WO2016017582A1 - Matériau composite dentaire présentant un état de pâte stable - Google Patents

Matériau composite dentaire présentant un état de pâte stable Download PDF

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Publication number
WO2016017582A1
WO2016017582A1 PCT/JP2015/071247 JP2015071247W WO2016017582A1 WO 2016017582 A1 WO2016017582 A1 WO 2016017582A1 JP 2015071247 W JP2015071247 W JP 2015071247W WO 2016017582 A1 WO2016017582 A1 WO 2016017582A1
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WIPO (PCT)
Prior art keywords
composite material
polymerizable monomer
filler
silane
mixed
Prior art date
Application number
PCT/JP2015/071247
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English (en)
Japanese (ja)
Inventor
門林勇生
繁澤麻紗子
Original Assignee
株式会社松風
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2014154179A external-priority patent/JP5716119B1/ja
Priority claimed from JP2014154177A external-priority patent/JP5716118B1/ja
Application filed by 株式会社松風 filed Critical 株式会社松風
Priority to BR112017001829-2A priority Critical patent/BR112017001829B1/pt
Publication of WO2016017582A1 publication Critical patent/WO2016017582A1/fr

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Classifications

    • 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
    • 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
    • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
    • 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
    • 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
    • A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers

Definitions

  • the present invention relates to a dental composite material used for filling or prosthetic restoration in the dental field, temporary sealing, temporary attachment, production of a prosthesis, adhesion / fitting, and pit and fissure sealing.
  • silane-treated fillers and polymerizable monomers used in composite resins including those for front crowns and preservation / restoration
  • temporary sealing / temporary bonding materials resin cements
  • adhesives fisher sealants
  • a composite material is manufactured in a paste form by mixing a silane-treated filler and a polymerizable monomer, and the paste-like composite material is filled in a packaging container and is a dentist or technician who is a user.
  • Adhesive monomers and pigments are blended depending on the intended use of the composite material.
  • the silane-treated filler and the polymerizable monomer are mixed in an appropriate blending amount to form a paste, and then filled into a packaging container.
  • Paste composite material is difficult to stabilize the paste properties. For example, in a composite material filled in a syringe container, the final paste discharged from the syringe is different from the initial paste discharged from the syringe.
  • paste properties and quality are known to vary depending on the mixing procedure and method, but it has not been known that the paste properties are stabilized by a specific mixing procedure or mixing method.
  • the conventional paste has a large variation in the quality of the final product, such as mixing of bubbles, variation in paste properties, resulting in non-uniform polymerization, and large fluctuations in the flow value after production.
  • Composite materials used in dentistry are required to be always available to dentists and technicians with a certain feeling of use.
  • Japanese Patent Application Laid-Open No. 09-194474 describes that a silane coupling agent is blended in order to stabilize the paste properties, but the blending of the silane coupling agent sufficiently solves the property stability. I could't. Specifically, the flow value of the paste, which is an index of the feeling of use of the paste, could not be stabilized.
  • Japanese Patent Application Laid-Open No. 08-143747 describes a method for treating a filler with a silane, but only a refluxing and drying process, and no relation to paste properties has been studied.
  • JP 09-194474 A Japanese Patent Laid-Open No. 08-143747
  • a stable paste-like composite material is a composite material that has a good feeling in use and is maintained in a constant state. Even when a paste-like composite material is filled in a number of syringe containers having different forms, it has been required to maintain a stable paste property.
  • the pasty composite material filled in the syringe container has been required to obtain the same paste properties as the initial composite material discharged from the syringe and the final composite material discharged from the syringe. Further, it has been demanded that the same paste properties can be obtained with a composite material immediately after production and a composite material stored for a certain period of time.
  • Bubbles were entrained in the composite material filled in the syringe, and therefore, it was necessary to add an operation for removing the bubbles during the packaging operation for filling the syringe with the composite material.
  • an appropriate time for performing the inspection process to stably manufacture a paste-like composite material has not been known.
  • the present invention finds that an appropriate inspection process in the production process is performed at an appropriate time, and makes it possible to manufacture a composite material having a stable paste property.
  • the present invention is a method for producing a composite material comprising a filler, a polymerizable monomer, and a polymerization initiator, It is a method for producing a composite material, which comprises a mixed polymerizable monomer preparation step, a silane treatment step, a silane treatment filler storage step, and a composite material production step shown below.
  • the mixed polymerizable monomer preparation step is a step of mixing a polymerizable monomer and a polymerization initiator to prepare a mixed polymerizable monomer
  • ⁇ Silane treatment process is a silane treatment solution in which 1 to 40% of silane coupling agent and 99 to 60% of organic solvent and / or water are mixed.
  • the mixing time is 1 minute to 24 hours, and a silane treatment filler is produced by dropping a silane treatment liquid corresponding to 1 to 15% of the silane coupling agent with respect to the amount of the filler during mixing.
  • the silane treatment filler storage step is a step of storing the silane treated silane treatment filler for 30 to 600 days, -
  • the composite material manufacturing process is a process of manufacturing a composite material by mixing a mixed polymerizable monomer and a silane-treated filler. In the composite material production process, after adding 0.1 to 9 parts by weight of the silane treatment filler in 1 part by weight of the mixed polymerizable monomer, the silane treatment is performed at 5 to 60 ° C. for a mixing time of 5 to 40 minutes.
  • the filler kneading step it is preferable to carry out the filler kneading step, and then carry out the defoaming while kneading the mixed polymerizable monomer and the silane-treated filler at 5 to 200 Torr and a defoaming time of 5 to 30 minutes.
  • 0.01 to 0.2 parts by weight of the fine particle filler is added to 1 part by weight of the mixed polymerizable monomer and then mixed at 5 to 60 ° C. for 5 to 30 minutes.
  • the polymerizable monomer and fine particle filler are kneaded, and then the mixed polymerizable monomer and fine particle filler are defoamed at 5 to 200 Torr and the defoaming time is 5 to 30 minutes.
  • the mixed polymerizable monomer, the fine particle filler, and the silane-treated filler are kneaded at 5 to 60 ° C. for a mixing time of 5 to 40 minutes, and thereafter 5 to 200 Torr. Defoaming is preferably carried out while kneading the mixed polymerizable monomer, the fine particle filler, and the silane-treated filler under the condition that the defoaming time is 5 to 30 minutes.
  • the mixing temperature is preferably 1 to 60 ° C.
  • the mixing time is preferably 1 minute to 24 hours.
  • the composite material storage process is a process of storing 1 to 8 liters of composite material manufactured in the composite material manufacturing process at a storage temperature of 1 to 25 ° C. and a storage period of 10 days to 1.5 years. It is preferable to have a composite material evaluation step in the composite material storage step. After completion of the composite material storage step, it is preferable to further undergo a composite material filling step shown below.
  • the composite material filling step is a step of filling a small amount storage container having a capacity of 1 to 50 cc with the composite material extruded from the nozzle using a filling machine. It is preferable to have a mixed polymerizable monomer evaluation step in the mixed polymerizable monomer storage step.
  • the present invention is a composite material produced by the above-described method for producing a composite material, wherein the composite material has a flow value of 120 a day after the completion of production and a b value of 3 years after the completion of production.
  • the reduction rate (ab) / a of the composite material is 10% or less.
  • the present invention provides a composite material containing a filler, a polymerizable monomer, and a polymerization initiator.
  • the composite material is characterized in that a flow value after 120 days from the end of production is a, a flow value after 3 years from the end of production is b, and the
  • the present invention provides a composite material containing a filler, a polymerizable monomer, and a polymerization initiator.
  • a composite material produced by using the method of the present invention aimed at stably supplying a paste-like composite material can obtain the following effects.
