AU2002301366B2 - Paste-like polymerizable composition - Google Patents
Paste-like polymerizable composition Download PDFInfo
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- AU2002301366B2 AU2002301366B2 AU2002301366A AU2002301366A AU2002301366B2 AU 2002301366 B2 AU2002301366 B2 AU 2002301366B2 AU 2002301366 A AU2002301366 A AU 2002301366A AU 2002301366 A AU2002301366 A AU 2002301366A AU 2002301366 B2 AU2002301366 B2 AU 2002301366B2
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AUSTRALIA
Patents Act COMPLETE SPECIFICATION
(ORIGINAL)
Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority Related Art: Name of Applicant: GC Corporation Actual Inventor(s): Mizuki Nakayama, Tomohiro Kumagai Address for Service and Correspondence: PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Invention Title: PASTE-LIKE POLYMERIZABLE COMPOSITION Our Ref: 679437 POF Code: 170550/202222 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): PASTE-LIKE POLYMERIZABLE COMPOSITION BACKGROUND OF THE INVENTION 1. Field of the Invention: The present invention relates to a paste-like polymerizable composition in which two or three pastes are intimately mixed with each other to polymerize, the pastes do not gel and their polymerization curing times being stable, even when the pastes before the polymerization are preserved for a long period of time. The paste-like polymerizable composition of the present invention can be used for various industrial adhesives and molding resins, and one of its suitable applications is a dental application, especially for dental adhesives. More specifically, the present invention relates to a paste-like polymerizable composition containing a ternary catalyst comprised of a pyrimidinetrione derivative, an organic halide, and an organometallic compound.
2. Description of the Conventional Art: As means for polymerizing a paste-like composition containing a radical polymerizable monomer at an ambient temperature, there has been old employed means for using a combination of an organic YAM.N"KI NO DEL\202301366_15107.dc peroxide and an aromatic tertiary amine as a chemical polymerization catalyst. In this means, by not only adjusting the amounts of the organic peroxide and the aromatic tertiary amine to be compounded in the paste-like composition but also using a polymerization inhibitor in combination, the polymerization curing time is regulated, and the storage stability of the paste-like composition before the polymerization is enhanced. However, since the organic peroxide is an unstable substance having a half-life, when a large amount of the organic peroxide is compounded in the paste-like composition in order to accelerate the polymerization curing time, the paste-like composition per se is liable to form a gel before the polymerization in the case of preservation over a long period of time. Conversely, when a large amount of the polymerization inhibitor is compounded in the paste-like composition in order to ensure the storage stability over a long period of time, there is involved a problem that the polymerization curing time becomes extremely long.
Accordingly, a measure for preserving the paste-like composition under refrigeration to delay the half-life of the organic peroxide had to be taken.
In addition, polymerization means using oxidation of a trialkylborane is known. But, since the trialkylborane is very easily oxidized, it is impossible to compound it into a radical polymerizable monomer-containing paste-like composition. Accordingly, the trialkylborane must be preserved in a container separately from the monomer and added to the paste-like composition during the use, resulting in that the preservation is laborious and the operation is complicated.
SUMMARY OF THE INVENTION The present invention is aimed to overcome the abovedescribed problems of the conventional art and to provide a paste-like polymerizable composition in which two or three pastes are intimately mixed with each other to polymerize, the pastes do not gel and their polymerization curing times being stable, even when the pastes before the polymerization are preserved for a long period of time.
In order to achieve the above-described aim, I, the present inventor made extensive and intensive investigations. As a result, it has been found that, when, as polymerization means of a polymerizable composition comprised of a (meth)acrylate having at least one unsaturated double bond and a filler Y:a\yNWKI NO DELETE\2002301366_I0107.doc as major components, a ternary catalyst comprising (c) a pyrimidinetrione derivative, an organic halide, and an organometallic compound is used,, the ternary catalyst does not have a half-life, and hence, even in the case of preservation over a long period of time, the polymerization curing time is stable, leading to accomplishment of the present invention.
