CA1223696A - Dental compositions - Google Patents
Dental compositionsInfo
- Publication number
- CA1223696A CA1223696A CA000376461A CA376461A CA1223696A CA 1223696 A CA1223696 A CA 1223696A CA 000376461 A CA000376461 A CA 000376461A CA 376461 A CA376461 A CA 376461A CA 1223696 A CA1223696 A CA 1223696A
- Authority
- CA
- Canada
- Prior art keywords
- monomer
- composition according
- thiourea
- cupric
- reducing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Veterinary Medicine (AREA)
- Engineering & Computer Science (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Epidemiology (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dental Preparations (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A polymerizable dental composition having an accelerated curing rate comprising at least one methacrylate monomer having 2 to 4 polymerizable double bonds, from about 0 to 400% based on said monomer of inorganic part-iculate filler, from about 0 to 5% based on said monomer of silane coupling agent, an effective catalyst - activating amount of accelerator comprising cupric ion and from about 0.5 to 5.0% based on said monomer of compound selected from (a) free radical liberating polymerization catalyst comprising an organic peroxy compound (b) reducing agent for said peroxy compound and (c) mixtures of (a) and (b), and wherein the concentration of (b) does not exceed about 40% of the total quantity of (a) and (b). The degree and rate of cure of said filled and unfilled polymerizable dental compositions con-taining said methacrylate monomer such as bis glycidyl methacrylate (BIS-GMA) and one or more components of a redox polymerization catalyst system are improved by including therein an effective catalyst activating (accelerating) amount of cupric ion.
A polymerizable dental composition having an accelerated curing rate comprising at least one methacrylate monomer having 2 to 4 polymerizable double bonds, from about 0 to 400% based on said monomer of inorganic part-iculate filler, from about 0 to 5% based on said monomer of silane coupling agent, an effective catalyst - activating amount of accelerator comprising cupric ion and from about 0.5 to 5.0% based on said monomer of compound selected from (a) free radical liberating polymerization catalyst comprising an organic peroxy compound (b) reducing agent for said peroxy compound and (c) mixtures of (a) and (b), and wherein the concentration of (b) does not exceed about 40% of the total quantity of (a) and (b). The degree and rate of cure of said filled and unfilled polymerizable dental compositions con-taining said methacrylate monomer such as bis glycidyl methacrylate (BIS-GMA) and one or more components of a redox polymerization catalyst system are improved by including therein an effective catalyst activating (accelerating) amount of cupric ion.
Description
36~
BACKG~OUND OF T~IE INVENTION
... .
FIELD OF THE INVENTI~N
.... _ _ _ _ ~
The invention relates in general to polymerizable dental compositions and particularly to such compositions capable of undergoing a rapid rate of cure to produce a product polymer-izate having a relatively higher quantity of insoluble component.
Polymerizable dental compositions based on the use oE methacrylate monomers, e.y. the reaction product of the bis glycidyl ether of bis phenol A and methacrylic acid (herein-after designated BIS-GMA), are commonly used as fillings, pit and fissure sealants and are advantageously adapted to a wide variety of dental restorative techniques. Such compositions typically include one or more methacrylate monomers and at least one component of a free radical liberating (redox~ polymerization system for said monomer(s). Usually, the monomer composition so formulated includes thQ peroxy type catalyst (o~idant) which is later contacted with the reducing agent (reductant) shortly prior to dental use. Upon contact of the o~idant with the ~0 re~uctant compositions, usually for convenience provided as pastes, polymerization occurs leading to the formation of a polymerizate having the physical properties necessary to the maintenance of good structural integrity within the oral cavity, e.g. high compressive strength, high degree of insolubles, etc..
The latter condition is highly desirable -to minimize leaching out of vital ingredients and consequent deterioration of the polymer~
izate.
- 1 ~
~,.
36~6 Rapid and complete curing are thus highly desirable objectives. To some extent, increase in catalyst concentration enhances curing rate; however, correlative enhancement in the degree of cure does not necessarily obtain. In fact, it is often the case that large catalyst concentrations impair the degree of cure thus producing a relatively larger percentage of soluble and leachable components in the final polymerizate. Moreover, larger amounts of peroxy catalyst increase the possibility o~
pre-polymerization of methacrylate monomer, i.e. prior to contact with reductant thereby often necessitating the use of adjuvants, often in unusually large amounts having a stabilizing or polymerization retardant effect. However, such retardant effects are inevitably manifest to some extent during monomer-oxidant-reductant contact thereby depressing the cure rate and, un-avoidably the degree of cure.
A primary object of the invention is to provide polymerizable dental compositions wherein the foregoing and related disadvantages are eliminated or at least mitigated to a substantial extent.
Another objec~ of the invention is to provide poly-merizable dental composi-tions capable of undergoing a rapid r~te of cure to produce a polymerizate having a relatively high ~uantity of insoluble component.
Yet another object of the invention is to provide such 3~
a composition having good structural stability within the environment of the human oral cavity~
Still another object of the invention is to provide such a composition whereln any requirements for using higher catalyst concentrations to achieve effective rate and degree of cure are obviated.
A further object of the invention is to provide such compositions having the aforedescribed beneficial characteristics despite the absence of filler and~or coupling components and the like.
A still further object of the invention is to provide such compositions wherein in accordance with a particularly effective embodiment, stability of monomer in the presence of peroxy catalyst is effectively improved.
Yet a still further object of the invention is to provide a process of utilizing such compositions to prepare a high quality polymerizate.
Thus an aspect of the present invention provides a polymeri2able dental composition having an accelerated curing ~0 rate comprising at least one methacrylate monomer having 2 -to A polymerizable double bonds, from about O to 400% based on said monomer of inorganic particulate filler, from about O
to 5% bas~d on said monomer of silane coupling agent, an effect-ive catalyst - activating amount of accelerator comprising cupric ion and a redox system consisting of (a) from abou-t 0.5 to 5.0% based on said monomer of a free radical liberating polymerization catalyst comprising an organic hydroperoxide compound and (b) from about 0~5 to 5.0% based on said monomer of a substituted thiourea reducing agent for said organic ~3~
hydroperoxide compound, wherein the concentration of (b) does not exceed about 40% of the total quantity of (a) and (b).
In another aspect/ the invention provides a process for forming a dental polymerizate comprlsing contacting meth-acrylate monomer having 2 to 4 polymerizable double bonds with a redox polymerization catalyst capable of initiating the polymerization of said methacrylate monomer and comprising organic, peroxy compcund and reducing agent therefor said contacting being carried out in the presence of an effective catalyst activating amount of cupric ion.
Cupric ions are most conveniently supplied in the form of copper salts with organic and inorganic acids. Part-icularly preferred materials for use herein include, without necessary limitation, cupric acetate, cupric acetyl acetonate, cupric chloride, an~ cupric sulfate. The compounds may be used singly or in admixture comprising two or more. In add-ition, cuprous ion maybe present with the ~oregoing, although the cupric compounds are Eound to be generally more effective as regards the obtention of both high degree and rate of cure.
Accordingly, it is particularly preferred herein that cupric ion Cu-~, constitute at least about 50P~ of the total copper ion used. However, and as will be hereinafter demonstrated, the use of cuprous salts alone provides significant improVement when compared to test runs omitting entirely the copper ionO
Whether this is due to the presence of cupric ions invariably present in available cuprous salts or to the cuprous ion or to the combination has not been clearly established.
b ` `--- i ~2~3~
The amount of copper ion present in the monomer composition is exceedingly small generally ranging Erom about 5 to 100 ppm preferably ~ to 50 ppm based on total monomer.