  • the composite material discharged from the syringe container can be used with the same operability for any of the composite materials discharged in the initial, middle and final stages, and there is no variation in the composite material and it is stable. In particular, the properties of the composite material can be maintained.
  • the composite material discharged from the syringe container has the same operability.
  • Composite materials can be used.
  • the present invention has solved the problem. That is, the composite material of the present invention can maintain a certain paste property with reduced thixotropy for a certain period of time once squeezed out of the container. In addition, entrapment of bubbles in the composite material is prevented when filling into a small volume storage container. This is because the composite material stored in the composite material storage process at the time of production is stored in a storage container, but a larger amount of composite material is stored at the same time than a small amount storage container. This reduces the initial surface property change of the paste by reducing the surface area in contact with the outside of the paste.
  • pastes stored in large quantities tend to suppress property changes, but even so, it is difficult to suppress the phenomenon of “solidification” that is a property change of the surface.
  • the composite material is transferred from the storage container of the composite material storage process to the filling machine and continuously filled into the small volume storage container. When the composite material in the filling machine is low, the composite material is transferred from the storage container of the composite material storage process. Replenishment is performed.
  • the composite material of the present invention can reduce entrainment of bubbles.
  • a stable composite material can be easily manufactured by introducing an inspection process during the process of manufacturing the composite material. In order to produce a composite material stably, the minimum required inspection process was found. Performing many inspection processes can produce a stable composite material, but excessive inspection not only consumes the composite material but also increases the number of production steps. It has been found that there is an appropriate number of inspection processes and timing of inspection processes. As a result, it is possible to efficiently produce a composite material without producing a defective final composite material by detecting a defective product at an early stage.
  • Performing the fine particle filler kneading step, the defoaming step after kneading the fine particle filler, the silane treatment filler kneading step, and the defoaming step after kneading the silane treatment filler stabilizes the thixotropy of the composite material and obtains a uniform paste property of the composite material. Can do.
  • the present invention provides a composite material containing a filler, a polymerizable monomer, and a polymerization initiator.
  • Composite material filling process for filling a small amount of composite material into storage containers, The composite material is characterized by undergoing a small-scale storage container storage step for storing in a filled small-volume storage container.
  • the present invention is preferably a composite material containing a filler, a polymerizable monomer, and a polymerization initiator.
  • Composite material filling process for filling a small amount of composite material into storage containers, The composite material is characterized by undergoing a small-scale storage container storage step for storing in a filled small-volume storage container.
  • the present invention provides a composite material containing a filler, a polymerizable monomer, and a polymerization initiator.
  • Composite material filling process for filling a small amount of composite material into storage containers A composite material obtained through a small-volume storage container storage process for storing in a filled small-volume storage container,
  • the composite material is a composite material characterized by passing through a fine particle filler kneading step, a fine particle filler kneading defoaming step, a silane
  • the small-volume storage container is preferably a syringe container, and the composite material is stabilized by being stored in a syringe container, which is a final container that reaches the user's hand, for a certain period of time.
  • the present invention provides a composite material containing a filler, a polymerizable monomer, and a polymerization initiator. Obtained through the mixed polymerizable monomer preparation process, silane treatment process, silane treatment filler storage process, composite material manufacturing process, composite material storage process, composite material filling process, and small volume storage container storage process shown below. It is a composite material.
  • the present invention is preferably a composite material containing a filler, a polymerizable monomer, and a polymerization initiator.
  • the mixed polymerizable monomer preparation step is a process in which a polymerization initiator is added to the polymerizable monomer in the mixing vessel, the mixing temperature is 1 to 60 ° C., and the mixing time is 1 minute to 24 hours. In this step, a polymerizable monomer and a polymerization initiator are mixed to produce a mixed polymerizable monomer.
  • the silane treatment step is to prepare a silane treatment liquid in which 1 to 40% of a silane coupling agent and 99 to 60% of an organic solvent and / or water are mixed, and a filler is put into a mixing container under a condition of 1 to 60 ° C.
  • the mixing time is from 1 minute to 24 hours, and a silane-treated filler is produced by dropping a silane treatment agent corresponding to 1 to 15% of the silane coupling agent with respect to the amount of the filler during mixing.
  • a preferred silane treatment liquid is a mixture of silane coupling agent 1-20%, water 1-20%, and organic solvent 60-98%.
  • the silane-treated filler storage step is a step of storing the silane-treated silane-treated filler for 1 to 600 days.
  • the mixed polymerizable monomer storage step refers to 1 to 50 liters of mixed polymerizable monomer prepared in the mixed polymerizable monomer preparation step, the storage temperature is 1 to 23 ° C., and the storage period is This is a process of storage under conditions of 10 days to 1.5 years.
  • the composite material production process is a process of performing a kneading process and a defoaming process. In the kneading process, 0.1 to 9 parts by weight of the silane-treated filler is mixed and polymerized with respect to 1 part by weight of the mixed polymerizable monomer. In this step, a silane-treated filler is introduced into the functional monomer.
  • the fine particle filler kneading step and the fine particle filler kneading defoaming step are performed first, followed by the silane treatment filler kneading step and the silane treatment filler kneading defoaming step.
  • kneading is performed.
  • the fine particle filler kneading step is performed under conditions of a kneading temperature of 5 to 60 ° C. and a kneading time of 5 to 30 minutes. Thereafter, a defoaming step is performed.
  • the defoaming step is performed after the fine particle filler is kneaded under the conditions of a vacuum degree of 5 to 200 Torr and a defoaming time of 5 to 30 minutes. Thereafter, after the silane-treated filler is added, the silane-treated filler kneading step is performed at a kneading temperature of 5 to 60 ° C. and a kneading time of 5 to 40 minutes, and then the degree of vacuum is 5 to 200 Torr and the defoaming time. Performs a defoaming step after kneading the silane-treated filler for 5 to 30 minutes.
  • the composite material storage process is a process of storing 0.3 to 8 liters of composite material manufactured in the composite material manufacturing process at a storage temperature of 1 to 25 ° C. and a storage period of 10 days to 1.5 years. is there.
  • the composite material filling step is a step of filling a small amount storage container having a capacity of 0.3 to 50 cc with the composite material extruded from the nozzle using a filling machine.
  • the small volume storage container storage step is a process in which the storage temperature is 1 to 40 ° C. and the storage period is 10 days to 5 years in the small volume storage container.
  • the mixed polymerizable monomer evaluation step performed during the mixed polymerizable monomer storage step is a step of performing at least one of a differential scanning calorimetry (DSC) test, a curing test, and a viscosity test. . It is preferable to carry out three tests of a differential scanning calorimetry (DSC) test, a curing test, and a viscosity test.
  • DSC differential scanning calorimetry
  • the composite material evaluation step performed during the composite material storage step is a step of performing at least one of a differential scanning calorimetry (DSC) test, a curing test, and a fluidity (flow) test.
  • DSC differential scanning calorimetry
  • a curing test a curing test
  • a flow test a test that is, a differential scanning calorimetry (DSC) test, a curing test, and a flow test.
  • the final evaluation process performed during the small volume storage container storage process is a process of performing at least one of a differential scanning calorimetry (DSC) test, a curing test, and a fluidity (flow) test.
  • DSC differential scanning calorimetry
  • a curing test a curing test
  • a flow test a test that is, a differential scanning calorimetry (DSC) test, a curing test, and a flow test are performed.
  • the filler before the silane treatment used in the present invention is not particularly limited, and known fillers such as inorganic fillers and / or organic fillers and / or organic-inorganic composite fillers can be used without any limitation.
  • the shape of the filler before the silane treatment may be any particle shape such as spherical shape, block shape, needle shape, plate shape, crushed shape, and scale shape, and is not particularly limited.
  • the filler before the silane treatment is preferably spherical.
  • the circularity indicating the spherical shape of the filler before silane treatment is in the range of 0.7 to 1.0, more preferably in the range of 0.9 to 1.0, and still more preferably in the range of 0.95 to 1.00. It is in.
  • the circularity can be obtained by processing a photographed image of an optical microscope or a scanning electron microscope (hereinafter referred to as SEM) with an image analyzer.
  • the number of samples to be image-processed is 50 or more fillers, and is calculated from the area of the filler before silane treatment and the peripheral length of the filler.
  • inorganic fillers include quartz, amorphous silica, aluminum silicate, aluminum oxide, titanium oxide, zirconium oxide, various glasses (glass by melting method, synthetic glass by sol-gel method, produced by gas phase reaction) Glass, etc.), calcium carbonate, talc, kaolin, clay, mica, aluminum sulfate, calcium sulfate, barium sulfate, calcium phosphate, hydroxyapatite, silicon nitride, aluminum nitride, titanium nitride, silicon carbide, boron carbide, water Examples thereof include calcium oxide, strontium hydroxide, and zeolite.
  • aluminosilicate glass, borosilicate, aluminoborate, boroaluminosilicate glass containing heavy metals such as sodium, strontium, barium and lanthanum and / or fluorine are preferable.
  • the average particle size of these inorganic fillers is not particularly limited, but is preferably in the range of 0.5 to 10 ⁇ m, more preferably in the range of 0.7 to 5 ⁇ m.
  • fine particle inorganic fillers such as silica-zirconia oxide particles produced from a solution such as aerosil or sol-gel reaction produced by a gas phase method can be used.
  • the fine particle inorganic filler has an average particle diameter of 1 nm to 300 nm.
  • the fine particle inorganic filler is not limited, but colloidal silica (trade names: Aerosil R972, Aerosil 200, Aerosil 380, Aerosil 50, Nippon Aerosil Co., 5 to 50 nm) is preferable.
  • organic filler it can obtain by superposing
  • the kind is not specifically limited.
  • the organic filler include unsaturated aromatics such as styrene, ⁇ -methylstyrene, halogenated styrene, and divinylbenzene; unsaturated esters such as vinyl acetate and vinyl propionate; unsaturated nitriles such as acrylonitrile.
  • a monomer having a polymerizable group such as butadiene, isoprene, or a plurality of (co) polymerized monomers. Particularly preferred is a polymerized monomer having the aforementioned polymerizable group already known in the dental field.
  • the method for producing the organic filler there is no particular limitation on the method for producing the organic filler, and any method such as emulsion polymerization, suspension polymerization and dispersion polymerization of a monomer having a polymerizable group may be used, and a method of pulverizing a polymer bulk produced in advance. But you can do it.
  • an organic-inorganic composite filler containing inorganic particles in an organic polymer can also be used.
  • the inorganic particles to be contained in the organic polymer are not particularly limited and known ones can be used, and examples thereof include the inorganic fillers described above.
  • the method for producing the organic-inorganic composite filler there are no particular limitations on the method for producing the organic-inorganic composite filler, and any method can be employed.
  • a method of microencapsulating or grafting the surface of inorganic particles with an organic material a method of radical polymerization after introducing a polymerizable functional group or a polymerizable initiating group to the surface of inorganic particles, a polymer bulk containing inorganic particles generated in advance And the like.
  • the average particle size of the organic filler or organic-inorganic composite filler is preferably in the range of 1 to 100 ⁇ m. More preferably, it is 3 to 50 ⁇ m, and further preferably 5 to 30 ⁇ m.
  • Fillers such as inorganic, organic, and organic-inorganic composite fillers can be used for composite materials by treating the surface of the particles by a known method.
  • surfactants for example, surfactants, fatty acids, organic acids, inorganic acids, silane coupling agents, titanate coupling agents, polysiloxanes and the like can be mentioned.
  • These surface treatment methods are preferable in terms of improving the wettability of the resin component and the filler surface and imparting excellent properties to the composite material, and the surface treatment can be appropriately selected according to the required properties.
  • a silane treatment filler obtained through a silane treatment step of treating with a silane coupling agent It is preferable to use a silane treatment filler obtained through a silane treatment step of treating with a silane coupling agent. Moreover, it is preferable to obtain the silane treatment filler preservation
  • a filler is treated by preparing a silane treatment solution containing 1 to 40% of a silane coupling agent and 60 to 99% of an organic solvent and / or water. The filler and the silane treatment liquid are put into the treatment container, the treatment temperature at that time is in the range of 1 to 60 ° C., and the treatment time (treatment time) is 1 minute to 24 hours.
  • a silane treatment liquid corresponding to 1 to 15% of the silane coupling agent with respect to the amount of the filler is added to the mixing.
  • a slurry of silane treated filler may be produced.
  • the silane treatment liquid is preferably dropped or sprayed.
  • an aggregate By drying the treated product at 60 to 200 ° C. for 1 to 120 hours, an aggregate can be obtained, and a silane-treated filler can be obtained by crushing the aggregate.
  • a silane coupling agent can be contained in an amount of 5 to 30%, an organic solvent in an amount of 50 to 70% and / or water in an amount of 0.5 to 25%.
  • the silane coupling agent is not particularly limited, but methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane.
  • hexamethyldisilazane is preferably used, particularly preferably, methyl trichlorosilane, dimethyl dichlorosilane, hexamethyldisilazane is used.
  • the organic solvent is preferably a volatile water-soluble organic solvent, and examples thereof include methanol, ethanol, n-propanol, isopropyl alcohol, acetone, and methyl ethyl ketone. A plurality of these organic solvents can be mixed and used as necessary. In view of toxicity to the living body, ethanol, isopropyl alcohol and acetone are preferable.
  • the silane-treated filler storage step is a step of storing the silane-treated silane-treated filler for 30 to 600 days.
  • the silane-treated filler is stored in a hermetically sealed container.
  • the container is a 10 to 50 liter container, preferably resinous, and preferably in the form of a polyethylene bag.
  • the storage temperature is 1 to 50 ° C. Preferably, it is 5 to 25 ° C. Storage at high temperature inhibits the effect of the silane coupling agent.
  • the proportion of these silane-treated fillers in the composite material can be arbitrarily set according to the requirements of the material characteristics required for the composite material.
  • low-viscosity materials such as sealants, bonding materials, primers, tooth surface treatment agents, opaque materials, and cement that are commonly used in the dental field
  • high fluidity is required as a required property of the material. It must be set relatively low. Therefore, the range of 5.0 to 80.0 parts by weight with respect to all components of the composite material is preferable, and the range of 30.0 to 70.0 parts by weight is more preferable.
  • the required amount of the material requires form imparting property that does not cause deformation after shape adjustment, so the filling amount is set to be relatively high. There is a need to. Therefore, the range of 50.0 to 98.0 parts by weight with respect to all the components of the composite material is preferable, and the range of 75.0 to 98.0 parts by weight is more preferable.
  • the polymerizable monomer used in the present invention is not limited, but known monofunctional and / or polyfunctional polymerizable monomers generally used for composite materials can be used.
  • a preferred polymerizable monomer is a polymerizable monomer having an acryloyl group and / or a methacryloyl group.
  • polymerizable monomers having no acidic group examples include Monofunctional monomer (uncrosslinkable monomer): methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl ( (Meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate , (Meth) acrylic acid esters such as glycerol (meth) acrylate and isobornyl (meth) acrylate; ⁇ - (meth) acryloyloxypropyl
  • Aromatic bifunctional monomer crosslinkable monomer: 2,2-bis (4- (meth) acryloyloxyphenyl) propane, 2,2-bis (4- (3- (meth) acryloyloxy-2) -Hydroxypropoxy) phenyl) propane, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) Propane, 2 (4- (meth) acryloyloxyethoxyphenyl) -2 (4- (meth) acryloyloxydieto Xylphenyl) propane, 2 (4- (meth) acrylo
  • Aliphatic bifunctional monomer crosslinking monomer: 2-hydroxy-3-acryloyloxypropyl methacrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meta) ) Acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butane Diol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, etc.
  • Trifunctional monomer (crosslinkable monomer): trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, etc.
  • Tetrafunctional monomer pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and the like.
