JP2008174461A - Dental polymerizable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dental two composition type polymerizable composition which can be used for multi-purposes, such as final prostheses for repairing denture bases or artificial teeth, for tooth crowns, tentative prostheses used until completed, excellent in color tones, a polishing property, discoloration during and after cured, mechanical characteristics, and the like, in good operability in states little containing air bubbles. <P>SOLUTION: This dental polymerizable composition is characterized by comprising a composition I and a composition II, wherein the composition I comprises a polymerizable monomer (a) and a reducing agent (c) capable of decomposing a radical-producing agent (b), and the composition II comprises (meth)acrylate-based polymer particles (de) consisting mainly of a component (d) having a particle size distribution of 10 to 400 μm, a median diameter in a range of 70 to 120 μm, and a number-average mol.wt. (Mn) in a range of 50,000 to 250,000 and a component (e) having the same particle size distribution and the same median diameter as the those and a number-average mol.wt. (Mn) in a range of 300,000 to 700,000, and the radical-producing agent (b), and wherein the dental polymerizable composition can be cured, when the composition I is mixed with the composition II. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a dental polymerizable composition. More specifically, in a two-composition type room temperature polymerization type resin, a denture that has good operability by a brushing method and a mixing method, little air bubbles, and excellent color tone, polishing properties, mechanical properties, resistance to discoloration, etc. The present invention relates to a dental polymerizable composition used for various purposes such as restoration of floors, artificial teeth, prosthetics for crowns, and bridge dentures until completion.

Powder-mixed immediate polymerization resins of (meth) acrylic acid ester polymer powder and (meth) acrylic acid ester monomer are frequently used for repair of denture bases, preparation of temporary crowns, repair of artificial teeth, and the like. In recent years, there is a need for temporary crowns that have stable color tone, mechanical strength, and discoloration resistance over a long period of time, such as when implanting a final prosthesis after waiting for long-term gingival recovery. There are various products on the market. This temporary crown is made mainly by wetting a technical brush with a liquid material mainly composed of (meth) acrylic acid ester and attaching (meth) acrylic acid ester polymer powder to the brush. Is frequently used. When making this crown with the brush stacking method, it is difficult to build up if the liquid mud collected in the brush is easy to sag, and it will interfere with the production of the fine shape of the crown, and if it does not sag, it can be thinly stretched with a brush. Problems such as not occurring. In addition, since organic peroxides and tertiary aromatic ring amines are used as polymerization initiators, yellowing occurs during curing, resulting in a loss of aesthetics, or the cured product is discolored and colored in the oral cavity, resulting in early aesthetics. There are drawbacks such as damage. In order to solve this problem, using a powder material containing a pyrimidinetrione derivative and an organometallic compound and a liquid material containing an organohalogen compound and an aromatic ring tertiary amine, writing operability, mixing of bubbles and aesthetics A method for improving the property has been proposed (Patent Document 1). A method of adding a specific triazole compound for preventing discoloration during curing has also been proposed (Patent Document 2).
JP-A-6-219919 Japanese Examined Patent Publication No. 5-78531

  The object of the present invention is a two-composition type, especially a powder liquid type, room temperature polymerization type resin, which has good operability by a brushing method and a blending method, little mixing of bubbles, color tone, abrasiveness, mechanical properties Another object of the present invention is to provide a dental polymerizable composition that can be used for various purposes such as a temporary crown until a denture base having excellent discoloration resistance and the like, restoration of an artificial tooth, a prosthesis for a crown, and a bridge denture are completed.

  Other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are:
A dental polymerizable composition comprising two compositions I and II,
Composition I contains a reducing agent (c) capable of decomposing polymerizable monomer (a) and radical generator (b),
A component (d) in which composition II has a particle size distribution of 10 to 400 μm, a median diameter in the range of 70 to 120 μm and a number average molecular weight (Mn) in the range of 50,000 to 250,000;
(Meth) acrylic acid ester system having as a main component a component (e) having a particle size distribution of 10 to 400 μm, a median diameter in the range of 70 to 120 μm and a number average molecular weight (Mn) in the range of 300,000 to 700,000 Containing polymer particles (de) and a radical generator (b),
And it achieves by the dental polymerizable composition characterized by being able to harden when the composition I and the composition II are mixed.
The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the component (d) is preferably 4.4 to 12, and (Mw) / (Mn) of the component (e) is 2.2. It is preferable that it is -4.4, and it is more preferable to contain these together.

The composition II preferably further contains inorganic oxide particles (f) and / or composite particles (g) of a polymer and an inorganic oxide.
It is preferable to further contain a polymer (j) derived from a trifunctional or higher polyfunctional polymerizable monomer together with the composite particles of the polymer and the inorganic oxide.
The composite particles (g) preferably have a particle size distribution of 1 to 100 μm and a median diameter of 1 to 40 μm.
The radical generator (b) preferably has a decomposition half-life at 80 ° C. of 10 hours or less.
It is preferable that the composition I further contains a polymerization inhibitor of the hindered phenol compound (h).
The composition I preferably further contains a benzophenone-based ultraviolet absorber (i).
Composition I is 90-99.5 parts by weight of component (a) with respect to 100 parts by weight of the total of component (a), component (c), component (h) and component (i), and component (c) Is 0.5 to 10 parts by weight, component (h) is 0 to 0.5 parts by weight, component (i) is 0 to 5 parts by weight, and composition II is component (d), (e ) Component, (f) component and / or (g) component, and (b) component is 100 to 100 parts by weight in total, (d) component is 20 to 75 parts by weight, and (e) component is 20 to 75 parts by weight. It is particularly preferable that the component (f) and / or the component (g) is 1 to 20 parts by weight and the component (b) is 0.05 to 10 parts by weight.

  The two-composition type room temperature polymerization resin of the present invention has good operability by brushing and blending methods, has less air bubbles, and has excellent color tone, abrasiveness, mechanical properties, discoloration resistance, etc. It is used for various purposes such as artificial tooth restoration, crown prosthesis and bridge dentures until completion.

  In the present invention, unless otherwise specified, the compound name or functional group name "(meth) acryl ..." means "acryl ... and / or methacrylate ..." In the preferred numerical range, “XX to YY” (XX and YY are respectively corresponding numerical values) means “XX or more and / or YY or less”.