Otherwise stated, -the amount of copper ion is at least that necessary to pro~ide effective catalyst activating or acceler-ating effects. The term "total monomer" as used herein refers to the total monomer which would be present at the time polymer-ization actually occurs. Thus, in accordance with a preferred embodiment, peroxy catalyst, monomer and filler if used are included in a first paste composition referred to as the "oxidant"
paste and the reducing agent for said peroxy catalyst is included in a second "reductan~" paste preferably including -the same components as the first paste except for the peroxy catalyst.
The pastes are mixed shortly prior to dental use whereupon polymerization is initiated. The copper ion may be added to either or both of the paste compositions with its presence in the oxidant composition being most preferred. In any event, copper ion concentration in this embodiment has reference to the total monomer present in both the oxidant and reductant pastes.
On the basis of catalyst, the concentration of copper ion ranges ~rom about 0.02 to 0.4% of the peroxy compound. Generally, it is preferred to add the copper compound to the fluid monomer system (absent filler) which is intended as the oxidant paste.
The copper compound can be added to the composition by dispensing same in the normally liquid monomer(s) component.
The requisite dispersion can be achieved by adding the copper compound to the monomer as a solution in a solvent preferably a polar organic solvent of low boiling point such as ether or ~23~9~
lower alkanol, e.g. methanol. Since the solvent is merely a carrier for the copper compound it is most desirable that it be of high volability so that generally, most if not all of the solvent is removed in subsequent handling operations, e.g.
mixing, etc. The amount of solvent used is quite low, thus to provide 80 ppm ~u~+, and using only a 1~ solution in methanol, the volume of solvent would be only 12.5% of monomer volume and
BACKG~OUND OF T~IE INVENTION
... .
FIELD OF THE INVENTI~N
.... _ _ _ _ ~
The invention relates in general to polymerizable dental compositions and particularly to such compositions capable of undergoing a rapid rate of cure to produce a product polymer-izate having a relatively higher quantity of insoluble component.
Polymerizable dental compositions based on the use oE methacrylate monomers, e.y. the reaction product of the bis glycidyl ether of bis phenol A and methacrylic acid (herein-after designated BIS-GMA), are commonly used as fillings, pit and fissure sealants and are advantageously adapted to a wide variety of dental restorative techniques. Such compositions typically include one or more methacrylate monomers and at least one component of a free radical liberating (redox~ polymerization system for said monomer(s). Usually, the monomer composition so formulated includes thQ peroxy type catalyst (o~idant) which is later contacted with the reducing agent (reductant) shortly prior to dental use. Upon contact of the o~idant with the ~0 re~uctant compositions, usually for convenience provided as pastes, polymerization occurs leading to the formation of a polymerizate having the physical properties necessary to the maintenance of good structural integrity within the oral cavity, e.g. high compressive strength, high degree of insolubles, etc..
The latter condition is highly desirable -to minimize leaching out of vital ingredients and consequent deterioration of the polymer~
izate.
- 1 ~
~,.
36~6 Rapid and complete curing are thus highly desirable objectives. To some extent, increase in catalyst concentration enhances curing rate; however, correlative enhancement in the degree of cure does not necessarily obtain. In fact, it is often the case that large catalyst concentrations impair the degree of cure thus producing a relatively larger percentage of soluble and leachable components in the final polymerizate. Moreover, larger amounts of peroxy catalyst increase the possibility o~
pre-polymerization of methacrylate monomer, i.e. prior to contact with reductant thereby often necessitating the use of adjuvants, often in unusually large amounts having a stabilizing or polymerization retardant effect. However, such retardant effects are inevitably manifest to some extent during monomer-oxidant-reductant contact thereby depressing the cure rate and, un-avoidably the degree of cure.
A primary object of the invention is to provide polymerizable dental compositions wherein the foregoing and related disadvantages are eliminated or at least mitigated to a substantial extent.
Another objec~ of the invention is to provide poly-merizable dental composi-tions capable of undergoing a rapid r~te of cure to produce a polymerizate having a relatively high ~uantity of insoluble component.
Yet another object of the invention is to provide such 3~
a composition having good structural stability within the environment of the human oral cavity~
Still another object of the invention is to provide such a composition whereln any requirements for using higher catalyst concentrations to achieve effective rate and degree of cure are obviated.
A further object of the invention is to provide such compositions having the aforedescribed beneficial characteristics despite the absence of filler and~or coupling components and the like.
A still further object of the invention is to provide such compositions wherein in accordance with a particularly effective embodiment, stability of monomer in the presence of peroxy catalyst is effectively improved.
Yet a still further object of the invention is to provide a process of utilizing such compositions to prepare a high quality polymerizate.
Thus an aspect of the present invention provides a polymeri2able dental composition having an accelerated curing ~0 rate comprising at least one methacrylate monomer having 2 -to A polymerizable double bonds, from about O to 400% based on said monomer of inorganic particulate filler, from about O
to 5% bas~d on said monomer of silane coupling agent, an effect-ive catalyst - activating amount of accelerator comprising cupric ion and a redox system consisting of (a) from abou-t 0.5 to 5.0% based on said monomer of a free radical liberating polymerization catalyst comprising an organic hydroperoxide compound and (b) from about 0~5 to 5.0% based on said monomer of a substituted thiourea reducing agent for said organic ~3~
hydroperoxide compound, wherein the concentration of (b) does not exceed about 40% of the total quantity of (a) and (b).
In another aspect/ the invention provides a process for forming a dental polymerizate comprlsing contacting meth-acrylate monomer having 2 to 4 polymerizable double bonds with a redox polymerization catalyst capable of initiating the polymerization of said methacrylate monomer and comprising organic, peroxy compcund and reducing agent therefor said contacting being carried out in the presence of an effective catalyst activating amount of cupric ion.
Cupric ions are most conveniently supplied in the form of copper salts with organic and inorganic acids. Part-icularly preferred materials for use herein include, without necessary limitation, cupric acetate, cupric acetyl acetonate, cupric chloride, an~ cupric sulfate. The compounds may be used singly or in admixture comprising two or more. In add-ition, cuprous ion maybe present with the ~oregoing, although the cupric compounds are Eound to be generally more effective as regards the obtention of both high degree and rate of cure.
Accordingly, it is particularly preferred herein that cupric ion Cu-~, constitute at least about 50P~ of the total copper ion used. However, and as will be hereinafter demonstrated, the use of cuprous salts alone provides significant improVement when compared to test runs omitting entirely the copper ionO
Whether this is due to the presence of cupric ions invariably present in available cuprous salts or to the cuprous ion or to the combination has not been clearly established.
b ` `--- i ~2~3~
The amount of copper ion present in the monomer composition is exceedingly small generally ranging Erom about 5 to 100 ppm preferably ~ to 50 ppm based on total monomer.
Otherwise stated, -the amount of copper ion is at least that necessary to pro~ide effective catalyst activating or acceler-ating effects. The term "total monomer" as used herein refers to the total monomer which would be present at the time polymer-ization actually occurs. Thus, in accordance with a preferred embodiment, peroxy catalyst, monomer and filler if used are included in a first paste composition referred to as the "oxidant"
paste and the reducing agent for said peroxy catalyst is included in a second "reductan~" paste preferably including -the same components as the first paste except for the peroxy catalyst.
The pastes are mixed shortly prior to dental use whereupon polymerization is initiated. The copper ion may be added to either or both of the paste compositions with its presence in the oxidant composition being most preferred. In any event, copper ion concentration in this embodiment has reference to the total monomer present in both the oxidant and reductant pastes.
On the basis of catalyst, the concentration of copper ion ranges ~rom about 0.02 to 0.4% of the peroxy compound. Generally, it is preferred to add the copper compound to the fluid monomer system (absent filler) which is intended as the oxidant paste.
The copper compound can be added to the composition by dispensing same in the normally liquid monomer(s) component.
