶離液=テトラヒドロフラン)を測定し、標準ポリスチレン換算のMnおよび分子量分布(Mw/Mn)を求めた。
実際に工程[I]で得られた重合体のMnをMn(R-1)とし、重合開始効率が100%である場合の工程[I]で得られる重合体のMn(計算値)をMn(I-1)とすると、工程[I]における重合開始効率(F1)は以下の式から算出される。
F1(%)=100×Mn(I-1)/Mn(R-1)
実際に工程[II]で得られたブロック共重合体(A)のMnをMn(R-2)とし、ブロック効率が100%である場合の工程[II]で得られるブロック共重合体(A)のMn(計算値)をMn(I-2)とすると、工程[I]終了後から工程[II]終了までのブロック効率(F2)は以下の式から算出される。
F2(%)=10000・{Mn(I-2)-Mn(I-1)}/[F1・{Mn(R-2)-Mn(R-1)}]
(工程[I])
内部を乾燥し、窒素置換した3Lのフラスコに、トルエン1.5Lを添加したのち、フラスコ内の溶液を攪拌しながら、ルイス塩基として1,1,4,7,10,10-ヘキサメチルトリエチレンテトラミン7.4ml(27.3mmol)、有機アルミニウム化合物としてイソブチルビス(2,6-ジ-t-ブチル-4-メチルフェノキシ)アルミニウムの0.450mol/Lトルエン溶液63.6ml(28.6mmol)を順次添加したのち、-20℃に冷却した。これに有機リチウム化合物としてsec-ブチルリチウムの1.30mol/Lシクロヘキサン溶液20ml(26.0mmol)を加え、単量体として1,1-ジメチルプロパン-1,3-ジオールジメタクリレート18.7ml(78mmol)とメタクリル酸メチル16.6ml(156mmol)との混合物35.3mlを一括で添加し、アニオン重合を開始した。混合物の添加から80分後に重合反応液は当初の黄色から無色に変わった。さらに20分撹拌後に反応液をサンプリングした。
工程[I]における1,1-ジメチルプロパン-1,3-ジオールジメタクリレートおよびメタクリル酸メチルの消費率は100%であった。また、得られた重合体のMn(Mn(R-1))は1,340、Mw/Mnは1.16であった。さらに、工程[I]における重合開始効率(F1)は99%であった。
引き続き反応液を-20℃で撹拌しつつ、有機アルミニウム化合物としてイソブチルビス(2,6-ジ-t-ブチル-4-メチルフェノキシ)アルミニウムの0.450mol/Lトルエン溶液を31.8ml(14.3mmol)加え、その1分後に単量体としてアクリル酸n-ブチル504ml(3.5mol)を10ml/分の速度で添加した。アクリル酸n-ブチルの添加終了直後に反応液をサンプリングした。
工程[II]におけるアクリル酸n-ブチルの消費率は100%であった。また、得られた重合体のMn(Mn(R-2))は21,300、Mw/Mnは1.18であった。さらに、工程[I]から工程[II]にかけてのブロック効率(F2)は100%であった。
引き続き反応液を-20℃で撹拌しつつ、単量体として1,1-ジメチルプロパン-1,3-ジオールジメタクリレート16.3ml(67.8mmol)とメタクリル酸メチル14.4ml(136mmol)の混合物30.7mlを一括で添加したのち、2℃/分の速度で20℃に昇温した。上記混合物の添加終了から60分後に反応液をサンプリングした。
工程[III]における1,1-ジメチルプロパン-1,3-ジオールジメタクリレートおよびメタクリル酸メチルの消費率は100%であった。
引き続き反応液を20℃で撹拌しつつ、メタノール100mlを添加することにより、アニオン重合を停止させた。得られた溶液を10Lのメタノール中に注ぎ、重合体を沈殿させ、濾過によって回収し、100℃、30Paで乾燥し、471gの(メタ)アクリル系ブロック共重合体(A)(以下「(メタ)アクリル系ブロック共重合体(A-1)」と称する)を得た。
得られた(メタ)アクリル系ブロック共重合体(A-1)のMnは22,600、Mw/Mnは1.19であった。
(工程[I])