  First, the properties of Composition I and Composition II will be described. Since composition I contains monomers, it is usually often in liquid form. In some cases it is pasty. On the other hand, since composition II contains polymer particles and contains a radical generator that is not very stable, it is preferably in a solid form such as a powder. Therefore, in the following description, the composition I will be described in a liquid form, and the composition II will be described in a powder form. However, the present invention is not limited to these aspects. Is not to be done. The present invention is a dental polymerizable composition in which compositions I and II are mixed and, if necessary, the mixture can be cured by redox polymerization or the like.

  The polymerizable monomer (a) contained in the composition I will be described. As the polymerizable monomer (a), a known polymerizable compound can be used. Specific examples thereof include (i) a monofunctional polymerizable monomer, (ii) a bifunctional polymerizable monomer, (iii) a trifunctional polymerizable monomer, and (iv) a tetrafunctional or higher polymerizable monomer. And (meth) acrylic acid ester compounds are particularly preferred. Specific examples are given below. The polymerizable monomer (a) can be used alone or in combination of two or more.

(I) Monofunctional polymerizable monomer Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isopropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-lauryl (meth) Acrylate, n-stearyl (meth) acrylate, behenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) Acrylate, methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, Ethoxyethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxytriethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytriethylene Glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl ( (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl Kishiechiru (meth) acrylate, N- (meth) acryloyl morpholine, trifluoroethyl (meth) acrylate, perfluorooctyl (meth) acrylate of (meth) acrylic acid ester-based polymerizable monomers.

  Moreover, a well-known acidic group containing polymerizable monomer can be used together if the performance of the present invention can be expressed. Examples of such a compound include a phosphoric acid group-containing polymerizable monomer, a pyrophosphate group-containing polymerizable monomer, a thiophosphate group-containing polymerizable monomer, a carboxylic acid group-containing polymerizable monomer, Examples thereof include sulfonic acid group-containing polymerizable monomers. The amount used in combination is preferably 10% by weight or less, more preferably 5% by weight or less, and still more preferably 3% by weight or less of the polymerizable monomer (a). Here, if it exceeds 10% by weight, the water resistance of the cured product may be inferior due to the acidic group, which is not preferable.

  Among these, as the phosphoric acid group-containing polymerizable monomer, for example, 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 10- (meth) acryloyloxydecyldi Examples thereof include hydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, (meth) acryloyloxyethyl phenyl phosphate, (8- (meth) acryloyloxy) octyl-3-phosphonopropinate.

  Examples of the pyrophosphate group-containing polymerizable monomer include di [2- (meth) acryloyloxyethyl pyrophosphate], di [4- (meth) acryloyloxybutyl pyrophosphate], and di [8- (meth) pyrophosphate. Acryloyloxyoctyl], di [12- (meth) acryloyl oxide decyl] pyrophosphate, and the like.

  Examples of the thiophosphate group-containing polymerizable monomer include 2- (meth) acryloyloxyethyl dihydrogenthiophosphate, 3- (meth) acryloyloxypropyl dihydrogenthiophosphate, 10- (meth) acryloyloxydecyldi. Examples thereof include hydrogenthiophosphate, 12- (meth) acryloyl oxide decyl dihydrogenthiophosphate, and the like.

  Examples of the carboxylic acid group-containing polymerizable monomer include (meth) acrylic acid, 4- (meth) acryloyloxyethyloxycarbonylphthalic acid, 4- (meth) acryloyloxybutyloxycarbonylphthalic acid, 4- (meth). Acryloyloxyoctyloxycarbonylphthalic acid, 4- (meth) acryloyloxydecyloxycarbonylphthalic acid and their anhydrides, 6- (meth) acryloylaminohexylcarboxylic acid, 8- (meth) acryloylaminooctylcarboxylic acid, 11 -(Meth) acryloyloxy-1,1-undecanedicarboxylic acid and the like can be mentioned.

  Examples of the sulfonic acid group-containing polymerizable monomer include 2- (meth) acrylamide ethyl sulfonic acid, 3- (meth) acrylamide propyl sulfonic acid, 4- (meth) acrylamide butyl sulfonic acid, 10- (meth) acrylamide decyl. A sulfonic acid etc. can be mentioned.

(Ii) Bifunctional polymerizable monomer Examples of the aromatic polymerizable compound include 2,2-bis ((meth) acryloyloxyphenyl) propane and 2,2-bis (4- (meth) acryloyloxy-2-). Hydroxypropoxyphenyl) 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) acryloylloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propa (Meth) acrylate compounds containing hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxyethylpropyl (meth) acrylate and 3-chloro-2-hydroxypropyl (meth) acrylate, and methylbenzene diisocyanate Examples thereof include urethane-based polymerizable monomers obtained by addition with diisocyanate compounds such as -to and 4,4-diphenylmethane diisocyanate.

  Examples of the aliphatic compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and pentamethylene glycol di (meth). Acrylate, hexaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (Meth) acrylate, pentapropylene glycol di (meth) acrylate, hexpropylene glycol di (meth) acrylate, nonapropylene glycol Cyclic, linear, branched aliphatics such as ethylene glycol-based or propylene glycol-based di (meth) acrylate such as di (meth) acrylate, or ethoxylated cyclohexane di (meth) acrylate, and also ethylene glycol or propylene Di (meth) acrylate compound bonded with glycol, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol Aliphatic di (meth) acrylate compounds such as di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, or 2-hydroxyethyl (meth) acrylate , 2- (Meth) acrylates containing hydroxyl groups such as droxyethylpropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethylpropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate Examples thereof include urethane-based polymerizable monomers obtained by addition of a compound and a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, and methylenebis (4-cyclohexyl isocyanate).

(Iii) Trifunctional polymerizable monomer Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, tris (2- (meth) acryloxyethyl) isocyanurate, etc. Is mentioned.

(Iv) Tetrafunctional or higher polymerizable monomers Tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate and dipentaerythritol tetra (meth) acrylate, or hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylcyclohexane A diisocyanate compound having an aliphatic group among diisocyanates such as diisocyanate, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate), and a diisocyanate compound having an aromatic group such as methylbenzene diisocyanate and 4,4, -diphenylmethane diisocyanate; Dipentaethane, a urethane-based polymerizable monomer obtained by addition with a bifunctional or higher functional (meth) acrylate compound containing a hydroxyl group Examples include lithitol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Moreover, the polyethylenically unsaturated carbamoyl isocyanurate type compound described in Japanese Patent Publication No. 7-80736 can also be used.

  Among the above polymerizable monomers, preferred compounds are compounds having a boiling point at normal pressure of 150 ° C. or less, preferably 120 ° C. or less, such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate. It is. When a polymerizable monomer having this characteristic is used, it can be preferably used because the unreacted polymerizable monofunctional is volatilized by the heat of polymerization at the time of polymerization and curing and no unpolymerized layer is formed.

  Further, in order to accelerate the polymerization rate and improve the abrasion resistance of the cured product, it is preferable to use a monofunctional polymerizable monomer and a bifunctional or higher polymerizable monomer simultaneously mixed. The ratio may be appropriately selected from the polymerization performance of the polymerizable compound, the formation state of the unpolymerized layer, and the like, but the monofunctional polymerizable monomer to the bifunctional or higher polyfunctional polymerizable monomer is preferably 99. 5 to 60 to 0.5 to 40% by weight, more preferably 98 to 65 to 2 to 35% by weight, and still more preferably 95 to 70 to 5 to 30% by weight. Here, if the polyfunctional polymerizable monomer is less than 0.5% by weight, improvement in abrasion resistance cannot be expected. Conversely, if it exceeds 40% by weight, an unpolymerized layer remains at the time of curing, and a solvent such as acetone is removed. It is not preferable because the operability becomes complicated because the tissue must be wiped off. Here, preferable compounds of the polyfunctional polymerizable monomer are exemplified by 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxy). Phenyl) propane; (meth) acrylate compounds having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxyethylpropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate and hexamethylene diso Urethane polymerizable monomers obtained from addition with diisocyanate compounds such as cyanate, methylbenzene diisocyanate, 4,4, -diphenylmethane diisocyanate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Examples include 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (2- (meth) acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, and the like. Among them, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,4-butanediol di (meth) acrylate because the cured product has good water resistance. 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate are preferably used.

  Next, the reducing agent (c) that can decompose the radical generator (b) will be described. As (c), an organic compound and an inorganic compound can be used without limitation, but an organic compound can be preferably used in order to suppress the water absorption of the cured product. Aromatic amines that can efficiently decompose the radical generator (b) described later are preferred, and among them, N, N-dimethyl-p-toluidine, N, N-dimethylaniline, N, N-diethyl- Aromatic ring tertiary amines such as p-toluidine, N, N-diethylaniline, N, N-di (hydroxypropyl) -p-toluidine, N, N-di (β-hydroxyethyl) -p-toluidine; N, N-diphenylglycine, N-phenylglycine and the like, or alkali metal salts thereof, and the like can be given. These reducing agents may be used alone or in combination of two or more.

  In order to improve the storage stability of the composition I and to suppress yellowing during polymerization, a polymerization inhibitor may be added to the composition I. The type of the composition I is not limited as long as it has an effect of suppressing storage stability of the composition I, discoloration during polymerization and curing, and discoloration of the cured product in the oral cavity, but 2,6-dimethyl-6-tert is not limited. -Butylphenol, 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4- A hindered phenol-based polymerization inhibitor (h) such as hydroxybenzoyl) benzene or 2,5-di-tert-butylhydroquinone can be preferably used in order to exhibit the above effects. Moreover, in order to suppress discoloration at the time of storage of the composition I, you may add a ultraviolet absorber. The type of the ultraviolet absorber is not limited as long as it has an effect of suppressing discoloration during storage of the composition I, but 2,4-dihydrobenzophenone, which suppresses discoloration of the composition I and the cured product simultaneously, 2- Benzophenone-based ultraviolet absorbers (i) such as hydroxy-4-methoxybenzophenone and 4-benzoyl-2-hydroxybenzophenone are preferred. The addition amount of these (h) and (i) components is mentioned later.

  Next, the (meth) acrylic acid ester polymer particles (de) in the composition II will be described. Known compounds can be used as the (meth) acrylic acid ester polymer. Specifically, polymer powders of homopolymers, copolymers, and mixtures thereof prepared by suspension polymerization, emulsion polymerization or the like from the polymerizable monomers described above can be used. Examples of preferred polymers are methyl (meth) acrylate polymer, ethyl (meth) acrylate polymer, butyl (meth) acrylate polymer, propyl (meth) acrylate polymer, methyl (meth) acrylate and (meth) acrylic. Copolymer of ethyl acrylate, copolymer of methyl (meth) acrylate and butyl (meth) acrylate, copolymer of methyl (meth) acrylate and propyl (meth) acrylate, and methyl (meth) acrylate Copolymers of styrene and the like can be mentioned. Among them, methyl (meth) acrylate polymer, ethyl (meth) acrylate polymer, copolymer of methyl (meth) acrylate and ethyl (meth) acrylate, Since these can use the hardened | cured material with favorable mechanical characteristics, they can be used especially preferable. Furthermore, in order to improve the stain resistance, if familiarity with the composition I is good, a fluorine group-containing (meth) acrylic acid ester polymer such as trifluoroethyl (meth) acrylate polymer, perfluorooctyl (meth) acrylate A polymer, a copolymer of methyl (meth) acrylate and trifluoroethyl (meth) acrylate, a copolymer of ethyl (meth) acrylate and trifluoroethyl (meth) acrylate, and the like can also be used.

  Further, methyl (meth) acrylate and trimethylol are within the range of improving the wear resistance, mechanical properties and coloring resistance of the cured product without impairing the operability and curability of the dental polymerizable composition of the present invention. Crosslinkable polymer powder of propane tri (meth) acrylate, crosslinkable polymer powder of trimethylolpropane tri (meth) acrylate, powder of copolymer of monofunctional polymerizable monomer and polyfunctional polymerizable monomer A crosslinked polymer powder (j) such as may be added. The addition amount is preferably 1 to 50 parts by weight, more preferably 1 to 30 parts by weight, still more preferably 3 to 20 parts by weight with respect to 100 parts by weight of the above (de). Here, if the amount is less than 1 part by weight, improvement in the wear resistance of the cured product cannot be expected. Moreover, when it exceeds 50 weight part, the mixing to the powder material (composition II) of a polymer powder will worsen, and it will become difficult to build up. Since the liquid material (composition I) hardly penetrates into the polymer cross-linked portion, the matrix portion and the polymer portion of the cured product are peeled off, which is not preferable because there is a possibility that the wear resistance and mechanical properties are deteriorated. In addition, the particle size distribution and median diameter in the case of using a crosslinked product may be in the above range, but the molecular weight is not soluble in a solvent and is difficult to measure by the measurement method described later, and thus cannot be specified. The degree of swelling of the powder material and the like can be measured in advance to obtain a molecular weight standard.

The properties of the polymer powder are not particularly limited as long as the properties of the present invention are exhibited.
(Meth) acrylate polymer particles (de) having a component (d) having a number average molecular weight (Mn) in the range of 50,000 to 250,000 and a component (e) in the range of 300,000 to 700,000. is there. The particle size distribution width of the component (d) and the component (e) is 10 to 400 μm, preferably 15 to 400 μm, and more preferably 20 to 350 μm. Here, when the particle size is less than 10 μm, the viscosity of the powder liquid mud is increased during the operation and the operability is deteriorated, which is not preferable. On the other hand, if it exceeds 400 μm, it is difficult to dissolve the composition II in the composition I, and the powder liquid mud becomes rough and the operability is deteriorated. The particle distribution and median diameter of (de) are values when using a Shimadzu laser diffraction particle size distribution analyzer SALD-2000A, measuring range 0.03 to 700 μm, and ethanol as a dispersion aid.

The median diameter is 70 to 120 μm, preferably 70 to 100 μm, and more preferably 75 to 100 μm for the component (d), the component (e) and the component (de). Here, when the particle size is 70 μm or less, the particle is too fine and the viscosity of the powder liquid mud increases and the build-up operability is deteriorated. Conversely, when the particle size exceeds 120 μm, the particle is too coarse and the powder liquid mud is rough and the operability is increased. Becomes worse. Further, the difference between the median diameter and the average particle diameter is 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less, and the mode diameter is 70 to 100 μm, preferably 75 to 95 μm, more preferably 75 to 90 μm. A dental polymerizable composition having good stacking operability can be obtained. If the difference between the median diameter and the average particle diameter and the mode diameter are out of the lower limit, the viscosity of the powder liquid mud is increased during the operation and the operability is deteriorated. Further, if the upper limit is exceeded, the composition II becomes difficult to dissolve in the composition I, the powder liquid mud becomes rough and the operability is deteriorated, and the composition II which is difficult to swell in the composition I remains. This is not preferable because the mechanical properties of the cured product are inferior.
Exceeding the upper limit is not preferable because the composition II is difficult to dissolve in the composition I, resulting in inferior mechanical properties of the cured product. Here, the median diameter, average particle diameter, and mode diameter using a laser diffraction particle size distribution measuring device can be searched on the homepage of Shimadzu Corporation.

  The polymer of the polymer powder (de) mainly contains a component (d) having a number average molecular weight (Mn) in the range of 50,000 to 250,000 and a component (e) in the range of 300,000 to 700,000. It is essential to have it as a component. In the polymer, the sum of components (d) and (e) is 70% by weight or more, preferably 75% by weight or more, more preferably 80% by weight or more.

  The molecular weight and molecular weight distribution of components (d) and (e) will be described in more detail. Measurement of molecular weight and molecular weight distribution of polymer powder using GPC, using column (PLgel 10μ MIXED-B, Polymer laboratories), column temperature (room temperature), moving bed (tetrahydrofuran), data calculated in PMMA conversion Is preferred. The molecular weight, molecular weight distribution, and top peak molecular weight of (d) and (e) are not limited as long as the performance of the present invention is exhibited, but the number average of (meth) acrylate polymer component (d) The molecular weight (Mn) is preferably a component in the range of 70,000 to 250,000, more preferably 70,000 to 200,000. The weight average molecular weight (Mw) is preferably in the range of 600,000 to 1.1 million, more preferably 700,000 to 1,100,000, still more preferably 800,000 to 1,100,000, and the top peak molecular weight (Mp) is preferably 70. The range is 10,000 to 1.1 million, more preferably 800,000 to 1.1 million, and still more preferably 900,000 to 1,000,000. The number average molecular weight (Mn) of the (meth) acrylic acid ester polymer component (e) is preferably a component in the range of 300,000 to 600,000, more preferably 300,000 to 500,000. The weight average molecular weight (Mw) is preferably in the range of 115 to 1.6 million, more preferably 1.2 million to 1.6 million, still more preferably 1.25 to 1.6 million, and Mp is preferably 1.2 million to 1.6 million, more preferably 120. It is in the range of 10,000 to 150,000, more preferably 1.25 to 150,000. The molecular weight distributions of (d) and (e) are also important because they affect the solubility in the powder material (composition I), the swellability, and the operability of the powdered mud. The molecular weight distribution (Mw / Mn) of the above (d) is preferably 4.4 to 12, more preferably 5 to 10, and particularly preferably 5 to 7. Further, the molecular weight distribution (Mw / Mn) of (e) is preferably 2.2 to 3.8, more preferably 2.5 to 3.8, and particularly preferably 3 to 8. Here, if the molecular weight distribution width of (d) exceeds the lower limit, dripping occurs, and if it exceeds the upper limit, internal bubbles increase, which is not preferable. Further, if the molecular weight width of (e) exceeds the lower limit, it tends to sag, and if it exceeds the upper limit, it becomes difficult to elongate.

  One of the features of the present invention is that, as described above, the polymer components (d) and (e) having preferable particle size characteristics are used, but it is important to simultaneously use those having specific molecular weight characteristics. It is. This is because if only component (d) is used, the familiarity of composition I is so good that sagging occurs, which is not preferable for building up by the writing method. Further, when only the component (e) is used, the familiarity with the composition I is poor, and no dripping occurs, but there is no elongation. However, when (d) and (e) are blended at least at the same time, it surprisingly offsets the disadvantages of both, and the composition II is applied to a brush for a technician who is familiar with the composition I and is wet with the composition I. It has been found that it is easy to collect the powder, is difficult to sag at the time of build-up, and has a very good operability because it becomes a stretched powdery liquid mud. Further, it has been found that the mechanical properties are good because there is little air bubble mixing. Here, the mixing ratio of (d) and (e) may be appropriately blended from the operation of the present invention, but generally (d) to (e) is 5 to 95 to 95 to 5% by weight, preferably, It is 20-80 to 80-20 weight%, More preferably, it is 30-70 to 70-30 weight%. When (d) is less than 5% by weight, it is unsuitable for the composition I, does not sag but does not stretch, and contains more bubbles than the dental resin composition of the present invention, so the writing method It is not preferable for building up by. On the other hand, when (d) exceeds 95% by weight, the familiarity of the composition I is too good, and dripping occurs, which is not preferable for the build-up by the writing method.

In addition, the mixing form of component (d) and (e) is not specifically limited,
(1) a form in which particles consisting essentially of component (d) and particles consisting essentially of component (e) are mixed;
(2) A form in which particles are formed from a blend polymer in which components (d) and (e) are mixed,
(3) A form in which (1) and (2) are mixed,
And the like.

  In addition, in order to improve the abrasiveness and wear resistance of the cured product, the inorganic oxide particles (f) and the composite particles (g) of the polymer and the inorganic oxide may be added to the composition II alone or simultaneously. (F) and (g) may be used alone or in combination of two or more. Further, the types and shapes of (f) and (g) are not limited. As a kind of inorganic oxide particle (f), a well-known thing is not limited but can be used. For example, periodic groups I, II, III, IV, oxides containing transition metal atoms, hydroxides, chlorides, sulfates, sulfites, carbonates, phosphates, silicates, and mixtures thereof, Examples include complex salts. More specifically, glass powder such as silicon dioxide, strontium glass, lanthanum glass, barium glass, (boro) silicate glass, quartz powder, aluminum oxide powder, titanium oxide powder, glass fiber, barium fluoride powder Body, glass powder containing talc, zirconium oxide powder, tin oxide powder, other ceramic powder, metal whisker and the like. The inorganic oxide powder may be blended in the composition II as it is, but it may be used after being hydrophobized in order to produce a cured product having good mechanical performance and wear resistance. As the surface treatment agent, known ones can be used. For example, γ- (meth) acryloxypropyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropylethoxysilane, 3-chloropropyltrimethoxysilanesilyl isocyanate, vinyl Examples thereof include silane coupling agents such as trichlorosilane, dimethyldichlorosilane, and dioctyldichlorosilane hexamethylene disilazane, zirconium coupling agents, titanium coupling agents, and silicones (system coupling agents). As the surface treatment method, (A) a method of directly mixing the inorganic oxide powder and the surface treatment agent with a ball mill, V-blender, Henschel mixer or the like (dry method), (B) a surface treatment agent such as an ethanol aqueous solution, etc. A method in which a solution diluted with an organic solvent-containing aqueous solution in which an organic solvent and water are uniformly mixed is added to and mixed with the inorganic oxide powder, followed by heat treatment at 50 ° C. to 150 ° C. for several minutes to several hours (wet method) And (C) a method (spray method) in which the surface treatment agent is directly applied to the high-temperature inorganic oxide powder or the above aqueous solution is directly sprayed. Of course, commercially available products that have already been surface-treated may be used as they are, or surface treatment may be further added by the above-described method or the like. The amount of the surface treatment agent with respect to the inorganic oxide powder may be determined optimally from the specific surface area of the inorganic oxide powder, etc., but is generally 0.1% with respect to 100 parts by weight of the inorganic oxide powder. It is -20 weight part, Preferably it is 0.1-15 weight part, More preferably, it is the range of 0.1-10 weight part. The particle size distribution of the inorganic oxide powder is not limited as long as it exhibits the characteristics of the present invention, but is in the range of 1 to 100 μm, preferably 1 to 50 μm, and more preferably 1 to 30 μm.

  The median diameter is 1 to 40 μm, preferably 1 to 10 μm, more preferably 1 to 5 μm. If the particle size distribution and the median diameter are out of the lower limits, it is not preferable because improvement in mechanical properties and wear resistance of the cured product cannot be expected. When the upper limit is exceeded, not only a glossy surface can be obtained during polishing, but the (meth) acrylic acid ester polymer particles (d) and (e) in the composition II and the inorganic oxide particles (f) Is not preferable because it may cause a layer separation due to a difference in specific gravity and a uniform powder may not be obtained.

  The composite particle (g) of a polymer and an inorganic oxide will be described. First, the type of polymer is not limited, but a polymer derived from the polymerizable monomer (a) described above or an oligomer thereof can be preferably used. Of course, the polymer may be a homopolymer or a copolymer derived from two or more kinds of polymerizable monomers. Moreover, in order to improve the mechanical strength of the composite, a polymer derived from a polyfunctional polymerizable monomer having two or more polymerizable groups (including a polymerizable monomer or an oligomer thereof) is preferable. Furthermore, when a polymer derived from a polymerizable monomer containing a polyfunctional polymerizable monomer having three or more polymerizable groups is used, a reactive double bond remains on the surface of the composite, and at the time of curing. As a result of copolymerization with the polymerizable monomer (a) in the composition I, the falling of the filler is suppressed, so that a cured product having excellent mechanical properties over the long term can be obtained. Here, the ratio of the polymer derived from the polyfunctional polymerizable monomer having three or more polymerizable groups in the polymer is not particularly limited as long as the performance of the present invention is exhibited, but constitutes a composite. It is 20% by weight or more, preferably 50% by weight or more, and more preferably 60% by weight or more based on the total polymer (including a polymer derived from a polyfunctional polymerizable monomer having 3 or more). Here, when the amount is less than 20% by weight based on the total polymer constituting the composite, the amount of the double bond having reactivity on the surface of the composite is small, and the polymerizable monomer (a As a result, it becomes difficult to copolymerize with the resin), and the filler falls off, resulting in a decrease in mechanical properties.

  Preferred compounds of the polymerizable monomer having three or more polymerizable groups are, for example, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate and the like, and the polymerizable monomer combined therewith is di ( (Meth) acryloxyethyl) having a urethane-based polymerizable monomer such as trimethylhexamethylenediurethane or an aromatic ring such as 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane and an ether bond A (meth) acrylate polymerizable monomer is preferred. In the case of producing a composite under heating, the polymerizable monomer having an aromatic ring, an ether bond or a urethane bond, a hetero atom or the like is 50% by weight or less, preferably 40% by weight based on the total polymerizable monomer. When used in an amount of not more than% by weight, more preferably not more than 30% by weight, it is possible to produce a composite that hardly undergoes yellowing when it is heated and polymerized to produce a composite or heat treatment described later, and hardly colored. Preferred polymerizable monomer combinations and weight ratios are trimethylolpropane tri (meth) acrylate and / or ditrimethylolpropane tetra (meth) acrylate and di ((meth) acryloxyethyl) trimethylhexamethylenediurethane and / or 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 40 to 99% by weight of trimethylolpropane tri (meth) acrylate and / or dimethylolpropane tetra (meth) acrylate, preferably 50 It is -95 weight%, More preferably, it is 50-90 weight%.

  The inorganic oxide used in the composite is not particularly limited, and the inorganic oxide particles (f) and AEROSIL (for example, 50, 70, 130, 200, 200 V, 200 CF, 200 FDA, 300, 300 CF, 380, R972, R972V, R972CF, R974, RX200, RY200, R202, R805, R809, R812, RX200, RX300, TT600, K320D, R976, R976S, OX50, TT600, MOX80, MOX170, COK84, RM50: Nihon Aero And fine particle inorganic oxide (f1) having an average particle diameter of 0.001 to 1 μm. Of course, you may manufacture a composite_body | complex using the mixture of two or more types of inorganic oxide powder. In addition, as the inorganic oxide particles added to the composite, the above (f1) is preferably used because of the good polishing properties of the cured product containing the composite powder (g), and among these, AEROSIL is more preferable. .

  The inorganic oxide powder used in the composite may be used for the production of the composite as it is, but the surface of the inorganic oxide powder is used to improve the mechanical properties of the cured product containing the composite powder. Is preferably surface-treated by the method described above. In addition, when using inorganic oxide powder (f1) that has been hydrophobized in advance at the time of purchase of the above-mentioned AEROSIL R972, R812, etc., the surface treatment may be performed again by the above method. Also good.

  The content of the inorganic oxide powder in the composite is not particularly limited, but if the content is too low, improvement of the mechanical properties of the cured product cannot be expected, and conversely if too high, polymerization occurs during the production of the composite. When the inorganic oxide is kneaded into the functional monomer, the powder is not sufficiently dispersed, resulting in unevenness, and the transparency and mechanical properties of the cured product containing the composite powder may be inferior. Absent. Therefore, the ratio of the inorganic oxide powder in the composite is 30 to 80% by weight, preferably 30 to 75% by weight, and more preferably 35 to 60% by weight.

The method for producing the composite is not limited. As an example of the production method, a polymerizable monomer (a), an inorganic oxide (f, f1), and a radical generator (b) described later are mechanically mixed with a mortar, roll, kneader, high viscosity stirrer, etc. And a method of bulk polymerization. Here, the addition ratio of (b) is 0.01 to 5% by weight, preferably 0.1 to 1% by weight, based on the polymerizable monomer, and the paste is put into a mold plate such as a metal plate and heated. A method of producing a composite by pressurizing to about 1 to 50 MPa with a compression molding machine or the like and bulk polymerizing at 80 to 200 ° C., preferably 100 to 150 ° C. for several minutes to several hours, preferably 5 minutes to 1 hour. Is preferred.
Of course, as long as the polymerizable monomer used in the production of the composite or its oligomer itself is thermally polymerized, it may be produced by heating and polymerizing a precursor containing no polymerization initiator as it is.

  If the produced composite is a powder, it may be used as it is or classified, and if it is a lump, it may be pulverized into a powder. The pulverization method is not particularly limited, but generally, a method of mechanically pulverizing using a ball mill, a vibration mill or the like, and collecting a powder having a predetermined particle size with a sieve or a classifier is preferably used. The The particle size distribution, median diameter, and advantages of the composite particles are the same as those of the inorganic oxide (f).

  The composite particle may be used as a component of the composition II as it is, but the stability reducing factor such as a polymerization initiator remaining in the composite particle is deactivated to improve the storage stability of the composition II. Is preferred. The deactivation method is not particularly limited, but for the reason that the operation is simple, the powder is heated to 60 to 250 ° C., preferably 80 to 150 ° C. for several tens of minutes to several tens of hours, preferably 5 hours to 200 hours. A heat treatment method can be suitably employed. The heat treatment may be performed by any method under normal pressure, reduced pressure, or increased pressure. Moreover, in order to make it difficult to yellow the powder, heat treatment may be performed in an inert gas atmosphere such as nitrogen or argon or in an air stream. Further, in order to further enhance the removal of the composite particles from the cured body, the composite particles are surface-treated with the above-described surface treatment agent or treated with a solvent capable of substantially dissolving the polymerizable monomer constituting the composite. Then, some or all of the unreacted monomer present on the surface is dissolved and removed, and fine irregularities are formed on the surface to provide an anchoring effect. Also, the composite particles are glycidyl (meth) acrylate, tetrahydro It may be reacted with a polymerizable monomer containing an epoxy group such as furfuryl (meth) acrylate.

  Next, the radical generator (b) will be described. (B) is not limited to an organic compound or an inorganic compound as long as it is a compound that generates radicals by the reducing agent (c) described above, but an organic compound is preferred in view of the water resistance of the cured product. Of the organic compounds, organic peroxides are preferred, and there are no restrictions on the type thereof, but compounds with a decomposition half-life at 80 ° C. of 10 hours or less are preferred in order to increase the radical generation efficiency of redox polymerization. . More preferably, it is 7 hours or less, More preferably, it is 5 hours or less. Moreover, about a lower limit, Preferably it is 1 hour or more, More preferably, it is 2 hours or more, More preferably, it is 3 hours or more. If the upper limit of the numerical range is exceeded, the curing time is delayed and the time until the prosthesis is completed for a while is delayed, and if the lower limit is exceeded, the curing becomes too fast and the powder liquid mud solidifies during the build-up operation, etc. Any of them is not preferable because it hinders technical operation. Specific examples of suitable compounds include diacyl peroxides such as acetyl peroxide, isobutyl peroxide, decanoyl peroxide, benzoyl peroxide, and succinic acid peroxide; diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxide Peroxydicarbonates such as dicarbonate and diallylperoxydicarbonate; peroxyesters such as tert-butyl peroxyisobutyrate, tert-butyl neodecanate, cumenepa-oxyneodecanate; acetylcyclohexylsulfonyl peroxide, etc. A peroxide sulfonate etc. can be mentioned, A benzoyl peroxide can be used conveniently. Moreover, you may use the polymerization initiator system which combined the barbituric acid or its derivative (s) with the radical generator (b) and the reducing agent (c).

  The component composition ratio of the composition I and the composition II described above is not particularly limited as long as the characteristics of the present invention are exhibited, but the storage stability of the composition I is improved and the discoloration is suppressed. In order to improve the mechanical properties, abrasion resistance, and the like of the cured product formed, the composition I composition is a total of 100 parts by weight of the composition I composition (polymerizable monomer (a) + (A) is 90 to 99.5 parts by weight, preferably 95 to 98 parts by weight, more preferably 96 to 98 parts by weight with respect to the reducing agent (c) + polymerization inhibitor (h) + ultraviolet absorber (i)). Part. (C) is 0.5 to 10 parts by weight, preferably 0.5 to 5 parts by weight, and more preferably 0.5 to 3 parts by weight. (H) is 0 to 0.5 parts by weight, preferably 0.005 to 0.3 parts by weight, and more preferably 0.01 to 0.1 parts by weight. And (i) is 0-5 weight part, Preferably it is 0.05-2.5 weight part, More preferably, it is 0.5-2 weight part. In composition I, there is no problem if storage stability and discoloration are clinically acceptable even if (h) and (i) are not added, but it is added because storage stability and discoloration are suppressed by addition. Is preferable.

  The composition II composition is 20 to 75 parts by weight, preferably 25 to 70 parts by weight, more preferably 100 parts by weight of the (meth) acrylate polymer particles (d) with respect to 100 parts by weight of the total composition II composition. 30-60 parts by weight, 20-75 parts by weight of (meth) acrylic acid ester polymer particles (e), preferably 25-70 parts by weight, more preferably 30-60 parts by weight, inorganic oxide particles (f) and / or Alternatively, the polymer and inorganic oxide composite particles (g) are 0 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 3 to 10 parts by weight, and the radical generator (b) is 0.05 to 10 parts by weight. Parts, preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight. When the composite oxide particles (g) and / or the polymer and inorganic oxide particles (g) are contained together, (f) is based on 100 parts by weight of the total of (f) and (g). The range is 1 to 95 parts by weight, preferably 20 to 80 parts by weight, and more preferably 30 to 70 parts by weight. When the composition ratio is outside the range of the composition ratio of the composition I and the composition II, the buildability is impaired, and the mechanical properties of the cured body may not be exhibited.

Here, the ratio between the composition II and the composition I by the brushing method may be adjusted by appropriately adjusting the amount of the composition I soaked into the brush and used in a composition that can be easily put into a brush. Generally 0.1 to 0.5 g is used. The ratio of the composition II and the composition I obtained by the mixing method may be appropriately adjusted so that the viscosity becomes a preferable value for preparing the temporary prosthesis. Generally, the ratio of the composition II to the composition I is 1: 1 to 2. : 1 weight ratio.
Moreover, you may add an organic pigment, an inorganic pigment, an aggregate, etc. to the composition II.
The content of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Production Example 1 (Manufacture of silica / zirconia filler and surface treatment: manufacture of ZMF )
A silica / zirconia filler was produced as an inorganic oxide powder by the following method. 1.50 L of isopropanol (IPA), 441 g (2.12 mol) of tetraethoxysilane (TES), 15 g of 1.3 wt% hydrochloric acid aqueous solution (H ₂ O / TES molar ratio = 0.39, HCl / TES molar ratio = 0) Then, the mixture was homogenized and allowed to stand at room temperature for 2 hours (preparation of A1 solution). A solution obtained by adding 120 g (0.31 mol) of tetrabutoxyzirconium (TBZR) to IPA 0.38 L at room temperature was added to the previously prepared A1 solution for homogenization (preparation of B1 solution). To a separable flask, 3.75 L of IPA and 1.5 L of 25% aqueous ammonia were added and stirred at room temperature to obtain a uniform solution (C1 solution). Then, 7.5 g (0.04 mol) of TES was dissolved in 0.09 L of IPA. The solution (D1 solution) was placed in the dropping funnel and dropped in 5 minutes, and then the B1 solution was put in the dropping funnel and dropped over 5 hours. After completion of the dropwise addition, stirring was further continued at room temperature for 16 hours, and then stirring was stopped. The solution was filtered under reduced pressure to collect a white reaction precipitate. The white precipitate was dried under reduced pressure at 80 ° C. under a nitrogen atmosphere to remove the solvent to obtain 191 g of a dried product. This dried product was put into a 2 L alumina pot containing 10 φ40 mm alumina balls and pulverized for 10 hours, followed by firing at 350 ° C. for 3 hours and 650 ° C. for 3 hours to obtain 152 g of a white silica / zirconia filler. 152 g of this filler was suspended in 0.30 L of ethanol, 7.2 g of γ-methacryloxypropyltrimethoxysilane and 1.4 g of purified water were added and refluxed for 2 hours. After removing the solvent with an evaporator, it was treated at 80 ° C. for 2 hours under a nitrogen atmosphere to surface-treat the filler. When the median diameter and particle size distribution of the surface-treated filler were measured, the median diameter was 11.0 μm and the particle size distribution was 1 to 100 μm. Hereinafter, this filler is referred to as ZMF.

Production Example 2 ( Production of composite powder of inorganic oxide powder and polymer: TU )
Trimethylolpropane trimethacrylate / di (methacryloxyethyl) trimethylhexanediurethane = 70/30 (wt%) 50 g of R972 (Nippon Aerosil Co., Ltd.) 50 g is used by Test Mixing Roll (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) Then, it was kneaded mechanically and made into a paste. 0.3 g of benzoyl peroxide was further added to this paste, and then placed in a mold having a hole of 170 mm × 170 mm × 5 mm, and 20 MPa was applied with a compression molding machine (YSR-10: manufactured by Shindo Metal Industry Co., Ltd.). Polymerization was performed at 120 ° C. for 10 minutes under pressure. The polymer was crushed to about 1 cm square with a hammer and then placed in a 1 L magnetic pot (30 Φ25 mm magnetic balls, 30 Φ15 mm magnetic pots) and pulverized for 20 hours. The powder that passed through a 100-mesh sieve was heat-treated under reduced pressure at 140 ° C. for 8 hours under a nitrogen stream to obtain a composite powder (hereinafter referred to as TU) of inorganic oxide powder and polymer. The median diameter of TU was 23.0 μm, and the particle size distribution was 1 to 100 μm.
Test conditions are shown below.

Strokeability (1) Dripping: About 0.5 g of powdered mud ball (X) collected by the brushing method is placed on a Teflon (registered trademark) flat plate, and about 0.5 g of powder collected again after 10 seconds. A drool ball (Y) was placed on X, and the degree of sag was examined from the change in the ball shape of X and Y after standing for 5 seconds.
○: X and Y shapes are maintained as they are.
X: The shape of X and Y has collapsed into a mountain shape.
(2) Elongation: Place about 0.5g of powdered mud ball (X) collected by brushing on a Teflon (registered trademark) flat plate, and stretch X using a brush with nothing attached. It was.
○: X stretched with a brush is not cut and can be extended smoothly.
X: Cutting is recognized in X extended with a brush, and it cannot be smoothly extended.