The requisite dispersion can be achieved by adding the copper compound to the monomer as a solution in a solvent preferably a polar organic solvent of low boiling point such as ether or ~23~9~
lower alkanol, e.g. methanol. Since the solvent is merely a carrier for the copper compound it is most desirable that it be of high volability so that generally, most if not all of the solvent is removed in subsequent handling operations, e.g.
mixing, etc. The amount of solvent used is quite low, thus to provide 80 ppm ~u~+, and using only a 1~ solution in methanol, the volume of solvent would be only 12.5% of monomer volume and
2.5% of a suitable paste on a weight basis. Alternatively, the copper compound may be sorbed onto the filler component, e.g. silica, should such material be used, for mixing with the monomer component(s).
In addition to the copper compound, the preferred compositions herein are as follows.
Parts by weight Monomer(s) 100 Inorganic particulate filler 0-400 Silane coupling agent 0.5-5.0 Peroxy catalyst 0.5-5.0 Reducing agent 0.3-2.0 The methacrylate monomer is selected from materials having at least two, and preferably two to four polymerizable double bonds per molecule in order that the cured composite be crosslinked and thus better suited for use in the oral cavity.
The most preferred monomers are those having two polymerizable double bonds per molecule. Desirable characteristics for such ~ 6 -~2~36~6 monomers include low polymerization shrinkage, low exotherm during polymerization, low water sorption and the ability to ~ure rapidly and completely in the mouth. It is also desirable that the monomers be low in volatility and non-irritating to -the tooth pulp .
Methacrylate monomers particularly useful in this invention are those represented by the following general ~ormulae:
[ (M - A - )n ~ Ar ]2 ~ B(M - A - OCO)2Ar I II
(M - A)m CR M2R' (M - A - OCO - NH)2R3 III IV V
~H2 M
CH - M' VI
wherein M is methacryloyloxy, i.e. CH~ - C(CH3)COO-;
M' is methacryloyloxy or hydroxyl; A is alkylene having 1-3 carbon atoms, such as methylene, propylene, isopropylene ~ 7 -~2236~
hydroxyalkylene having 1-3 carbon atoms, such as hydroxy-methylene, 2-hydroxypropylene or acetoxyalkylene having 3-5 carbon atoms in the alkylene group such as 2-acetoxypropylene, 3-acetoxyamylene etc.; n is 1 to 4 preferably 1 or 2; m is 2 or 3 and p is 1 or 2 with the proviso that the sum of m and p is 4;
R is hydrogen, methyl, ethyl or -A-M wherein A and M are pre-viously described; Ar is phenylene, e.g. o-phenylene, m-phenyl-ene or p-phenylene, alkyl substituted phenylene, e.g. tolylene or 5-t-butyl-m-phenylene or cycloaliphatic having 6 to 10 carbon atoms such as 1,3-cyclohexylene;
B is ~ C wherein R4 and R5 are independently hydrogen, alkyl e.g. Cl to C4, or substituted alkyl and R' is alkylene having 2 to 12 carbon atoms such as ethylene, dodecyl-ene etc~, or -R2(0-R2) oR2 wherein R2 is alkylene having 2 or
In addition to the copper compound, the preferred compositions herein are as follows.
Parts by weight Monomer(s) 100 Inorganic particulate filler 0-400 Silane coupling agent 0.5-5.0 Peroxy catalyst 0.5-5.0 Reducing agent 0.3-2.0 The methacrylate monomer is selected from materials having at least two, and preferably two to four polymerizable double bonds per molecule in order that the cured composite be crosslinked and thus better suited for use in the oral cavity.
The most preferred monomers are those having two polymerizable double bonds per molecule. Desirable characteristics for such ~ 6 -~2~36~6 monomers include low polymerization shrinkage, low exotherm during polymerization, low water sorption and the ability to ~ure rapidly and completely in the mouth. It is also desirable that the monomers be low in volatility and non-irritating to -the tooth pulp .
Methacrylate monomers particularly useful in this invention are those represented by the following general ~ormulae:
[ (M - A - )n ~ Ar ]2 ~ B(M - A - OCO)2Ar I II
(M - A)m CR M2R' (M - A - OCO - NH)2R3 III IV V
~H2 M
CH - M' VI
wherein M is methacryloyloxy, i.e. CH~ - C(CH3)COO-;
M' is methacryloyloxy or hydroxyl; A is alkylene having 1-3 carbon atoms, such as methylene, propylene, isopropylene ~ 7 -~2236~
hydroxyalkylene having 1-3 carbon atoms, such as hydroxy-methylene, 2-hydroxypropylene or acetoxyalkylene having 3-5 carbon atoms in the alkylene group such as 2-acetoxypropylene, 3-acetoxyamylene etc.; n is 1 to 4 preferably 1 or 2; m is 2 or 3 and p is 1 or 2 with the proviso that the sum of m and p is 4;
R is hydrogen, methyl, ethyl or -A-M wherein A and M are pre-viously described; Ar is phenylene, e.g. o-phenylene, m-phenyl-ene or p-phenylene, alkyl substituted phenylene, e.g. tolylene or 5-t-butyl-m-phenylene or cycloaliphatic having 6 to 10 carbon atoms such as 1,3-cyclohexylene;
B is ~ C wherein R4 and R5 are independently hydrogen, alkyl e.g. Cl to C4, or substituted alkyl and R' is alkylene having 2 to 12 carbon atoms such as ethylene, dodecyl-ene etc~, or -R2(0-R2) oR2 wherein R2 is alkylene having 2 or
3 carbon atoms such as ethylene, propylene or isopropylene and ~ is zero to 5; and R3 is phenylene, tolylene, methylene-bis-phenylene or alkylene ha~ing 2 to 12 carbon atoms.
Monomers having the above formulae are well known and generally commercially available materials. Alternately, tlley are xeadily provided by conventional synthetic routes, for example, by reacting a phenolic compound such as diphenolic acid, phloroglucinol or bisphenol A with glycidyl methacrylate in the presence of various tertiary amines or by reacting methacrylic acid with an epoxide containing compound such as the diglycidyl ether of a bisphenol. Some of these monomers also are made by reacting appropriate alcohols with methacrylic acid, methacrylyl ~chloride or methacrylic anhydride.
. - 8 -~ 2 ~ 3 ~ ~
Illus-trative monomers having these ~ormulae include:
CH2=C(CH3)C3OCH2CH2~OCO ~ COOCH2CH20COC(CH3) CH2;
CH2=C(CH3)-CO ~ H20C ~ COC(CH3) = CH2 H~ 3 ~ OH
C ~ CH20COC(CH3) = CH2]4 ;
CH3CH2C ~ CH2-O-C-ICI=CIH2)3;
CH2 = C(CH3)COO(CH2) 40COC (CH3)=CH2;
CH2 = C(CH3)COOCH2CH20CH2CH20CH2CH20COC(CH2)=CH2;
CH2=C(CH3)COOCH2CH(OH)CH2- ~ ~CH2-CH(OH)CH2OCOC(CH3)=CH
CH2= C(CH3)CO ~ (CH3)2 ~ -COC(CH3)=CH2 ;
CH2=C(C~I3)COO-CH2CH(OH)CH2- ~ ~ CH2CH(OH)CH20COC(CH3)-CH
OCH2CH(OH)OCOC(CH3)=CH2 CH2= C(CH3)COO-CH2CH2OCONH ~
~ICOOCH2CH20COC(CH3)=CH2 CH2=C(CH3 j COO-CH27H-OCONH-CH2CH2IC-HC f CH2 f 2 3 , ~23~6 Monomers having the formulae I, II, III and IV are preferred in the practice of this invention. Of these monomers, I, II and III are particularly preferred, monomers IV being employed more often in admixture with one or more of monomers I, II and III.