Specifically, the invention is concerned with a paste-like polymerizable composition comprising a first paste comprising a (meth)acrylate having at least one unsaturated double bond, a filler and a pyrimidinetrione derivative; and a second paste comprising a (meth)acrylate having at least one unsaturated double bond, a filler, an organic halide and an organometallic compound, or a third paste comprising a (meth)acrylate having at least one unsaturated double bond, a filler and an organic halide and a fourth paste comprising a (meth)acrylate having at least one unsaturated double bond, a filler and an organometallic compound.
When the filler as the component is one or two or more members selected from anhydrated silica, hydrated silica, hydrated calcium silicate, and hydrated aluminum silicate, even in the case of preservation over a long period of time, the paste-like polymerizable composition 'before the polymerization does not gel, and hence, such is preferred.
DETAILED DESCRIPTION OF THE INVENTION in the paste-like polymerizable composition according to the present invention, examples of the (moth) acrylate having at least one unsaturated double bond as the component that is used for the respective pastes include methyl (zeth)acrylate, ethyl (meth)acxylate, isopropyl (meth)acrylatB, n-butyl (methacrylate, isobutyl (reth)acry3.ate, hydroxyproPY). (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidy- (meth) ecrylate, 2-hydroxyathyl (ineth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-methoxysthyl (meth)acrylate,. 2-ethoxyethyl (meth)acrylate, 2-methoxyethy. (meth)acrylate, 2-ethyihexyl (meth)acrylate, benzyl (ueth)acrylate, 2-bydroxy-I, 3-di (meth) acryloxypropane, ethylene glycol di(zneth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol diL(meth)acrylate, 1,3-butanediol dii(mevth.) aerylate, 1, 4-butanedio). di (math) acryl'ate, 1, 6-hexanediol di (meth) acrylate-, trimethyJlolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolmethane tri (meth)acrylate, pentaerythritol tetra (meth) acrylate, polybutylene glycol di(meth)acrylate, and bisphenol A diglycidyl (meth)acrylate. Further, examples of (meth)acrylates having a urethane bond include di-2- (meth) acryloxyethyl-2, 2, 4-trimethyihexa--methylene dicarbamate and l,3,5-tris[1,3-bis{ (meth)-acryloyloxy)-2propoxycarbonylaminohexane]-l,3,5-(lH,3H,5H) triazin-2,4, 6trione. Besides, there are exemplified a (meth)acrylate of a urethane oligomer comprising 2,2'-di(4hydroxycyclohexyl) propane, 2-oxypanone, hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate and a (meth)acrylate of a urethane oligomer comprising 1,3butanediol, hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate. These (meth)acrylates may be used alone or in admixture of two or more thereof. Of these, are particularly preferred tetrahydrofurfuryl (meth) arylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxy-l,3-di (meth)acrylate, because they well V AMuyW~KI NO DELLITE2O23OI366J50107do.
dissolve the pyrimidinetrione derivative and the organic halide therein.
In the paste-like polymerizable composition according to the present invention, examples of the filler as the component that is used for the respective pastes are powders of anhydrated silica, glasses such as barium glass, alumina glass, potassium glass, and fluoroaluminosilicate glass, synthetic zeolite, calcium phosphate, feldspar, fumed silica, aluminum silicate, calcium silicate, magnesium carbonate, hydrated silica, hydrated calcium silicate, hydrated aluminum silicate, and quartz. These fillers may be subjected to a surface treatment with, e.g., y-methacryloxypropyl trimethoxysilane, vinyl trichlorosilane, vinyl triethoxysilane, vinyl trimethoxysilane, vinyl triacetoxysilane, vinyl tri(methoxyethoxy)silane. Further, are employable organic-inorganic composite fillers prepared by mixing the foregoing filler with a polymerizable monomer or oligomer, curing the mixture and then pulverizing the cured mixture. These fillers may be used alone or in admixture of two or more thereof. Of these, are preferred anhydrated slica, hydrated silica, hydrated calcium silicate, and hydrated aluminum silicate, because, even in the case of preservation over a long period of time, they have an effect for preventing the paste-like polymerizab-Q composition before polymerization from gelling.