Bubble .phi.4 mm, place the glass lined with cellophane on one side hole of Teflon mold opened thick 2 mm, sandwiched glass with a clip and Teflon.
Powdered mud was placed in the mold holes by the brushing method, glass with cellophane was placed, and the glass was sandwiched between clips. I tried to see through the transmitted light and checked the state of bubbles.
Low: 5 bubbles or less High: 6 or more bubbles

Bending characteristics Put cellophane on a glass plate, place a Teflon (registered trademark) mold with a 2x30x2mm hole, and pour the mud adjusted to the mixing method at a 2: 1 powder to liquid weight ratio into the hole. A glass plate on which cellophane was laid was placed and the glass plates were sandwiched with clips. After polymerization for 5 minutes in a pressure polymerization vessel (NO-1: Matsukaze Co., Ltd.), the sample was taken out of the mold and immersed in 37 ° C. water for 24 hours. The bending test was performed by a three-point bending strength test method at room temperature with a distance between fulcrums of 20 mm and a crosshead speed of 1.0 mm / min using (Shimadzu Corporation Autograph AGS-2000G).

Glass with cellophane was placed on one side of a Teflon (registered trademark) mold with a hole of yellow change φ4 mm and thickness 2 mm at the time of polymerization curing , and Teflon (registered trademark) and the glass were sandwiched between clips. Powdered mud was placed in the mold holes by the brushing method, glass with cellophane was placed, and the glass was sandwiched between clips. After polymerizing for 5 minutes with a pressure polymerization device (NO-1: Matsukaze Co., Ltd.), the sample was taken out of the mold, placed on a white plate, and visually checked for yellowing.
○: No yellowing △: Pale yellow change ×: Yellow change or brownish

The discoloration composition I of the composition I was sampled in a transparent glass bottle and was observed over the transmitted light.
○: Composition I is colorless and transparent liquid ×: Composition I is a raw material using a colored transparent liquid.

Composition I
MMA: methyl methacrylate 1,6Hx: 1,6-hexyl dimethacrylate DMPT: N, N-dimethyl-p-toluidine BHT: 2,6-di-tert-butyl-p-cresol MEHQ: p-methoxyphenol BZ: 2 , 4-Dihydroxybenzophenone CN: 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole

Composition II
Y: Copolymer powder of methyl methacrylate and ethyl methacrylate (component d)
Particle size distribution: 22 to 313 μm, median diameter: 83.8 μm, average particle size: 84.3 μm, mode diameter: 84.6 μm; number average molecular weight: 141,000, weight average molecular weight: 951,000, molecular weight distribution: 6. 75, peak top molecular weight: 990,000
Z: Copolymer powder of methyl methacrylate and ethyl methacrylate (component e)
Particle size distribution: 28-382 μm, median diameter: 85.1 μm, average particle size: 85.4 μm, mode diameter: 84.6 μm; number average molecular weight: 42,4000, weight average molecular weight: 1,490,000, molecular weight distribution: 3.52, peak top molecular weight: 1,440,000
ZMF: silica-zirconia filler, powder characteristics are described in Production Example 1. TU: composite powder of inorganic oxide powder and polymer, powder characteristics are described in Production Example 2. BPO: benzoyl peroxide Examples 1 to 9
Composition 1 and Composition II were adjusted and combined as shown in Table 1, and operability, discoloration, and mechanical properties were examined.

Comparative Examples 1-4
Composition I and Composition II were adjusted and combined as shown in Table 2, and operability, discoloration, and mechanical properties were examined.

Examples 10-12 and Comparative Examples 5-8
As shown in Table 3, the discoloration was examined by combining Composition I and Composition II.

Claims (9)

A dental polymerizable composition comprising two compositions I and II,
Composition I contains a reducing agent (c) capable of decomposing polymerizable monomer (a) and radical generator (b),
A component (d) in which composition II has a particle size distribution of 10 to 400 μm, a median diameter in the range of 70 to 120 μm and a number average molecular weight (Mn) in the range of 50,000 to 250,000;
(Meth) acrylic acid ester system having as a main component a component (e) having a particle size distribution of 10 to 400 μm, a median diameter in the range of 70 to 120 μm and a number average molecular weight (Mn) in the range of 300,000 to 700,000 Polymer particles (de) and a radical generator (b),
And the dental polymerizable composition characterized by being able to harden when the composition I and the composition II are mixed.   The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the component (d) and the component (e) is 4.4 to 12 and 2.2 to 4.4, respectively. The dental polymerizable composition as described.   The dental polymerizable composition according to claim 1 or 2, wherein the composition II further contains inorganic oxide particles (f) and / or composite particles (g) composed of a polymer and an inorganic oxide.   The dental polymerizable composition according to any one of claims 1 to 3, further comprising a polymer (j) derived from a trifunctional or higher polyfunctional polymerizable monomer.   The dental polymerizable composition according to claim 3 or 4, wherein the inorganic oxide particles (f) and the composite particles (g) have a particle size distribution of 1 to 100 µm and a median diameter of 1 to 40 µm.   The dental polymerizable composition according to any one of claims 1 to 5, wherein the radical generator (b) has a decomposition half-life at 80 ° C of 10 hours or less.   The dental polymerizable composition according to any one of claims 1 to 6, wherein the composition I further contains a hindered phenolic compound (h) polymerization inhibitor.   The dental polymerizable composition according to any one of claims 1 to 7, wherein the composition I further contains a benzophenone-based ultraviolet absorber (i).   Composition I is 90-99.5 parts by weight of component (a) with respect to 100 parts by weight of component (a), component (b), component (h) and component (i), and component (c) Is 0.5 to 10 parts by weight, component (h) is 0 to 0.5 parts by weight, component (i) is 0 to 5 parts by weight, and composition II is component (d), ( The component (d) is 20 to 75 parts by weight and the component (e) is 20 to 75 parts by weight with respect to a total of 100 parts by weight of the component e), component (f) and / or component (g), and component (b). The component (f) and / or the component (g) is 1 to 20 parts by weight, and the component (b) is 0.05 to 10 parts by weight. Polymerizable composition.