内部を乾燥し、窒素置換した3Lのフラスコに、トルエン1.5Lを添加したのち、フラスコ内の溶液を攪拌しながら、ルイス塩基として1,1,4,7,10,10-ヘキサメチルトリエチレンテトラミン1.5ml(5.5mmol)、有機アルミニウム化合物としてイソブチルビス(2,6-ジ-t-ブチル-4-メチルフェノキシ)アルミニウムの0.450mol/Lトルエン溶液12.7ml(5.7mmol)を順次添加したのち、-20℃に冷却した。これに有機リチウム化合物としてsec-ブチルリチウムの1.30mol/Lシクロヘキサン溶液4.0ml(5.2mmol)を加え、単量体として1,1-ジメチルプロパン-1,3-ジオールジメタクリレート37.4ml(156mmol)とメタクリル酸メチル8.3ml(78mmol)との混合物35.7mlを一括で添加し、アニオン重合を開始した。混合物の添加から80分後に重合反応液は当初の黄色から無色に変わった。さらに20分撹拌後に反応液をサンプリングした。
工程[I]における1,1-ジメチルプロパン-1,3-ジオールジメタクリレートおよびメタクリル酸メチルの消費率は100%であった。また、得られた重合体のMn(Mn(R-1))は7,860、Mw/Mnは1.23であった。さらに、工程[I]における重合開始効率(F1)は99%であった。
引き続き反応液を-20℃で撹拌しつつ、有機アルミニウム化合物としてイソブチルビス(2,6-ジ-t-ブチル-4-メチルフェノキシ)アルミニウムの0.450mol/Lトルエン溶液を6.4ml(2.9mmol)加え、その1分後に単量体としてアクリル酸n-ブチル300ml(2.1mol)を10ml/分の速度で添加した。アクリル酸n-ブチルの添加終了直後に反応液をサンプリングした。
工程[II]におけるアクリル酸n-ブチルの消費率は100%であった。また、得られた重合体のMn(Mn(R-2))は72,500、Mw/Mnは1.20であった。さらに、工程[I]から工程[II]にかけてのブロック効率(F2)は100%であった。
引き続き反応液を-20℃で撹拌しつつ、単量体として1,1-ジメチルプロパン-1,3-ジオールジメタクリレート37.4ml(156mmol)とメタクリル酸メチル8.3ml(78mmol)との混合物35.7mlを一括で添加したのち、2℃/分の速度で20℃に昇温した。上記混合物の添加終了から60分後に反応液をサンプリングした。
工程[III]における1,1-ジメチルプロパン-1,3-ジオールジメタクリレートおよびメタクリル酸メチルの消費率は100%であった。
引き続き反応液を20℃で撹拌しつつ、メタノール100mlを添加することにより、アニオン重合を停止させた。得られた溶液を10Lのメタノール中に注ぎ、重合体を沈殿させ、濾過によって回収し、100℃、30Paで乾燥し、280gの(メタ)アクリル系ブロック共重合体(A)(以下「(メタ)アクリル系ブロック共重合体(A-2)」と称する)を得た。
得られた(メタ)アクリル系ブロック共重合体(A-2)のMnは80,000、Mw/Mnは1.21であった。
(工程[I])
内部を乾燥し、窒素置換した3Lのフラスコに、トルエン1.5Lを添加したのち、フラスコ内の溶液を攪拌しながら、ルイス塩基として1,1,4,7,10,10-ヘキサメチルトリエチレンテトラミン7.4ml(27.3mmol)、有機アルミニウム化合物としてイソブチルビス(2,6-ジ-t-ブチル-4-メチルフェノキシ)アルミニウムの0.450mol/Lトルエン溶液63.6ml(28.6mmol)を順次添加したのち、-20℃に冷却した。これに有機リチウム化合物としてsec-ブチルリチウムの1.30mol/Lシクロヘキサン溶液20ml(26.0mmol)を加え、単量体として1,1-ジメチルプロパン-1,3-ジオールジメタクリレート18.7ml(78mmol)とメタクリル酸t-ブチル16.6ml(103mmol)との混合物35.3mlを一括で添加し、アニオン重合を開始した。混合物の添加から80分後に重合反応液は当初の黄色から無色に変わった。さらに20分撹拌後に反応液をサンプリングした。
工程[I]における1,1-ジメチルプロパン-1,3-ジオールジメタクリレートおよびメタクリル酸メチルの消費率は100%であった。また、得られた重合体のMn(Mn(R-1))は1,250、Mw/Mnは1.18であった。さらに、工程[I]における重合開始効率(F1)は99%であった。