  • urethane-based polymerizable monomers examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate; and polymerizable compounds having a hydroxyl group such as 3-chloro-2-hydroxypropyl (meth) acrylate.
  • diisocyanate compounds such as methylcyclohexane diisocyanate, methylenebis (4-cyclohexylisocyanate), hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, diisocyanate methylmethylbenzene, 4,4-diphenylmethane diisocyanate And di (meth) acrylate having a difunctional or trifunctional or higher urethane bond.
  • diisocyanate compounds such as methylcyclohexane diisocyanate, methylenebis (4-cyclohexylisocyanate), hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, diisocyanate methylmethylbenzene, 4,4-diphenylmethane diisocyanate And di (meth) acrylate having a difunctional or trifunctional or higher urethane bond.
  • the polymerizable monomer of the composite material according to the present invention is a polymerizable monomer other than the (meth) acrylate polymerizable monomer, for example, at least one polymerizable group in the molecule, depending on the purpose. Monomers, oligomers or polymers having the following may be used.
  • the polymerizable monomer other than the (meth) acrylate polymerizable monomer may have a substituent such as an acidic group or a fluoro group in the same molecule.
  • the polymerizable monomer may be a single component or a mixture of polymerizable monomers composed of a plurality of polymerizable monomers.
  • the polymerizable monomer when the viscosity of the polymerizable monomer is extremely high at room temperature or is solid, the polymerizable monomer is combined with a polymerizable monomer having a low viscosity and used as a mixture of polymerizable monomers. It is preferable to do this. In the above combination, two or more polymerizable monomers may be used.
  • the polymerizable monomer of the composite material according to the present invention may contain only a monofunctional polymerizable monomer or may further contain a polyfunctional polymerizable monomer.
  • Preferred polymerizable monomers include an aromatic compound of a bifunctional polymerizable monomer and an aliphatic compound of a bifunctional polymerizable monomer. More preferably, the polymerizable monomer of the present invention is 2,2-bis (4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl) propane (Bis-GMA) and triethylene glycol dimethacrylate (TEGDMA). including.
  • the polymerizable monomer has a phosphate group, a carboxylic acid group, a phosphonic group as a part or all of the polymerizable monomer in order to impart tooth or base metal adhesion to the composite material of the present invention.
  • a polymerizable monomer containing an acid group such as an acid group or a sulfonic acid group in the molecule may be included.
  • the polymerizable monomer according to the present invention may include a polymerizable monomer containing a sulfur atom in the molecule.
  • Examples of the polymerizable monomer according to the present invention include carboxylic acid group-containing polymerizable monomers: (meth) acrylic acid, 1,4-di (meth) acryloyloxyethyl pyromellitic acid, 6- (meth).
  • polymerization initiators include chemical polymerization initiators that start polymerization by mixing immediately before use, thermal polymerization initiators that start polymerization by heating or heating, and photopolymerization initiators that start polymerization by light irradiation. Separated.
  • the chemical polymerization initiator may be a redox comprising an organic peroxide / amine compound or an organic peroxide / amine compound / sulfinate, an organic peroxide / amine compound / borate compound.
  • Type polymerization initiator systems organometallic type polymerization initiator systems that react with oxygen or water to initiate polymerization, and the like.
  • organic peroxide examples include benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tertiary butyl peroxide, cumene hydroperoxide, 2, Examples include 5-dimethylhexane, 2,5-dihydroperoxide, methyl ethyl ketone peroxide, and tertiary butyl peroxybenzoate.
  • Examples of the amine compound include secondary or tertiary amines in which an amine group is bonded to an aryl group, and specifically include pN, N′-dimethyl-toluidine, N, N′-dimethyl.
  • Examples of the sulfinates include sodium benzenesulfinate, lithium benzenesulfinate, sodium p-toluenesulfinate and the like.
  • borate compound examples include sodium salt, lithium salt, potassium salt of trialkylphenyl boron, trialkyl (p-fluorophenyl) boron (wherein the alkyl group is n-butyl group, n-octyl group, n-dodecyl group, etc.) Examples thereof include salts, magnesium salts, tetrabutylammonium salts, and tetramethylammonium salts.
  • organometallic polymerization initiator examples include organoboron compounds such as triphenylborane, tributylborane, and tributylborane partial oxide.
  • azo compounds such as azobisisobutyronitrile, methyl azobisisobutyrate, azobiscyanovaleric acid can be used in addition to the organic peroxide. .
  • the photopolymerization initiator may be used alone, or a photosensitizer and a photopolymerization accelerator may be used in combination.
  • the photosensitizer include benzyl, camphorquinone, ⁇ -naphthyl, acetonaphthene, p, p′-dimethoxybenzyl, p, p′-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1, ⁇ -diketones such as 4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone and naphthoquinone; benzoin alkyl ethers such as benzoin, benzoin methyl ether and benzoin ethyl ether; thioxanthone, 2-chlorothioxanthone, Thioxanthones such as 2-
  • ketals such as benzyl dimethyl ketal, benzyl diethyl ketal, benzyl (2-methoxyethyl ketal); bis (cyclopentadienyl) -bis [2,6-difluoro-3- (1-pyrrolyl) Phenyl] -titanium Titanocenes such as bis (cyclopentadienyl) -bis (pentanefluorophenyl) -titanium and bis (cyclopentadienyl) -bis (2,3,5,6-tetrafluoro-4-disiloxyphenyl) -titanium Etc.
  • photopolymerization accelerator examples include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, pN, N-dimethyl.
  • -Toluidine mN, N-dimethyl-toluidine, pN, N-diethyl-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde , P-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amino ester, N, N-dimethylanthranic acid methyl ester, N, N -Dihydroxyethylaniline, pN, N-dihydroxyethyl-to Idin, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyr
  • citric acid malic acid, tartaric acid, glycolic acid, gluconic acid, ⁇ -oxyisobutyric acid, 2-hydroxypropanoic acid, 3-hydroxypropanoic acid, 3
  • Oxycarboxylic acids such as -hydroxybutanoic acid, 4-hydroxybutanoic acid and dimethylolpropionic acid may be contained.
  • polymerization initiators used in the present invention can be used alone or in admixture of two or more. Moreover, these polymerization initiators are not limited to a polymerization form or the kind of polymerization initiator, and can also be used in combination.
  • the addition amount of a polymerization initiator can be suitably selected according to a use application. Generally, the addition amount of the polymerization initiator is selected from the range of 0.1 to 10 parts by weight with respect to the polymerizable monomer.
  • a preferable polymerization initiator is a photopolymerization initiator.
  • a composite material containing a photopolymerization initiator is relatively easy to polymerize in a state with little air contamination.
  • a preferred photopolymerization initiator of the present invention is a combination of an ⁇ -diketone and a tertiary amine, and more preferably an amino group such as camphorquinone and ethyl pN, N-dimethylaminobenzoate is directly bonded to the benzene ring. And a combination with an aliphatic amine having a double bond in the molecule such as aromatic amine or N, N-dimethylaminoethyl methacrylate.
  • the composite material according to the present invention is a Bronsted acid by light irradiation of sensitizing dyes such as coumarin, cyanine and thiazine, halomethyl group-substituted-s-triazine derivatives, diphenyliodonium salt compounds, etc., depending on the intended use.
  • sensitizing dyes such as coumarin, cyanine and thiazine, halomethyl group-substituted-s-triazine derivatives, diphenyliodonium salt compounds, etc.
  • photoacid generators that generate Lewis acids, quaternary ammonium halides, transition metal compounds, and the like can be used as appropriate.
  • the composite material is manufactured by mixing a silane-treated filler, a polymerizable monomer, and a polymerization initiator.
  • these composite materials may be colored with a coloring pigment according to product characteristics.
  • the colored pigments are roughly classified into inorganic pigments and organic pigments.
  • inorganic pigments include chromates such as yellow lead, zinc lead and barium yellow; ferrocyanides such as bitumen; sulfides such as silver vermilion, cadmium yellow, zinc sulfide, antimony white and cadmium red; barium sulfate, sulfuric acid Sulfates such as zinc and strontium sulfate; oxides such as zinc white, titanium white, bengara, iron black and chromium oxide; hydroxides such as aluminum hydroxide; silicates such as calcium silicate and ultramarine; carbon black, Examples thereof include carbon such as graphite.
  • organic pigments examples include nitroso pigments such as naphthol green B and naphthol green Y; nitro pigments such as naphthol S and resol fast yellow 2G, insoluble azo such as permanent red 4R, brilliant fast scarlet, hansa yellow, and benzidine yellow.
  • the color pigment is an inorganic pigment, preferably titanium white, red iron oxide, black iron or yellow iron oxide.
  • the composite material according to the present invention is preferably an ultraviolet absorber such as 2-hydroxy-4-methylbenzophenone, hydroquinone, hydroquinone monomethyl ether, 2,5-ditertiary butyl-4-methylphenol, butylated hydroxytoluene ( BHT) and other polymerization inhibitors, discoloration inhibitors, antibacterial agents, and other known additives may be further included.
  • the packaging form of the composite material of the present invention is not particularly limited, and may be any of a 1-pack packaging form, a 2-pack packaging form, or other forms depending on the type of polymerization initiator or the purpose of use. Depending on the application, it can be appropriately selected.
  • the present invention has at least the steps of a mixed polymerizable monomer preparation step, a mixed polymerizable monomer storage step, a composite material manufacturing step, a composite material storage step, a composite material filling step, and a small amount storage container storage step. The effect is improved.
  • the mixed polymerizable monomer preparation step is a step of mixing at least the polymerizable monomer and the polymerization initiator, and the mixing method is not particularly specified.
  • the mixed polymerizable monomer obtained from the mixed polymerizable monomer preparation step needs to be in a uniform state after mixing, and needs to be mixed so that there is no undissolved residue such as a polymerization initiator.
  • the defoaming operation is usually a step in which mixing is performed under atmospheric pressure, but the pressure is reduced to atmospheric pressure to remove bubbles after the mixing in order to remove bubbles.
  • Performing the defoaming step deteriorates the polymerizable monomer and causes a decrease in physical properties, and a part of the polymerizable monomer may be cured. Moreover, it is necessary to introduce a polymerization initiator into the polymerizable monomer. By introducing a polymerization initiator into the polymerizable monomer, it may cause a decrease in physical properties, and a part of the polymerizable monomer may be cured. Therefore, an excessive amount of polymerization initiator cannot be mixed.
  • the mixing amount of the mixed polymerizable monomer at one time is 1 to 50 liters, and preferably 5 to 11 liters. If the mixing amount is small, not only the production process becomes longer, but also the mixed polymerizable monomer.
  • the mixer is not particularly limited, but is preferably a mixer type that mixes with a blade in a mixing vessel containing a polymerizable monomer and a polymerization initiator. Further, a tumbler mixer that mixes by rotating or swinging a mixing container containing a polymerizable monomer and a polymerization initiator is more preferable. The tumbler mixer can reduce the deterioration of the contents and can be easily mixed.
  • the mixing time varies depending on the mixer, but about 1 minute to 24 hours is appropriate. More preferably, it is 15 minutes to 10 hours.
  • the mixing temperature is 1 to 60 ° C., preferably 5 to 30 ° C.
  • the polymerization initiator used in the present invention is a chemical polymerization initiator, mixing at a low temperature is preferred, and mixing is performed at 5 to 10 ° C.
  • additives such as a polymerization inhibitor, a discoloration inhibitor, an antibacterial agent, and an ultraviolet absorber are simultaneously mixed during the mixing in this step. Prevents deterioration of composite materials and contributes to stability.
  • the permeability of the mixed polymerizable monomer is preferably 80 to 100%.
  • the mixed polymerizable monomer storage step is a step of storing the mixed polymerizable monomer produced in the mixed polymerizable monomer production step.
  • the mixed polymerizable monomer is stored in a mixed polymerizable monomer storage container.
  • the volume of the mixed polymerizable monomer to be stored is 1 to 50 liters, and preferably 5 to 11 liters.
  • the mixing method used in the step of preparing the mixed polymerizable monomer is a tumbler mixer
  • the mixed container is preferably used as it is as a mixed polymerizable monomer storage container.
  • the mixed polymerizable monomer storage container is preferably resinous and is preferably made of polyethylene. Further, it is preferably opaque and preferably excellent in light shielding properties.
  • the light shielding rate is preferably 99.99% or more, but the light shielding property may be enhanced with aluminum foil or the like to reproduce the light shielding rate of 99.99% or more. Moreover, it is preferable that it is an airtight container.
  • the storage temperature of the mixed polymerizable monomer storage container is 1 to 23 ° C., preferably 1 to 10 ° C. in a cool and dark place.
  • the storage period of the mixed polymerizable monomer storage container is 10 days to 1.5 years, more preferably 30 days to 1 year.
  • the mixed polymerizable monomer evaluation step performed during the mixed polymerizable monomer storage step is an evaluation of the mixed polymerizable monomer performed during the mixed polymerizable monomer storage step.
  • the mixed polymerizable monomer is placed in a mixed polymerizable monomer evaluation container other than the mixed polymerizable monomer storage container. It is also possible to separate directly from the mixed polymerizable monomer storage container.
  • the mixed polymerizable monomer evaluation item it is preferable to carry out a differential scanning calorimetry (DSC) test, a curability test, a viscosity test (B-type viscometer) and the like. Each measurement method is tested by a normal method, and pass / fail is judged. Judgment is made based on whether or not it is within a predetermined range.
  • DSC differential scanning calorimetry
  • B-type viscometer a viscosity test
  • a filler is treated by preparing a silane treatment solution containing 1 to 40% of a silane coupling agent and 60 to 99% of an organic solvent and / or water.
  • the filler and the silane treatment liquid are put into the treatment container, the treatment temperature at that time is in the range of 1 to 60 ° C., and the treatment time (treatment time) is 1 minute to 24 hours.
  • a silane treatment liquid corresponding to 1 to 15% of the silane coupling agent with respect to the amount of filler is added to the mixing. As a result, a slurry of silane treated filler may be produced. Further, the silane treatment liquid is preferably dropped or sprayed. By drying the treated product at 60 to 200 ° C.
  • the silane coupling agent may contain 5-30% organic solvent 50-70% and / or water 0.5-25%.
  • the silane coupling agent is not particularly limited, but methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane.
  • hexamethyldisilazane is preferably used, particularly preferably, methyl trichlorosilane, dimethyl dichlorosilane, hexamethyldisilazane is used.
  • the organic solvent is preferably a volatile water-soluble organic solvent, and examples thereof include methanol, ethanol, n-propanol, isopropyl alcohol, acetone, and methyl ethyl ketone. A plurality of these organic solvents can be mixed and used as necessary. In view of toxicity to the living body, ethanol, isopropyl alcohol and acetone are preferable.
  • the silane-treated filler storage step is a step of storing the silane-treated silane-treated filler for 30 to 600 days.
  • the silane-treated filler is stored in a hermetically sealed container.
  • the container is a 10 to 50 liter container, preferably resinous, and preferably in the form of a polyethylene bag.
  • the storage temperature is 1 to 50 ° C. Preferably, it is 5 to 25 ° C. Storage at high temperature reduces the stability of the silane coupling agent.
  • the composite material production process is a process for producing a composite material by mixing a mixed polymerizable monomer and a silane-treated filler.
  • the kneading method is not specified.
  • the composite material obtained from the composite material manufacturing process needs to be in a uniform state after mixing.
  • a normal kneader can be used.
  • a kneader manufactured by Inoue Seisakusho, etc.
  • a planetary mixer manufactured by Inoue Seisakusho, etc.
  • the kneading container is attached to the kneader, and its volume is 0.5 to 50 liters, preferably 2 to 20 liters.
  • the kneading machine is kneaded at an amount of 30 to 70%, more preferably 40 to 60% of the volume of the kneader.
  • the silane treated filler is 0.1 to 9 weight units per 1 weight unit of the mixed polymerizable monomer
  • the fine particle filler is 0.01 to 0.2 weight unit. More specifically, it is 1 to 3 liters of mixed polymerizable monomer, 1 to 6 kg of silane-treated filler, and 30 to 500 g of fine particle filler.
  • the composite material manufacturing process includes a kneading process and a defoaming process, and the procedure is as follows.
  • the silane-treated filler is introduced, and kneading and defoaming are performed.
  • the step of performing the kneading operation is a kneading step, and the step of performing the defoaming operation is a defoaming step. It is important to add the mixed polymerizable monomer before adding the silane-treated filler, and the kneading time can be shortened and the occurrence of variations in the paste can be prevented.
  • a fine particle filler In the case of producing a composite material, it is preferable to use a fine particle filler. In that case, after adding a mixed polymerizable monomer, a fine particle filler is added, and a fine particle filler kneading step, a fine particle filler kneading step and a defoaming step are performed. Thereafter, a silane treatment filler is further added, and a silane treatment filler kneading step and a defoaming step after silane treatment filler kneading are performed.
  • the fine particle filler and the silane-treated filler into a plurality of parts can facilitate kneading.
  • defoaming may be performed after kneading each time, but it is preferable to perform defoaming after all the silane treatment filler has been added.
  • the fine particle filler has poor kneadability with the mixed polymerizable monomer and may not be sufficiently kneaded.
  • the fine particle filler kneading confirmation and the fine particle filler kneading confirmation for confirming that the kneaded material obtained after the fine particle filler kneading and defoaming step has transparency and is sufficiently kneaded and defoamed. It is preferable to provide a process. If a composite material is manufactured without performing the fine particle filler kneading confirmation step, a portion where the fine particle filler is not sufficiently mixed is formed, which leads to variations in the composite material which is the final product, and a stable paste cannot be obtained. .
  • the silane-treated filler before kneading the fine particle filler because the fine particle filler kneading confirmation step cannot be performed. It is preferable to introduce a silane-treated filler after kneading the fine particle filler.
  • the kneading of the mixed polymerizable monomer and the fine particle filler needs to be performed until the whole becomes uniform, but whether it is uniform or not is uniform if the paste has transparency after the defoaming step after the fine particle filler kneading. It can be judged that it became. If it is not uniform, repeat kneading and defoaming.
  • non-transparent fine particle filler still remains in the kneaded paste, it is necessary to remove the remaining part of the fine particle filler and stop the production of the kneaded product. There is. Even if the process is not completely transparent or translucent, the same operation can be performed.
  • the silane treatment filler kneading step the silane treatment filler is kneaded until a uniform paste is formed with the kneaded mixture of the mixed polymerizable monomer or the mixed polymerizable monomer and the fine particle filler.
  • the defoaming step it is necessary to remove air from the composite material, and it is preferable to defoam while mixing.
  • a defoaming step after kneading the silane treatment filler is required.
  • the defoaming step is a step of defoaming by lowering the degree of vacuum in the kneading vessel to 5 to 200 Torr.
  • the bubbles inside the composite material expand and the composite material foams.
  • the kneading speed for collapsing the bubbles is preferably performed in accordance with the destruction of the bubbles, and it is preferable to determine the kneading conditions while adjusting the pressure reduction speed or to knead while adjusting the degree of pressure reduction.
  • the fine particle filler kneading step is carried out under the conditions that the kneading temperature is 5 to 60 ° C. and the kneading time is 5 to 30 minutes.
  • the defoaming step is carried out after kneading the fine particle filler under the condition that the kneading time is 5 to 30 minutes at 5 to 200 Torr.
  • the silane-treated filler kneading step is carried out at a kneading temperature of 5 to 60 ° C.
  • the degree of vacuum is kneaded at 5 to 200 Torr. It is preferable to carry out the defoaming step after kneading the silane treatment filler for 5 to 30 minutes.
  • the polymerization initiator used in the present invention is a chemical polymerization initiator, kneading at a low temperature is preferred, and in the kneading step, the kneading temperature is 1 to 25 ° C., 1 ° C. to room temperature, or 5 to 23 ° C.
  • the kneading time is 5 to 30 minutes, and even in the defoaming step, the temperature is 1 to 25 ° C., 1 ° C. to room temperature, or 5 to 23 ° C., the kneading time is 5 to 30 minutes, and the degree of vacuum is reduced to 60 to 200 Torr. It is preferable to implement.
  • These kneading times and temperatures vary depending on the type of kneader or planetary mixer.
  • the composite material storage step is a step of storing the composite material obtained in the composite material manufacturing step.
  • the composite material is stored in a composite material storage container.
  • the volume of the composite material stored in the composite material storage container is 1 to 8 liters, more preferably 2 to 5 liters.
  • the composite material is separated from the mixing container used in the composite material manufacturing process into the composite material storage container.
  • the composite material storage container is preferably resinous and is preferably made of polyethylene. Further, it is preferably opaque and preferably excellent in light shielding properties.
  • the light shielding rate is preferably 99.99% or more, but the light shielding property may be enhanced with aluminum foil or the like to reproduce the light shielding rate of 99.99% or more. Moreover, it is preferable that it is an airtight container.
  • the storage temperature of the composite material storage container for storing the composite material obtained in the composite material manufacturing process is 1 to 25 ° C., preferably 1 to 8 ° C. in a cool dark place.
  • the storage period of the composite material storage container storing the composite material obtained in the composite material manufacturing process is 10 days to 1.5 years, more preferably 30 days to 1 year. By storing, the composite material can be stabilized, and a composite material having a uniform paste property can be obtained. If the storage period of the composite material storage container exceeds 1.5 years from the time when the composite material storage container is filled with the composite material, the storage period of the composite material storage container is a small storage container used by the dentist or dental technician who is the end user.
  • the storage period is shortened, the polymerizable monomer is deteriorated, and the composite material is in a non-uniform state.
  • the composite material evaluation during the composite material evaluation process is performed as follows. After kneading in the composite material manufacturing process, the composite material is arranged in a composite material evaluation container other than the composite material storage container. Immediately after kneading in the composite material production process, it is preferable to separate the composite material evaluation containers. Even if it is separated directly from the kneading container, it can be evaluated without problems.
  • DSC differential scanning calorimetry
  • curability test a curability test
  • fluidity (flow) test a fluidity test
  • each measurement method is tested by a normal method, and pass / fail is judged. Judgment is made based on whether or not it is within a predetermined range. Further, these ranges are important ranges for judging the stability of the composite material, but these ranges vary greatly depending on the type of the composite material.
  • the test methods of the curability test and the fluidity (flow) test will be described in detail in the “characteristic confirmation test method” described later.
  • the composite material filling process is a process of filling a small amount of the composite material stored in the composite material storage container.
  • the small-volume storage container is a container that reaches the end user, and is generally called a syringe container.
  • the syringe container is a 1 to 200 cc container.
  • the composite material is discharged from the nozzle at the tip by pushing a push rod with a cylindrical syringe mold.
  • the syringe container used for the high-viscosity composite material is a cylindrical syringe type like the low-viscosity, but the push rod is pushed out by screwing.
  • a small amount is called a compute and refers to a container for filling a cavity in one operation.
  • Each container is a cylinder-shaped container that pushes and discharges the composite material with a piston. In the case of the cylindrical container, the effect of the present invention is remarkably exhibited when the discharge port of the composite material is narrow.
  • the composite material is stored in a small storage container.
  • the capacity of the composite material stored in the small volume storage container is 1 to 50 cc, preferably 2 to 5 cc.
  • the composite material storage container is preferably resinous and is preferably made of polyethylene. Further, it is preferably opaque and preferably excellent in light shielding properties.
  • the light shielding rate is preferably 99.99% or more. Moreover, it is preferable that it is an airtight container.
  • the push rod of the cylinder may be pressed to push the composite material, or the screw may be used to push the composite material.
  • electric and desktop types are also seen, and these syringe-like containers may be used.
  • the filling method from the composite material storage container to the small volume storage container may be performed by an existing method. Usually, it can be filled with a filling machine and can be filled with an existing filling machine.
  • the filling machine includes a feeder for containing the composite material and a nozzle for discharging the composite material.
  • the composite material charged into the feeder is discharged from the nozzle and filled in a small amount of storage container.
  • the feeder may be a piston mechanism or a screw feeder.
  • a plurality of composite materials stored in the composite material storage container are put into the filling machine. So far, air has been mixed between the composite materials.
  • the composite material of the present invention has been found to be able to reduce or prevent the mixing of these bubbles through a composite material storage step and a small amount storage container storage step.
  • the composite material can be heated at the time of filling, and is preferably heated to 15 to 45 ° C.
  • the small-scale storage container storage step is a step of storing the small-scale storage container filled in the composite material filling step for a certain period of time.
  • the storage temperature of the small volume storage container is 1 to 40 ° C., and it is preferable to store in a cool and dark place, preferably 1 to 25 ° C.
  • the storage period of the composite material storage container is 50 days to 5 years. Preferably, it is 100 days to 3 years.
  • the final evaluation during the final evaluation process is an evaluation of the composite material that is performed during the low-volume storage container storage process. After the composite material filling step, evaluation is performed in an arbitrary small volume storage container from among many small volume storage containers. As composite material evaluation items, it is preferable to carry out a differential scanning calorimetry (DSC) test, a curability test, a fluidity (flow) test, and the like. Each measurement method is tested by a normal method, and pass / fail is judged. Judgment is made based on whether or not it is within a predetermined range.
  • DSC differential scanning calorimetry
  • the test methods of the curability test and the fluidity (flow) test will be described in detail in the “characteristic confirmation test method” described later. It is shipped and used by dentists and technicians who are users of the small volume storage container storage process.
  • the composite material produced by the above production method has a flow value decrease rate (ab) / a of 10% or less, assuming that the flow value after 120 days of production is a and the flow value after 3 years of production is b. It is preferably 5% or less, and more preferably 2% or less.
  • Viscosity test This test is also an evaluation item for mixed polymerizable monomers
  • the viscosity is 5000 to 10,000 mPa ⁇ s, and preferably 7000 to 9000 mPa ⁇ s.
  • Evaluation criteria “A” indicates that the mixture is sufficiently mixed and has no spots, and “C” indicates that the mixture is not sufficiently mixed and remains undissolved.
  • This test is also a mixed polymerizable monomer evaluation item and a composite material evaluation item) A mixed polymerizable monomer or composite material is filled in a mold having a hole with a thickness of 2 mm and a diameter of 15 mm, and a transparent plate glass is press-contacted to the surface of the filled mixed polymerizable monomer or composite material. Cured by polymerization method.
  • the composite material in the mold was irradiated with light for 180 seconds with a dental light irradiator (manufactured by Matsukaze Co., Ltd., “Soridelite II”) to polymerize and cure the mixed polymerizable monomer or composite material.
  • the Vickers hardness (kgf / mm 2) of the cured product was determined by the following measurement method. Remove the pressure-bonded plate glass, and apply a load of 200 g on the surface of the cured product (mixed polymerizable monomer or composite material) on which the plate glass is pressure-contacted with a micro hardness tester (manufactured by Akashi Seisakusho, product code “MVK-E”). The Vickers hardness was measured over 10 seconds.
  • the transmittance was measured using a cured product produced by the same method as that produced by the curability test. The transmittance was measured in a wavelength range of 780 nm to 380 nm using [Spectrophotometer U-3200] (manufactured by Hitachi, Ltd.). A transmittance of 95% or more is necessary, and a transmittance of 99% or more is preferable.
  • A After the surface composite material is scratched with a resin spatula, it shows a slight gloss, and the polymerizable monomer and the silane-treated filler are used. The composite material inside is glossy after being scratched with a resin spatula, and the polymerizable monomer and the silane-treated filler are well adapted.
  • B The surface composite material is slightly whitened after being scratched with a resin spatula, and the polymerizable monomer and the silane-treated filler are used. The composite material inside is glossy after being scratched with a resin spatula, and the polymerizable monomer and the silane-treated filler are well adapted. The surface and internal properties are different.
  • the composite material on the surface becomes white after being scratched with a resin spatula, and the familiarity between the polymerizable monomer and the silane-treated filler is not good. After the internal composite material is scratched with a resin spatula, it shows a slight gloss, and the polymerizable monomer and the silane-treated filler are familiar. The surface and interior properties are completely different.
  • AA The composite material showed gloss after being scratched with a resin spatula, and the polymerizable monomer and the silane-treated filler were well used.”
  • A There is no variation in all 20 small volume storage containers.
  • B The variation is 5 or less among 20 small quantity storage containers.
  • C The variation is 6 or more out of 20 small volume storage containers.
  • Polymerizable monomer Bis-GMA: 60 parts by weight of 2,2-bis (4- (3- (meth) acryloyloxy-2-hydroxypropoxy) phenyl) propane UDMA: 70 parts by weight of di (methacryloxyethyl) trimethylhexamethylene diurethane , -TEGDM: 30 parts by weight of reethylene glycol dimethacrylate-3G: 40 parts by weight of triethylene glycol (meth) acrylate-HEMA: 2-hydroxyethyl methacrylate: [Polymerizable monomer having a phosphate group] 2-MEP: 2- (methacryloxy) ethyl phosphate Bis-MEP: bis [2- (methacryloxy) ethyl] phosphate 6-MHPA: (6-methacryloxy) hexyl phosphonoacetate [Polymerizable monomer having dibasic acid carboxyl group] ⁇ 4-AET: 4-acryloxy
  • Manufacture of the composite material of this invention manufactures material on the conditions as described in Table 1, and obtained the evaluation of the description. Specifically, it is as follows. (Preparation of mixed polymerizable monomer) The polymerizable monomer and the polymerization initiator shown in Table 1 are mixed by a mixer (manufactured by Aikosha: BM) or a tumbler mixer (manufactured by Seiwa Giken: TM) which is mixed with a blade. Each mixing time and mixing temperature are shown in Table 1.
  • the value of the polymerization inhibitor (BHT) is a value that can be added to 100 parts by weight of the total value of the components other than the polymerization inhibitor (so-called outside). Multiply).
  • Storage of mixed polymerizable monomers After mixing, the mixture was filled in a mixed polymerizable monomer storage container, which was a polyethylene bottle-type container (capacity 10 liters) with a light shielding rate of 99.99%, and stored at 23 ° C.
  • the viscosity test, curability test, and transmittance of the mixed polymerizable monomer stored were measured. The test results are shown in Table 1.
  • Silane treatment adjustment products Silane mixture a: silane coupling agent ⁇ -methacryloyloxypropyltrimethoxysilane 3%, ethyl alcohol 77%, water 20%
  • Silane mixture b silane coupling agent ⁇ -methacryloyloxypropyltrimethoxysilane 30%, ethyl alcohol 69%, water 1%
  • the silane mixed solution is prepared, and 10 kg of the filler heated to 40 ° C. is treated with 10 kg of the silane mixed solution a or 2 kg of the silane treatment solution b. Stir and mix. Tables 2 and 3 show the mixing machines used. After mixing, the silane-treated filler was aged in a hot air dryer at 50 ° C.
  • silane-treated filler aggregate was placed in a Henschel mixer and pulverized at 1800 rpm for 5 minutes to prepare silane-treated fillers a and b whose surfaces were coated with poly (organo) siloxane.
  • silane treatment storage method The silane-treated filler coated with poly (organo) siloxane was stored in a polyethylene bag in units of 25 kg between 10 and 25 ° C. for a storage period as shown in Table 1.
  • the composite material of the composite material storage container is continuously put into the cylinder of the filling machine and filled into a syringe as a small volume storage container.
  • the syringe which is 2000 small quantity storage containers filled with a small amount of composite materials was obtained.
  • the syringe was equipped with a push rod, nozzle, cap, etc., and filling into a small amount of storage container was completed.
  • the paste produced by the method of the present invention has a stable paste property although there is no particular change in properties from 120 days to 3 years, and a slight change in properties is also seen from 3 years to 5 years. Within 60 days, the paste was not stable and a large change in properties was observed. In addition, after 5 years, a change in properties that seems to be due to a large secular change was confirmed.
  • Table 4 shows the difference from the previous measurement of the fluidity test result when stored in a small amount of storage container. It can be seen that the composite material of the present invention is stable. “Difference from previous measurement” shows the difference from 60 days after filling in the column after 60 days, and the difference from 60 days to 120 days in the column after 120 days. The column shows the difference from 120 days to 3 years later, the column after 5 years shows the difference from 3 years to 5 years, and the column after 6 years shows from 5 years to 6 years Looking at the later difference.
  • Table 5 shows the rate of decrease in the flow value of the composite material. Among them, the flow value 120 days after the end of production is a, the flow value 3 years after the end of production is b, and the decrease rate of the flow value is (ab) / a. As can be seen from Table 5, the reduction rate of the flow value of all the composite materials of the present invention is 10% or less, that is, stable fluidity can be maintained.
  • the present invention is used, stable properties of the paste material can be secured, and in particular, a dental material or a technician can stably use a composite material for a dental material.

Landscapes

  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dental Preparations (AREA)

Abstract

La présente invention concerne un procédé de production d'un matériau composite qui contient une charge, un monomère polymérisable et un initiateur de polymérisation, ledit procédé de production étant caractérisé en ce qu'il comprend l'étape de préparation du monomère polymérisable mélangé, l'étape de traitement au silane, l'étape de stockage de la charge traitée au silane, et l'étape de production du matériau composite. L'étape de préparation du monomère polymérisable mélangé est une étape dans laquelle le monomère polymérisable est mélangé avec l'initiateur de polymérisation afin de préparer un monomère polymérisable mélangé. L'étape de traitement au silane est une étape dans laquelle on prépare un liquide de traitement au silane comprenant un mélange formé de 1 à 40 % d'un agent de couplage à base de silane et de 99 à 60 % d'un solvant organique et/ou d'eau, on introduit la charge dans un récipient de mélange, et on verse en mode goutte-à-goutte une quantité de liquide de traitement au silane correspondant à entre 1 et 15 % de l'agent de couplage au silane par rapport à la quantité de la charge, dans le mélange à une température comprise dans la plage allant de 1 à 60 °C pendant un temps de mélange compris entre 1 minute et 24 heures afin de produire une charge traitée au silane. L'étape de stockage de la charge traitée au silane est une étape dans laquelle la charge traitée au silane qui a été soumise à un traitement au silane est stockée pendant 30 à 600 jours. L'étape de production du matériau composite est une étape dans laquelle le monomère polymérisable mélangé et la charge traitée au silane sont mélangés afin de produire le matériau composite.
PCT/JP2015/071247 2014-07-29 2015-07-27 Matériau composite dentaire présentant un état de pâte stable WO2016017582A1 (fr)

Priority Applications (1)

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BR112017001829-2A BR112017001829B1 (pt) 2014-07-29 2015-07-27 material compósito com propriedades de pasta estáveis para uso odontológico e método para a produção do mesmo

Applications Claiming Priority (4)

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JP2014154179A JP5716119B1 (ja) 2014-07-29 2014-07-29 安定したペースト性状をした歯科用複合材料
JP2014-154179 2014-07-29
JP2014154177A JP5716118B1 (ja) 2014-07-29 2014-07-29 ペースト性状の劣化を軽減した複合材料
JP2014-154177 2014-07-29

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PCT/JP2015/071246 WO2016017581A1 (fr) 2014-07-29 2015-07-27 Matériau composite avec une moindre détérioration de l'état de pâte

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
US10265248B2 (en) 2014-07-29 2019-04-23 Shofu Inc. Composite material having reduced degradation of pasty property

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JPH08143747A (ja) * 1994-11-24 1996-06-04 San Medical Kk 複合充填材、複合充填材の製造法及びそれらを用いた歯科用レジンの組成物
JPH09194674A (ja) * 1996-01-25 1997-07-29 San Medical Kk 歯科用充填組成物
WO2007088628A1 (fr) * 2006-02-03 2007-08-09 Kabushiki Kaisha Shofu ciment en resine composite a usage dentaire, appret a usage dentaire et kit adhesif a usage dentaire les contenant
JP2009067746A (ja) * 2007-09-14 2009-04-02 Shiyoufuu:Kk 一液型歯科用接着性組成物
JP2009120849A (ja) * 2009-02-23 2009-06-04 Shofu Inc スズ化合物を用いた歯科用接着剤
JP2010018524A (ja) * 2008-07-08 2010-01-28 Shofu Inc 歯科用ツーペースト型自己接着性レジンセメント
JP2012153640A (ja) * 2011-01-26 2012-08-16 Tokuyama Dental Corp 歯科用複合修復材料

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Publication number Priority date Publication date Assignee Title
JPH08143747A (ja) * 1994-11-24 1996-06-04 San Medical Kk 複合充填材、複合充填材の製造法及びそれらを用いた歯科用レジンの組成物
JPH09194674A (ja) * 1996-01-25 1997-07-29 San Medical Kk 歯科用充填組成物
WO2007088628A1 (fr) * 2006-02-03 2007-08-09 Kabushiki Kaisha Shofu ciment en resine composite a usage dentaire, appret a usage dentaire et kit adhesif a usage dentaire les contenant
JP2009067746A (ja) * 2007-09-14 2009-04-02 Shiyoufuu:Kk 一液型歯科用接着性組成物
JP2010018524A (ja) * 2008-07-08 2010-01-28 Shofu Inc 歯科用ツーペースト型自己接着性レジンセメント
JP2009120849A (ja) * 2009-02-23 2009-06-04 Shofu Inc スズ化合物を用いた歯科用接着剤
JP2012153640A (ja) * 2011-01-26 2012-08-16 Tokuyama Dental Corp 歯科用複合修復材料

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10265248B2 (en) 2014-07-29 2019-04-23 Shofu Inc. Composite material having reduced degradation of pasty property
US10780027B2 (en) 2014-07-29 2020-09-22 Shofu Inc. Composite material having reduced degradation of pasty property

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BR112017001829B1 (pt) 2020-12-08
BR112017001822A2 (pt) 2017-11-21
BR112017001822B1 (pt) 2020-12-08
BR112017001829A2 (pt) 2017-11-21
WO2016017581A1 (fr) 2016-02-04

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