Incidentally, as a matter of course, with respect to the components and to be used in the present invention, different substances may be used for the respective pastes.
In the paste-like polymerizable composition according to the present invention, examples of the pyrimidinetriole derivative as the component that is used for the first paste comprising a (meth) acrylate having at least one unsaturated double bond, a filler and a pyrimidinetrione derivative include pyrimidinetrioie, pyrimidinetrione, l,3-dimethyl-5- cyclopentylpyrimidinetrione, 1,3- pyrlimldinetrioie, 1,3- dimethyl-S-ethylpyrimidinetriole, 1,3-dimethyl-5- isobutylpyrimidinetriole, 1, 3-dimethyl-5- phenylpyrimIdInetriole, 1, pyrimidinetriole, 1, pyrimidinetrione, 5-iasobutyl-pyrimidinetriofl6, pyrimidinetrione, 5-phenylpyrimidinetrione, and 1,3,5- C- trimethyl-pyrimidinetrione. These pyrimidinetrione Sderivatives may be used alone or in admixture of two or more thereof. A suitable amount of the pyrimidinetrione derivative as the component is 0.05 to 5 parts by
IO
IO
Sweight based on 100 parts by weight of the total sum of the (meth)acrylate having at least one unsaturated double bond Sas the component and the filler as the component in
(N
the first paste.
In the paste-like polymerizable composition according to the present invention, examples of the organic halide as the component that is used for other paste(s) than the first paste comprising a (meth)acrylate having at least one unsaturated double bond, a filler and a pyrimidinetrione derivative include benzyltributylammonium chloride, benzyldimethylcetylammonium chloride, benzyldimethylsteaxylammonium chloride, benzyltriethyl-ammonium bromide, benzyltrimethylammonium chloride, cetalkonium chloride, cetylpyridinium bromide, cetylpyridinium chloride, cetyltriethylammonium bromide, didecyldimethylammonium chloride, dilauryldimethylammonium chloride, domiphen bromide, lauryldimethylammonium chloride, Y AMqNKI NO DELETE\2002301366_10107doc tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium iodide, tetradecyltrimethylammonium bromide, tetraethylammonium bromide, tetraethylammonium iodide, and trioctylmethylammonium chloride. These organic halides may be used alone or in admixture of two or more thereof. A suitable amount of the organic halide as the component is 0.05 to 5 parts by weight based on 100 parts by weight of the total sum of the (meth)acrylate having at least one unsaturated double bond as the component and the filler as the component in the paste other than the first paste.
In the paste-like polymerizable composition according to the present invention, examples of the organometallic compound as the component that is used for other paste(s) than the first paste comprising a (meth)acrylate having at least one unsaturated double bond, a filler and a pyrimidinetrione derivative include acetylacetone copper, copper 4-cyclohexylbutyrate, cupric acetate, copper oleate, acetylacetone manganese, manganese naphthenate, manganese octylate, acetylacetone cobalt, cobalt naphthenate, acetylacetone lithium, lithium acetate, acetylacetone zinc, zinc naphthenate, acetylacetone nickel, nickel acetate, acetylacetone aluminum, acetylacetone calcium, acetylacetone chromium, acetylacetone iron, sodium naphthenate, and rare earth octoate. These organometallic compounds may be used alone or in admixture of two or more thereof.
A suitable amount of the organometallic compound as the component is 0.0001 to 0.1 parts by weight based on 100 parts by weight of the total sum of the (meth)acrylate having at least one unsaturated double bond as the component and the filler as the component in the paste other than the first paste.
In the paste-like polymerizable composition according to the present invention, with respect to the organic halide as the component and the organometallic compound as the component to be used for other paste(s) than the first paste comprising a (meth)acrylate having at least one unsaturated double bond, a filler and a pyrimidinetrione derivative, there are the case where they are compounded in one paste as in the second paste comprising a (meth)acrylate having at least one unsaturated double bond, a filler, an organic halide and an organometallic compound; and the case where they are separately compounded in two pastes as in the third paste comprising a (meth)acrylate having at least one unsaturated double bond, a filler and an organic halide and the fourth paste comprising a (meth)acrylate having at least one unsaturated double bond, a filler and an organometallic compound.
This is because, when the organic halide as the component or the organometallic compound as the component is simultaneously compounded in the first paste having the pyrimidinetrione derivative as the component compounded therein, radicals are generated at an ambient temperature in the first paste, whereby the polymerization is initiated.
It is possible to further compound a photopolymerization type polymerization initiator in the paste-like polymerizable composition according to the present invention and irradiate the mixture with light such as ultraviolet light and visible lights, thereby initiating the polymerization. During this operation, as a light source, are employable various mercury vapor lamps of super high pressure, high pressure, medium pressure and low pressure, a chemical lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a xenon lamp, and an argon ion laser. A suitable compounding amount of the photopolymerization type polymerization initiator is 0.01 to 5 parts by weight based on 100 parts by weight of the total sum of the (meth)acrylate having at least one unsaturated double bond as the component and the filler as the component To the paste-like polymerizable composition according to the present invention, can be added various components other than those as described above, such as organic solvents, polymerization inhibitors, antioxidants, ultraviolet light absorbers, and pigments, it desired in practical use.
The present invention will be described below in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.
Preparation of Paste-Like Composition: According to the formulations as shown in Table 1 below, the respective components of Examples 1 to 3 and Comparative Example 1 were compounded, and predetermined amounts of the components were intimately mixed to prepare paste-like polymerizable compositions comprising two or three pastes. Incidentally, in Example 3, the second paste was additionally compounded with camphor quinone as a sensitizer of the photopolymerization type polymerization initiator and ethyl 4-dimethylaminobenzoate as a reducing agent; and in Y:NMUYyNKNO OELETE2002301366 I0107do.
Comparative Example 1, the first paste was compounded with wet benzoyl peroxide as an organic peroxide, and the second paste was compounded with N,N-dimethyl-p-toluidine as an aromatic tertiary amine, respectively.
2002301366 17 Jan 2007 Table 1 (Formulation of paste-like polymerizable composition) (Meth)acrylate Filler Pyrimidinetrione Organic halide Organometailic Others by weight] by weight] derivative [parts by weight based compound [parts by weight based [parts by weight based on 100 parts by weight [parts by weight based on 100 parts by weight on 100 parts by weight of on 100 parts by weight of of Example 1 First UDMA 24.4 2 66.7 1-Cyclohexyl-5- 0.9 Bylrotlu0.04 paste silane-trealed ethyl- ene Mixing ratio =aluminosilicat pyrimidinetrione 1:1 e glass powder 2-Hydroxy-1,3- 5.3 Fine di- anhydrated methacryloxy- silica powder propane Triethylene 1.6 glycol dimethacrylate _____Total 31.3 Total 68.7 Second UDMA 29.4 2 64.2 Benzyltriethyl 0.16 Acetyla- 0.0013 Butylhyroxytolu 0+04 paste silane-trealed ammonium cetone ene aluminosilicat chrolide copper e glass powder 2-Hydroxy 3.4 Fine methacrylate anhydrated silica powder Triethylene 1.0 Fine hydrated glycol silica powder dimethacrylate Toal 33.8 Total 66.2 2002301366 17 Jan 2007 Table 1 (Cont'd.) (Formulation of paste-like polymerizable composition) (Meth)acrylate Filler Pyrimidinetrione Organic halide Organometallic Others by weight] by weight] derivative [parts by weight based compound [parts by weight based [parts by weight based on 100 parts by weight [parts by weight based on 100 parts by weight on 100 parts by weight of on 100 parts by weight of (b)J of of Example First UDMA 24.4 2 66.7 5-n-Butylpyrlmid 0.8 Butylhyroxytolu 0.04 2 paste silane-treated inetrione ene aluminosillcate Mixing glass powder ratio 2-Hydroxy-1 5.3 Fine anhydrated 1::1di- silica powder methacryloxypropane Tetrahydrofurf 1.6 u ryl methacrylate Total 31.3 Total 68.7 Third UDMA 29.4 2 64.2 Dilauryldimethy 0.25 Butylhyroxytolu 0.04 paste silane-treated lammonium ene aluminosilicate chloride glass powder 2-Methoxyethyl 3.4 Fine anhydrated methacrylate silica powder Triethylene 1.0 Fine hydrated glycol silica powder di meth acry late Total 33.8 Total 66.2 Fourth Bisphenol A 29.4 2 64.2 Copper 0.0013 Bulylhyroxytolu 0.04 paste diglycidyl silane-treated 4-cyclohexyl- ene methacrylate aluminosilicate butyrate glass powder 2-Hydroxy 3.4 Fine anhydrated methacrylate silica powder Triethylene glycol dl me th Tot al1 33.8 Total 6 6.2 2002301366 17 Jan 2007 Table 1 (Cont'd.) (Formulation of paste-like polymerizable composition) (Meth)acrylate Filler Pyrimidinetrione Organic halide Organometallic Others by weight] by weight] derivative [parts by weight based compound [parts by weight based [parts by weight based on 100 parts by weight [parts by weight based on 100 parts by weight on 100 parts by weight of on 100 parts by weight of of of Example 3 First UIDMA 24.4 2 66.7 1-Benzyl-5-phen 1.2 Butylhyroxytolu 0.04 paste silane-treated yl- ene Mixing ratio aluminosilicate pyrimidinetrione 1:1 glass powder 2-Hydroxy-1,3- 5.3 Fine anhydrated di- silica powder met ha cry lox ypropane Triethylene 1.6 glycol dimethacrylate Total 31.3 Total 68.7 Second UDMA 29.4 2 64.2 Camphor 0.1 Benzylmelhylce 0.20 Acelylacetone 0.0013 Butylhyroxytolu 0.04 paste silane-treated quinone tylammonium copper ene aluminosilicate Ethyl 0.5 chloride glass powder 4-dimethylamino 2-ilydroxy 3.4 Fine anhydrated 1.0 benzoate methacrylate silica powder Triethylene 1.0 Fine hydrated glycol silica powder dimethacryla te _2 Tot al1 33.8 1Total 66.2 2002301366 17 Jan 2007 Table 1 (Cont'd.) (Formulation of paste-like polymerizable composition) (Meth)acrylate Filler Pyrimidinetrione Others by weight] by weight] Derivative [parts by weight based [parts by weight based on 100 parts by weight on 100 parts by weight of of Comparative First UDMA 24.4 2 66.7 Wet benzoyl 2.0 Butylhyroxytolu 0.04 Example 1 paste silane-treated peroxide ene aluminosilicate Mixing ratio =glass. powder 1:1 2-Hydroxy-1,3- 5.3 Fine anliydrated di- silica powder met ia cry lox ypropane Triethylene 1.6 glycol dim eth acryIa te 31.3 Total 68.7 Second UDMA 29.7 2 64.2 N,N-Dimethyl-p- 0.3 Butylhyroxytolu 0.04 paste silane-treated toluidine ene aluminosilicate glass powder 2-Hydroxy 3.4 Fine anhydrated methacrylate silica powder Triethylene glycol d imethacrylate____________ Toal1 34.1 1Total 6 5.9 (Measurement of polymerization curing time and temperature) In a thermostat chamber at a temperature of 23 "C and at a humidity of 50%, the paste-like polymerizable compositions in each of Examples 1 to 3 and Comparative Example 1 were intimately mixed with each other in a predetermined weight ratio as shown in Table 1 for seconds, and the intimate mixture was poured into a columnar mold having an inner diameter of 7 mm and a height of 0.5 mm. The intimate mixture was measured for a polymerization curing time from the start of intimate mixing to a heat generation peak and a temperature at that time by using a thermocouple.
Further,-each of the first pastes, second pastes and third paste of Examples 1 to 3 and Comparative Example 1 was preserved in a thermostat chamber at a temperature of 45 OC or 60 °C and at a humidity of and then examined whether the pastes gelled or not- Also, the polymerization curing time and temperature at that time of each of the paste-like polymerizable compositions were measured under the same conditions as described above.
The results obtained are summarized and shown in Table 2.
Table 2 (Changes in curing time and heat generation peak temperature by preservation test) Initial stage Preservation for 7 days Preservation for 14 days Preservation for 21 days oC 60 C 45 *C 60 "c 45 OC 60 "C Example 1 Time 7' 48" 7' 52' 7' 00" 7' 50' 8' 27' 7' 57' 8' 36' Temperature 28 OC 28 *C 28 "C 28 C 27 C 27 °C Example 2 Time 5' 12" 5' 08' 5' 35' 4' 58" 5' 42' 5' 18' 5' 49' Temperature 30 OC 30 C 29 *C 30 0 C 29 OC 29 OC 28 °C Example 3 Time 2' 36' 2' 49" 3' 05' 2' 39" 3' 13' 3' 01' 3' 12' Temperature 34 OC 33 PC 33 "C 34 OC 33 OC 33 "C 32 "C Comparative Time 13' 00 14' 21" Galled 1 35' Gelled 18' 55" Gelled Example 1 Temperature 38 OC 31 OC 26 0 C 25 "C
FI
V
As is clear from Table 2, in each of Examples 1 to 3 that is the paste-like polymerizable composition according to the present invention, even when each of the pastes before the polymerization was preserved over a long period of time, the paste did not gel; and when the paste was mixed and polymerized, a delay of the polymerization curing time was small as within 1 minute, and the temperature at that time was approximately constant and stable. On the other hand, in Comparative Example 1, when each of the pastes before the polymerization was preserved over a long period of time, the paste often gelled; and even though it did not gel, when the paste was mixed and polymerized, a.delay of the pqlymerization curing time was about 6 minutes, and the change 'in the temperature at that time was remarkable.
As described above in detail, in the paste-like polymerizable composition according to the present invention, even when each of the pastes before the polymerization is preserved over a long period of time, the paste does not gel, and the polymerization curing time and the temperature at that time are stable.
Accordingly, it can be said that the paste-like polymerizable composition according to the present invention is one having very superior properties- .3 While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (12)
1. A paste-like polymerizable composition comprising (A) and or and wherein: is a first paste comprising a (meth)acrylate having at least one unsaturated double bond, a filler and a pyrimidinetrione derivative, is a second paste comprising a (meth)acrylate having at least one unsaturated double bond, a filler, an organic halide and an organometallic compound, and is a third paste comprising a (meth)acrylate having at least one unsaturated double bond, a filler and an organic halide and a fourth paste comprising (a) a (meth)acrylate having at least one unsaturated double bond, a filler and an organometallic compound, wherein the first paste does not contain components or and wherein neither the second paste, nor the third paste, nor the fourth paste contains component
2. The paste-like polymerizable composition according to claim 1, wherein the filler as the component is selected from the group consisting of anhydrated silica, hydrated silica, hydrated calcium silicate, hydrated aluminum silicate, and mixtures thereof. Y:MaryNKI NO DELETEU2002301366_150107 do
3. The paste-like polymerizabie composition according to claim 1, wherein the pyrimidinetrione derivative is selected from the group consisting of pyrimidinetrione, 1, 3-dimethyl-5-cyclopentyl-pyrimidinetrione, 1, 3-dimethyl- 1, pyrimidinetrione, 1, 1, 3-dimethyl-5-phenyl-pyrimidinetrione, 1,3-dimethyl-5-n- butyl-pyrimidinetrione, 1, 5-dimethyl-pyrimidinetrione, butyl-pyrimidinetrione,
5-phenylpyrimidinetrione, and 1,3, 4. The paste-like polymerizable composition according to claim 1, wherein the organic halide is selected from the group consisting of ben zylt ribut ylammonium chloride, benzyldimethylcetylammonium chloride, benzyl- dimethylsteaxylammonium chloride, benzyltriethylammonium bromide, benzyltrimethylammonium chloride, cetalkonium chloride, cetylpyridinium bromide, cetylpyridinium chloride, cetyltriethylammonium bromide, didecyldimethyl ammionium chloride, dilauryldimethylammonium chloride, domiphen bromide, lauryldimethylammonium chloride, tetra-n-butylammonium bromide, tetra-n- butylarnmonium chloride, tetra-n-butyl-ammonium iodide, Y:V~aryNKI NO DELETE\2002301366 IS50O0dOC tetradecyltrimethylammonium bromide, tetraethylammonium Ci bromide, tetraethylammonium iodide, and C trioctylmethylammonium chloride. 5. The paste-like polymerizable composition according to IO IO Sclaim 1, wherein the organometallic compound is O selected from the group consisting of acetylacetone copper, 0 copper 4-cyclohexylbutyrate, cupric acetate, copper oleate, acetylacetone manganese, manganese naphthenate, manganese octylate, acetylacetone cobalt, cobalt naphthenate, acetylacetone lithium, lithium acetate, acetylacetone zinc, zinc naphthenate, acetylacetone nickel, nickel acetate, acetylacetone aluminum, acetylacetone calcium, acetylacetone chromium, acetylacetone iron, sodium naphthenate, and rare earth octoate.
6. The paste-like polymerizable composition according to claim 3, wherein the pyrimidinetrione derivative is present in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the total of and of the first paste.
7. The paste-like polymerizable composition according to claim 4, wherein the amount of organic halide is 0.05 to 5 parts by weight based on 100 parts by weight of the total of and in the second paste, or of the total Y:\MarAKNI NO DELETE2002301366_150107 doc of and in the third paste and the fourth paste combined.
8. The paste-like polymerizable composition according to claim 5, wherein the amount of the organometallic compound is 0.0001 to 0.1 parts by weight based on 100 parts by weight of the total of and in the second paste, or of the total of and in the third paste and the fourth paste combined.
9. The paste-like polymerizable composition according to claim 1, wherein the pyrimidinetrione derivative is pyrimidinetrione.
10. The paste-like polymerizable composition according to claim 1, wherein the organic halide is benzyltrimethylammonium chloride.
11. The paste-like polymerizable composition according to claim 1, wherein the organometallic compound is acetylacetone copper.
12. The paste-like polymerizable composition according to claim 1, wherein the first paste and the second paste are present. Y:A\MiNKI NO DELETE\2002301366_150107.doc
13. The paste-like polymerizable composition according to claim 1, wherein the first paste, the third paste and the fourth paste are present. Y:\MaWNKI NO DELETE2002301366_ 150107 do
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| US5250641A (en) * | 1991-11-13 | 1993-10-05 | Gc Dental Products Corp. | Curing of dental resin |
| US5770638A (en) * | 1995-04-05 | 1998-06-23 | Gc Corporation | Adhesive for dental resin composite materials |
| US6001896A (en) * | 1995-04-05 | 1999-12-14 | Gc Corporation | Adhesive for dental resin composite materials |
| US6265508B1 (en) * | 1997-12-11 | 2001-07-24 | Gc Corporation | Metal surface treatment agent having thiophenecarboxylic acid ester-containing and phosphoric acid ester-containing polymerizable monomer groups |
| US6221931B1 (en) * | 1998-09-02 | 2001-04-24 | Gc Corporation | Dental restorative composition |
| US6506815B2 (en) * | 2000-09-26 | 2003-01-14 | Gc Corporation | Resin composition for denture base |
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|---|---|
| AU2002301366A1 (en) | 2004-04-29 |
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