引き続き反応液を-20℃で撹拌しつつ、有機アルミニウム化合物としてイソブチルビス(2,6-ジ-t-ブチル-4-メチルフェノキシ)アルミニウムの0.450mol/Lトルエン溶液を31.8ml(14.3mmol)加え、その1分後に単量体としてアクリル酸2-エチルヘキシル504ml(2.4mol)を10ml/分の速度で添加した。アクリル酸2-エチルヘキシルの添加終了直後に反応液をサンプリングした。
工程[II]におけるアクリル酸n-ブチルの消費率は100%であった。また、得られた重合体のMn(Mn(R-2))は19,200、Mw/Mnは1.19であった。さらに、工程[I]から工程[II]にかけてのブロック効率(F2)は100%であった。
引き続き反応液を-20℃で撹拌しつつ、単量体として1,1-ジメチルプロパン-1,3-ジオールジメタクリレート18.7ml(78mmol)とメタクリル酸t-ブチル16.6ml(103mmol)との混合物35.3mlを一括で添加したのち、2℃/分の速度で20℃に昇温した。上記混合物の添加終了から60分後に反応液をサンプリングした。
工程[III]における1,1-ジメチルプロパン-1,3-ジオールジメタクリレートおよびメタクリル酸t-ブチルの消費率は100%であった。
引き続き反応液を20℃で撹拌しつつ、メタノール100mlを添加することにより、アニオン重合を停止させた。得られた溶液を10Lのメタノール中に注ぎ、重合体を沈殿させ、濾過によって回収し、100℃、30Paで乾燥し、450gの(メタ)アクリル系ブロック共重合体(A)(以下「(メタ)アクリル系ブロック共重合体(A-3)」と称する)を得た。
得られた(メタ)アクリル系ブロック共重合体(A-3)のMnは21,600、Mw/Mnは1.20であった。
工程[I]’
1リットルの三口フラスコの内部を脱気し、窒素で置換した後、室温にてトルエン390g、N,N’,N’,N’’,N’’-ペンタメチルジエチレントリアミン1.4ml、およびイソブチルビス(2,6-ジ-t-ブチル-4-メチルフェノキシ)アルミニウム11mmolを含有するトルエン溶液18mlを加え、さらに、sec-ブチルリチウム2.2mmolを含有するシクロヘキサンとn-ヘキサンの混合溶液1.7mlを加えた。これにメタクリル酸メチル14mlを加え、室温で1時間反応させた。この時点で反応液1gを採取してサンプリング試料1とした。引き続き、反応液の内部温度を-15℃に冷却し、アクリル酸n-ブチル120mlを6時間かけて滴下した。滴下終了後、反応液1gを採取してサンプリング試料2とした。続いてメタクリル酸メチル14mlを加えて反応液を室温に昇温して、約10時間撹拌した。この反応液にメタノール1gを添加して重合を停止した。この重合停止後の反応液を大量のメタノールと水の混合溶液(メタノール90質量%)に注ぎ、析出した白色沈殿物を回収してサンプリング試料3とした。
上記[I]’の採取または回収したサンプリング試料1~3について、上記した方法でGPC測定、1H-NMR測定を行って、その結果に基づいて、各重合段階で得られた重合体およびブロック共重合体のMw、Mw/Mn、メタクリル酸メチル重合体(PMMA)ブロックとアクリル酸-n-ブチル重合体(PnBA)ブロックの質量比を求めたところ、上記の(1)で最終的に得られた白色沈殿物は、PMMA-PnBA-PMMAからなるトリブロック共重合体(以下、「(メタ)アクリル系ブロック共重合体1」と称する)であり、その全体のMwは85,000、Mw/Mnは1.13、各重合体ブロックの割合はPMMA(10質量%)-PnBA(80質量%)-PMMA(10質量%)であること(PMMAの合計20質量%)が判明した。また、試料1は、PMMAであって、そのMwは7,300、Mw/Mnは1.06であり;試料2はPMMA-PnBAのジブロック共重合体であって、そのMwは77,000,Mw/Mnは1.16であった。
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
3G:トリエチレングリコールジメタクリレート
UDMA:2,2,4-トリメチルヘキサメチレンビス(2-カルバモイルオキシエチル)ジメタクリレート
DFHM:1H,1H,7H-ドデカフルオロヘプチルメタクリレート
BEM:2-ブトキシエチルメタクリレート
D-2.6E:2,2-ビス(4-メタ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)
CQ:カンファーキノン
BAPO:ビス-(2,4,6-トリメチルベンゾイル)フェニルホスフィンオキサイド
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
CHP:クメンハイドロパーオキサイド
PDE:4-(N,N-ジメチルアミノ)安息香酸エチル
PTU:1-(2-ピリジル)-2-チオ尿素
DMETU:4,4-ジメチル-2-イミダゾリンチオン
VOAA:バナジルアセチルアセトナート(IV)
CUA:酢酸第2銅
フィラー(E)-1:コロイドシリカ粉(日本アエロジル社製「アエロジル380」、平均粒子径:7nm)
シリカ(日本アエロジル社製「アエロジル130」)を振動ボールミルで粉砕して得たシリカ粉100g、3-メタクリロイルオキシプロピルトリメトキシシラン0.5gおよびトルエン200mlを500mlのナスフラスコに入れ、室温で2時間撹拌した。続いて、減圧下でトルエンを留去した後、40℃で16時間、次いで90℃で3時間真空乾燥し、3-メタクリロイルオキシプロピルトリメトキシシラン処理シリカ粉(フィラー(E)-2)を得た。フィラー(E)-2の平均粒子径をレーザー回折式粒度分布測定装置(島津製作所製、型式「SALD-2100」、分散媒:0.2%ヘキサメタリン酸ナトリウム水溶液)を用いて測定したところ、0.02μmであった。
バリウムガラス(エステック社製「E-3000」)を振動ボールミルで粉砕して得たバリウムガラス粉100g、3-メタクリロイルオキシプロピルトリメトキシシラン(信越シリコーン社製「KBM-503」)0.5g(核フィラー100重量部に対して0.5重量部)およびトルエン200mLを500mLのナスフラスコに入れ、室温で2時間攪拌した。続いて、減圧下でトルエンを留去した後、40℃で16時間、次いで90℃で3時間真空乾燥し、3-メタクリロイルオキシプロピルトリメトキシシラン処理バリウムガラス粉〔フィラー(E)-3〕を得た。フィラー(E)-3の平均粒子径をレーザー回折式粒度分布測定装置(島津製作所製、型式「SALD-2100」、分散媒:0.2%ヘキサメタリン酸ナトリウム水溶液)を用いて測定したところ、2.4μmであった。
BHT:3,5-ジ-t-ブチル-4-ヒドロキシトルエン
動揺歯固定材を想定した実施例1~6および比較例1~2、ならびに歯科用自己接着性コンポジットレジンを想定した実施例19~24および比較例7~8で得られた歯科用重合性組成物を、先端に内径0.5mmのガイドチップを装着した、市販の歯科用コンポジットレジン(クラレノリタケデンタル社製、クリアフィル マジェスティLV、容量1.5mL)の容器に収納した。次いで、オートグラフ(株式会社島津製作所製、AG-100kNI)を用いて、圧縮強度試験用の治具を装着したクロスヘッドを25℃で4mm/分で降下させることで、容器に押出部材を進入させて、ガイドチップを通して吐出部から吐出させ、最大荷重を吐出力とした。結果を表1および表4に示す。
縦59mm×横83mmの歯科用練和紙に直径4mmの円を描き、動揺歯固定材を想定した実施例1~6および比較例1~2、ならびに歯科用自己接着性コンポジットレジンを想定した実施例19~24および比較例7~8で得られた歯科用重合性組成物0.3gを上記円内いっぱいに半球状に載せ、かかる歯科用練和紙を37℃の恒温器内に垂直に立て、3分間静置して歯科用重合性組成物の円内からの移動距離を測定した。この試験を3回行い、3回の測定値の平均値を垂れ距離(mm)とした。垂れ距離が大きいほど歯科用重合性組成物が流れやすいことを示す。結果を表1および表4に示す。
動揺歯固定材を想定した実施例1~6でおよび比較例1~2で得られた歯科用重合性組成物を、スライドガラス上に設置した筒状の金型(ステンレス製、口径2mm×25mm(長方形)、厚さ2mm)内に充填し、金型上にさらにスライドガラスを設置した。次いで、歯科用可視光照射器(株式会社モリタ製、ペンキュア2000)で、上下両面のスライドガラスを通して各5箇所に10秒間ずつ光を照射することで歯科用重合性組成物を硬化させて試験片を作製した。
義歯床裏装材を想定した実施例7~12および比較例3~4で得られた歯科用重合性組成物であるAペーストとBペーストを混練し、スライドガラス上に設置したリング状の金型(ステンレス製、内径1.5cm、厚さ2mm)に充填し、金型上にさらにスライドガラスを設置した後、37℃の恒温器中で30分間静置することで硬化させて、円盤状の試験片を作製した。得られた試験片を用いて、JIS K7215に基づいて、タイプAデュロメータで37℃における硬化物の硬度(A硬度)を測定し、柔軟性の指標とした。結果を表2にそれぞれ示す。
リング状の金型(ステンレス製、内径1.5cm、厚さ2mm)に代えて、リング状の金型(ステンレス製、内径1.5cm、厚さ5mm)を用いた以外は試験例4と同様にして、円盤状の試験片を作製した。得られた試験片を用いて、温度37℃、圧縮変形量25%の条件下に24時間放置した後の圧縮永久歪みを測定した。圧縮永久歪みは以下の式で算出した。
圧縮永久歪み[%]={5-(試験後の厚さ(mm))}/1.25×100
結果を表2にそれぞれ示す。37℃における圧縮永久歪みが30%以下である場合、形状保持性の観点から好ましい。
動揺歯固定材を想定した実施例1~6および比較例1~2ならびに歯科用自己接着性コンポジットレジンを想定した実施例19~24および比較例7~8で得られた歯科用重合性組成物を、スライドガラス上に設置したリング状の金型(ステンレス製、内径20mm、厚さ2mm)に充填した後、金型上にさらにスライドガラスを設置した。次いで、歯科用可視光照射器(株式会社モリタ製、ペンキュア2000)によって、上下両面のスライドガラスを通して、各6箇所ずつ10秒間ずつを照射することで歯科用重合性組成物を硬化させて試験片を作製した。
ΔL=L*W-L*B
分光測色計(日本電色工業株式会社製、SE2000、D65光源)を用いて表面光沢試験で用いた試験片の色度(L*1、a*1、b*1)(耐着色性試験前の色度)を測定した。
ΔE={(L*1-L*2)2+(a*1-a*2)2+(b*1-b*2)2}1/2
結果を表1~4に示す。
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(日本研紙株式会社製)で研磨し、次いで#1000のシリコン・カーバイド紙(日本研紙株式会社製)でさらに研磨した後、表面の水を歯科用エアシリンジで除去して、エナメル質の平坦面を有する牛歯を得た。また同様にして象牙質の平坦面を有する牛歯を得た。
粒径50μmのアルミナパウダーでサンドブラスト処理したガラス板(厚さ4.0mm)上に設置したリング状の金型(ステンレス製、内径5.5mm×厚さ0.8mm)内に、実施例1~24および比較例1~8で得られた歯科用重合性組成物を充填した。かかる充填した歯科用重合性組成物上に、オートグラフ(株式会社島津製作所製、AG-100kNI)と連結したステンレス製治具(φ5mm)を設置した。ガラス板を通して、表1および表4の実施例、比較例については、歯科用可視光線照射器(株式会社モリタ製、ペンキュア2000)を用いて20秒間光を照射した。かかる光の照射によって進行する歯科用重合性組成物の重合(硬化)に伴う重合収縮応力を、上記オートグラフで測定した。結果を表1および表4に示す。表2と表3の実施例および比較例については、23℃で1時間静置し、歯科用重合性組成物の重合(硬化)に伴う重合収縮応力を、上記オートグラフで測定した。結果を表2および表3に示す。
Claims (9)
- 一般式(2)において、R1は水素原子またはメチル基を表し、XがOである、請求項2に記載の歯科用重合性組成物。
- 重合促進剤(D)をさらに含有する、請求項1~3のいずれか1項に記載の歯科用重合性組成物。
- フィラー(E)をさらに含有する、請求項1~4のいずれか1項に記載の歯科用重合性組成物。
- 請求項1~5のいずれか1項に記載の歯科用重合性組成物からなる動揺歯固定材。
- 請求項1~5のいずれか1項に記載の歯科用重合性組成物からなる義歯床裏装材。
- 請求項1~5のいずれか1項に記載の歯科用重合性組成物からなる歯科用セメント。
- 請求項1~5のいずれか1項に記載の歯科用重合性組成物からなる歯科用自己接着性コンポジットレジン。
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