Other useful methacrylate monomers suitable for use in the practice of this invention include those having the fol-lowing formulae wherein ~ and Ar are as previously described;
(MR OAr)2C(CH3)2 wherein R4 is isopropylene;
(MR50Ar)2 and (MR50)2 Ar wherein R5 is 2-hydroxy-propylene; MA R6M wherein R6 is hydroxycyclopentyl or hydroxycyclohexyl, and A is 2-hydroxyethylene; and M2R8 wherein R is:
(A) ~ F ~
(B) -CH2 ~ CH2-(C) -CH2 ~ ~ H2_ or (D) -~H2 ~ CH2--' 10 -~2~3~
Preparative details for many of those monomers are given in U.S. Patent Nos. 3,066,112; 3,721~64~; 3,730,947; 3,770,881 and 3,774,305. A tertiary eutectic monomer mixture also suitable for use in this invention is described in U.S. Patent No. 3,539,526.
It is to be understood that mixture of two or more appropriate methacrylate monomers are within the scope of this invention. In fact, depen~ing on the choice of monomers, mixture are often highly desirable to optimize the characteristics of the resulting dental composition. Thus~ it is preferred that the monomer or monomer blend have a viscosity of from about 100 to about 10,000 centipoises as determined using a Brookfield vis-cometer at 20 rpm, at room temperature.
The inorganic particulate filler employed in the compositions of this invention include fused silica, quartz, crystalline silica, amorphous silica, soda glass beads, glass rods, ceramic oxides, particulate silicate glass, radiopaque glasses (barium and strantium glasses), and synthetic minerals such as beta-eucryptic (LiAlSiO4), the latter having a negative coefficient of thermal expansion. It is also feasible to employ ~0 ~inely divided materials and powdered hydroxylapatite~ although materials that react with silane coupling agents are preferred.
Also available as a filler are colloidal or submicron silicas coated with a polymer~ Small amounts of pigments to allow matching of the composition to various shades of teeth can be included. Suitable pigments include iron oxide black, cadmium yellows and oranges, fluorescent zinc oxides, titanium dioxide, etc.. The filler particles would be generally smaller than about 50 microns in diameter and preferably smaller than 30 microns.
~36~
It will ~e noted that the ~iller is an optional ingredient, unfilled formulations being employed where the dental composition is intended for use as a coating, margin sealant for amalgam restorations or adhesive.
The silane coupling agents or keying agents are materials that contain at least one polymerizable dou~le bond to react with the methacrylate monomers. Examples of suitable coupling agents are vinyl trichlorosilane, tris(acetoxy) vinyl silane, l-N(vinylben~ylaminoethyl) aminopropyl trimethoxysilane-3, or 3-methacryloxypropyl trim-ethoxy silane. The last named material is preferred for use with methacrylate monomers because of the similarity in reactivity of the double bonds.
Peroxy catalysts useful herein and capable of initiating polymerization of the methacrylate monomer(s) are well known in the art for such use and include, without limita-tion, conventional peroxy as well as hydroperoxy compounds such as cumene hydropero~ide, p-methane hydroperoxide, diisopropyl benzene hydroperoxide and t-butyl hydroperoxides. Hydroperoxides ~n are the preferred species of organic peroxy polymerization catalyst with cumene hydroperoxide (CHP) heing particularly preferred. If desired, peroxide stabilizers such as ascorbic acid, maleic acid and the like may be included in small amounts.
Reducing agents useful herein generally are substi-tuted thioureas capable of reacting with the peroxy compound to form polymerization initiating, free radical species as is known in the art. Particularly useful herein is a substituted thiourea having the formula:
X~ N-------C----Z
3~6 wherein X is H or Y and Y is alkyl having 1 to 8 carbon atoms, such as methyl, butyl, octyl; cycloalkyl having 5 or 6 carbon atoms such as cyclopentyl, cyclohexyl; chloro, hydroxy or mercapto substituted alkyl having 1 to 8 carbon atoms such as chloroethyl, mercapto-ethyl, hydroxymethyl and chlorooctyl;
alkenyl having 3 to 4 carbon atoms, such as allyl or methallyl;
aryl having 6 to 8 carbons, such as phenyl or xylyl, and chloro-, hydroxy-, methoxy-, or sulfonyl substituted phenyl such as chlorophenyl, phenylsulfonyl, hydroxyphenyl and methoxyphenyl;
acyl having 2 to 8 carbon atoms such as acetyl, butyryl, octanoyl; chloro or methoxy substituted acyl, such as chloro-acetyl, chlorobenzoyl, chlorotoluoyl and methoxybenzoyl;
aralkyl having 7 to 8 carbon atoms, such as benzyl, or chloro or methyl substituted aralkyl such as methoxybenzyl; and ~
is NH2, NHX or NX2. ~xamples of illustrative compounds suitable for use .in the practice of this invention are methyl thiourea, isopropyl thiourea, butyl thiourea octyl thiourea, benzyl thio-urea, acetyl thiourea, benzoyl thiourea, octanoyl thiourea, cyclohexyl thiourea, allyl thiourea, 1,1,3-triphenyl thiourea, ~0 1,1,3-trimethyl thiourea, 2~4-xylyl thiourea, p-tolylsulfonyl thiourea, l-octyl-3-phenyl thiourea, o-methoxyphenyl thiourea, m-hydroxyphenyl thiourea, l,l-dia]lyl thiourea, 1,3-diallyl thiourea, 2-methallyl thiourea, o-methoxybenzyl thiourea, l-(hydroxymethyl)-3-methyl thiourea, l,l-dibutyl thiourea, 1,3-dibutyl thiourea, l-(p chloro phenyl)-3-methyl thiourea, 1 butyl-3-butyryl thiourea, 1-acetyl-3-phenyl thiourea, 1 methyl-3-(p-vinylphenyl) thiourea, 1-methyl-3-0 tolyl thiourea, l-methyl-3-pentyl thiourea, 3-methyl-1, l-diphenyl thiourea and l-acetyl 3-(2 mercaptoethyl~ thiourea. While any of the ~0 aforementioned thioureas can be employed in the practice of this - 13 ~
~3~
invention, preferred are the monosubstituted thioureas, that is, those ha~7ing the aforementioned formula wherein X is H
and Z is NH2. Particularly preferred are phenyl. thiourea, acetyl thiourea and allyl thiourea. Preferably, the composition contains about 0.5 to about 1% by weight of reducing agent.
The following examples axe given for purposes o~
illustration only and are not to be considered as limiting the invention.
10 Radiopaque reductant pastes having the followiny compositions are prepared:
Composition % by Weight Ingredient A B _ D E F G H
NUPOL 10.2710.24 10.27 10.27 10.27 10.27 10.27 10.27 2~DMA 10~2710.24 10.27 10.27 10.27 10.27 10.27 10.27 A-174 1.031.02 1.03 1.03 1.03 1.03 1.03 1.03 Acetyl Thiourea 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 Ascorbic acid -- 0.07 ~Cu ~ -.00022 .00044.. 0011 .0022 .0033 .0044 5Imsil A-10 41.86 41.86 41.86 41.86 41.86 41.86 41~86 41.86 6Corning 7724 36.14 36.14 36.14 36.14 36.14 36.14 36.14 36.14 `~`
3~
1 ~ Bis (GMA) - Trade Mark 2 _ 1.6 hexanedioldimethacrylate 3 - z methacryloxy propyl trimethoxy silane
Monomers having the above formulae are well known and generally commercially available materials. Alternately, tlley are xeadily provided by conventional synthetic routes, for example, by reacting a phenolic compound such as diphenolic acid, phloroglucinol or bisphenol A with glycidyl methacrylate in the presence of various tertiary amines or by reacting methacrylic acid with an epoxide containing compound such as the diglycidyl ether of a bisphenol. Some of these monomers also are made by reacting appropriate alcohols with methacrylic acid, methacrylyl ~chloride or methacrylic anhydride.
