CA1294946C - Prevention of outgassing in polyvinylsiloxane elastomers by the use of finely divided platinum black - Google Patents
Prevention of outgassing in polyvinylsiloxane elastomers by the use of finely divided platinum blackInfo
- Publication number
- CA1294946C CA1294946C CA000535603A CA535603A CA1294946C CA 1294946 C CA1294946 C CA 1294946C CA 000535603 A CA000535603 A CA 000535603A CA 535603 A CA535603 A CA 535603A CA 1294946 C CA1294946 C CA 1294946C
- Authority
- CA
- Canada
- Prior art keywords
- polyethylene glycol
- sorbitan
- polyoxyethylene
- platinum black
- catalyst paste
- 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 - Lifetime
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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
- A61K6/90—Compositions for taking dental impressions
Abstract
Abstract of the Disclosure A polyvinylsiloxane catalyst paste which comprises up to 20,000 ppm of finely divided platinum black which functions to adsorb hydrogen gas generated in the reaction of said catalyst paste with a hydrofunctional polydimethylsiloxane.
Description
Back~r~un______he In e t ion The liberation of small quantities of hydrogen gas fro~ RTV
addi~ion eured polyvinylsiloxane elas~omers, due to the reaction belween the platinum ca~alyst and hydrofunc~ional polydimethylsiloxane, is a recognized probl~m. The eYolution of the hydrogen gas results in the formation of pores in the model formed from the impression, producing an undesirable pi~ted surface.
In the U.S. Patent 4,273,902, issued JuIle 16, 1981, and assigned to G-C Dental Industrial Corp., of Tokyo, this problem is well described and a solution is claimed using 0. 5 ppm or more fin~ly divided palladium and/or a finely divided palladium alloy.
containing 10% by weight or more of palladium, withou~ inhibi~ing the addition reaction. In Column 3, line 33 et seq., various other elemental metals are cited, including platinum, bu~ are stated to be inferior ~o palladium and fail to elimina~e the undeslrable pores ln the surface of th~ resulting model.
~L2~346 The adsorption of hydrogen by palladium is variously quoled as 502, 935 and even 2952 times its own volume, J.W. Mellor, Inorganic Chemistry Vol XVII 1947, page 616 et seq., while the adsorption of hydrogen by platinum black is quoted as 310 volumes in Vol. XYI. It therefore becomes apparent that these adsorption variabilities arise from dif~erences in the available surface areaC of the finely divided me~als, but are not significant in ~he case of ~he polyvinylsiloxane elastomer application, since if sufficiently finely divided and present in adequa~e concentration, the adsorption saturation level will never be reached.
Another problem associated with polyvinylsiloxane dental impression materials is their extremely hydrophobic characteristics which lead to comparatively large ~ubble shaped artifacts in the surface of such impressions.
Summary of the Invention Accordinglyr it has been discovered tha~ when-samples o extremely finely divided platinum black were obtained with the highest possible surface area, specifically 24 M2gram, and were compared with equal weight percent concentrations of palladium black, by incorporation in identical polyvinylsiloxane elastomer pastes they were found to be equally and co3npletely effective, down to a concentra~ion level of abou~ Or2 ppm by weight. An efective concentration range for the platinum black is about 0.2 12991~6 to 20~000 ppm by weight. The size range ~or the platinum blacX
should be as sm~ll as possible. ~ preferred size range for ~he platinum black is from abo~t 18 to 28 An~stro~ Units;
The use o~ platinum blac~ in conjunction with ~he present invention is in controlling or prevsnting outgassing in all addition cured polyvinylsiloxane ela~tomers which are primarily used in making dental impressions.
The platinum black is used to adsorb gaseous hydrogen ~enera~ed during the curing reaction, and generally at a concentration level of about 0.2 to 20,000 ppm. A pre~erred concentration range is ~rom about .001 ~o 0;01 weight percen~
(i.e., 1,000 to 10,000 ppm). The platinum black is added or blended with the catalyst paste in any convenient manner such as illustrated in U.S. Patent ~,273,902.
Il has also been discovered tha~ in a preferred embodiment of the invention that the ex~remely hydrophobic characterisitcs of polyvinylsiloxane dental impression materials, which lead to comparatively large bubble shaped artifacts in the surface of such impressions, can be overcome by ~he incorporation of relatiYely small quantitîes of selected surfactan~s.
Detailed_Dcscription o~ the Invention .
~oth base and catalys~ pastes contain vinyl polydime~hyl siloxane and silica or other similar inert ~iller(s) and the base paste A~
. . . .
~Z9~9 ~6 contains a moiety of hydrofunctional polydimethylsil~xane whereas ~he catalyst contains both a chloroplatinic acid catalyst complex and pla~inum black, to adsorb any gaseous hydrogen formed duri~g mixing of the pastes and curing of the impression.
A cured impression is produced by mixing ~he base pajte and catalyst such as ~hat illustrated by Example I, in a 1:1 or other suitable ratio to form a homogeneous plastic mass which is applied over the den~ition and adjacent gingival ~issue and allowed tO cure during a time frame of several minutes prior tO
mouth removal. Models were made from impressions taken with the platinum black containing impression materials immediately after mouth remoYal and found to be free of pores in all cases at or above the 0.005 weight percent platinum level.
Impressions and resulting molds or models formed using ~he concept of the present invention result in a surfac~ smoothness which is significantly better than ~hose formed withou~ the use of platinum black.
Another problem associated with polyYinylsiloxane dental impression materials of this in~ention is their ~xtremely hydrophobic characteristics which lead ~o comparatively larg~
bubble shaped artifacts in the sur:Eace o~ such impression-s.
U.S. Pa~ent 4~600,751 teaches the controlled release of bioactive agen~s, and serves to demonstrate the synthesis of silicone based prepolymers which are extre~ely hydrophilic.
In dentistry, impression materials, particularly for making crown and bridge i~pressions, require a high de~ree of ~ Z ~ ~ 9 ~ ~
dimensional stability to facilita~e the production of extremely accurate prostheses, for which the t~chniques of U.S. Patent 4,600,751 would be totally unsuitable because high water sorp~ion is consistent with swelling and distortion of ~hese polymers.
Fur~hermore there are, other definite advantages to dental impressions with low water sorption, such as ease of disinfection and sterilization.
With respect to the problem associated with the hydrophobic characteristics of the dental impression materials of the present invention it has been found possible to utilize several species of hydrophilic compounds as low concentration additives to conventional, extremely hydrophobic, addition-cured polyvinylsiloxane dental impression materials to impart truly hydrophilic surface characteristics to these materials. This results in the pre~ention of compartitively large bubble shaped artifacts in the surface of these impressions, due to the effects of surface tension at a strongly hydrophobic/hydrophilic interface causing a film of moisture to form water droplets.
In a preferred embodiment of this inYen~ion~ any one or more of the following surfactant type sompounds are added to conventional addition-cured polyvinylsiloxane dental impr~ssion materials in relatively low concentrations of about l.0~ to 10.0%
by weight.
COMPOUND NAME CAS NO. WHERE KNOWN
n-Dodecyl, Tetradecyl, Hexadecyl Alcohol Ethoxylate 685Sl-12-2 Polyethylene Glycol Monolaura~e 9004-81-3 Polye~hylene Glycol Dilaurate Polyelhylene Glycol Monoleate Polyethylene Glycol Dioleate Polyethylene Glycol Monotallate Polyethylene Glycol Ditallate Sorbitan Monolaurate Sorbi~an Monoleate Sorbitan Trioleate Sorbitan Monotallate Sorbitan Tritallate Polyethylene Glycol Glycerol Cosoea~e Caprylic Triglyceride Polyoxye~hylene Tridecyl Alcohol 2493B-91-8 Polyoxyethylene Lauryl Ether 5274-68-0 Nonylphenoxypoly ~ethyleneoxy) ethanol 9016-45-9 Polyoxyethylene Sorbitan Monolaurate Sorbitan Monolaurate Polyoxyethylene Polysorbate 9005-64-5 Polyoxyethylene Oleyl Alcohol The above listing of suitable surfactants is not exhaustive, but serves to illustrate twenty representative examples of the manny chemical permutations possible with the family of Polyol fatty acid ester and ethoxylated ester type surfactants useful for this invention.
The effectiveness of these surfactant additives is readily apparent in th~ir ability to reduce ~he aqueous con~act angle with oured or uncured addition-cured polyvinylsiloxane d~n~al impression ma~erials from the range of 95-110 down ~o 30 or less. Upon contact of the dental impression materials with the denti~ion and gingiva any moisture present on ~he surface of these oral tissues is readily miscible with the surfactant moiesy arailable at the surface of the impression material, which ~ ~ 9 ~
provides uniform wetting of the in~erface between the impression material and the oral tissues, thereby drama~ically reducing surface tension.
The following example illus~rates one embodimen~ of the presen~ invention. The concentrations are in weight percen~
unless otherwise sta~ed.
EXAMPLE I
Embodiments of Platinum Black or_~aseous adsorption:
BASE PASTE (VERY HEAYY VISCOSITY) CATALYST PASTE tVERY HEA W VISCOSITY) WT% WT~
Vinyl Polydimethylsiloxane 20~%Vinyl Polydimethylsiloxane 20%
Hydropolydimethyl Siloxane3%*Cyclic Vinyl Siloxane 0.4~
Silica FiIler 70%*~Chloroplatinic Acid Complex 1.0%
Liquid Petroleum or other 7%Lîquid Petroleu~ or other inert plasticizer inert plasticizer 7S
Silica or other inert filler 71.6%
The following illustrates suitable compositional ranges for the components of the base and catalyst pas~e.
BASE PASTE WT% CATALYST PASTE WT~
Vinyl Polydimethylsiloxane 10-60 Vinyl Polydimethylsiloxane 10-60 Hydropolydimethyl Siloxane 1-10 Cyclic Vinyl Siloxane 0-2 Silica Filler 20-80 Chloroplatinic Acid Complex Ool~5~0 Liquid Petroleum 0 15 Platinum Black 0.2-20,000 ppm Plas ti Ci zer 0-15 Filler 20-80 -The following illustrates sui~a~le compositional ranges for a cure~
dental impression material of the presen~ inven~ion.
~29~9~6 VERY ~EAVY VISCOSITY M~TERIAL (PUTTY) WTS
Vînyl Polydimc~hylsiloxane 10-60 Cyclic Vinyl Siloxane 0-1 Hydropolydimethyl Siloxane 0.5-5 0 Filler 20-80 Chloroplat;nic ~cid Complex 0.05-2.5 Platinum ~lack 0.1-10,000 ppm Plasticizer 0-15 Surfactant (op~ional but pre~erred) 2-10 Availab].e under the ~rade-mark PSW 2204 from Petrarch Silico-;
nes of Bristo], PA.
Avai].ab]e under the trade-mark PSW 2206 from Petrarch;
Si].icones of Brito]., PA.
Embodiments usin~ surEactants to con~er hydrophilic ch~rac~eristics:
Low viscosit Catal st aste wi~h surfactant WT~
Y Y P
Vinyl unctional polydimethylsiloxane 51.785 Silaceous Filler 43 0 n-Dodecyl, Te~radecyl, ~lexadecyl Alcohol E~hoxylate 4.0 Pigmen~ 1.0 Cyclic vinyl function~l prepolymer 0.2 Chloroplatinic acid catalyst complex 0.01 Platinum Black 0.005 Excellent hydrophilic surface characteristics, but unpleasant tasle.
Low viscosity ~ase paste with surf~ctant Vinyl functional polydime~hlsiloxane 46.0 Silaceous Eiller 42.0 Hydrofunctional Polydimethylsiloxane 7.0 Pigment 2.0 Nonylphenoxypoly(ethyleneoxy~ethanol 5.0 Exce~lent hydrophilic surface characteristics ~nd acceptable taste.
,. .~
.. 1i Z~
Low viscosity Base paste with surfactant Vinyl functional polydimethylsiloxane 46.0 Silaceous Filler . 41.0 Hydrofunctional polydimethylsiloxane 7.0 n-Dodecyl~ Tetradecyl 9 Hexadecyl Alcohol Ethoxylate 4 . O
Pigment 2.0 1'00, 00 Excellent hydrophilic surfaee characteristics~ but unpleasant taste.
Although the above examples are restrictsd ~o low viscosity polyvinylsiloxane den~al impression materials the same family of Polyol fatty acid ester and ethoxylated ester type surfactant can be used as additives in the regular and heavy, even pu~ty viscosities of the same type of material with equally effeceive results, The following illustrates suitable compositional ranges for the components of ~he base and catalyst pastes of Examples 2 Ihrough 4.
BASE PASTES WT% CATALYST PASTES WT%
Vinyl polydimethylsiloxane 25-75 Vinyl Polydimethylsiloxane 25-75 Hydropolydimethyl siloxane 1-12 Cyclic Vinyl Siloxane 0,5 Silaceous Fillerts) 25-75 Silaceous Filler(s) - 25-72 Surfactantts) 1-10 Surfactantts) 1-10 Pigment(s) 0.5 Pigment(s) 0.5 Chloroplatinic Acid Complex 0.1-5.0 Platinum Black 0.2-20,000 ppm The following illus~rates sui~able compositional ranges for a cured dental impression material of Examples 2 throu~h 4 of ~he presen~
inYention:
LOW VISCOSITY MATERIAL (LIGIIT ~ODY on W~SH) WT%
Vinylpolydimethyls iloxane 2 5-75 Hydro polydimelhylsiloxane . 0.5-5.0 Cyclic ~inyl siloxane 0-1 Silaceous Filler(s) 25-75 5urfactant(s) 1-10 P;gment(s) O-S
Chloraplatinic ~cid Complex 0.05-2.5 Platinum Black 0.01-109000 ppm The ollowing is a preferred embodiment o~ the present inven~ion which exhibits the desired properties with respec~ to con~rollin~
outgassing and hydrophilic characteristics:
LOW VISCOSITY BASE P~STE ~YIT~ SURFACTANT WT~
Vinyl ~unctional polydime~hylsiloxane (4000 cps) 46.0 Calcium Silicate ~iller 42.0 Hydrofunctional polydimethylsiloxane 7.0 Nonylphenoxypoly (ethyleneoxy) ethanol 3.0 Cobalt Blue Pigment LOW V I S COS I TY CAT~LYST P~ST E WITII PL~TINUM
Vinyl ~unctîonal polydimelhylsilox~ne (~000 cps) 54.73 Calcium Silicate Filler 43.98 Cobalt Blue Pigment 1.0 Cyclic Vinyl functional prepolymer 0.27 Chloropla~inic ~cid Catalys~ complex 0.01 Pla~inum Black (2~ ~2/gm) 0 01 The following is a typical method used in preparing ~he compounds of the present inven~ion. Other methods and compounds, such as those set orth in ~he above mentioned U.S. Patent 47273,902 may also be used in conjunction with this invention.
, . . .
~9 RASE PASTE
Blend together in a double planetary mixer the three li~uid components, Vinyl unctional polydimethylsiloxane, Hydrofunctional polydimethylsiloxane and Nonylphenoxypoly(ethyleneoxy)ethanol. Add pi~ment, and then reblend to evenly disperse the pigment, filler is then added and mixed until thoroughly homogenous to form a low viscosity fluid paste. The resulting paste is then rollmilled tO maximize homogeneity followed by packaging as desired.
CATALYST PASTE
. ~
Preblends are made of the Chloroplatinic acid complex with a portion of the Vinyl functional polydimethylsiloxane and of the Platinum Black with a portion of the Calcium Silica~e filler.
Blend together the three liquid components, Catalyst complex preblend, balance of Vinyl functional polydimethylsiloxane and Cyclic Vinyl prepolymer. Add pigment, reblend to disperse, ~hen add Platinum Black preblend, followed by balance of the filler and mix until throughly homogenous. Rollmill to maxi~ize homogeneity and then package as desired.
While the invention has been described in detail with respect to specific embodiments thereof, it will be understood by those skilled in the art that variations and modifica~ions may be made wi~hout departing from the essential features thereof.
addi~ion eured polyvinylsiloxane elas~omers, due to the reaction belween the platinum ca~alyst and hydrofunc~ional polydimethylsiloxane, is a recognized probl~m. The eYolution of the hydrogen gas results in the formation of pores in the model formed from the impression, producing an undesirable pi~ted surface.
In the U.S. Patent 4,273,902, issued JuIle 16, 1981, and assigned to G-C Dental Industrial Corp., of Tokyo, this problem is well described and a solution is claimed using 0. 5 ppm or more fin~ly divided palladium and/or a finely divided palladium alloy.
containing 10% by weight or more of palladium, withou~ inhibi~ing the addition reaction. In Column 3, line 33 et seq., various other elemental metals are cited, including platinum, bu~ are stated to be inferior ~o palladium and fail to elimina~e the undeslrable pores ln the surface of th~ resulting model.
~L2~346 The adsorption of hydrogen by palladium is variously quoled as 502, 935 and even 2952 times its own volume, J.W. Mellor, Inorganic Chemistry Vol XVII 1947, page 616 et seq., while the adsorption of hydrogen by platinum black is quoted as 310 volumes in Vol. XYI. It therefore becomes apparent that these adsorption variabilities arise from dif~erences in the available surface areaC of the finely divided me~als, but are not significant in ~he case of ~he polyvinylsiloxane elastomer application, since if sufficiently finely divided and present in adequa~e concentration, the adsorption saturation level will never be reached.
Another problem associated with polyvinylsiloxane dental impression materials is their extremely hydrophobic characteristics which lead to comparatively large ~ubble shaped artifacts in the surface of such impressions.
Summary of the Invention Accordinglyr it has been discovered tha~ when-samples o extremely finely divided platinum black were obtained with the highest possible surface area, specifically 24 M2gram, and were compared with equal weight percent concentrations of palladium black, by incorporation in identical polyvinylsiloxane elastomer pastes they were found to be equally and co3npletely effective, down to a concentra~ion level of abou~ Or2 ppm by weight. An efective concentration range for the platinum black is about 0.2 12991~6 to 20~000 ppm by weight. The size range ~or the platinum blacX
should be as sm~ll as possible. ~ preferred size range for ~he platinum black is from abo~t 18 to 28 An~stro~ Units;
The use o~ platinum blac~ in conjunction with ~he present invention is in controlling or prevsnting outgassing in all addition cured polyvinylsiloxane ela~tomers which are primarily used in making dental impressions.
The platinum black is used to adsorb gaseous hydrogen ~enera~ed during the curing reaction, and generally at a concentration level of about 0.2 to 20,000 ppm. A pre~erred concentration range is ~rom about .001 ~o 0;01 weight percen~
(i.e., 1,000 to 10,000 ppm). The platinum black is added or blended with the catalyst paste in any convenient manner such as illustrated in U.S. Patent ~,273,902.
Il has also been discovered tha~ in a preferred embodiment of the invention that the ex~remely hydrophobic characterisitcs of polyvinylsiloxane dental impression materials, which lead to comparatively large bubble shaped artifacts in the surface of such impressions, can be overcome by ~he incorporation of relatiYely small quantitîes of selected surfactan~s.
Detailed_Dcscription o~ the Invention .
~oth base and catalys~ pastes contain vinyl polydime~hyl siloxane and silica or other similar inert ~iller(s) and the base paste A~
. . . .
~Z9~9 ~6 contains a moiety of hydrofunctional polydimethylsil~xane whereas ~he catalyst contains both a chloroplatinic acid catalyst complex and pla~inum black, to adsorb any gaseous hydrogen formed duri~g mixing of the pastes and curing of the impression.
A cured impression is produced by mixing ~he base pajte and catalyst such as ~hat illustrated by Example I, in a 1:1 or other suitable ratio to form a homogeneous plastic mass which is applied over the den~ition and adjacent gingival ~issue and allowed tO cure during a time frame of several minutes prior tO
mouth removal. Models were made from impressions taken with the platinum black containing impression materials immediately after mouth remoYal and found to be free of pores in all cases at or above the 0.005 weight percent platinum level.
Impressions and resulting molds or models formed using ~he concept of the present invention result in a surfac~ smoothness which is significantly better than ~hose formed withou~ the use of platinum black.
Another problem associated with polyYinylsiloxane dental impression materials of this in~ention is their ~xtremely hydrophobic characteristics which lead ~o comparatively larg~
bubble shaped artifacts in the sur:Eace o~ such impression-s.
U.S. Pa~ent 4~600,751 teaches the controlled release of bioactive agen~s, and serves to demonstrate the synthesis of silicone based prepolymers which are extre~ely hydrophilic.
In dentistry, impression materials, particularly for making crown and bridge i~pressions, require a high de~ree of ~ Z ~ ~ 9 ~ ~
dimensional stability to facilita~e the production of extremely accurate prostheses, for which the t~chniques of U.S. Patent 4,600,751 would be totally unsuitable because high water sorp~ion is consistent with swelling and distortion of ~hese polymers.
Fur~hermore there are, other definite advantages to dental impressions with low water sorption, such as ease of disinfection and sterilization.
With respect to the problem associated with the hydrophobic characteristics of the dental impression materials of the present invention it has been found possible to utilize several species of hydrophilic compounds as low concentration additives to conventional, extremely hydrophobic, addition-cured polyvinylsiloxane dental impression materials to impart truly hydrophilic surface characteristics to these materials. This results in the pre~ention of compartitively large bubble shaped artifacts in the surface of these impressions, due to the effects of surface tension at a strongly hydrophobic/hydrophilic interface causing a film of moisture to form water droplets.
In a preferred embodiment of this inYen~ion~ any one or more of the following surfactant type sompounds are added to conventional addition-cured polyvinylsiloxane dental impr~ssion materials in relatively low concentrations of about l.0~ to 10.0%
by weight.
COMPOUND NAME CAS NO. WHERE KNOWN
n-Dodecyl, Tetradecyl, Hexadecyl Alcohol Ethoxylate 685Sl-12-2 Polyethylene Glycol Monolaura~e 9004-81-3 Polye~hylene Glycol Dilaurate Polyelhylene Glycol Monoleate Polyethylene Glycol Dioleate Polyethylene Glycol Monotallate Polyethylene Glycol Ditallate Sorbitan Monolaurate Sorbi~an Monoleate Sorbitan Trioleate Sorbitan Monotallate Sorbitan Tritallate Polyethylene Glycol Glycerol Cosoea~e Caprylic Triglyceride Polyoxye~hylene Tridecyl Alcohol 2493B-91-8 Polyoxyethylene Lauryl Ether 5274-68-0 Nonylphenoxypoly ~ethyleneoxy) ethanol 9016-45-9 Polyoxyethylene Sorbitan Monolaurate Sorbitan Monolaurate Polyoxyethylene Polysorbate 9005-64-5 Polyoxyethylene Oleyl Alcohol The above listing of suitable surfactants is not exhaustive, but serves to illustrate twenty representative examples of the manny chemical permutations possible with the family of Polyol fatty acid ester and ethoxylated ester type surfactants useful for this invention.
The effectiveness of these surfactant additives is readily apparent in th~ir ability to reduce ~he aqueous con~act angle with oured or uncured addition-cured polyvinylsiloxane d~n~al impression ma~erials from the range of 95-110 down ~o 30 or less. Upon contact of the dental impression materials with the denti~ion and gingiva any moisture present on ~he surface of these oral tissues is readily miscible with the surfactant moiesy arailable at the surface of the impression material, which ~ ~ 9 ~
provides uniform wetting of the in~erface between the impression material and the oral tissues, thereby drama~ically reducing surface tension.
The following example illus~rates one embodimen~ of the presen~ invention. The concentrations are in weight percen~
unless otherwise sta~ed.
EXAMPLE I
Embodiments of Platinum Black or_~aseous adsorption:
BASE PASTE (VERY HEAYY VISCOSITY) CATALYST PASTE tVERY HEA W VISCOSITY) WT% WT~
Vinyl Polydimethylsiloxane 20~%Vinyl Polydimethylsiloxane 20%
Hydropolydimethyl Siloxane3%*Cyclic Vinyl Siloxane 0.4~
Silica FiIler 70%*~Chloroplatinic Acid Complex 1.0%
Liquid Petroleum or other 7%Lîquid Petroleu~ or other inert plasticizer inert plasticizer 7S
Silica or other inert filler 71.6%
The following illustrates suitable compositional ranges for the components of the base and catalyst pas~e.
BASE PASTE WT% CATALYST PASTE WT~
Vinyl Polydimethylsiloxane 10-60 Vinyl Polydimethylsiloxane 10-60 Hydropolydimethyl Siloxane 1-10 Cyclic Vinyl Siloxane 0-2 Silica Filler 20-80 Chloroplatinic Acid Complex Ool~5~0 Liquid Petroleum 0 15 Platinum Black 0.2-20,000 ppm Plas ti Ci zer 0-15 Filler 20-80 -The following illustrates sui~a~le compositional ranges for a cure~
dental impression material of the presen~ inven~ion.
~29~9~6 VERY ~EAVY VISCOSITY M~TERIAL (PUTTY) WTS
Vînyl Polydimc~hylsiloxane 10-60 Cyclic Vinyl Siloxane 0-1 Hydropolydimethyl Siloxane 0.5-5 0 Filler 20-80 Chloroplat;nic ~cid Complex 0.05-2.5 Platinum ~lack 0.1-10,000 ppm Plasticizer 0-15 Surfactant (op~ional but pre~erred) 2-10 Availab].e under the ~rade-mark PSW 2204 from Petrarch Silico-;
nes of Bristo], PA.
Avai].ab]e under the trade-mark PSW 2206 from Petrarch;
Si].icones of Brito]., PA.
Embodiments usin~ surEactants to con~er hydrophilic ch~rac~eristics:
Low viscosit Catal st aste wi~h surfactant WT~
Y Y P
Vinyl unctional polydimethylsiloxane 51.785 Silaceous Filler 43 0 n-Dodecyl, Te~radecyl, ~lexadecyl Alcohol E~hoxylate 4.0 Pigmen~ 1.0 Cyclic vinyl function~l prepolymer 0.2 Chloroplatinic acid catalyst complex 0.01 Platinum Black 0.005 Excellent hydrophilic surface characteristics, but unpleasant tasle.
Low viscosity ~ase paste with surf~ctant Vinyl functional polydime~hlsiloxane 46.0 Silaceous Eiller 42.0 Hydrofunctional Polydimethylsiloxane 7.0 Pigment 2.0 Nonylphenoxypoly(ethyleneoxy~ethanol 5.0 Exce~lent hydrophilic surface characteristics ~nd acceptable taste.
,. .~
.. 1i Z~
Low viscosity Base paste with surfactant Vinyl functional polydimethylsiloxane 46.0 Silaceous Filler . 41.0 Hydrofunctional polydimethylsiloxane 7.0 n-Dodecyl~ Tetradecyl 9 Hexadecyl Alcohol Ethoxylate 4 . O
Pigment 2.0 1'00, 00 Excellent hydrophilic surfaee characteristics~ but unpleasant taste.
Although the above examples are restrictsd ~o low viscosity polyvinylsiloxane den~al impression materials the same family of Polyol fatty acid ester and ethoxylated ester type surfactant can be used as additives in the regular and heavy, even pu~ty viscosities of the same type of material with equally effeceive results, The following illustrates suitable compositional ranges for the components of ~he base and catalyst pastes of Examples 2 Ihrough 4.
BASE PASTES WT% CATALYST PASTES WT%
Vinyl polydimethylsiloxane 25-75 Vinyl Polydimethylsiloxane 25-75 Hydropolydimethyl siloxane 1-12 Cyclic Vinyl Siloxane 0,5 Silaceous Fillerts) 25-75 Silaceous Filler(s) - 25-72 Surfactantts) 1-10 Surfactantts) 1-10 Pigment(s) 0.5 Pigment(s) 0.5 Chloroplatinic Acid Complex 0.1-5.0 Platinum Black 0.2-20,000 ppm The following illus~rates sui~able compositional ranges for a cured dental impression material of Examples 2 throu~h 4 of ~he presen~
inYention:
LOW VISCOSITY MATERIAL (LIGIIT ~ODY on W~SH) WT%
Vinylpolydimethyls iloxane 2 5-75 Hydro polydimelhylsiloxane . 0.5-5.0 Cyclic ~inyl siloxane 0-1 Silaceous Filler(s) 25-75 5urfactant(s) 1-10 P;gment(s) O-S
Chloraplatinic ~cid Complex 0.05-2.5 Platinum Black 0.01-109000 ppm The ollowing is a preferred embodiment o~ the present inven~ion which exhibits the desired properties with respec~ to con~rollin~
outgassing and hydrophilic characteristics:
LOW VISCOSITY BASE P~STE ~YIT~ SURFACTANT WT~
Vinyl ~unctional polydime~hylsiloxane (4000 cps) 46.0 Calcium Silicate ~iller 42.0 Hydrofunctional polydimethylsiloxane 7.0 Nonylphenoxypoly (ethyleneoxy) ethanol 3.0 Cobalt Blue Pigment LOW V I S COS I TY CAT~LYST P~ST E WITII PL~TINUM
Vinyl ~unctîonal polydimelhylsilox~ne (~000 cps) 54.73 Calcium Silicate Filler 43.98 Cobalt Blue Pigment 1.0 Cyclic Vinyl functional prepolymer 0.27 Chloropla~inic ~cid Catalys~ complex 0.01 Pla~inum Black (2~ ~2/gm) 0 01 The following is a typical method used in preparing ~he compounds of the present inven~ion. Other methods and compounds, such as those set orth in ~he above mentioned U.S. Patent 47273,902 may also be used in conjunction with this invention.
, . . .
~9 RASE PASTE
Blend together in a double planetary mixer the three li~uid components, Vinyl unctional polydimethylsiloxane, Hydrofunctional polydimethylsiloxane and Nonylphenoxypoly(ethyleneoxy)ethanol. Add pi~ment, and then reblend to evenly disperse the pigment, filler is then added and mixed until thoroughly homogenous to form a low viscosity fluid paste. The resulting paste is then rollmilled tO maximize homogeneity followed by packaging as desired.
CATALYST PASTE
. ~
Preblends are made of the Chloroplatinic acid complex with a portion of the Vinyl functional polydimethylsiloxane and of the Platinum Black with a portion of the Calcium Silica~e filler.
Blend together the three liquid components, Catalyst complex preblend, balance of Vinyl functional polydimethylsiloxane and Cyclic Vinyl prepolymer. Add pigment, reblend to disperse, ~hen add Platinum Black preblend, followed by balance of the filler and mix until throughly homogenous. Rollmill to maxi~ize homogeneity and then package as desired.
While the invention has been described in detail with respect to specific embodiments thereof, it will be understood by those skilled in the art that variations and modifica~ions may be made wi~hout departing from the essential features thereof.
Claims (13)
1. A polyvinylsiloxane catalyst paste which comprises up to 20,000 ppm of finely divided platinum black which functions to adsorb hydrogen gas generated in the reaction of said catalyst paste with a hydrofunctional polydimethylsiloxane.
2. A polyvinylsiloxane catalyst paste which comprises finely divided platinum black which functions to adsorb hydrogen gas generated in the reaction of said catalyst paste with a hydrofunctional polydimethylsiloxane, having the following composition:
Vinyl Polydimethylsiloxane Cyclic Vinyl Siloxane Chloroplatinic Acid Complex Platinum Black Plasticizer Filler
Vinyl Polydimethylsiloxane Cyclic Vinyl Siloxane Chloroplatinic Acid Complex Platinum Black Plasticizer Filler
3. The catalyst paste of claim 2 in which the platinum black is present in a concentration of about 0.2 ppm to 20,000 ppm by weight.
4. The catalyst paste of claim 2 in which the platinum black has a size range of about 18 to 28 Angstroms.
5. A two component dental impression material which comprises the following:
6. A cured dental impression which comprises the following composition:
7. A two component dental impression material which comprises the following:
8. The impression material of claim 7 in which the surfactant is selected from the family of polyol fatty acid esters and ethoxylated esters.
9. The impression material of claim 7 in which the surfactant comprises n-Dodecyl, Tetradecyl, Hexadecyl Alcohol Ethoxylate.
10. The impression material of claim 7 in which the surfactant comprises at least one compound selected from the group comprising:
n-Dodecyl, Tetradecyl, Hexadecyl Alcohol Ethoxylate Polyethylene Glycol Monolaurate Polyethylene Glycol Dilaurate Polyethylene Glycol Monoleate Polyethylene Glycol Dioleate Polyethylene Glycol Monotallate Polyethylene Glycol Ditallate Sorbitan Monolaurate Sorbitan Monoleate Sorbitan Trioleate Sorbitan Monotallate Sorbitan Tritallate Polyethylene Glycol Glycerol Cocoeate Caprylic Triglyceride Polyoxyethylene Tridecyl Alcohol24938-91-8 Polyoxyethylene Lauryl Ether5274-68-0 Nonylphenoxypoly (ethyleneoxy) ethanol9016-45-9 Polyoxyethylene Sorbitan Monolaurate Sorbitan Monolaurate Polyoxyethylene Polysorbate Polyoxyethylene Oleyl Alcohol
n-Dodecyl, Tetradecyl, Hexadecyl Alcohol Ethoxylate Polyethylene Glycol Monolaurate Polyethylene Glycol Dilaurate Polyethylene Glycol Monoleate Polyethylene Glycol Dioleate Polyethylene Glycol Monotallate Polyethylene Glycol Ditallate Sorbitan Monolaurate Sorbitan Monoleate Sorbitan Trioleate Sorbitan Monotallate Sorbitan Tritallate Polyethylene Glycol Glycerol Cocoeate Caprylic Triglyceride Polyoxyethylene Tridecyl Alcohol24938-91-8 Polyoxyethylene Lauryl Ether5274-68-0 Nonylphenoxypoly (ethyleneoxy) ethanol9016-45-9 Polyoxyethylene Sorbitan Monolaurate Sorbitan Monolaurate Polyoxyethylene Polysorbate Polyoxyethylene Oleyl Alcohol
11. A cured dental impression which comprises the following composition:
12. A polyvinylsiloxane catalyst paste which comprises up to 20,000 ppm of finely divided platinum black which functions to adsorb hydrogen gas generated in the reacticn of said catalyst paste when mixed with a base paste containing hydrofunctional polydimethylsiloxane, said base paste further containing a hydrophilic surfacant selected from the family of polyol fatty acid esters and ethoxylated esters.
13. The composition of claim 12 in which the surfactant comprises at least one compound selected from the group consisting of:
n-Dodecyl, Tetradecyl, Hexadecyl Alcohol Ethoxylate Polyethylene Glycol Monolaurate Polyethylene Glycol Dilaurate Polyethylene Glycol Monoleate Polyethylene Glycol Dioleate Polyethylene Glycol Monotallate Polyethylene Glycol Ditallate Sorbitan Monolaurate Sorbitan Monoleate Sorbitan Trioleate Sorbitan Monotallate Sorbitan Tritallate Polyethylene Glycol Glycerol Cocoeate Caprylic Triglyceride Polyoxyethylene Tridecyl Alcohol24938-91-8 Polyoxyethylene Lauryl Ether5274-68-0 Nonylphenoxypoly (ethyleneoxy) ethanol9016-45-9 Polyoxyethylene Sorbitan Monolaurate Sorbitan Monolaurate Polyoxyethylene Polysorbate Polyoxyethylene Oleyl Alcohol
n-Dodecyl, Tetradecyl, Hexadecyl Alcohol Ethoxylate Polyethylene Glycol Monolaurate Polyethylene Glycol Dilaurate Polyethylene Glycol Monoleate Polyethylene Glycol Dioleate Polyethylene Glycol Monotallate Polyethylene Glycol Ditallate Sorbitan Monolaurate Sorbitan Monoleate Sorbitan Trioleate Sorbitan Monotallate Sorbitan Tritallate Polyethylene Glycol Glycerol Cocoeate Caprylic Triglyceride Polyoxyethylene Tridecyl Alcohol24938-91-8 Polyoxyethylene Lauryl Ether5274-68-0 Nonylphenoxypoly (ethyleneoxy) ethanol9016-45-9 Polyoxyethylene Sorbitan Monolaurate Sorbitan Monolaurate Polyoxyethylene Polysorbate Polyoxyethylene Oleyl Alcohol
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US932,246 | 1986-11-19 | ||
| US06/932,246 US4806575A (en) | 1986-11-19 | 1986-11-19 | Prevention of outgassing in polyvinylsiloxane elastomers by the use of finely divided platinum black |
| US07/027,499 US4782101A (en) | 1986-11-19 | 1987-03-25 | Prevention of outgassing in polyvinylsiloxane elastomers by the use of finely divided platinum black |
| US027,499 | 1987-03-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1294946C true CA1294946C (en) | 1992-01-28 |
Family
ID=26702552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000535603A Expired - Lifetime CA1294946C (en) | 1986-11-19 | 1987-04-27 | Prevention of outgassing in polyvinylsiloxane elastomers by the use of finely divided platinum black |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4782101A (en) |
| EP (1) | EP0268347B2 (en) |
| AU (1) | AU605766B2 (en) |
| CA (1) | CA1294946C (en) |
| DE (1) | DE3780576T3 (en) |
Families Citing this family (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3931416A1 (en) * | 1989-09-21 | 1990-03-29 | Dreve Dentamid Gmbh | Dental impression material - of low viscosity hydrophilised silicone addn. crosslinking hardener |
| DE4031759A1 (en) * | 1990-10-06 | 1992-04-09 | Bayer Ag | HYDROPHILIC MOLDING |
| US5152555A (en) * | 1991-03-26 | 1992-10-06 | Itt Corporation | Quick connect insertion indicator clip |
| DE19505496A1 (en) * | 1995-02-17 | 1996-08-22 | Roeko Gmbh & Co | Substance mixture, rubber dam material, use and manufacture |
| US5955513A (en) * | 1995-04-13 | 1999-09-21 | Dentsply Research & Development Corp. | Very high viscosity polyvinylsiloxane impression material |
| US5830951A (en) * | 1995-04-13 | 1998-11-03 | Dentsply Detrey G.M.B.H. | Polyvinylsiloxane impression material |
| US5661222A (en) * | 1995-04-13 | 1997-08-26 | Dentsply Research & Development Corp. | Polyvinylsiloxane impression material |
| CA2207857C (en) * | 1996-07-03 | 2002-08-27 | Gc Corporation | Dental impression silicone composition |
| US5998561A (en) * | 1997-03-11 | 1999-12-07 | Jeneric/Pentron Incorporated | Catalyst and composition for silicone dental impression materials |
| DE19711514B4 (en) * | 1997-03-19 | 2006-09-14 | 3M Espe Ag | Triglyceride-containing impression materials |
| US6054518A (en) * | 1997-09-17 | 2000-04-25 | Shin-Etsu Chemical Co., Ltd. | Silicone rubber molding compositions and method for producing silicone rubber molded parts |
| US6561807B2 (en) | 1998-05-27 | 2003-05-13 | Dentsply Research & Development Corp. | Polyvinylsiloxane impression material |
| DE19915004A1 (en) * | 1999-04-01 | 2000-10-05 | Espe Dental Ag | Silicone-based molding materials used for preparing dental molds include polyalkylene oxide compound to improve rigidity of molding material |
| DE19926728B4 (en) | 1999-06-11 | 2011-08-18 | 3M Espe Ag, 82229 | Use of carrier materials and diagnostically useful additives in imaging methods for intraoral diagnostic purposes |
| DE10061195B4 (en) | 2000-12-08 | 2004-12-02 | 3M Espe Ag | Use of impression materials for the production of treatment devices |
| DE10124426A1 (en) * | 2001-05-18 | 2002-11-28 | Omg Ag & Co Kg | Surface coating used e.g. as a protective layer against mechanical, chemical and thermal action is made from platinum in a black modification |
| US20050181324A1 (en) * | 2004-02-13 | 2005-08-18 | Hare Robert V. | Polyorganosiloxane dental impression materials with improved wetting and stability |
| ATE462401T1 (en) | 2003-05-09 | 2010-04-15 | 3M Espe Ag | CUREABLE SILICONE IMPRESSION MATERIALS WITH HIGH TEAR STRENGTH AND LOW CONSISTENCY |
| EP1502572B1 (en) | 2003-08-01 | 2012-03-07 | 3M Deutschland GmbH | Automixable putty impression material |
| DE60313164T2 (en) | 2003-09-04 | 2007-12-13 | 3M Espe Ag | Allylsilane-containing composition |
| WO2005072683A1 (en) * | 2004-01-21 | 2005-08-11 | 3M Innovative Properties Company | Dental compositions and kits containing bitterness inhibitors, and related methods |
| US20060100360A1 (en) * | 2004-10-21 | 2006-05-11 | Yvette Freese | Plastic mass for kneading, modeling, craftwork and decorating |
| WO2007001869A2 (en) | 2005-06-22 | 2007-01-04 | 3M Innovative Properties Company | Hydrophilized curable silicone impression materials with improved storage behavior |
| EP1882469A1 (en) | 2006-07-28 | 2008-01-30 | 3M Innovative Properties Company | Polyether-based preparations and use thereof |
| EP2044923A1 (en) | 2007-10-04 | 2009-04-08 | 3M Innovative Properties Company | Dental composition containing glass beads, process for production and use thereof |
| EP2231102B1 (en) | 2007-12-18 | 2011-09-21 | 3M Innovative Properties Company | Dental composition containing a surfactant and an f-containing compound, process of production and use thereof |
| EP2741729B1 (en) | 2011-08-12 | 2021-11-03 | 3M Innovative Properties Company | Curable composition with shortened setting time, process of production and use thereof |
| EP2626059B1 (en) * | 2012-02-10 | 2021-10-13 | Shofu Inc. | Silicone impression material having high hydrophilicity |
| CN107596530B (en) | 2012-06-25 | 2021-08-31 | 费雪派克医疗保健有限公司 | Medical component with microstructures for humidification and condensate management |
| EP2958538B1 (en) | 2013-02-25 | 2020-04-29 | 3M Innovative Properties Company | Stabilized dental impression composition, kit of parts and use thereof |
| EP2968830B1 (en) | 2013-03-14 | 2019-03-06 | Fisher & Paykel Healthcare Limited | Humidification chamber with microstructured surface |
| EP3233017A1 (en) | 2014-12-16 | 2017-10-25 | 3M Innovative Properties Company | Hardenable dental impression composition comprising a polymeric filler particles and use thereof |
| EP3302347B1 (en) | 2015-05-29 | 2021-01-20 | 3M Innovative Properties Company | Process for taking a dental impression and retraction process |
| US10682290B2 (en) | 2015-05-29 | 2020-06-16 | 3M Innovative Properties Company | Kit of parts for conducting a dental impression and retraction process |
| US11684553B2 (en) | 2017-01-18 | 2023-06-27 | 3M Innovative Properties Company | Curable composition for dental retraction |
| US11267968B2 (en) | 2018-02-05 | 2022-03-08 | 3M Innovative Properties Company | Radiation-curable composition containing mercapto-functional polyorganosiloxanes for additive-manufacturing technology |
| US20220112377A1 (en) | 2019-02-18 | 2022-04-14 | 3M Innovative Properties Company | Radiation-Curable Composition Containing Mercapto-Functional Polyorganosiloxanes for Additive-Manufacturing Technology |
| WO2020250129A1 (en) | 2019-06-12 | 2020-12-17 | 3M Innovative Properties Company | Process of taking a dental impression with a radiation-curable composition containing mercapto-functional polyorganosiloxanes and vqm resins |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4020014A (en) * | 1976-01-21 | 1977-04-26 | General Electric Company | Semi-conductive silicone elastomers |
| DE3031894A1 (en) * | 1980-08-23 | 1982-09-16 | Bayer Ag, 5090 Leverkusen | VINYL SILICONE PASTE FOR MOLDING |
| JPS59133252A (en) * | 1983-01-19 | 1984-07-31 | Toray Silicone Co Ltd | Organopolysiloxane composition |
| US4657959A (en) * | 1985-11-15 | 1987-04-14 | Minnesota Mining And Manufacturing Company | Hydrophilic silicones |
-
1987
- 1987-03-25 US US07/027,499 patent/US4782101A/en not_active Expired - Lifetime
- 1987-04-27 CA CA000535603A patent/CA1294946C/en not_active Expired - Lifetime
- 1987-05-18 EP EP87304390A patent/EP0268347B2/en not_active Expired - Lifetime
- 1987-05-18 DE DE3780576T patent/DE3780576T3/en not_active Expired - Fee Related
- 1987-05-19 AU AU73203/87A patent/AU605766B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| EP0268347B2 (en) | 1997-02-26 |
| DE3780576D1 (en) | 1992-08-27 |
| DE3780576T3 (en) | 1997-06-05 |
| EP0268347A1 (en) | 1988-05-25 |
| EP0268347B1 (en) | 1992-07-22 |
| DE3780576T2 (en) | 1993-03-11 |
| AU7320387A (en) | 1988-06-09 |
| US4782101A (en) | 1988-11-01 |
| AU605766B2 (en) | 1991-01-24 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed |