CA1112397A - Peroxide-catalyzed composition useful for sealing pits and fissures in teeth - Google Patents
Peroxide-catalyzed composition useful for sealing pits and fissures in teethInfo
- Publication number
- CA1112397A CA1112397A CA267,718A CA267718A CA1112397A CA 1112397 A CA1112397 A CA 1112397A CA 267718 A CA267718 A CA 267718A CA 1112397 A CA1112397 A CA 1112397A
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- Prior art keywords
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- weight
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- 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
Abstract
ABSTRACT OF THE DISCLOSURE
A peroxide-catalyzed composition useful for the sealing of pits and fissures in teeth to prevent decay therein comprises from about 40 to about 60 parts by weight of a mixture of BIS-GMA and from 0 to about 3 parts by weight BADM
for every 9 parts BIS-GMA, from about 60 to about 40 parts by weight of TEGDM, and amounts of peroxide catalyst and N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline as accelerator for the catalyst such that the set time of the composition is from about 40 to about 90 seconds, all of the catalyst and the accelerator is dissolved in the composition. This composition has a contact angle with respect to dry etched tooth surface tooth of less than 10° and a Brookfield viscosity of up to about 1200 centipoises.
A peroxide-catalyzed composition useful for the sealing of pits and fissures in teeth to prevent decay therein comprises from about 40 to about 60 parts by weight of a mixture of BIS-GMA and from 0 to about 3 parts by weight BADM
for every 9 parts BIS-GMA, from about 60 to about 40 parts by weight of TEGDM, and amounts of peroxide catalyst and N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline as accelerator for the catalyst such that the set time of the composition is from about 40 to about 90 seconds, all of the catalyst and the accelerator is dissolved in the composition. This composition has a contact angle with respect to dry etched tooth surface tooth of less than 10° and a Brookfield viscosity of up to about 1200 centipoises.
Description
3~'~
This invention relates to -free-radical catalyzed polymers and more particularly to the use o-f such polymers in dental pit and fissure-sealing compositions.
Polymerizable dental restorative materials are well-known in the art. They are described in, for example, sOwen United States Patent Number 3,066,112, Lee, et al., United States Patent Number 3,539,533, and Gander, et al, United States Patent Number 3,835,090. These dental restorative materials generally comprise at least one liquid polymerizable acrylate or methacrylate monomer, a diacyl peroxide polymeriza-tion catalyst or initiator, and an amine accelerator for producing free radicals upon reaction with said catalyst for polymerizing the monomer. The material may further comprise an inorganic filler and stabilizers to prevent premature polymerization.
A polymerizable dental restorative material must possess three characteristics to be of use to the dentist.
-- First, the composi-tion should remain fluid for a time sufficiently long to allow the dentist to mix the material and put it in place; this time period is called the "working time". Second, once it is pu-t in place it should set to a hard finish rapidly; this time period from mixing to setting is called the "set time". Third, the set material should harden as close as possible to the exposed surface thereof;
this hardening near the sur~ace is called "surface cure."
: .
;
"., - .
.
_~ -.
.
. - , .::
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A dental res~ora~ive material should therefore be designed so that it has a short a set time as possible consonant with the time required to put it in place and so that the surface cure is as complete as possible~ A restorative material is obviously of lit~le use if it begins to hard~on appreciably before the dentist can get it applied to the desired location.
The set time should be short to prevent inadvertant sonta~ination by oral fluid~ or damage to the material prior to the ~inal setting thereof and further for the convenience of the patient and dentist. Finally, the excellonce of the surface cure determines how cl.ose to the surface of the restoration the ~olidly polymerized binder ex~ends. In fissure-filling applications, the degree of surface cure is extremely important because only a thin layer of the restorative material is present therein.
Peroxide catalyzed polymerizable dental restorative materials are generally prepared as two separate compositions for storage and distribution prior ~o use, one composi.tion containing the catalyst and no accelerator and the other containing ac~elerator and no catalyst. These two compositions may be both liquid, both pastes, one liquid and one paste, one liquid and one solid, or the like.
Each composition usually contains a liquid polymerizable ~onomer ~"th~ binder") as the major component. Prior art liquid, polymerizable monomers are disclosed in the aforesaid Bowen, Lee, and Gander U~5. Patents.
3~'~
The first composition (the "ca~alys~ compositio~") contains in addition to the binder a~ appropriate amount of a peroxide polymerization catalyst, typically a diacyl peroxide, as disclosed in Reinhardt United .~tates Patent Number 3,256,254 and Baford Uni~ed States Patent ~umber 3,580,955, which latter describes methods of makîng same and provides a comprehensive list thereofO
The second composition ~the "accelerator composition"
ox "universal composition") contains in addition to the binder an appropriate amount of an amine accelerator for the catalyst~ typically substituted anilines. Some prior art accelerators are disclosed in the aforesaid Lee, et al, U.S. patent, Taylor U~S. Patent No. 3,541,068, and Erickson U.S. patent No. 3,799,985. These anilines are usually N,N-bis-(2-hydroxyethyl)-substituted, as described in the aforesaid Taylor U.S. Patent, to provide enhanced color stability.
The aforesaid Erickson patent discloses the accelerator M,N- :
bis-(2-hydroxy-ethyl~-3,4-dimet}lylaniline.
Both compositions may also conkain stabili2ers to pre~ent premature polymexization thereof and to adjust the set time to the desired length.
Although priGr art polymerizable dental restorative materials have enjoyed success in the area of highly~f:illed restorations~ attempts to use them ~ox pit and fi~sure sealing h~e met with difficulkies. Fissure seali~g ma~erials .
3~
are applied to healthy teeth to prevent the formation of dental caries (decay) -therein. By sealing up defects and fissures where decay may begin, a significant reduction in decay can be achieved. To accomplish this objective, however, fissure-sealing compositions must be tenaciously retained on the tooth or a long period of time, preferably longer than three years. Without such ~enacious long-term retention, a fissure-sealing composi~ion i~ of li~tle value because it will not prevent caries on teeth where it is not rétained.
Even a retention of 50~ means that half the treated teeth are unprotected from decay. The term "tenacious retention"
as used herein mean~ complete retention after one year by at least 90% and preferably by at least 95% of the first molars txeated. Retention on first molars is used as the criterion because they are the site of lowest retention and hence provide the mo~t meaningful test. Prior art fissure-sealing compositions have not had ~his tenacious long-term retention and for this reason have met with only limited success dispite large expenditures of time and money.
As early as 1967, Buonocore suggested (Journal of ~me~ican Dentistry Association, July 1967, Vo. 75, ppl21-128) the use of methyl-~ -cyanoacrylate in a pit and fissure-sealing composition. Overhults U.S. Patent ~o. 3,839,065, filed April 8~ 1968, and Adams U.S. Patent ~o. 3,663,501, filed Jul~e 11, 1970, describe and claim cyanoacrylate compositions as pi~ and fissure sealants. Many years of efort were spent attempting to develop a cyanoacrylate pit and fissure-sealing composition, but the retention of these compositions i5 poor. The clinieal study by Lo Ripa and WO Cole ~J.Dental Research, 49:171(1970)~ is exemplary o the effectivenless of ~2 ;3~
cyanoacrylate pit and -fissure-sealing compositions. Only 36.2% of first molars completely retainecl the composition after one year.
Attempts to use the binder syst;ems of prior art hiyhly filled dental restorative materials in pit and fissure-sealing have likewise met with little success~ Many materials of this type did not even merit commercial development because of poor retention. Even commercial materials are not tena-ciously retained. For example, a commercial pit and fissure-sealing composition sold by Lee Pharmaceutical Co. under thetrademark EPOXYLITE 9075 is a peroxide-catalyzed material having diethyleneglycol dimethacrylate as the polymerizable monomer~ In the method of Lee, the accelerator composition and catalys-t composition are separately applied to an etched tooth which has previously been treated with a si:Lane primer solution. W. P. Rock (Brit. Dent~ J., 317 (197~)) has sho~n this material applied by this method to be completely retai-ned in only 51.5% of teeth treated (most of which were not first molars) after two years. There was no sealant reten-tion on any of the six first molars in the study after twoyears.
Some success has been obtained with the fissure-sealing composition sold by L o D~ Caulk Company under the trademark ~UVA SEAL~ This ~aterial, which comprises about 75% by weight BIS-GMA and about 25% by weiyht methyl metha-crylate~ is polymerized by irradiation with ultraviolet (UV) llght, rather than by a peroxide catalyst. This W irradia tion method requires expensive equipment, and careful pre-cautions must be employed in using same to insure the safety of both patient and operator. The retention of ~UVA ~EAL
was found in the Kalispel, Montana, ~tudy reported by .r -6-~ i,?~
' McCune, et al, JADA:87, 1177(1973), to be less than desirable, the retention on first molars bein~ 71~8% after one year, 47.6% after two ~ears, and 11.6% after four years. The percent effectiveness (percent reduction in decay due to txeating) of NUVA SEAL on first molars was 80.3~ after one year, 65.0% after two years, and 30.5% after four years.
None of these prior art pit and fi~sure sealants contain an inorganic filler. Filled compositions are generally undesirable as pit and fissure sealants because they require grinding to readjust occlusion, whereas unfilled compositions do not.
In discussion of prior a.rt fissure-sealing compositions above, data for first molar retention has been presented whenever possible~ because the first molar is the site of lowest retention and thus provides the most meaningful site for evaluation and comparison of compositions.
Even I~W A SEAL, the best prior art composition, has not provided tenacious retention of sealant, because le~s than 50~ of the treated first molars completely retain sealant after two years. It can therefore be seen that ~o prior art fissure-filling composition or method of treating teeth (and particularly no prior art peroxide-catalyzed is~ure-filling compo~ition) has provided tenacious long-term rekention. There has-thus been a long-felt need for a method of treating teeth and a pit and fissure~sealing composition which would be tenaciously retained on tPeth for a long period of time - , SUMM~RY OF TIE INVENTION
______ _ .
The present invention provides a method of -treating teeth to prevend decay th~rein which coats the tooth surface with a tenacious protective polymer layer. The present invention further provid~es pi.t and Eissure-sealin~ com~ositions whi~h are particularly useful in this met:hodO It has surprisingly been found that the method of the invention provides a tenacious and long-retained protective film over the tooth surfaceD
The method of the invention comprises the following :1.0 stepsO .
1) removing surface film9 if necessary9 by cleaning the tooth to be treated, ..
This invention relates to -free-radical catalyzed polymers and more particularly to the use o-f such polymers in dental pit and fissure-sealing compositions.
Polymerizable dental restorative materials are well-known in the art. They are described in, for example, sOwen United States Patent Number 3,066,112, Lee, et al., United States Patent Number 3,539,533, and Gander, et al, United States Patent Number 3,835,090. These dental restorative materials generally comprise at least one liquid polymerizable acrylate or methacrylate monomer, a diacyl peroxide polymeriza-tion catalyst or initiator, and an amine accelerator for producing free radicals upon reaction with said catalyst for polymerizing the monomer. The material may further comprise an inorganic filler and stabilizers to prevent premature polymerization.
A polymerizable dental restorative material must possess three characteristics to be of use to the dentist.
-- First, the composi-tion should remain fluid for a time sufficiently long to allow the dentist to mix the material and put it in place; this time period is called the "working time". Second, once it is pu-t in place it should set to a hard finish rapidly; this time period from mixing to setting is called the "set time". Third, the set material should harden as close as possible to the exposed surface thereof;
this hardening near the sur~ace is called "surface cure."
: .
;
"., - .
.
_~ -.
.
. - , .::
3~'~
A dental res~ora~ive material should therefore be designed so that it has a short a set time as possible consonant with the time required to put it in place and so that the surface cure is as complete as possible~ A restorative material is obviously of lit~le use if it begins to hard~on appreciably before the dentist can get it applied to the desired location.
The set time should be short to prevent inadvertant sonta~ination by oral fluid~ or damage to the material prior to the ~inal setting thereof and further for the convenience of the patient and dentist. Finally, the excellonce of the surface cure determines how cl.ose to the surface of the restoration the ~olidly polymerized binder ex~ends. In fissure-filling applications, the degree of surface cure is extremely important because only a thin layer of the restorative material is present therein.
Peroxide catalyzed polymerizable dental restorative materials are generally prepared as two separate compositions for storage and distribution prior ~o use, one composi.tion containing the catalyst and no accelerator and the other containing ac~elerator and no catalyst. These two compositions may be both liquid, both pastes, one liquid and one paste, one liquid and one solid, or the like.
Each composition usually contains a liquid polymerizable ~onomer ~"th~ binder") as the major component. Prior art liquid, polymerizable monomers are disclosed in the aforesaid Bowen, Lee, and Gander U~5. Patents.
3~'~
The first composition (the "ca~alys~ compositio~") contains in addition to the binder a~ appropriate amount of a peroxide polymerization catalyst, typically a diacyl peroxide, as disclosed in Reinhardt United .~tates Patent Number 3,256,254 and Baford Uni~ed States Patent ~umber 3,580,955, which latter describes methods of makîng same and provides a comprehensive list thereofO
The second composition ~the "accelerator composition"
ox "universal composition") contains in addition to the binder an appropriate amount of an amine accelerator for the catalyst~ typically substituted anilines. Some prior art accelerators are disclosed in the aforesaid Lee, et al, U.S. patent, Taylor U~S. Patent No. 3,541,068, and Erickson U.S. patent No. 3,799,985. These anilines are usually N,N-bis-(2-hydroxyethyl)-substituted, as described in the aforesaid Taylor U.S. Patent, to provide enhanced color stability.
The aforesaid Erickson patent discloses the accelerator M,N- :
bis-(2-hydroxy-ethyl~-3,4-dimet}lylaniline.
Both compositions may also conkain stabili2ers to pre~ent premature polymexization thereof and to adjust the set time to the desired length.
Although priGr art polymerizable dental restorative materials have enjoyed success in the area of highly~f:illed restorations~ attempts to use them ~ox pit and fi~sure sealing h~e met with difficulkies. Fissure seali~g ma~erials .
3~
are applied to healthy teeth to prevent the formation of dental caries (decay) -therein. By sealing up defects and fissures where decay may begin, a significant reduction in decay can be achieved. To accomplish this objective, however, fissure-sealing compositions must be tenaciously retained on the tooth or a long period of time, preferably longer than three years. Without such ~enacious long-term retention, a fissure-sealing composi~ion i~ of li~tle value because it will not prevent caries on teeth where it is not rétained.
Even a retention of 50~ means that half the treated teeth are unprotected from decay. The term "tenacious retention"
as used herein mean~ complete retention after one year by at least 90% and preferably by at least 95% of the first molars txeated. Retention on first molars is used as the criterion because they are the site of lowest retention and hence provide the mo~t meaningful test. Prior art fissure-sealing compositions have not had ~his tenacious long-term retention and for this reason have met with only limited success dispite large expenditures of time and money.
As early as 1967, Buonocore suggested (Journal of ~me~ican Dentistry Association, July 1967, Vo. 75, ppl21-128) the use of methyl-~ -cyanoacrylate in a pit and fissure-sealing composition. Overhults U.S. Patent ~o. 3,839,065, filed April 8~ 1968, and Adams U.S. Patent ~o. 3,663,501, filed Jul~e 11, 1970, describe and claim cyanoacrylate compositions as pi~ and fissure sealants. Many years of efort were spent attempting to develop a cyanoacrylate pit and fissure-sealing composition, but the retention of these compositions i5 poor. The clinieal study by Lo Ripa and WO Cole ~J.Dental Research, 49:171(1970)~ is exemplary o the effectivenless of ~2 ;3~
cyanoacrylate pit and -fissure-sealing compositions. Only 36.2% of first molars completely retainecl the composition after one year.
Attempts to use the binder syst;ems of prior art hiyhly filled dental restorative materials in pit and fissure-sealing have likewise met with little success~ Many materials of this type did not even merit commercial development because of poor retention. Even commercial materials are not tena-ciously retained. For example, a commercial pit and fissure-sealing composition sold by Lee Pharmaceutical Co. under thetrademark EPOXYLITE 9075 is a peroxide-catalyzed material having diethyleneglycol dimethacrylate as the polymerizable monomer~ In the method of Lee, the accelerator composition and catalys-t composition are separately applied to an etched tooth which has previously been treated with a si:Lane primer solution. W. P. Rock (Brit. Dent~ J., 317 (197~)) has sho~n this material applied by this method to be completely retai-ned in only 51.5% of teeth treated (most of which were not first molars) after two years. There was no sealant reten-tion on any of the six first molars in the study after twoyears.
Some success has been obtained with the fissure-sealing composition sold by L o D~ Caulk Company under the trademark ~UVA SEAL~ This ~aterial, which comprises about 75% by weight BIS-GMA and about 25% by weiyht methyl metha-crylate~ is polymerized by irradiation with ultraviolet (UV) llght, rather than by a peroxide catalyst. This W irradia tion method requires expensive equipment, and careful pre-cautions must be employed in using same to insure the safety of both patient and operator. The retention of ~UVA ~EAL
was found in the Kalispel, Montana, ~tudy reported by .r -6-~ i,?~
' McCune, et al, JADA:87, 1177(1973), to be less than desirable, the retention on first molars bein~ 71~8% after one year, 47.6% after two ~ears, and 11.6% after four years. The percent effectiveness (percent reduction in decay due to txeating) of NUVA SEAL on first molars was 80.3~ after one year, 65.0% after two years, and 30.5% after four years.
None of these prior art pit and fi~sure sealants contain an inorganic filler. Filled compositions are generally undesirable as pit and fissure sealants because they require grinding to readjust occlusion, whereas unfilled compositions do not.
In discussion of prior a.rt fissure-sealing compositions above, data for first molar retention has been presented whenever possible~ because the first molar is the site of lowest retention and thus provides the most meaningful site for evaluation and comparison of compositions.
Even I~W A SEAL, the best prior art composition, has not provided tenacious retention of sealant, because le~s than 50~ of the treated first molars completely retain sealant after two years. It can therefore be seen that ~o prior art fissure-filling composition or method of treating teeth (and particularly no prior art peroxide-catalyzed is~ure-filling compo~ition) has provided tenacious long-term rekention. There has-thus been a long-felt need for a method of treating teeth and a pit and fissure~sealing composition which would be tenaciously retained on tPeth for a long period of time - , SUMM~RY OF TIE INVENTION
______ _ .
The present invention provides a method of -treating teeth to prevend decay th~rein which coats the tooth surface with a tenacious protective polymer layer. The present invention further provid~es pi.t and Eissure-sealin~ com~ositions whi~h are particularly useful in this met:hodO It has surprisingly been found that the method of the invention provides a tenacious and long-retained protective film over the tooth surfaceD
The method of the invention comprises the following :1.0 stepsO .
1) removing surface film9 if necessary9 by cleaning the tooth to be treated, ..
2~ etching the tooth surface with an etchin~
solut.ion as descrihed below,
solut.ion as descrihed below,
3) cleansing the etched tooth surface to remove the etching solution and debris,
4) drying the etched tooth surface,
- 5) coating the dry etched tooth surface with a hard 7 tenaciously adherent polymer layer by ~,~o applying to said dry etched tooth surface a drop of liquid pol~merizable monomer material having dissolved therein a peroxide catalyst for said material and an accelerator for said catalyst 9 said liquid polymerizable monomer material being a mixture of 292-bis-L4-(3- methacryloxy-2- :
hydroxypropyl~ phenyl] propane, bisphenol~A-dimethacrylate and a triethylene glycol dimethacrylate9 having a contact angle with respect to dry etched tooth surface of less than -~() 10~ and a Brookfield viscosity of up to ahout 1200 centipoises9 ~ .
~ -8 3'~
whereby said liquid polymerizable monomer material is caused to flow over said -~ooth surface; and
hydroxypropyl~ phenyl] propane, bisphenol~A-dimethacrylate and a triethylene glycol dimethacrylate9 having a contact angle with respect to dry etched tooth surface of less than -~() 10~ and a Brookfield viscosity of up to ahout 1200 centipoises9 ~ .
~ -8 3'~
whereby said liquid polymerizable monomer material is caused to flow over said -~ooth surface; and
6) keeping said tooth surface dry until said monomer material has polymerized into a hard, tenacious protec~ive layer.
Suitable liquid polymerizable monomer mat~rials are, for example, those of the ~foresaid ~ee, et al, patent and the binder systems disclosed in the aforesaid Gander, et al, patent.
Teeth accumulate a surface film or pellicle which, along with plaque, is usually cleaned away at regular intervals.
If the tooth to be treated has this surface film or pellicle on it, then it is preferably removed by any known cleaning procedure before the etching step. In some cases, however, the etching process itself may sufficiently clean the tooth surfaceO
A suitable etching solution for use in the method of the invent.ion is 35~ aqueous phosphoric acid, 50~ aqueous phosphoric acid, and the like~ While these etching solutions are preferre~, it is contemplated that any solution which effectively etches the teeth could be used.
The etched tooth surface is preferably cleaned by rinsing the mouth with water, but other types of cleansing such as wiping, swabbing, and the like may be used.
Applicant believes, without wishing to be ~ound thereby, that the good wetting and viscosity proper~ies of the monomer material applied in the present method are greatly responsible for the tenacious retention thereof to the tooth. Compositions may successfully he used in the present method which have a contact angle with respect to dry etched tooth surface of less than 10 measured at ~5DC
and ambient humidity with a Rame-Hart NRL goniometer and a Brookfield viscosity up to about 1200 centipoises measured at ~5C and 100 RPM with a No~ 2 spindle. Compositions useful in the present method preferably have a contact angle of less than 5 measured as abo~e immediately upon application to the dry etched tooth surface. It should b~ understood that the actual contact angle of these preferred compositions is very close to 0, but that contact angles smaller than 5 are not readily measured.-~ pplicant further believes that the set ~ime ofthe compositions of the invention should preferably be in the range from about 40 to about 90 seconcls to yield kenacious retention to the tooth.
It is contemplated tha~ the monomer material ma~
be applied to the tooth surface with a dropper, glass rod, brush, or any other suitable device.
The pit and fissure-sea]ing cosnposition of the invention for use in the present me-thod is a peroxide catalyzed composition comprising from about ~0 -to about 60 parts by weight of a mixture of BIS~GMA and from 0 to about 3 parts by weight BADM for every 9 parts BIS GMA, from about 60 to about 40 parts by weight of T~GDM, and amounts of peroxide catalyst and N,N-bis-(2-hydroxyethyl)-3,4-dimeth~laniline as accelerator for the catalyst such that the set time of the composition is from about ~0 to about 90 seconds, all o~ the catalyst and the accelerator being dissolved in the composi-tion, the composition having a contact angle with respect to dry etched tooth surface tooth of less than 10 and a Brookfield viscosity of up to about 1200 centipoises.
This composition has good surface cure and tenacious long-term retention on the tooth.
The monomer BIS-GMA is the glycidyl methacrylate derivative of bis phenol-A9 more precisely: 2,2-bis-[4-(3-methacryloxy-2-hydroxypropyl) phenyl] propane.
- There may further be included in the composition the monomer bis phenol-A dimethacrylate (BADM), ~referably up to about three parts by weight BADM for every nine parts BIS-G~ and more preerably about one part by weight BADM
for every nine parts BIS-GMA.
; The preferred pit and fissure-sealing compositions of the invention should have a set time from about ~0 to abouk 90 seconds. Thus~ the identity and amounts of peroxide catalyst~ amine accelerator, and stabilizer (if any) must be adjusted so that a set time within the desired range results~
It is well known in the dental restorati~e art that set time may be increased by addition of stabilizers~ It is contempla-ted that as much as two to three times the preferred amounts of peroxide catalyst and amine accelerator may be used, up to the solubility limit of each in the li~uid polymeriæable "? ~
3~
monomer mixture. If a large amount of one of these two is employed, the amount of the other may be corre~pondingly small to maintain the set time within the desired range. If stabilizers axe added, the amounts of accelera~or and catalyst may be increased to maintain the set time in the desired range.
It is contemplated that any prior art accelerator may be used, so long as the set time of the resul~ing composition is within the desired range. The preferred acceleratox is a member selected from the group consisting of N,N-bis-(2~
hydroxyethyl)-4-methylaniline and N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline, and the more preferred accelerator is N,N-bis-~2-hydroxyethyl)-3,4-dimethylaniline.
While the preferred peroxide catalyst or the compositions of the invention is benzoyl peroxide, it is contemplated that other peroxide catalysts could be employed so lony as the set time of the composition is in the desired range. Because the compositions of the invention are peroxide catalyzed, the disadvantages of UV catalysis are obviated.
Stabilizexs may be added to the material, if desired, to inhibit the premature polymerization thereof during storage or to adjust the set time~ Such stabilizers are generally free-xadical chain reaction terminators such as, for example, a substituted phenol, exemplified by ~methoxyphenol '' ' , 2,5-di-t-butyl-4-methylphenol (known as BHT~, a compound of formula:
/ t-butyl~
C CH~OC-CH2CH2 ~ OH
t=butyl 4 (Sold by Geigy Chemical Company under ~he name Irganox 1010), and the like.
A more preferred composition of the in~ention comprises from about 40 to about 50 parts by weight of BIS-GMA, from about 60 to about 40 parts by weight of TEGDM, from about 1.0 to about 3.0 parts ~y weight of N,N-bis-(2-hydroxyethyl)-4-methylaniline and from about 0.5 to about 1.5 parts by weight oP benzoyl peroxide. A more preferred composition of this type comprises rom about 40 to about 60 parts by weight of a mixture of 9 par~s by weight of BIS-GMA
and up to about 3 parts and preferably about 1 par'c by weight BADM, ~rom about 60 to abou~ 40 parts of TE&DM, from about 1.0 to about 3.0 parts by weight of N,~-bis-(2-hydroxy-ethyl)-4-methylaniline, and from about 0.5 to ahout 1.5 parts by weight of benzoyl peroxide.
' A most preferred composition of the invention compri~es all the materials set forth in either of the above, except that from about 0.6 to about 1.8 parts by weight of N,N-bis-t2-hydroxyethyl)-3,4-dimethylaniline is ; subs~ituted for the N,N-bis~ hydroxyethyl)-4-methylaniline used therein.
~: :
.
It should be understood that the above compositions are preferably prepared as two separate compositions, one containing catalyst and no accelera-tor, and the other containing accelerator and no catalyst. Each of these materials would - prefexably con~ain the idential quantity of polymerizable monomer, but would vary only in the presence of the peroxide or amine accelerator and amount of stabilizer. These ~wo separate compositions may then be combined to yield the pit and fissure-sealing composi~ion~ of the invention, which latter is then applied to the tooth. These separate compositions are also considered to be part of the present inven~ion.
Preferred accelerator and catalyst compositions of the invention are identical to the preferred compositions disclosed above except that each contains only accelerator or catalyst (and is substantially free of the other) and contains in it double the amount disclosed above (e.y., from about 1.0 to about 3.0 parts by weight of benzoyl peroxid~
rather than from about 0.5 to about 1.5 parts).
The practice of the present invention is furt~er O illustra~ed by the following Examples, which are given for purposes of illustration only and not to limit the invention thereto. All parts are by weight unless otherwise noted.
'7 EXAMPLE I
Two compositions are prepared by mixing the following ingredients:
A B
90:10 BIS-GMA:BADM 45.00 45.00 TE~DM 55.00 55.00 BHT(Stabilizer) . 0.05 0.15 benzoyl peroxide 2.00 N,N-bis-~2-hydroxyethyl)-3,4-dimethylaniline2~40 Equal weights of composition A and composition B are mixed together and applied to a dry etched tooth. The set material exhibits good surface cure and tenacious reten~ion to the tooth as shown in Example III.
:
~XAMPLE I}
- Followin~ the procedure of Example I, but substituting in composition ~ 4000 parts of N,N-bis-(2-hydroxyethyl)-~-methylaniline for the N,N-bis-~2 hydroxyethyl)-3,4-dimethylaniline and 0.04 parts of ~HT for the O.OS parts us~d therein, two corresponding compositions are prepared. The set material prepared by mixing equal weights of the ~wo compositions exhibits good surace cure and tenacious retention to the tooth as shown in Example IV.
::
~' ', . ' :' ~ ' '7 EXAMPLE III
A study (0766-01-19) of the retent:ion o the composition of Example I and i~s efectiveness in preventing dental caries was conducted on 200 children .six to seven years o~ age. Each child had at least one pair of healthy homologous first molars, one member of each pair being selected at random to be treated and the other ser~ing as controlO
The following procedure was used in the study~
1) All teeth were cleaned by brushing with dental cream.
2) The teeth were examined twice to see if there was a decay-free pair of homologous first molars.
These two independent examinations must have a~reed for the child to have been included in the study.
, 3) The tooth to be treated was determined by consulting a random number table.
4) The tooth to be treated was prepared by etching with a 35% aqueous pho~phoric acid,and xinsing wi~h water, and was then dried and blocked off with cotton rolls.
5) The sealant was applied as a dropt aIlowed to flow ovar the tooth surface, and allowed to set.
The status of the 304 pairs of teeth ~304 treatled and 304 control) 5iX months after ~reatment is shown in the following table.
3~'7 TABLE I-Sta~us of Treated-Control Pairs at Six Months UPPER TEETH LOWER TEETH TOTAL
.. .
Both teeth sound 138 94 232 Both tee~h decayed 1 0 Treated-Sound Control-Decayed 32 38 70 Treated-Decayed, Control Sound - O
Net Gain 32 37 69 Percent Effectiveness - ~ 97.2%
The Table illustrates that the effectiveness of the composition of the invention in the prevention of de~ay was 97.2% (Net Gain divided by number of decayed control teeth). Of the 304 treated teeth, 296(97.4~) completely retained the sealant. Of the 8 teeth which lost sealant, none lo~t it completely and 7 were upper teeth~
EXAMPLE IV
,, A. comparative study (0766~ ~-18) of the retention of the composition of Example II and NUVA SEAL was conducted on 385 children seven years of age or less following the procedure of Example III, except that NUVA SEAL was brushed on the tooth surface~ Each child had at least one pair of healthy homologous first molars, one member of each pair being selected at random for ~rea~ment with either NUV~ SEAL
or the composition of Example II and the other ser~ing as controln The following Tables depicts the results one year after treatment on examination of 30Q children (145 with N W A 5EAL, 155 with Example II) and.576 pairs of teeth (237 w.ith M W A SEAL, 239 with Example II).
TABLE IT-Sealant Retention Complete Partial No Retention Retention Retention NVV~SEAL 83.5% 10.6% 5.9%
EXAMPLE II ~4.6% 2~5~o 2.9%
TABLE IIIa-~S-tatus of NUVA SEAL-Control Pairs .
U~er Teeth Lower Teeth Total __ , Both teeth sound 93 108 201 Bo~th teeth de-cayed Treated-Sound, Control-decayed 22 8 30 Treated-Decayed, Control-Sound 1 3 4 Net Gain 21 5 26 Pexcent Effectiveness91~3 55.Ç 81.2 : 18 .
`
: - .
TABLE IIIb-Sta~us of Example II-Control Pairs IJpper Teeth Lower Teeth Total Booth tee~h sound 90 103 193 Booth teeth decayed 3 4 7 Treated-Sound, Control-Decayed 25 14 39 Treated-Decayed, Control-Sound 0 0 0 Net Gain 25 14 39 Percent Effectiveness 89.3 77.8 84.8 It can be seen from the a~ove tables that the composition of Example ~X had greater than eleven percentage points better complete retention than NUVA SEAL and had a greater percentage effectiveness, especially for lowex teeth. It should b~ noted that there is a significant relationship between complete retention and decay prevention in the long term which is not clearly demonstrated ~y this study, because of the short period involved.
:
3~'7 EXAMPLE V
Two compositions are prepared by mixing the following ingredients:
A B
90:10 BIS-GMA:BADM 74 TE&DM ~ 23.5 100 methacrylic acid 1.0 benzoyl peroxide 1.2 N,N-bis-12-hydroxyethyl)~
4-methylaniline 1.5 Three parts of composition A and two parts of composition B
are mixed together and applied to a dry etched tooth. The set material exhibits good surface cure and tenacious retention to the tooth as shown in the following Example.
~~' . .
EXAMPLE VI
~ r ~
A study (0766 01-12) of the retention of the composition of Example V and its effectiveness in preventing dental caries was conducted on 24 children six to seven years of age, following the procedure of Example III. Each child had at least one pair o~ healthy ho~ologous first molars, one member of each pair being selected at random to be treated:and the other serv1ng as con~rol.
The status of the teeth examined at period~ after treatment is shown in the following table.
TABLE IV
3 months12 months 18 mGnt'hs 30 months No. of pairs examined 22 22 22 19 Complete reten-tion21 21 ~ 20 17 Partial reten-tion 1 0 No retention 0 Both teeth sound 10 7 4 3 Both teeth decayed 0 1 2 2 T.reated-Sound Control-Decayed12 14 16 14 Treated-decayed, Control Sound 0 0 0 0 Net Gain 12 14 16 14 Percent Effectiveness100% 93.3% 88.9% 87.5%
The table illustrates that 89~5% of the treated first molars completely retained the composition of Example V after 2 1/2 year~ and that it6 percent effectiveness in the prevention of decay in the ~clme time period was 87O5%~
' ~1 EXAMPLE VII
Two compositions are prepared by mixing the following in~redients:
A B
BIS GMA 40.00 40.00 TEGDM 60.00 6~.00 BHT(Stabilizer) * *
benzoyl peroxide ~.00 N,N-bis-t2-hydroxyethyl)-3,4-dimethylaniline 2.40 *Amounts of stabilizer to give a set time of 40-90 secondsO
Equal weights of composition A and composition B are mixed together and applied to a dry etched tooth. The set material exhibits good surfac~ cure and tenacious xetention to the tooth.
EXA~PLE ~III
Following the pxocedure of ~xample VII but substituting 4.00 parts of N,N~bis-(2-hydroxyethyl)-4-methylaniline for the N,N-bis-(2-hydroxyethyl~3,4-dimethylaniline used therein, two corresponding compo~itions are preparedO The set material prepared by mixing equal we ghts of the two composi.tions exhibits good sur~aGe cure and tenacious retention to the ~ot~.
3~'~
EXAMPLE IX
Two compositions are prepared by mixing the following ingredients:
A B
BIS-GMA 60.O0 60.OO
TEGDM 40.00 40.00 BHT(Stabilizer) ~ *
benzoyl peroxide 2.00 N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline 2.40 *Amounts of stabilizex to give a set time of 40-90 seconds.
.
Equal weights of composition A and composition B are mixed together and applied to a dry etched tooth. The set material exhibits good surface cure and tenacious retention to the tooth.
.
EXAMPLE_X
Following the proceduxe of ~xample IX, but substituting 4.00 parts of N,N-bis-(2-hydroxyethyl)~4~methylaniline fvr the N,M-bis-(2-hydroxyethyl-3,4 dimethylaniline used therein, two corresponding compositicns are prepared. The set material prepared by mixing equal weights of ~he two compositions exhibiks good surface cure and tenacious re~Pntion to the ~oo~
'7 EXAMP~E XI
Two compositions are prepared by mixing the following ingredients:
A B
90:10 BIS-~MA:BADM 40.00 40.00 TEGDM 60.00 60.00 BHT(Stabilizer) * *
benzoyl peroxide 2.00 N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline 2.40 *Amounts of stabilizer to give ~ set time o~ 40--90 seconds.
Equal weights of composition A and composition B are mixed together and applied to a dry etched tooth~ The set material exhibits good surface cure and tenacious retention to the tooth O
~ ,.
EXAMPLE XII
Following the procedure of Example XI, but substituting 4.00 parts of N,N-bis-t2-hydroxyethyl)-4-methylaniline for the N~N-bis-(2-hydroxyethyl-3,4 dimethylaniline used therein, two corresponding compositions are prepared. The set material prepared by mixing equal weights of the two composi~ions : exhibits good surface cure and tenacious retention to the tooth.
: 24 .%~'7 EXAMPLE XIII
Two compositions are prepared by mixing the following ingredients:
A
90:10 BIS-GMA:BADM 60.00 60.00 TEGDM 40.00 40.00 BHT(Stabilizer) *
b~nzoyl peroxide 2.00 N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline 2.40 *Amounts of stabilizer ko give a set time of 40- :
90 seconds.
Equal weights of composition A and composition B are mixed together and applied to a dry ~tched tooth. The set material exhibits good surface cure and tenacious retention to the tooth.
, "
EXAMP~E XIY
Following the procedure of Example XIII, but substituting 4.00 parts of N,N-bis-(2-hydroxyethyl)-4 methylaniline for the N,N-bis-(2-hydroxyethyl)-3~4-dimethylaniline used therein~
two corresponding compositions are pxepared. The set material prepared ~y mixing equal weights of the two compositions exhibits good surface cure and tenacious xetention to the tooth.
EXAMPLE XV
Two compositions are prepared by mixing ~he ~ollowing ingredients:
A B
90:10 BIS~GMA:BADM 45.00 45.00 TEGDM 55.00 55.00 BHT(Stabilizer~ * *
benzoyl peroxide 3.00 N,N-bis-~2-hydroxyethyl)-3,4-dimethylaniline 1.40 *Amounts oE stabilizer to gi~e a set time of 40~90 second~.
Equal weights of composition A and composition B are mixed together and applied to a dry etched tooth. The set material ~xhibits good surface cure and tenacious retention to the . tooth.
: EXAMPLE XVI
Following the procedure of Example XV, but substituting 2.50 parts of N,N-bis-(2-hydroxyethyl)-4-methylaniline for the N,N-bis-~2-hydroxyethyl)-3~4-dimethylaniline used thereini two corresponding compositions are prepared. The s~t mat rial prepared by mixing equal weights of t~e two compositions exhibits good surface cure and tenacious retention to the tooth.
:
, : ' 26 ~ .
. . . ~ . ', : :
.
, ~ .
~ 3 EXAMPLE XVII
Two compositions are prepared by rnixin~ the following ingredients:
A B
90:10 BIS-GM~:BADM 45.00 45.00 TEGDM 55.00 55.00 BHT(Stabilizer~ ~ *
; ben20yl peroxide l.00 N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline 3,20 *Amounts o stabilizer to give a set time of 40-90 seconds.
Equal weights o~ composition A and composition B are mixed together and applied to a dry etched tooth. The set material exhibits good surface cure and,tenacious retention to the tooth.
EXAMPLE XVIII
Following the procedure of Example XVII, but substitu~ing 6.00 parts of N,N-bis-(2~hydroxyethyl)-4-methylaniline for the N,N-bis-(2~hydroxyethyl)-3,4-dimethylaniline used therein, two corresponding compo~itions are prepared~ The set material prepared by mixing equal weights of the two composi~ions I exhibits ~ood surface cure and tenacious retention to the tooth.
'' .. . ' ~ , 3~'~
EXAMPLE XIX
Two compositions are prepared by mix.ing the following ingredients:
A B
90:10 BIS-GM~:BADM 45.00 45~00 TEGDM 55.00 55.00 BHT(Stabili~er) * *
benzoyl peroxide 3O00 N t N-bis ~2~hydroxyethyl~-3,4-dime~hylaniline 3.20 *Amounts of stabilizer to give a set time of 40-90 secondsO
Equ~l weights of composit.ion A and composition B are mixed together and applied to a dry etched tooth. The set material exhibits.good surface cure and tenacious retention to the tooth.
EX~NPLE XX
~ Following the procedure of Example XIX, but substituting : 6.00 parts of N,N-bis-(2-hydroxyethyl~-4-methylaniline for the N,N-bis-(2~hydroxyethyl)-3,4 dimethylaniline used therein, wo corxesponding compositions are prepared. The set materi~l .
prepared by mixing equal weights of the two compositions e~hibits good surface cure and ten~cious retention to the tooth~
EXAMPLE XXI
Two compositiGns are prepared by mixing the following ingredients:
A B
90:10 BIS-GMA:BADM 45.00 45.00 TEGDM 55. 00 55.00 BH~(Stabilizer) * *
benzoyl peroxide 1.00 N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline 1.40 *Amounts of stabilizex to give a set time of 40-90 seconds.
Equal weights o composition A and composition B are mixed together and applied to a dry etched tooth. The set material exhibits good surface cure and tenacious reterlkion to the tooth.
.
EXAMPLE XXXII
; Following the procedure of Example XXI, but substituting 2.50 parts of N,N-bis (2-hydroxyethyl)~4-methylaniline for the N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline used therein, : two corresponding compositions are prepared. .The set material prepared by mixing equal weights of the two compositions :
O exhi~its good surface cure and tenacious retention to the . ':
tooth.
Th~ above Examples have been provided for illustrative purposes only and not to res rict the scope of the present appLicatibn, which scope i5 defined in the appended c:Laims.
.
~,
Suitable liquid polymerizable monomer mat~rials are, for example, those of the ~foresaid ~ee, et al, patent and the binder systems disclosed in the aforesaid Gander, et al, patent.
Teeth accumulate a surface film or pellicle which, along with plaque, is usually cleaned away at regular intervals.
If the tooth to be treated has this surface film or pellicle on it, then it is preferably removed by any known cleaning procedure before the etching step. In some cases, however, the etching process itself may sufficiently clean the tooth surfaceO
A suitable etching solution for use in the method of the invent.ion is 35~ aqueous phosphoric acid, 50~ aqueous phosphoric acid, and the like~ While these etching solutions are preferre~, it is contemplated that any solution which effectively etches the teeth could be used.
The etched tooth surface is preferably cleaned by rinsing the mouth with water, but other types of cleansing such as wiping, swabbing, and the like may be used.
Applicant believes, without wishing to be ~ound thereby, that the good wetting and viscosity proper~ies of the monomer material applied in the present method are greatly responsible for the tenacious retention thereof to the tooth. Compositions may successfully he used in the present method which have a contact angle with respect to dry etched tooth surface of less than 10 measured at ~5DC
and ambient humidity with a Rame-Hart NRL goniometer and a Brookfield viscosity up to about 1200 centipoises measured at ~5C and 100 RPM with a No~ 2 spindle. Compositions useful in the present method preferably have a contact angle of less than 5 measured as abo~e immediately upon application to the dry etched tooth surface. It should b~ understood that the actual contact angle of these preferred compositions is very close to 0, but that contact angles smaller than 5 are not readily measured.-~ pplicant further believes that the set ~ime ofthe compositions of the invention should preferably be in the range from about 40 to about 90 seconcls to yield kenacious retention to the tooth.
It is contemplated tha~ the monomer material ma~
be applied to the tooth surface with a dropper, glass rod, brush, or any other suitable device.
The pit and fissure-sea]ing cosnposition of the invention for use in the present me-thod is a peroxide catalyzed composition comprising from about ~0 -to about 60 parts by weight of a mixture of BIS~GMA and from 0 to about 3 parts by weight BADM for every 9 parts BIS GMA, from about 60 to about 40 parts by weight of T~GDM, and amounts of peroxide catalyst and N,N-bis-(2-hydroxyethyl)-3,4-dimeth~laniline as accelerator for the catalyst such that the set time of the composition is from about ~0 to about 90 seconds, all o~ the catalyst and the accelerator being dissolved in the composi-tion, the composition having a contact angle with respect to dry etched tooth surface tooth of less than 10 and a Brookfield viscosity of up to about 1200 centipoises.
This composition has good surface cure and tenacious long-term retention on the tooth.
The monomer BIS-GMA is the glycidyl methacrylate derivative of bis phenol-A9 more precisely: 2,2-bis-[4-(3-methacryloxy-2-hydroxypropyl) phenyl] propane.
- There may further be included in the composition the monomer bis phenol-A dimethacrylate (BADM), ~referably up to about three parts by weight BADM for every nine parts BIS-G~ and more preerably about one part by weight BADM
for every nine parts BIS-GMA.
; The preferred pit and fissure-sealing compositions of the invention should have a set time from about ~0 to abouk 90 seconds. Thus~ the identity and amounts of peroxide catalyst~ amine accelerator, and stabilizer (if any) must be adjusted so that a set time within the desired range results~
It is well known in the dental restorati~e art that set time may be increased by addition of stabilizers~ It is contempla-ted that as much as two to three times the preferred amounts of peroxide catalyst and amine accelerator may be used, up to the solubility limit of each in the li~uid polymeriæable "? ~
3~
monomer mixture. If a large amount of one of these two is employed, the amount of the other may be corre~pondingly small to maintain the set time within the desired range. If stabilizers axe added, the amounts of accelera~or and catalyst may be increased to maintain the set time in the desired range.
It is contemplated that any prior art accelerator may be used, so long as the set time of the resul~ing composition is within the desired range. The preferred acceleratox is a member selected from the group consisting of N,N-bis-(2~
hydroxyethyl)-4-methylaniline and N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline, and the more preferred accelerator is N,N-bis-~2-hydroxyethyl)-3,4-dimethylaniline.
While the preferred peroxide catalyst or the compositions of the invention is benzoyl peroxide, it is contemplated that other peroxide catalysts could be employed so lony as the set time of the composition is in the desired range. Because the compositions of the invention are peroxide catalyzed, the disadvantages of UV catalysis are obviated.
Stabilizexs may be added to the material, if desired, to inhibit the premature polymerization thereof during storage or to adjust the set time~ Such stabilizers are generally free-xadical chain reaction terminators such as, for example, a substituted phenol, exemplified by ~methoxyphenol '' ' , 2,5-di-t-butyl-4-methylphenol (known as BHT~, a compound of formula:
/ t-butyl~
C CH~OC-CH2CH2 ~ OH
t=butyl 4 (Sold by Geigy Chemical Company under ~he name Irganox 1010), and the like.
A more preferred composition of the in~ention comprises from about 40 to about 50 parts by weight of BIS-GMA, from about 60 to about 40 parts by weight of TEGDM, from about 1.0 to about 3.0 parts ~y weight of N,N-bis-(2-hydroxyethyl)-4-methylaniline and from about 0.5 to about 1.5 parts by weight oP benzoyl peroxide. A more preferred composition of this type comprises rom about 40 to about 60 parts by weight of a mixture of 9 par~s by weight of BIS-GMA
and up to about 3 parts and preferably about 1 par'c by weight BADM, ~rom about 60 to abou~ 40 parts of TE&DM, from about 1.0 to about 3.0 parts by weight of N,~-bis-(2-hydroxy-ethyl)-4-methylaniline, and from about 0.5 to ahout 1.5 parts by weight of benzoyl peroxide.
' A most preferred composition of the invention compri~es all the materials set forth in either of the above, except that from about 0.6 to about 1.8 parts by weight of N,N-bis-t2-hydroxyethyl)-3,4-dimethylaniline is ; subs~ituted for the N,N-bis~ hydroxyethyl)-4-methylaniline used therein.
~: :
.
It should be understood that the above compositions are preferably prepared as two separate compositions, one containing catalyst and no accelera-tor, and the other containing accelerator and no catalyst. Each of these materials would - prefexably con~ain the idential quantity of polymerizable monomer, but would vary only in the presence of the peroxide or amine accelerator and amount of stabilizer. These ~wo separate compositions may then be combined to yield the pit and fissure-sealing composi~ion~ of the invention, which latter is then applied to the tooth. These separate compositions are also considered to be part of the present inven~ion.
Preferred accelerator and catalyst compositions of the invention are identical to the preferred compositions disclosed above except that each contains only accelerator or catalyst (and is substantially free of the other) and contains in it double the amount disclosed above (e.y., from about 1.0 to about 3.0 parts by weight of benzoyl peroxid~
rather than from about 0.5 to about 1.5 parts).
The practice of the present invention is furt~er O illustra~ed by the following Examples, which are given for purposes of illustration only and not to limit the invention thereto. All parts are by weight unless otherwise noted.
'7 EXAMPLE I
Two compositions are prepared by mixing the following ingredients:
A B
90:10 BIS-GMA:BADM 45.00 45.00 TE~DM 55.00 55.00 BHT(Stabilizer) . 0.05 0.15 benzoyl peroxide 2.00 N,N-bis-~2-hydroxyethyl)-3,4-dimethylaniline2~40 Equal weights of composition A and composition B are mixed together and applied to a dry etched tooth. The set material exhibits good surface cure and tenacious reten~ion to the tooth as shown in Example III.
:
~XAMPLE I}
- Followin~ the procedure of Example I, but substituting in composition ~ 4000 parts of N,N-bis-(2-hydroxyethyl)-~-methylaniline for the N,N-bis-~2 hydroxyethyl)-3,4-dimethylaniline and 0.04 parts of ~HT for the O.OS parts us~d therein, two corresponding compositions are prepared. The set material prepared by mixing equal weights of the ~wo compositions exhibits good surace cure and tenacious retention to the tooth as shown in Example IV.
::
~' ', . ' :' ~ ' '7 EXAMPLE III
A study (0766-01-19) of the retent:ion o the composition of Example I and i~s efectiveness in preventing dental caries was conducted on 200 children .six to seven years o~ age. Each child had at least one pair of healthy homologous first molars, one member of each pair being selected at random to be treated and the other ser~ing as controlO
The following procedure was used in the study~
1) All teeth were cleaned by brushing with dental cream.
2) The teeth were examined twice to see if there was a decay-free pair of homologous first molars.
These two independent examinations must have a~reed for the child to have been included in the study.
, 3) The tooth to be treated was determined by consulting a random number table.
4) The tooth to be treated was prepared by etching with a 35% aqueous pho~phoric acid,and xinsing wi~h water, and was then dried and blocked off with cotton rolls.
5) The sealant was applied as a dropt aIlowed to flow ovar the tooth surface, and allowed to set.
The status of the 304 pairs of teeth ~304 treatled and 304 control) 5iX months after ~reatment is shown in the following table.
3~'7 TABLE I-Sta~us of Treated-Control Pairs at Six Months UPPER TEETH LOWER TEETH TOTAL
.. .
Both teeth sound 138 94 232 Both tee~h decayed 1 0 Treated-Sound Control-Decayed 32 38 70 Treated-Decayed, Control Sound - O
Net Gain 32 37 69 Percent Effectiveness - ~ 97.2%
The Table illustrates that the effectiveness of the composition of the invention in the prevention of de~ay was 97.2% (Net Gain divided by number of decayed control teeth). Of the 304 treated teeth, 296(97.4~) completely retained the sealant. Of the 8 teeth which lost sealant, none lo~t it completely and 7 were upper teeth~
EXAMPLE IV
,, A. comparative study (0766~ ~-18) of the retention of the composition of Example II and NUVA SEAL was conducted on 385 children seven years of age or less following the procedure of Example III, except that NUVA SEAL was brushed on the tooth surface~ Each child had at least one pair of healthy homologous first molars, one member of each pair being selected at random for ~rea~ment with either NUV~ SEAL
or the composition of Example II and the other ser~ing as controln The following Tables depicts the results one year after treatment on examination of 30Q children (145 with N W A 5EAL, 155 with Example II) and.576 pairs of teeth (237 w.ith M W A SEAL, 239 with Example II).
TABLE IT-Sealant Retention Complete Partial No Retention Retention Retention NVV~SEAL 83.5% 10.6% 5.9%
EXAMPLE II ~4.6% 2~5~o 2.9%
TABLE IIIa-~S-tatus of NUVA SEAL-Control Pairs .
U~er Teeth Lower Teeth Total __ , Both teeth sound 93 108 201 Bo~th teeth de-cayed Treated-Sound, Control-decayed 22 8 30 Treated-Decayed, Control-Sound 1 3 4 Net Gain 21 5 26 Pexcent Effectiveness91~3 55.Ç 81.2 : 18 .
`
: - .
TABLE IIIb-Sta~us of Example II-Control Pairs IJpper Teeth Lower Teeth Total Booth tee~h sound 90 103 193 Booth teeth decayed 3 4 7 Treated-Sound, Control-Decayed 25 14 39 Treated-Decayed, Control-Sound 0 0 0 Net Gain 25 14 39 Percent Effectiveness 89.3 77.8 84.8 It can be seen from the a~ove tables that the composition of Example ~X had greater than eleven percentage points better complete retention than NUVA SEAL and had a greater percentage effectiveness, especially for lowex teeth. It should b~ noted that there is a significant relationship between complete retention and decay prevention in the long term which is not clearly demonstrated ~y this study, because of the short period involved.
:
3~'7 EXAMPLE V
Two compositions are prepared by mixing the following ingredients:
A B
90:10 BIS-GMA:BADM 74 TE&DM ~ 23.5 100 methacrylic acid 1.0 benzoyl peroxide 1.2 N,N-bis-12-hydroxyethyl)~
4-methylaniline 1.5 Three parts of composition A and two parts of composition B
are mixed together and applied to a dry etched tooth. The set material exhibits good surface cure and tenacious retention to the tooth as shown in the following Example.
~~' . .
EXAMPLE VI
~ r ~
A study (0766 01-12) of the retention of the composition of Example V and its effectiveness in preventing dental caries was conducted on 24 children six to seven years of age, following the procedure of Example III. Each child had at least one pair o~ healthy ho~ologous first molars, one member of each pair being selected at random to be treated:and the other serv1ng as con~rol.
The status of the teeth examined at period~ after treatment is shown in the following table.
TABLE IV
3 months12 months 18 mGnt'hs 30 months No. of pairs examined 22 22 22 19 Complete reten-tion21 21 ~ 20 17 Partial reten-tion 1 0 No retention 0 Both teeth sound 10 7 4 3 Both teeth decayed 0 1 2 2 T.reated-Sound Control-Decayed12 14 16 14 Treated-decayed, Control Sound 0 0 0 0 Net Gain 12 14 16 14 Percent Effectiveness100% 93.3% 88.9% 87.5%
The table illustrates that 89~5% of the treated first molars completely retained the composition of Example V after 2 1/2 year~ and that it6 percent effectiveness in the prevention of decay in the ~clme time period was 87O5%~
' ~1 EXAMPLE VII
Two compositions are prepared by mixing the following in~redients:
A B
BIS GMA 40.00 40.00 TEGDM 60.00 6~.00 BHT(Stabilizer) * *
benzoyl peroxide ~.00 N,N-bis-t2-hydroxyethyl)-3,4-dimethylaniline 2.40 *Amounts of stabilizer to give a set time of 40-90 secondsO
Equal weights of composition A and composition B are mixed together and applied to a dry etched tooth. The set material exhibits good surfac~ cure and tenacious xetention to the tooth.
EXA~PLE ~III
Following the pxocedure of ~xample VII but substituting 4.00 parts of N,N~bis-(2-hydroxyethyl)-4-methylaniline for the N,N-bis-(2-hydroxyethyl~3,4-dimethylaniline used therein, two corresponding compo~itions are preparedO The set material prepared by mixing equal we ghts of the two composi.tions exhibits good sur~aGe cure and tenacious retention to the ~ot~.
3~'~
EXAMPLE IX
Two compositions are prepared by mixing the following ingredients:
A B
BIS-GMA 60.O0 60.OO
TEGDM 40.00 40.00 BHT(Stabilizer) ~ *
benzoyl peroxide 2.00 N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline 2.40 *Amounts of stabilizex to give a set time of 40-90 seconds.
.
Equal weights of composition A and composition B are mixed together and applied to a dry etched tooth. The set material exhibits good surface cure and tenacious retention to the tooth.
.
EXAMPLE_X
Following the proceduxe of ~xample IX, but substituting 4.00 parts of N,N-bis-(2-hydroxyethyl)~4~methylaniline fvr the N,M-bis-(2-hydroxyethyl-3,4 dimethylaniline used therein, two corresponding compositicns are prepared. The set material prepared by mixing equal weights of ~he two compositions exhibiks good surface cure and tenacious re~Pntion to the ~oo~
'7 EXAMP~E XI
Two compositions are prepared by mixing the following ingredients:
A B
90:10 BIS-~MA:BADM 40.00 40.00 TEGDM 60.00 60.00 BHT(Stabilizer) * *
benzoyl peroxide 2.00 N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline 2.40 *Amounts of stabilizer to give ~ set time o~ 40--90 seconds.
Equal weights of composition A and composition B are mixed together and applied to a dry etched tooth~ The set material exhibits good surface cure and tenacious retention to the tooth O
~ ,.
EXAMPLE XII
Following the procedure of Example XI, but substituting 4.00 parts of N,N-bis-t2-hydroxyethyl)-4-methylaniline for the N~N-bis-(2-hydroxyethyl-3,4 dimethylaniline used therein, two corresponding compositions are prepared. The set material prepared by mixing equal weights of the two composi~ions : exhibits good surface cure and tenacious retention to the tooth.
: 24 .%~'7 EXAMPLE XIII
Two compositions are prepared by mixing the following ingredients:
A
90:10 BIS-GMA:BADM 60.00 60.00 TEGDM 40.00 40.00 BHT(Stabilizer) *
b~nzoyl peroxide 2.00 N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline 2.40 *Amounts of stabilizer ko give a set time of 40- :
90 seconds.
Equal weights of composition A and composition B are mixed together and applied to a dry ~tched tooth. The set material exhibits good surface cure and tenacious retention to the tooth.
, "
EXAMP~E XIY
Following the procedure of Example XIII, but substituting 4.00 parts of N,N-bis-(2-hydroxyethyl)-4 methylaniline for the N,N-bis-(2-hydroxyethyl)-3~4-dimethylaniline used therein~
two corresponding compositions are pxepared. The set material prepared ~y mixing equal weights of the two compositions exhibits good surface cure and tenacious xetention to the tooth.
EXAMPLE XV
Two compositions are prepared by mixing ~he ~ollowing ingredients:
A B
90:10 BIS~GMA:BADM 45.00 45.00 TEGDM 55.00 55.00 BHT(Stabilizer~ * *
benzoyl peroxide 3.00 N,N-bis-~2-hydroxyethyl)-3,4-dimethylaniline 1.40 *Amounts oE stabilizer to gi~e a set time of 40~90 second~.
Equal weights of composition A and composition B are mixed together and applied to a dry etched tooth. The set material ~xhibits good surface cure and tenacious retention to the . tooth.
: EXAMPLE XVI
Following the procedure of Example XV, but substituting 2.50 parts of N,N-bis-(2-hydroxyethyl)-4-methylaniline for the N,N-bis-~2-hydroxyethyl)-3~4-dimethylaniline used thereini two corresponding compositions are prepared. The s~t mat rial prepared by mixing equal weights of t~e two compositions exhibits good surface cure and tenacious retention to the tooth.
:
, : ' 26 ~ .
. . . ~ . ', : :
.
, ~ .
~ 3 EXAMPLE XVII
Two compositions are prepared by rnixin~ the following ingredients:
A B
90:10 BIS-GM~:BADM 45.00 45.00 TEGDM 55.00 55.00 BHT(Stabilizer~ ~ *
; ben20yl peroxide l.00 N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline 3,20 *Amounts o stabilizer to give a set time of 40-90 seconds.
Equal weights o~ composition A and composition B are mixed together and applied to a dry etched tooth. The set material exhibits good surface cure and,tenacious retention to the tooth.
EXAMPLE XVIII
Following the procedure of Example XVII, but substitu~ing 6.00 parts of N,N-bis-(2~hydroxyethyl)-4-methylaniline for the N,N-bis-(2~hydroxyethyl)-3,4-dimethylaniline used therein, two corresponding compo~itions are prepared~ The set material prepared by mixing equal weights of the two composi~ions I exhibits ~ood surface cure and tenacious retention to the tooth.
'' .. . ' ~ , 3~'~
EXAMPLE XIX
Two compositions are prepared by mix.ing the following ingredients:
A B
90:10 BIS-GM~:BADM 45.00 45~00 TEGDM 55.00 55.00 BHT(Stabili~er) * *
benzoyl peroxide 3O00 N t N-bis ~2~hydroxyethyl~-3,4-dime~hylaniline 3.20 *Amounts of stabilizer to give a set time of 40-90 secondsO
Equ~l weights of composit.ion A and composition B are mixed together and applied to a dry etched tooth. The set material exhibits.good surface cure and tenacious retention to the tooth.
EX~NPLE XX
~ Following the procedure of Example XIX, but substituting : 6.00 parts of N,N-bis-(2-hydroxyethyl~-4-methylaniline for the N,N-bis-(2~hydroxyethyl)-3,4 dimethylaniline used therein, wo corxesponding compositions are prepared. The set materi~l .
prepared by mixing equal weights of the two compositions e~hibits good surface cure and ten~cious retention to the tooth~
EXAMPLE XXI
Two compositiGns are prepared by mixing the following ingredients:
A B
90:10 BIS-GMA:BADM 45.00 45.00 TEGDM 55. 00 55.00 BH~(Stabilizer) * *
benzoyl peroxide 1.00 N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline 1.40 *Amounts of stabilizex to give a set time of 40-90 seconds.
Equal weights o composition A and composition B are mixed together and applied to a dry etched tooth. The set material exhibits good surface cure and tenacious reterlkion to the tooth.
.
EXAMPLE XXXII
; Following the procedure of Example XXI, but substituting 2.50 parts of N,N-bis (2-hydroxyethyl)~4-methylaniline for the N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline used therein, : two corresponding compositions are prepared. .The set material prepared by mixing equal weights of the two compositions :
O exhi~its good surface cure and tenacious retention to the . ':
tooth.
Th~ above Examples have been provided for illustrative purposes only and not to res rict the scope of the present appLicatibn, which scope i5 defined in the appended c:Laims.
.
~,
Claims (12)
1. A peroxide-catalyzed composition useful for the sealing of pits and fissures in teeth to prevent decay therein which comprises from about 40 to about 60 parts by weight of a mixture of BIS-GMA and from 0 to about 3 parts by weight BADM for every 9 parts BIS-GMA, from about 60 to about 40 parts by weight of TEGDM, and amounts of peroxide catalyst and N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline as accelera-tor for said catalyst such that the set time of the composi-tion is from about 40 to about 90 seconds, all of said catalyst and said accelerator being dissolved in said composition, said composition having a contact angle with respect to dry etched tooth surface tooth of less than 10° and a Brookfield viscosity of up to about 1200 centipoises.
2. The composition of claim 1 wherein the peroxide catalyst is benzoyl peroxide.
3. The composition of claim 2 wherein the benzoyl peroxide is present in from about 0.5 to about 1.5 parts by weight and the N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline is present in from about 0.6 to about 1.8 parts by weight.
4. The composition of claim 1 which comprises about one part by weight of BADM for every nine parts of BIS-GMA.
5. The compound of claim 4 wherein the peroxide catalyst is benzoyl peroxide.
6. The composition of claim 5 wherein the benzoyl peroxide is present in from about 0.5 to about 1.5 parts by weight and the N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline is present in from about 0.6 to about 1.8 parts by weight.
7. Two compositions which, when mixed together, yield a mixed composition useful for the sealing of pits and fissures in teeth, a) a catalyst composition comprising from about 40 to about 60 parts by weight of a mixture of BIS-GMA and from 0 to about 3 parts by weighg BADM for every 9 parts BIS-GMA, from about 60 to about 40 parts by weight of TEGDM, and a peroxide catalyst, said catalyst composition being essentially free of accelerator for said peroxide catalyst;
and b) an accelerator composition comprising from about 40 to about 60 parts by weight of a mixture of BIS-GMA
and from 0 to about 3 parts by weight BADM for every 9 parts BIS-GMA, from about 60 to about 40 parts by weight of TEGDM, and N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline as accele-rator for said peroxide catalyst, said accelerator composi-tion being essentially free of peroxides, c) the amounts of said catalyst and said accele-rator being such that the set time of the resulting mixed composition is from about 40 to about 90 seconds, all of said catalyst and said accelerator being dissolved in their respective compositions, said resulting mixed composition having a contact angle with respect to dry etched tooth surface of less than 10° and a Brookfield viscosity of up to about 1200 centipoises.
and b) an accelerator composition comprising from about 40 to about 60 parts by weight of a mixture of BIS-GMA
and from 0 to about 3 parts by weight BADM for every 9 parts BIS-GMA, from about 60 to about 40 parts by weight of TEGDM, and N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline as accele-rator for said peroxide catalyst, said accelerator composi-tion being essentially free of peroxides, c) the amounts of said catalyst and said accele-rator being such that the set time of the resulting mixed composition is from about 40 to about 90 seconds, all of said catalyst and said accelerator being dissolved in their respective compositions, said resulting mixed composition having a contact angle with respect to dry etched tooth surface of less than 10° and a Brookfield viscosity of up to about 1200 centipoises.
8. The compositions of claim 7 wherein the peroxide catalyst is benzoyl peroxide.
9. The compositions of claim 8 wherein the benzoyl peroxide is present in from about 1.0 to about 3.0 parts by weight based on the weight of the catalyst composition and the N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline is present in from about 1.2 to about 3.6 parts by weight based on the weight of the accelerator composition.
10. The compositions of claim 7 which comprises about one part by weight of BADM for every nine parts of BIS-GMA.
11. The compositions of claim 10 wherein the peroxide catalyst is benzoyl peroxide.
12. The compositions of claim 11 wherein the benzoyl peroxide is present in from about 1.0 to about 3.0 parts by weight based on the weight of the catalyst composition and the N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline is present in from about 1.2 to about 3.6 parts by weight based on the weight of the accelerator composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US64100275A | 1975-12-15 | 1975-12-15 | |
| US641,002 | 1975-12-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1112397A true CA1112397A (en) | 1981-11-10 |
Family
ID=24570536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA267,718A Expired CA1112397A (en) | 1975-12-15 | 1976-12-13 | Peroxide-catalyzed composition useful for sealing pits and fissures in teeth |
Country Status (16)
| Country | Link |
|---|---|
| JP (1) | JPS5273592A (en) |
| AU (1) | AU511177B2 (en) |
| BE (1) | BE849447A (en) |
| BR (1) | BR7608427A (en) |
| CA (1) | CA1112397A (en) |
| CH (1) | CH633178A5 (en) |
| DE (1) | DE2656385C3 (en) |
| FR (1) | FR2335194A1 (en) |
| GB (1) | GB1557263A (en) |
| IL (1) | IL51105A (en) |
| IN (1) | IN145460B (en) |
| NL (1) | NL7613934A (en) |
| NZ (1) | NZ182875A (en) |
| PH (1) | PH12797A (en) |
| SE (1) | SE7614051L (en) |
| ZA (1) | ZA767432B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59130806A (en) * | 1983-01-17 | 1984-07-27 | Kuraray Co Ltd | Composition for sealing scissura of suleus of teeth |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3066112A (en) * | 1959-01-30 | 1962-11-27 | Rafael L Bowen | Dental filling material comprising vinyl silane treated fused silica and a binder consisting of the reaction product of bis phenol and glycidyl acrylate |
| US3256254A (en) * | 1962-08-28 | 1966-06-14 | Du Pont | Oxycarbocyclic ester compositions containing aryl peroxides and tertiary aromatic amines, polymerizable in air |
| BE788670R (en) * | 1968-04-08 | 1973-03-12 | Johnson & Johnson | COMPOSITIONS |
| US3580955A (en) * | 1968-04-18 | 1971-05-25 | Pennwalt Corp | Auto-oxidation of aldehydes in the presence of acylating agents |
| US3539533A (en) * | 1968-06-14 | 1970-11-10 | Johnson & Johnson | Dental filling material |
| US3541068A (en) * | 1968-07-12 | 1970-11-17 | Minnesota Mining & Mfg | Dental restorative compositions having enhanced stability |
| US3663501A (en) * | 1970-06-11 | 1972-05-16 | Johnson & Johnson | Adhesive cement |
| US3799985A (en) * | 1971-11-15 | 1974-03-26 | Erickson W Co | N,n-bis(2-hydroxyethyl)-3,4,5-trimethylaniline |
| ZA728928B (en) * | 1972-01-03 | 1973-09-26 | Lee Pharmaceuticals | Dental adhesive composites |
| US3835090A (en) * | 1972-02-03 | 1974-09-10 | Johnson & Johnson | Dental restorative cement compositions |
| NO754397L (en) * | 1975-01-02 | 1976-07-05 | Johnson & Johnson |
-
1976
- 1976-12-13 AU AU20513/76A patent/AU511177B2/en not_active Expired
- 1976-12-13 CA CA267,718A patent/CA1112397A/en not_active Expired
- 1976-12-13 DE DE2656385A patent/DE2656385C3/en not_active Expired - Lifetime
- 1976-12-13 NZ NZ182875A patent/NZ182875A/en unknown
- 1976-12-14 GB GB52095/76A patent/GB1557263A/en not_active Expired
- 1976-12-14 ZA ZA00767432A patent/ZA767432B/en unknown
- 1976-12-14 IL IL51105A patent/IL51105A/en unknown
- 1976-12-14 SE SE7614051A patent/SE7614051L/en unknown
- 1976-12-15 FR FR7637789A patent/FR2335194A1/en active Granted
- 1976-12-15 JP JP51149918A patent/JPS5273592A/en active Granted
- 1976-12-15 BE BE173297A patent/BE849447A/en not_active IP Right Cessation
- 1976-12-15 PH PH19253A patent/PH12797A/en unknown
- 1976-12-15 CH CH1578676A patent/CH633178A5/en not_active IP Right Cessation
- 1976-12-15 BR BR7608427A patent/BR7608427A/en unknown
- 1976-12-15 NL NL7613934A patent/NL7613934A/en not_active Application Discontinuation
- 1976-12-23 IN IN2254/CAL/76A patent/IN145460B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IL51105A0 (en) | 1977-02-28 |
| JPS555791B2 (en) | 1980-02-09 |
| IL51105A (en) | 1979-12-30 |
| CH633178A5 (en) | 1982-11-30 |
| BE849447A (en) | 1977-06-15 |
| NZ182875A (en) | 1978-09-20 |
| DE2656385C3 (en) | 1995-03-23 |
| NL7613934A (en) | 1977-06-17 |
| DE2656385C2 (en) | 1988-09-29 |
| GB1557263A (en) | 1979-12-05 |
| PH12797A (en) | 1979-08-17 |
| AU511177B2 (en) | 1980-07-31 |
| BR7608427A (en) | 1977-12-13 |
| FR2335194A1 (en) | 1977-07-15 |
| AU2051376A (en) | 1978-06-22 |
| ZA767432B (en) | 1978-07-26 |
| SE7614051L (en) | 1977-06-16 |
| JPS5273592A (en) | 1977-06-20 |
| IN145460B (en) | 1978-10-14 |
| FR2335194B1 (en) | 1982-04-30 |
| DE2656385A1 (en) | 1977-06-16 |
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