. - 8 -~ 2 ~ 3 ~ ~
Illus-trative monomers having these ~ormulae include:
CH2=C(CH3)C3OCH2CH2~OCO ~ COOCH2CH20COC(CH3) CH2;
CH2=C(CH3)-CO ~ H20C ~ COC(CH3) = CH2 H~ 3 ~ OH
C ~ CH20COC(CH3) = CH2]4 ;
CH3CH2C ~ CH2-O-C-ICI=CIH2)3;
CH2 = C(CH3)COO(CH2) 40COC (CH3)=CH2;
CH2 = C(CH3)COOCH2CH20CH2CH20CH2CH20COC(CH2)=CH2;
CH2=C(CH3)COOCH2CH(OH)CH2- ~ ~CH2-CH(OH)CH2OCOC(CH3)=CH
CH2= C(CH3)CO ~ (CH3)2 ~ -COC(CH3)=CH2 ;
CH2=C(C~I3)COO-CH2CH(OH)CH2- ~ ~ CH2CH(OH)CH20COC(CH3)-CH
OCH2CH(OH)OCOC(CH3)=CH2 CH2= C(CH3)COO-CH2CH2OCONH ~
~ICOOCH2CH20COC(CH3)=CH2 CH2=C(CH3 j COO-CH27H-OCONH-CH2CH2IC-HC f CH2 f 2 3 , ~23~6 Monomers having the formulae I, II, III and IV are preferred in the practice of this invention. Of these monomers, I, II and III are particularly preferred, monomers IV being employed more often in admixture with one or more of monomers I, II and III.
Other useful methacrylate monomers suitable for use in the practice of this invention include those having the fol-lowing formulae wherein ~ and Ar are as previously described;
(MR OAr)2C(CH3)2 wherein R4 is isopropylene;
(MR50Ar)2 and (MR50)2 Ar wherein R5 is 2-hydroxy-propylene; MA R6M wherein R6 is hydroxycyclopentyl or hydroxycyclohexyl, and A is 2-hydroxyethylene; and M2R8 wherein R is:
(A) ~ F ~
(B) -CH2 ~ CH2-(C) -CH2 ~ ~ H2_ or (D) -~H2 ~ CH2--' 10 -~2~3~
Preparative details for many of those monomers are given in U.S. Patent Nos. 3,066,112; 3,721~64~; 3,730,947; 3,770,881 and 3,774,305. A tertiary eutectic monomer mixture also suitable for use in this invention is described in U.S. Patent No. 3,539,526.
It is to be understood that mixture of two or more appropriate methacrylate monomers are within the scope of this invention. In fact, depen~ing on the choice of monomers, mixture are often highly desirable to optimize the characteristics of the resulting dental composition. Thus~ it is preferred that the monomer or monomer blend have a viscosity of from about 100 to about 10,000 centipoises as determined using a Brookfield vis-cometer at 20 rpm, at room temperature.
The inorganic particulate filler employed in the compositions of this invention include fused silica, quartz, crystalline silica, amorphous silica, soda glass beads, glass rods, ceramic oxides, particulate silicate glass, radiopaque glasses (barium and strantium glasses), and synthetic minerals such as beta-eucryptic (LiAlSiO4), the latter having a negative coefficient of thermal expansion. It is also feasible to employ ~0 ~inely divided materials and powdered hydroxylapatite~ although materials that react with silane coupling agents are preferred.
Also available as a filler are colloidal or submicron silicas coated with a polymer~ Small amounts of pigments to allow matching of the composition to various shades of teeth can be included. Suitable pigments include iron oxide black, cadmium yellows and oranges, fluorescent zinc oxides, titanium dioxide, etc.. The filler particles would be generally smaller than about 50 microns in diameter and preferably smaller than 30 microns.
~36~
It will ~e noted that the ~iller is an optional ingredient, unfilled formulations being employed where the dental composition is intended for use as a coating, margin sealant for amalgam restorations or adhesive.
The silane coupling agents or keying agents are materials that contain at least one polymerizable dou~le bond to react with the methacrylate monomers. Examples of suitable coupling agents are vinyl trichlorosilane, tris(acetoxy) vinyl silane, l-N(vinylben~ylaminoethyl) aminopropyl trimethoxysilane-3, or 3-methacryloxypropyl trim-ethoxy silane. The last named material is preferred for use with methacrylate monomers because of the similarity in reactivity of the double bonds.
Peroxy catalysts useful herein and capable of initiating polymerization of the methacrylate monomer(s) are well known in the art for such use and include, without limita-tion, conventional peroxy as well as hydroperoxy compounds such as cumene hydropero~ide, p-methane hydroperoxide, diisopropyl benzene hydroperoxide and t-butyl hydroperoxides. Hydroperoxides ~n are the preferred species of organic peroxy polymerization catalyst with cumene hydroperoxide (CHP) heing particularly preferred. If desired, peroxide stabilizers such as ascorbic acid, maleic acid and the like may be included in small amounts.
Reducing agents useful herein generally are substi-tuted thioureas capable of reacting with the peroxy compound to form polymerization initiating, free radical species as is known in the art. Particularly useful herein is a substituted thiourea having the formula:
X~ N-------C----Z
3~6 wherein X is H or Y and Y is alkyl having 1 to 8 carbon atoms, such as methyl, butyl, octyl; cycloalkyl having 5 or 6 carbon atoms such as cyclopentyl, cyclohexyl; chloro, hydroxy or mercapto substituted alkyl having 1 to 8 carbon atoms such as chloroethyl, mercapto-ethyl, hydroxymethyl and chlorooctyl;
alkenyl having 3 to 4 carbon atoms, such as allyl or methallyl;
aryl having 6 to 8 carbons, such as phenyl or xylyl, and chloro-, hydroxy-, methoxy-, or sulfonyl substituted phenyl such as chlorophenyl, phenylsulfonyl, hydroxyphenyl and methoxyphenyl;
acyl having 2 to 8 carbon atoms such as acetyl, butyryl, octanoyl; chloro or methoxy substituted acyl, such as chloro-acetyl, chlorobenzoyl, chlorotoluoyl and methoxybenzoyl;
aralkyl having 7 to 8 carbon atoms, such as benzyl, or chloro or methyl substituted aralkyl such as methoxybenzyl; and ~
is NH2, NHX or NX2. ~xamples of illustrative compounds suitable for use .in the practice of this invention are methyl thiourea, isopropyl thiourea, butyl thiourea octyl thiourea, benzyl thio-urea, acetyl thiourea, benzoyl thiourea, octanoyl thiourea, cyclohexyl thiourea, allyl thiourea, 1,1,3-triphenyl thiourea, ~0 1,1,3-trimethyl thiourea, 2~4-xylyl thiourea, p-tolylsulfonyl thiourea, l-octyl-3-phenyl thiourea, o-methoxyphenyl thiourea, m-hydroxyphenyl thiourea, l,l-dia]lyl thiourea, 1,3-diallyl thiourea, 2-methallyl thiourea, o-methoxybenzyl thiourea, l-(hydroxymethyl)-3-methyl thiourea, l,l-dibutyl thiourea, 1,3-dibutyl thiourea, l-(p chloro phenyl)-3-methyl thiourea, 1 butyl-3-butyryl thiourea, 1-acetyl-3-phenyl thiourea, 1 methyl-3-(p-vinylphenyl) thiourea, 1-methyl-3-0 tolyl thiourea, l-methyl-3-pentyl thiourea, 3-methyl-1, l-diphenyl thiourea and l-acetyl 3-(2 mercaptoethyl~ thiourea. While any of the ~0 aforementioned thioureas can be employed in the practice of this - 13 ~
~3~
invention, preferred are the monosubstituted thioureas, that is, those ha~7ing the aforementioned formula wherein X is H
and Z is NH2. Particularly preferred are phenyl. thiourea, acetyl thiourea and allyl thiourea. Preferably, the composition contains about 0.5 to about 1% by weight of reducing agent.
The following examples axe given for purposes o~
illustration only and are not to be considered as limiting the invention.
10 Radiopaque reductant pastes having the followiny compositions are prepared:
Composition % by Weight Ingredient A B _ D E F G H
NUPOL 10.2710.24 10.27 10.27 10.27 10.27 10.27 10.27 2~DMA 10~2710.24 10.27 10.27 10.27 10.27 10.27 10.27 A-174 1.031.02 1.03 1.03 1.03 1.03 1.03 1.03 Acetyl Thiourea 0.43 0.43 0.43 0.43 0.43 0.43 0.43 0.43 Ascorbic acid -- 0.07 ~Cu ~ -.00022 .00044.. 0011 .0022 .0033 .0044 5Imsil A-10 41.86 41.86 41.86 41.86 41.86 41.86 41~86 41.86 6Corning 7724 36.14 36.14 36.14 36.14 36.14 36.14 36.14 36.14 `~`
3~
1 ~ Bis (GMA) - Trade Mark 2 _ 1.6 hexanedioldimethacrylate 3 - z methacryloxy propyl trimethoxy silane
4 - In the form cupric acetate added from methanol solution to monomer mixture - Amorphous silica (Illinois Min.erals) - Trade Mark 6 _ Barium Glass (Corning) - Trade Mark Radiopaque oxidant pastes having the following compositions are prepared.
Composition % by weight Ingredient I. J
Nupol 9.94 9.78 ~DMA 9.94 9.78 A ~ 174 0.99 0.98 Maleic acid -- 0.41 Ascorbic acid 0.07 --Cumene hydroperoxide (80%)1.05 1.05 Imsil A-10 41.93 41.79 Corning 7724 36.06 36.22 Total 100 100 Oxidant and reductant pastes respectively are mixed in a weight ratio of 1:1 as indicated in the following examples.
~ 15 - , Curing times are given in minutes and include time required for mixing, approximately 30 seconds. The cessation of the curing reaction is determined by the material no longer being indentable by a spatula. It can also be done by measuring the percent of polymeriæate insoluble in methanol upon completion of the curing reaction. Samples of the polymer-forming mass are taken at timed inter~als during the curing ~eaction; cessation of the latter is indicated by the point at which present insolu-bles remains substiantially cons~ant. The results are summarized as follows:
Example Oxidan~ Reductant PPM Cu+~ Cure Temp No. Paste Paste in Reductant Minutes C
Paste . . .
1 J C 2.2 3.5~~.3 21 2 " D 4.4 2.8-3.2 23 3 " E11.0 1.8-2.2 23 4 " F22.0 1.7-2.2 20.5 " G33.0 1.5-1.8 21.5 6 " H44.0 1.3-1.8 23 7 " Anone 4.0-5.0 27 8 I C 2.2 3.3-3.8 21 9 " D 4.4 2.7-3.S 22.5 `' E11.0 1.8-2.2 23 11 " F22.0 1.7~2.0 20.5 12 " G33.0 1.3-1.7 21 13 " H44.0 1025-1.6 23 14 " Anone 3.3-4.0 21 ~3~
In each of the runs, curing is carried out in air, i.e. in an open vessel. Increased concentration of Cu provi~es more rapid cUreS. In comparison to Examples 7 and 14, which omit the copper accelerator, the data establish marked improvement in curing ra~e for the present inventionO
Similar combination5 (1:1) of reductant paste B
with I and J produce comparable results.
The procedure of the foregoing examples is repeated but using a Nupol: ~DMA (71:29) by weight monomer blend in each of the oxldant and reductant compositions.
Filler is omitted altogether in each of the examples.
Copper ions are provided by the ~ollowing compounds:
Example No. Accelerator cupric acetate 16 cupric chloride 17 cupric acetonyl acetonate (no solvent) $
In each case, improved rate o~ curing is achieved when compared to identical control runs omitting the copper compound.
The procedure of Examples 15-17 is repeated bu~
using the following materials as accel~rators:
Example No. Accelerator (weight ratios) . _ 18 cupric acetate/cupric chloride (50:50) 19 cupric acetate/cuprous chloride ~50:50) cupric chloride/cuprous chloride (50~50 The results are similar to those of the preceding examples.
_ Each of examples 1~14 is repeated with the exception that the cupric acetate is sorbed onto the filler and then added to the monomer composition. Similar improvement is obtained in curing rate by comparison with control runs omitting the copper compound.
36~
The following reductant-containing and oxidant-containing compositions are prepared:
REDUCTANT
Composition % by weight Ingredient K L M
__ _ _ NUPOL 9.9 9,9 9.9 HMDMA 9.9 9.9 9.9 Acetyl Thiourea 0.45 0.45 0.45 Cu++ 3O0002 0.0005 0.0010 Corning 7724a 36.25 36.25 36.25 IMSIL A-10a 42.25 42.25 42.25 Colloidal Silica 1.30 1~30 1.30 a. Silanized 3~
OXIDANT COMPOSITION - N
.
IngredientComposition ~O by weight NUPOL 9.325 HMDMA 9 . 325 CHP (80~) 1.05 Corning 7724a36.25 IMSIL A~lOa 42 o 25 Colloidal Silica 1.80 a. Silanized The Oxidant paste is mixed on a clean glass plate with each of the three reductant pastes in a 1:1 ratio.
Curing times for each of three mixes are determined by the time required for the blended material to be resistant to indentation by a plastic spatula. The results are summarized 2s follows:
PPM Cu in Reductant Cure Example No. Oxidant Paste Reductant Paste Paste Minutes .,_ _ . . ...
1 N K 2 4.2-5.0 2 N L 5 2.5~3.0 3 N M 10 2.3-2.8 a. at 23C
3Ei~
In each of the above runs, curing is carried out in air. (Shorter curing times would result under glass or in a cavity covered ~y a matrix strip.) It is evident that increas-ing the concentration of Cu++ results in a shorter cure time.
Similar results are obtained when the foregoing examples are repeated but utilizing, within the ranges hereinbefore specified the following peroxy catalysts and reductant compounds: peroxy catalysts - p-methane hydroperoxide, diisopropylbenzene hydroperoxide and t-butyl hydroperoxide;
reductants-allyl thiourea, phenyl thiourea, and 3-allyl-1, l-diethylthiourea.
Composition % by weight Ingredient I. J
Nupol 9.94 9.78 ~DMA 9.94 9.78 A ~ 174 0.99 0.98 Maleic acid -- 0.41 Ascorbic acid 0.07 --Cumene hydroperoxide (80%)1.05 1.05 Imsil A-10 41.93 41.79 Corning 7724 36.06 36.22 Total 100 100 Oxidant and reductant pastes respectively are mixed in a weight ratio of 1:1 as indicated in the following examples.
~ 15 - , Curing times are given in minutes and include time required for mixing, approximately 30 seconds. The cessation of the curing reaction is determined by the material no longer being indentable by a spatula. It can also be done by measuring the percent of polymeriæate insoluble in methanol upon completion of the curing reaction. Samples of the polymer-forming mass are taken at timed inter~als during the curing ~eaction; cessation of the latter is indicated by the point at which present insolu-bles remains substiantially cons~ant. The results are summarized as follows:
Example Oxidan~ Reductant PPM Cu+~ Cure Temp No. Paste Paste in Reductant Minutes C
Paste . . .
1 J C 2.2 3.5~~.3 21 2 " D 4.4 2.8-3.2 23 3 " E11.0 1.8-2.2 23 4 " F22.0 1.7-2.2 20.5 " G33.0 1.5-1.8 21.5 6 " H44.0 1.3-1.8 23 7 " Anone 4.0-5.0 27 8 I C 2.2 3.3-3.8 21 9 " D 4.4 2.7-3.S 22.5 `' E11.0 1.8-2.2 23 11 " F22.0 1.7~2.0 20.5 12 " G33.0 1.3-1.7 21 13 " H44.0 1025-1.6 23 14 " Anone 3.3-4.0 21 ~3~
In each of the runs, curing is carried out in air, i.e. in an open vessel. Increased concentration of Cu provi~es more rapid cUreS. In comparison to Examples 7 and 14, which omit the copper accelerator, the data establish marked improvement in curing ra~e for the present inventionO
Similar combination5 (1:1) of reductant paste B
with I and J produce comparable results.
The procedure of the foregoing examples is repeated but using a Nupol: ~DMA (71:29) by weight monomer blend in each of the oxldant and reductant compositions.
Filler is omitted altogether in each of the examples.
Copper ions are provided by the ~ollowing compounds:
Example No. Accelerator cupric acetate 16 cupric chloride 17 cupric acetonyl acetonate (no solvent) $
In each case, improved rate o~ curing is achieved when compared to identical control runs omitting the copper compound.
The procedure of Examples 15-17 is repeated bu~
using the following materials as accel~rators:
Example No. Accelerator (weight ratios) . _ 18 cupric acetate/cupric chloride (50:50) 19 cupric acetate/cuprous chloride ~50:50) cupric chloride/cuprous chloride (50~50 The results are similar to those of the preceding examples.
_ Each of examples 1~14 is repeated with the exception that the cupric acetate is sorbed onto the filler and then added to the monomer composition. Similar improvement is obtained in curing rate by comparison with control runs omitting the copper compound.
36~
The following reductant-containing and oxidant-containing compositions are prepared:
REDUCTANT
Composition % by weight Ingredient K L M
__ _ _ NUPOL 9.9 9,9 9.9 HMDMA 9.9 9.9 9.9 Acetyl Thiourea 0.45 0.45 0.45 Cu++ 3O0002 0.0005 0.0010 Corning 7724a 36.25 36.25 36.25 IMSIL A-10a 42.25 42.25 42.25 Colloidal Silica 1.30 1~30 1.30 a. Silanized 3~
OXIDANT COMPOSITION - N
.
IngredientComposition ~O by weight NUPOL 9.325 HMDMA 9 . 325 CHP (80~) 1.05 Corning 7724a36.25 IMSIL A~lOa 42 o 25 Colloidal Silica 1.80 a. Silanized The Oxidant paste is mixed on a clean glass plate with each of the three reductant pastes in a 1:1 ratio.
Curing times for each of three mixes are determined by the time required for the blended material to be resistant to indentation by a plastic spatula. The results are summarized 2s follows:
PPM Cu in Reductant Cure Example No. Oxidant Paste Reductant Paste Paste Minutes .,_ _ . . ...
1 N K 2 4.2-5.0 2 N L 5 2.5~3.0 3 N M 10 2.3-2.8 a. at 23C
3Ei~
In each of the above runs, curing is carried out in air. (Shorter curing times would result under glass or in a cavity covered ~y a matrix strip.) It is evident that increas-ing the concentration of Cu++ results in a shorter cure time.
Similar results are obtained when the foregoing examples are repeated but utilizing, within the ranges hereinbefore specified the following peroxy catalysts and reductant compounds: peroxy catalysts - p-methane hydroperoxide, diisopropylbenzene hydroperoxide and t-butyl hydroperoxide;
reductants-allyl thiourea, phenyl thiourea, and 3-allyl-1, l-diethylthiourea.
Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A polymerizable dental composition having an accelerated curing rate comprising at least one methacrylate monomer having 2 to 4 polymerizable double bonds, from about 0 to 400% based on said monomer of inorganic particulate filler, from about 0 to 5% based on said monomer of silane coupling agent, an effective catalyst - activating amount of accelerator comprising cupric ion and a redox system consisting of (a) from about 0.5 to 5.0% based on said monomer of a free radical liberating polymerization catalyst comprising an organic hydroperoxide compound and (b) from about 0.5 to 5.0%
based on said monomer of a substituted thiourea reducing agent for said organic hydroperoxide compound, wherein the concentr-ation of (b) does not exceed about 40% of the total quantity of (a) and (b).
based on said monomer of a substituted thiourea reducing agent for said organic hydroperoxide compound, wherein the concentr-ation of (b) does not exceed about 40% of the total quantity of (a) and (b).
2. A composition according to claim 1, wherein the ratio of (a) to (b) is about 2:1.
3. A composition according to claim 1, wherein said reducing agent comprises an allyl- or acetyl-substituted thiourea.
4. A composition according to claim 1, 2 or 3, wherein said organic hydroperoxide compound comprises cumene hydroperoxide and said reducing agent is acetyl thiourea.
5. A composition according to claim 1, 2 or 3, which consists of two paste compositions separated from each other;
the first paste composition comprising the monomer and the organic hydroperoxide compound; and the second paste composition comprising the monomer and the substituted thiourea reducing agent, wherein cupric ion is present in either one or both of the paste compositions.
the first paste composition comprising the monomer and the organic hydroperoxide compound; and the second paste composition comprising the monomer and the substituted thiourea reducing agent, wherein cupric ion is present in either one or both of the paste compositions.
6. A composition according to claim 1, 2 or 3, wherein said organic hydroperoxide compound comprises cumene hydroperoxide and said reducing agent comprises allyl thiourea.
7. A composition according to claim 1, 2 or 3, wherein said cupric ion is present as cupric acetate, cupric acetyl acetonate, cupric chloride, or a mixture thereof.
8. A composition according to claim 1, 2 or 3, wherein the concentration of said cupric ion is from about 5 to 100 ppm based on said monomer.
9. A composition according to claim 1, 2 or 3, wherein said cupric ion is dispersed in said monomer.
10. A composition according to claim 1, 2 or 3, wherein at least about 40% of said monomer comprises the reaction product of glycidyl methacrylate and bisphenol A.
11. A composition according to claim 1, 2 or 3, wherein at least about 40% of said monomer comprises the reaction product of glycidyl methacrylate and bisphenol A and up to 60% of said monomer comprises 1,6-hexanedioldimethacrylate.
12. A composition according to claim 1, 2 or 3, which includes up to 50% by weight based on the weight of cupric ion of cuprous ion.
13. A composition according to claim 1 having a paste-like consistency.
14. A process for forming a dental polymerizate comprising contacting methacrylate monomer having 2 to 4 polymerizable double bonds with a redox polymerization catalyst capable of initiating the polymerization of said methacrylate monomer and comprising organic, peroxy compound and reducing agent therefor said contacting being carried out in the presence of an effective catalyst activating amount of cupric ion.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14519980A | 1980-04-29 | 1980-04-29 | |
| US145,199 | 1980-04-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1223696A true CA1223696A (en) | 1987-06-30 |
Family
ID=22512027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000376461A Expired CA1223696A (en) | 1980-04-29 | 1981-04-28 | Dental compositions |
Country Status (20)
| Country | Link |
|---|---|
| JP (1) | JPS56169609A (en) |
| AT (1) | AT376125B (en) |
| AU (1) | AU554532B2 (en) |
| BE (1) | BE888599A (en) |
| BR (1) | BR8102607A (en) |
| CA (1) | CA1223696A (en) |
| CH (1) | CH649465A5 (en) |
| DE (1) | DE3116132A1 (en) |
| DK (1) | DK157727B (en) |
| ES (1) | ES501695A0 (en) |
| FR (1) | FR2481114A1 (en) |
| GB (2) | GB2075035B (en) |
| IE (1) | IE51152B1 (en) |
| MX (1) | MX156002A (en) |
| NL (1) | NL8102128A (en) |
| NO (1) | NO158991C (en) |
| NZ (1) | NZ196864A (en) |
| PH (1) | PH17044A (en) |
| SE (1) | SE450547B (en) |
| ZA (1) | ZA812567B (en) |
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| CN101129295A (en) * | 2005-08-19 | 2008-02-27 | 贺利氏古萨有限公司 | 2-component initiator system (amine free) with storage stability and especially suitable for acidic systems |
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| DE3928987A1 (en) * | 1989-09-01 | 1991-03-28 | Siegfried Reiss | METHOD AND SHAPE FORM FOR PRODUCING SHAPINGS FOR THE DENTAL AREA |
| DE4339399A1 (en) * | 1993-11-18 | 1995-05-24 | Thera Ges Fuer Patente | Dental inserts prodn. for use with composite filling materials. |
| US20070100019A1 (en) * | 2005-08-02 | 2007-05-03 | Fuming Sun | Catalyst system for dental compositions |
| EP1849449A1 (en) | 2006-04-26 | 2007-10-31 | 3M Innovative Properties Company | Filler containing composition and process for production and use thereof |
| WO2008134024A2 (en) * | 2007-04-25 | 2008-11-06 | Dentsply International Inc. | Self-adhesive dental cement |
| JP2009292761A (en) * | 2008-06-04 | 2009-12-17 | Kuraray Medical Inc | Curable composition for dental use |
| JP5388482B2 (en) * | 2008-06-04 | 2014-01-15 | クラレノリタケデンタル株式会社 | Dental curable composition |
| CN102702405B (en) * | 2012-07-05 | 2014-04-09 | 东营市诺尔化工有限责任公司 | Method for preparing ultralow-residue water absorbing resins |
| JP6112887B2 (en) * | 2013-02-05 | 2017-04-12 | 株式会社トクヤマデンタル | Dental curable composition |
| JP6086797B2 (en) * | 2013-04-25 | 2017-03-01 | クラレノリタケデンタル株式会社 | Dental polymerizable composition |
| CN106535861B (en) | 2014-07-10 | 2022-02-08 | 3M创新有限公司 | Two-component self-adhesive dental composition, method of making and using the same |
| AU2016218284A1 (en) * | 2015-02-09 | 2017-07-27 | Zest Ip Holdings, Llc | Dental compositions and methods of use |
| JP6948727B2 (en) * | 2017-12-26 | 2021-10-13 | 株式会社トクヤマデンタル | How to store chemical polymerization initiators, adhesive compositions, adhesive composition kits, dental materials, dental material kits and adhesive compositions |
| EP3808324A1 (en) * | 2019-09-26 | 2021-04-21 | Shofu Inc. | Curable composition containing transition metal adsorbent |
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| GB714868A (en) * | 1951-12-24 | 1954-09-01 | Dental Fillings Ltd | Improvements in or relating to polymerisation products |
| GB1177879A (en) * | 1967-09-04 | 1970-01-14 | Sumitomo Chemical Co | Catalyst System and process for the Polymerisation of Vinyl Compounds |
| JPS4842467B1 (en) * | 1970-12-04 | 1973-12-12 | ||
| JPS5223509B2 (en) * | 1973-04-26 | 1977-06-24 | ||
| JPS587646B2 (en) * | 1974-05-31 | 1983-02-10 | 東亞合成株式会社 | Niekiseikoukaseisoseibutsu |
| JPS516224A (en) * | 1974-07-05 | 1976-01-19 | Johnson & Johnson | |
| US3991008A (en) * | 1974-08-12 | 1976-11-09 | The Kendall Company | Dental compositions having improved color stability |
| JPS51131197A (en) * | 1975-05-08 | 1976-11-15 | Sankin Ind Co | Uniiliquid type dental cement |
-
1981
- 1981-04-16 ZA ZA00812567A patent/ZA812567B/en unknown
- 1981-04-16 NZ NZ196864A patent/NZ196864A/en unknown
- 1981-04-23 DE DE19813116132 patent/DE3116132A1/en not_active Withdrawn
- 1981-04-27 SE SE8102634A patent/SE450547B/en not_active IP Right Cessation
- 1981-04-27 AT AT0187781A patent/AT376125B/en not_active IP Right Cessation
- 1981-04-28 FR FR8108413A patent/FR2481114A1/en active Granted
- 1981-04-28 PH PH25567A patent/PH17044A/en unknown
- 1981-04-28 ES ES501695A patent/ES501695A0/en active Granted
- 1981-04-28 BE BE0/204628A patent/BE888599A/en not_active IP Right Cessation
- 1981-04-28 AU AU69911/81A patent/AU554532B2/en not_active Ceased
- 1981-04-28 NO NO811448A patent/NO158991C/en unknown
- 1981-04-28 CH CH2760/81A patent/CH649465A5/en not_active IP Right Cessation
- 1981-04-28 CA CA000376461A patent/CA1223696A/en not_active Expired
- 1981-04-28 BR BR8102607A patent/BR8102607A/en unknown
- 1981-04-29 IE IE958/81A patent/IE51152B1/en unknown
- 1981-04-29 MX MX187116A patent/MX156002A/en unknown
- 1981-04-29 DK DK189781A patent/DK157727B/en not_active Application Discontinuation
- 1981-04-29 GB GB8113265A patent/GB2075035B/en not_active Expired
- 1981-04-29 NL NL8102128A patent/NL8102128A/en not_active Application Discontinuation
- 1981-04-30 JP JP6615881A patent/JPS56169609A/en active Pending
-
1983
- 1983-08-11 GB GB838321611A patent/GB8321611D0/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101129295A (en) * | 2005-08-19 | 2008-02-27 | 贺利氏古萨有限公司 | 2-component initiator system (amine free) with storage stability and especially suitable for acidic systems |
Also Published As
| Publication number | Publication date |
|---|---|
| MX156002A (en) | 1988-06-14 |
| AU6991181A (en) | 1981-11-05 |
| SE8102634L (en) | 1981-10-30 |
| NO158991C (en) | 1988-11-23 |
| CH649465A5 (en) | 1985-05-31 |
| GB8321611D0 (en) | 1983-09-14 |
| ATA187781A (en) | 1984-03-15 |
| DK157727B (en) | 1990-02-12 |
| NZ196864A (en) | 1984-04-27 |
| AU554532B2 (en) | 1986-08-28 |
| GB2075035A (en) | 1981-11-11 |
| GB2075035B (en) | 1984-07-25 |
| ZA812567B (en) | 1982-11-24 |
| PH17044A (en) | 1984-05-17 |
| ES8206560A1 (en) | 1982-08-16 |
| DK189781A (en) | 1981-10-30 |
| IE810958L (en) | 1981-10-29 |
| DE3116132A1 (en) | 1982-02-04 |
| FR2481114B1 (en) | 1984-11-30 |
| IE51152B1 (en) | 1986-10-15 |
| FR2481114A1 (en) | 1981-10-30 |
| JPS56169609A (en) | 1981-12-26 |
| ES501695A0 (en) | 1982-08-16 |
| AT376125B (en) | 1984-10-10 |
| NO158991B (en) | 1988-08-15 |
| BR8102607A (en) | 1982-01-19 |
| SE450547B (en) | 1987-07-06 |
| BE888599A (en) | 1981-08-17 |
| NL8102128A (en) | 1981-11-16 |
| NO811448L (en) | 1981-10-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |