CA2060928C - Dental/medical composition and use - Google Patents
Dental/medical composition and use Download PDFInfo
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- CA2060928C CA2060928C CA002060928A CA2060928A CA2060928C CA 2060928 C CA2060928 C CA 2060928C CA 002060928 A CA002060928 A CA 002060928A CA 2060928 A CA2060928 A CA 2060928A CA 2060928 C CA2060928 C CA 2060928C
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
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- 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
- A61K6/889—Polycarboxylate cements; Glass ionomer cements
Abstract
The invention provides an improved dental/medical restorative/prosthetic composition employing a polymer-izable unsaturated substituted butane moiety with acid or reactive acid derivative functionality having the general formula:
(RO2C)x -- C4H6 -- (CO2R') y where R is an acid radical or a reactive acid derivative and R' is a polymerizable unsaturated radical having from 2 to 13 C and x is 2 to 3 and y is 1 to 2.
(RO2C)x -- C4H6 -- (CO2R') y where R is an acid radical or a reactive acid derivative and R' is a polymerizable unsaturated radical having from 2 to 13 C and x is 2 to 3 and y is 1 to 2.
Description
Q 6~D g2 ~
PATENT
DEI~TAL/MEDICAL COMPOSITION AND USE
The invention relates to a new class of dental/med-ical material based upon a relatively low molecular weight monomeric polymerizable unsaturated monomer of a substi-tuted butane moiety with an acid or reactive acid deriva-tive functionality, BACKGROUND
U.S. Patent 4,872,936 teaches dental cement mixtures containing polymerizable unsaturated monomers and/or oligomers and/or prepol;tmers containing acid groups and/or their reactive acid-derivative groups. However, the poly-merizable compounds taught are directed toward those of relatively high molecular weight as compared to the very specific and advantageous specific class of compounds of the present invention. U.S. Patent 4,589,756 relates to similar aromatic based compositions employed in dentistry.
By an aspect of th~~ invention a new group of dental materials is provided that are kind to the patient, non-toxic and give superior adhesion to dentin, enamel and bone when properly formulated and chat provide other favorable characteristics. The group"~of the preferred dental materials include especially cavity liner and bond-ing materials and filling materials.
The dental materials differ from earlier dental materials because they are based upon a new polymerizable composition system b~~sed upon a butane compound having in its preferred embodiment, as prj.mary preferred functional groups, olefins, more prefer~~.bly (me'th)acrylates and acid based radicals, especially preferred is carboxylic acid and included are reactive acid de:~ivative~ radicals. The butane (based) compound of this invention has the general formula:
( RO2C ) x - C4B6 - ( C02R ' ) y where R is hydrogen, an acid radical containing moiety or a moiety containing a n~eactive acid derivative and R' is a polymerizable unsaturated ester-containing radical having from 2 to 13 C and x is 2 to 3 and y is 1 to 2.
OBJECTB
An aim of i:his invention is the provision of new dental compositions useful a.s filling materials, cavity liners and bases, cements, ~~it and fissure sealants to prevent caries, as adhesive between tooth structure and/or bone and polymeric composites,. and similar dental and orthopedic 2() appl icat ions .
It is a further aj.m to provide such dental/medical restoratives/prosthet;ic compositions that have high purity, consistency and uniformity.
A further ~~~mportant aim is to provide dental/medical restorative/prosthetj'.c compositions that: are relatively inexpensive and easy to manufacture.
a ' Yet a further aim of the invention is to provide dental/medical restorative/prosthetic compositions that are highly reactive and are relatively low viscosity fluid alleviating the need far high concentrations of diluents to provide suitable vi~~cosity, thus giving superior dental/medical resto natives and prosthetics.
;SUMMARY OF THE INVENTION
By the prs~sent invention in one aspect a new dental/medical resto rative/prosthetic composition is provided that is based on a compound that is a polymerizable unsaturate substituted butane moiety with acid or reactive acid derivative functions~lity having the general formula (R02C)x - C4H6 - (C02R')y where R is hydrogen, an acid radical containing moiety or a moiety containing a reactive acid derivative and R' is a polymerizable unsaturated ester-containing radical having f nom 2 to 13 C and x is c. to 3 and y is 1 to 2. The preferred compound is butane tet racarboxyiic acid bis-(2-hydroxy ethylmethacrylate) ester. Preferably, the butane compound is the primary or only binder in the composition. Hy primary binder it is meant preferably in both quantity and funct ional it y .
The invention also provides a dental/medical restorative/prost-hetic polymerizable unsaturated substituted butane compound with acid or reactive acid derivative functionality having the general formula C
O O
II II
Ri-O-C C-O-R' ~
HO-C ~yOH
O O
wherein R1 and R'1 each independently is a moiety containing a reactive acid derivative which is polymerizable, unsaturated and has from 2 to 13 carbon atoms.
In one prefer=ed aspect the ccmposition is a dental liner consisting essentially of the butane compound and other active ingredients chosen from the group consisting ef curing catalysts, initiators, accelerators and mixtures thereof. '~'he dental liner in some preferred ,~nstances will contain ot'_her increc~~er.ts such as curing agents and a'~.de'_hyde.
In another preferred aspect the composition is a dentate composite comprising the butane compound, at least one finely divided reactive filler that can react ionic-ally with the acids or acid derivative of the butane com-pound and curing agent.
By further aspects of the present invention the compositions recited above are employed for their recited purposes as dental treatments by application to teeth in vivo.
In yet other aspects the butane compound is employed as a medical treatment as an ingredient in bone cement and preferably as the primary or only binder in the bone cement.
PATENT
DEI~TAL/MEDICAL COMPOSITION AND USE
The invention relates to a new class of dental/med-ical material based upon a relatively low molecular weight monomeric polymerizable unsaturated monomer of a substi-tuted butane moiety with an acid or reactive acid deriva-tive functionality, BACKGROUND
U.S. Patent 4,872,936 teaches dental cement mixtures containing polymerizable unsaturated monomers and/or oligomers and/or prepol;tmers containing acid groups and/or their reactive acid-derivative groups. However, the poly-merizable compounds taught are directed toward those of relatively high molecular weight as compared to the very specific and advantageous specific class of compounds of the present invention. U.S. Patent 4,589,756 relates to similar aromatic based compositions employed in dentistry.
By an aspect of th~~ invention a new group of dental materials is provided that are kind to the patient, non-toxic and give superior adhesion to dentin, enamel and bone when properly formulated and chat provide other favorable characteristics. The group"~of the preferred dental materials include especially cavity liner and bond-ing materials and filling materials.
The dental materials differ from earlier dental materials because they are based upon a new polymerizable composition system b~~sed upon a butane compound having in its preferred embodiment, as prj.mary preferred functional groups, olefins, more prefer~~.bly (me'th)acrylates and acid based radicals, especially preferred is carboxylic acid and included are reactive acid de:~ivative~ radicals. The butane (based) compound of this invention has the general formula:
( RO2C ) x - C4B6 - ( C02R ' ) y where R is hydrogen, an acid radical containing moiety or a moiety containing a n~eactive acid derivative and R' is a polymerizable unsaturated ester-containing radical having from 2 to 13 C and x is 2 to 3 and y is 1 to 2.
OBJECTB
An aim of i:his invention is the provision of new dental compositions useful a.s filling materials, cavity liners and bases, cements, ~~it and fissure sealants to prevent caries, as adhesive between tooth structure and/or bone and polymeric composites,. and similar dental and orthopedic 2() appl icat ions .
It is a further aj.m to provide such dental/medical restoratives/prosthet;ic compositions that have high purity, consistency and uniformity.
A further ~~~mportant aim is to provide dental/medical restorative/prosthetj'.c compositions that: are relatively inexpensive and easy to manufacture.
a ' Yet a further aim of the invention is to provide dental/medical restorative/prosthetic compositions that are highly reactive and are relatively low viscosity fluid alleviating the need far high concentrations of diluents to provide suitable vi~~cosity, thus giving superior dental/medical resto natives and prosthetics.
;SUMMARY OF THE INVENTION
By the prs~sent invention in one aspect a new dental/medical resto rative/prosthetic composition is provided that is based on a compound that is a polymerizable unsaturate substituted butane moiety with acid or reactive acid derivative functions~lity having the general formula (R02C)x - C4H6 - (C02R')y where R is hydrogen, an acid radical containing moiety or a moiety containing a reactive acid derivative and R' is a polymerizable unsaturated ester-containing radical having f nom 2 to 13 C and x is c. to 3 and y is 1 to 2. The preferred compound is butane tet racarboxyiic acid bis-(2-hydroxy ethylmethacrylate) ester. Preferably, the butane compound is the primary or only binder in the composition. Hy primary binder it is meant preferably in both quantity and funct ional it y .
The invention also provides a dental/medical restorative/prost-hetic polymerizable unsaturated substituted butane compound with acid or reactive acid derivative functionality having the general formula C
O O
II II
Ri-O-C C-O-R' ~
HO-C ~yOH
O O
wherein R1 and R'1 each independently is a moiety containing a reactive acid derivative which is polymerizable, unsaturated and has from 2 to 13 carbon atoms.
In one prefer=ed aspect the ccmposition is a dental liner consisting essentially of the butane compound and other active ingredients chosen from the group consisting ef curing catalysts, initiators, accelerators and mixtures thereof. '~'he dental liner in some preferred ,~nstances will contain ot'_her increc~~er.ts such as curing agents and a'~.de'_hyde.
In another preferred aspect the composition is a dentate composite comprising the butane compound, at least one finely divided reactive filler that can react ionic-ally with the acids or acid derivative of the butane com-pound and curing agent.
By further aspects of the present invention the compositions recited above are employed for their recited purposes as dental treatments by application to teeth in vivo.
In yet other aspects the butane compound is employed as a medical treatment as an ingredient in bone cement and preferably as the primary or only binder in the bone cement.
BEST MODE
General. Description By an aspect of the invention new dental/medical restorative/prosthetic compositions are provided. These compositions are the product of the use of a class of com-pounds new to such use. As a liner or bonding agent, especially a dental liner for application to tooth enamel and dentin (meaning~natural tooth structure), the compound can be applied in preferred forms neat or with only poly-merization initiators added to assure quick curing and aid in completion of th,e cure o f the compositions. Of course, 4a 64053-'260 a pending on the application ~.ntended other materials may be added. When dental cements and composites are the intended compositions the compound of the present inven-Lion is used as a complete or a partial substitute for conventional resins.
The Chemical Compound Employed The class of compounds that characterize the inven-tion are those having as a principle functional ingredient polymerizable unsaturated monomers of a substituted butane moiety with acid or reactive acid derivative functionality having the general formula:
(Rp2C) x ._- C4g6 ._- (COZR' ) Y
where R is an acid radical or a reactive acid derivative and R' is a palymerizable unsaturated radical having from 2 to l3 C and x is 2 to 3 and y is 1 to 2. Preferably at least one carbon adjacent tea each carbon carrying a (C02R')y is associated with a (RO2C)~ and the preferred polymerizable unsaturated radical is preferable a (meth) acrylate. (Meth) acrylate means either an acrylate or a methacrylate.
The compounds average molecular weight is preferably about 200 - 600, more preferable 2b0 - 499 and most pre-ferably 290 - 460. The preferred compounds are liquid at room temperature. By liquid it is meant that the material is fluid with viscosities of less than 100,000 cps at 23°C.
~~
The compounds essentially contain or include in a single chemical compour,~d at least two different functional substituent groups, one of which is capable of addition polymerization and the other of which is carboxyl or other acid or reactive acid derivative. Tt is important that there be at least one such addition polymerizable group, but not more than two ;end there must be two or more acid or reactive acid derivative groups but in the most pre-ferred compound there .are no more than three, The pre-ferred chemical compounds are in a preferred aspect derived from the reaction of butanetetracarboxylic acid or its anhydride with a hydroxyl or polyhydric compound to form esters and diesters.
The new dental/medical compositions of matter are capable of being polymerized to form linear or crosslinked polymers which contain multiple acid groups or reactive acid derivative groups that may be further reacted with rations, especially tho:~e of valence 2 or greater, to form poly-salts relatively :insoluble in water. Because the compounds are monomers of relatively low molecular weight with a high density of both ethylenic unsaturation and carboxylic reactive acid derivative sites, excellent curing with superior integrity occurs. The rations may be supplied by ingredients or components of the given formulation or they may be supplied from a solution of rations supplied from a second component of the formu-tion, or they may be supplied from the substrate against which the formulation is polymerized especially the tooth in the preferred dental compositions where this provides an especially good bond in the preferred applications. In such a case the carboxyl ions, other acid ions or reactive acid derivative ions may be chelated with surface cations of the substrate to provide an adhesive bond. In a pre-ferred dental composition not only is this substrate bonding available but bonding with an ion contributing inorganic filler aids in binding the entirety together.
It will be understood that. the term reactive acid derivative ions as used here includes the water soluble salts of cations, especially the monovalent species of cations, for example t:he sodium, ammonium and potassium salts, which are displaced by cations of greater valency by metathesis. However, the carboxyl group itself is most preferred over other acid groups or the reactive acid derivative ions. Especially appropriate acid groups are all those that can react with. oxidic, mineral, ceramic, vitreous, or metallic killers.
Examples of other acid radicals, the radicals in-clude:
O O C> O
II I~ il! 11 -P-OH, -P-OR, -O-P-OH, and -O-P-OR, i ( 1 OH OH OH OH
of phosphorus acids wherein R i.s alkyl, aryl, or vinyl for :ample, the radicals --S02H, S03H, OR --O-- S03H of sul-furic acids, and the radicals -i-OH, -~-OR. -O-'-OH, and -O-~-OR, OH OH 'OH OH
of boron acids wherein R is alkyl, aryl, or vinyl.
Cationic acid radicals like --NR2H+ or --PRZH+
(wherein R is H or alkyl) are also appropriate.
The reactive acid derivatives can be substituted with acid halides with acid anhydrides, and with acid amides, nitriles, and esters, i;,hat readily hydrolyze into acid, such can enter into ion-exchange, neutralization, salt formation, or chelation reactions with the reactive filler. Preferred acre acid groups or reactive acid derivatives in the form of carboxylate, phosphate, phos-phonate, sulfonate, or borate acid radicals or of their reactive derivatives.
Preferred polymerizable unsaturated radicals are alkenyl, alkenoxy, cyc:loalkenyl, radicals, with acryl, methacryl, vinyl, and ef these, the olefins are preferred with the acrylic and met:hacrylic radicals being especially preferred.
For a better under:~tanding of the characteristics and method of producing the preferred ethylenically unsatu-rated carboxylic acid compounds of the present invention the production of a most preferred series of the butane based compounds is described as follows showing a prefer-_.d method of their production:
For starting materials, Butane 1,2,3,4-tetracar-boxylic acid is refluxcad with acetic anhydride.
HO C--- i ~ ------C-,---C---C OH
H C=O C=O H
O O
H H
O O
/\/
Butane 1,2,3,4 tetracarboxylic acid acetic anhydride.
The reaction yields butane tetracarboxylic acid di anhydride and acetic acid.
HZ H H Hz O = C C---C C---C C = 4 _O-C C--O' il II
il Butane tetracarboxylic acid anhydride acetic acid.
One mole butane t:etracarboxylic acid anhydride is then reacted with two moles 2-hydroxyethyl methacrylate (HEMA) in the presence o~f HZS04 or other suitable catalyst.
~ H3 (I
CH2 = C ~ - C - O - C;Hz - CHI - OH
2-hydroxyethyl meithacrylate (HEMA) The reaction yields a liquid product, believed to be a mixture of isomer monomers of Butane tetracarboxylic acid bis (2-hydroxyethyl metha<:rylate) ester. The isomers differ in the positioning of the hydroxyethyl methacrylate moiety on the carboxylate groups.
~I If II ~I II II
~ ~'~ ~ iG
HO OH RO OR HO OR
R ~ ~ ~ R H ~ I I ~ H R ~ ~ % H
\, il ~ II i~ II
Butane tetracarbo~:ylic acid bis (2-Hydroxyethyl methacrylate) esters.
In this example, R is the hydroxyethyl methacrylate moiety. Thus, the second isomer above would be structur-ally diagrammed as follows.
H~~ /G ' ~ ~ H3 CHZ=C-C-O-CHz-CH2-O O-~CH2-CH2-O-~-C=GHZ
H ~ ~ H
I
O
Butanetetracarboxylic acid bis (2-hydroxyethyl meth-acrylate) ester.
The Butane tetraca~~boxylic acid bis (2-hydroxyethyl ahacrylate) esters a:re referred to by the initials BCA.
The above reaction gives a monomer molecule having two reacted carboxylic acid groups and two unreacted car-boxylic acid groups. In an analogous manner 1 mole of butane-dicarboxylic-acid-anhydride may be reacted with 1 mole of hydroxy ethyl. methac:rylate to similarly yield isomers of butane tetracarboxylic acid mono (2-hydroxy-ethyl methacrylate). Different combinations of reactive esters may be formed by different concentrations of reactants; but according to the invention there must be at least two unreacted carboxylic acid group in the monomer.
The number of reacted or unreacted carboxylic acid groups in the monomer is controlled by varying the reaction conditions.
The (meth)acrylate radical may be joined on in a number of ways, for example:
Exemplary radical: would be ethoxy acrylate -O-CfI2-CH2-O-C-CH=CHZ
iH3 ethoxy methacrylate -~O-CHZ-CHZ-O-~-C-=CHZ
H3 ~~ f H3 (iso) propoxy (meth)acrylate ~-O-CHZ-CH-O-C-C=CHZ
polyglycol methacrylate -O-CH2-CHz- (O-CHz-CH2) ~-O-~-C=CHZ
where n is preferably from 1 to 10.
amide -HN-CHZ-CHZ-O-C-C=CHZ
The preferred radicals would be the (meth) acrylates and especially the eth~oxy (meth)acrylate radicals.
The Denta:L/Medical Compositions The compounds of this invention can desirably be used as primers in some pre~Eerred aspects with only initiators present or initiators and accelerators or only accele-rators present. In some instances the butane compounds may be used neat or with only curing agents and ingred-Tents that would be considered incidental and thus not counted when considering "co:nsistency essentially of".
Such incidental ingredients would be anti-oxidants, stabi-liters and pigments and the like which may be included in proper instances.
The monomers of the present invention polymerize by well known addition polymerization procedures through the ethylenically unsaturated group by a variety of means.
Most often curing agents, catalysts and initiators and accelerators, are used to expedite and control the poly-merization. It is known in the dental art to practice addition polymerization by employing a peroxide, for example benzoyl peroxide, and heat to initiate the reac-tion. It is also known that accelerators enhance the reaction so that it may proceed more expeditiously at room temperature. Accelerators are reducing amines or sulfi-iz tes for example. It: is also known to polymerize such compounds by ultraviolet and visible light using initi-ators and accelerators known to the art. Visible light curing is preferred. 1.~'or preformed objects, or those cured outside the body, other forms of radiation, for example ionizing radiai~ion is known.
It will be appreciated that in-vivo polymerization must take into account the suitability of the method and composition so as not to harm the patient within whom polymerization of the monomer or oligomer compound and the curing of the composition occurs. Thus the elements of a polymerization system, for example a peroxide and an amine, may be components of a two part formulation in which polymerization i;s delayed until the two parts are combined and react to polymerize the monomer. Or all the necessary chemical components may be combined within a -single composition which is induced to polymerize by the application of heat or light or other initiating action.
It is known for example to initiate by irradiation with 'ultraviolet or visible light in which case the initiator, often a benzophenone o:r camphoroquinone may be combined within a single, premixed, ready to use shelf-stable composition. A particular ;polymerization method and system may be preferred depending on the application requirements of the material. Whatever the mode of poly-merization, or "cure" of the composition including the . homer or monomers an important characteristic of the polymers which form ar<, that they are capable of further reaction with di- or polyvalent cations through their acid or reactive acid derivative functionality. A further important aspect of the compounds and compositions of the invention is that they exhibit adhesion between the mono-mer compound and a cation containing surface, metal, metal oxide, tooth bone and the like, against which they are polymerized.
One preferred cla:as of compositions of the present invention are shelf-sizable compositions that initiate curing in response to visible light. By shelf-stable it is meant the composit:i.on retains good application and curing characteristic when stored in a visible light opaque container at room temperature for one year or more.
Curing by visible light refers to actinic light initiated compositions curing within the visible light range of approximately 360 to 600 nanometers.
In many dental and medical applications it is desir-able to include fillers supplying reactive cations, and optionally non reactive fillers or mixtures thereof in the compositions of the present invention in preferred aspects thereof. Among those fa.llers which are especially suited for use in this invention are inorganic glasses such as are presently known in the art to form glass ionomer cement compositions. Exemplary of such fillers are those of U.S. Patent 4,814,362.
Preferred species of glasses include, for example, barium. aluminosilicate, calcium aluminosilicate, and strontium, lanthanum, tantalum, tung-sten, etc. glasses. Silica, including submicron silica, or quartz may also be used. Ceramic fillers, for example, calcium hydroxy apatite: may also be used to good advant-age. The fillers used in the invention may be reduced in particle size and them preferably silanated by methods known in the art before they are incorporated into such compositions. Preferred levels of filler material are from about 20% to about: 80% based on the total weight of the adhesive composition, with from about 40% to about 70%
being more preferable and about 45 to 60% being most pre-ferred. If a more finely particulated filler is used, amounts of filler may be decreased due to the relative increase in surface area which attends the smaller sizes of particles. Preferred particle size distributions are from 0.02 to 50 microns, more preferably 0.1 to 10 microns, and most preferably 1 to 6 microns.
Other ingredients that may be present are, for example, solvents, plast,icizers, pigments, anti microbials and therapeutics which may be time released from the composition and oxi-dat.ion inhibitors such as butylated hydroxytoluene. The mixtures in accordance with the invention can also contain other polymerizable unsaturated .nomers and/or oligomers and/or prepolymers that do not contain any acid group, and/or salts thereof and/or reac-tive readily hydrolyzing acid-derivative groups thereof.
Particularly appropriate are monomers that are consti-tuents of conventional composites such as for example hydroxy alkyl methacr;tlate. The mixtures can also if necessary contain other compounds that, although they contain acid groups and/or their salts and/or their reactive readily hydr~alyzing derivative groups do not contain any groups that are unsaturated and polymerizable.
preferred in this case are multi-basic acids or their reactive, readily hyd~:olyzing~ derivatives. Especially preferred multibasic ;kids are hydroxy acids such as tartaric or citirc acid, but also polyacids such as poly-carboxylic, polyphosph~oric, polyphosphonic, or polysul-fonic acids.
Compounds that have chelating graups taut do not contain acid groups or readily hydrolyzing acid-derivative groups can be employed. Examp:Les of this type are vanil-eates, syringates, and salicylates.
While one of the special advantages of the use of the class of compounds of the present invention in treating mammals, especially humans and especially in the maxio-.facial, mouth area, in dentistry is the fact that the com-pounds are relatively fluid monomers and large amounts of diluents are not required, there are instances where .luents may be desiraxrle. For example, in bonding agent adhesive compositions to aid in more completely and quickly wetting the substrate. Suitable diluents would be, for example, ethanol, water, and less viscous reactive monomers.
Mixing of the compositions of the present invention may be achieved using standard compounding techniques.
for example, liquids, photoinitiator(s), and accele-rator s) are blended first, and then when fillers are to be included they are added incrementally thereafter. When blending light sensitive compositions, however, a photo-safe light, i.e., one that does not contain substantial amounts of wavelengths of electromagnetic radiation that would activate the photoinitiating system used, should be employed to avoid initiating polymerization prematurely.
The butane (based) compounds of the present invention also have medical applications, especially preferred would be the bone cements and adhesives. But the application of the present invention t:o dental treatment by application to a tooth or a number of teeth in viva, in the mouth of a live patient by a dentist or dental practitioner, is a most preferred use.
One preferred dental treatment is the application of the composition as a dental liner. The dental liner composition may in one most preferred embodiment consist essentially of the butane compound and other active o' .gredients chosen from the group consisting of none, curing catalysts, initiators, accelerators, and mixtures thereof. In other preferred compositions diluents may be present or other ingredients may be present.
The composition is applied as a liner using conven-tional techniques and preferably cured with application of visible light in conventional manner. In other preferred embodiments the composition is a two-part system and the curing agent is spatu~:ed in prior to placement and the placement is by standard technique. Yet another preferred embodiment is a comingation of the other two where there is a two-part system but after mixing the system is cured with visible light with substantial self-curing occurring.
Another preferred dental treatment is the application of the composition as a dental composite filling. The dental composite filling composition may in one most preferred embodiment consist essentially of the butane compound and other active ingredients chosen from the group consisting of finely divided reactive filler that can react sonically with the acids or acid derivative of said butane compound, curing agent and mixtures thereof.
In other preferred compositions diluents may be present or other ingredients may be present.
The composition is applied as a composite filling using conventional techniques and preferably is a one-component composite filling material cured with appli-~tion of visible light in conventional manner. In other preferred embodiments the composition is a two-part system and the curing agent is spatuled in prior to place-ment and the placement is by standard technique. Yet another preferred embodiment is a combination of the other two, where there is a t:wo-part system but after mixing the system is cured with visible 7.ight with substantial self-curing occurring.
Having generally described the invention, a more com-plete understanding can be obtained with reference to cer-tain specific examples, which are included for purposes of illustration only. 7~t should be understood that the invention is not limited to the specific details of the Examples.
EXAMPT~ES
Throughout the Examples once a material, procedure or test procedure has been described, the description will not be repeated in subsequent Examples in most instances 'where the description remains the same, it being under-stood that the description applies in subsequent Examples.
~~11 ingredients are by weight unless otherwise specified.
Method for measurement of compressive strength For each material to be tested, cylinders 4 mm diam-eter and 6 mm long were prepared by filling the mixed material into stainless steel molds and light curing from ,ach end for 40 seconds using a PrismeticsT" light. The cylinders were removed from the molds and stored in water at 37~C for 24 hours prior to testing. The force needed to load the specimens t:o breaking point was measured using a Zwick model 2455 set to a c~__~osshead speed of 1 mm/min.
Method of transverse flexural strength, The uncured material was filled into a split stain-less steel mold with internal dimensions 25 mm x 2 mm x 2 mm. The exposed faces were then covered with polyester foil and clamped between transparent plastic blocks approximately 5 mm thick. The material was light cured for a total of 120 seconds by moving a dental curing light evenly backwards and forwards along the mold with the wand of the light in contact with the plastic blocks. After curing, the hardened :specimens were stored in water at 37~C for 24 hours. Before being tested, any remaining flash along the edges of the specimens was carefully removed and the exact dimensions of each specimen measured. The specimens were then tested in three point bending made using a Zwick model 1455 set to a crosshead speed of 1 mm/min, with the sample resting on supports 20 mm apart and being loaded at the mid paint. The trans-verse bending strength was calculated from the standard formula in Mega Pascals (MPs).
ahod for measurement of diametral strencxth For each material to be tested, cylinders approxi-mately 6 mm diameter and 3 mm long were prepared by fill-ing the mixed material into stainless steel molds and light curing from each end for 40 seconds using a Pris-meticsTM light. The cylinders were removed from the molds and stored in water at 37°C for 24 hours prior to testing.
Immediately before testing, the exact dimensions of each cylinder was measured with a micrometer, for use Later in calculating the diametral strength. The force needed to load the specimens across the diameter to breaking point was measured using a Zwick model 1455 set to a crosshead speed of 10 mm/min.
~arcol hardness measurements The Barcol hardne:as tester model GYZJ 935 was used for all measurements.
To avoid errors and effects due to changes in ambient lighting, these tests were carried out in a room with yellow lighting to which the photoinitiators systems are not sensitive. A circular brass mold having an internal diameter of 8 mm and a thickness of 1.3 mm was used. This was placed on a white surface and filled with the material to be tested. The surface was then covered with a small piece of transparent polyester film and the sample cured from above for the required time (usually 30 seconds), ~~olding the end of the light guide lightly in contact with the foil. At the end of the craring time a stop watch was started and the hardness measured after 60 seconds.
It is necessary to wait ~0 seconds.after curing the materials and before measuring the hardness, since light cured compounds show a rapid .increase in hardness during the first few seconds after curing, and attempts to measure during this time can lead to unnecessary vari-ations and errors. A waiting period of sixty seconds was chosen since this could be reliably and reproducibly carried out, and the hardness of the compound is increas-ing relatively slowly at this time.
Measurement of Adhesioru to dentine Preparation of the teeth Extracted human teeth were cleaned and sterilized in 1% sodium hypochlorite solution. The teeth were then stored in fresh la sodium hypochlorite solution at 4°C
until needed. Both antearior and posterior teeth were used at random. Before use a dentine surface was exposed on each tooth by grinding an area of the crown flat with 300 grit abrasive paper, and then polishing this with 600 grit paper. All this work ways carried out under water to avoid desiccation of the dentine.
reparation of adhesion samples Immediately before use, t:he prepared dentine surface was quickly blotted with a paper tissue. This removes excess surface water without drying out the tubules and the dentine retains its translucent appearance, rather than the white opaque <~ppearance which occurs when exces-sive drying has taken place. A length of a plastic drink-ing straw approximately 4 mm long and 3 mm in diameter was then filled with the m<~terial to be tested, pressed lightly onto the dentine surface, and the material light cured through the straw for 4o seconds using a PrismeticsTM
curing light. The prepared samples were normally tested after storage in water at 37~c: for 24 hours, though some were tested after only to minutes.
Testinq_the prepared sam les After storage for the required time, the samples were set in plaster so that the dentine surface was vertical.
The samples were kept covered with a damp paper tissue during this time to avoid their desiccation. The force needed to shear the cylinders from the dentine was then measured using a Zwick model 1455 set to a crosshead speed of 1 mm/min, and the adhesion calculated in Mega Pascals.
Samples which were to be tested after 10 minutes were set in plaster before use.
reparation of pow er samples The ingredients were weighed into a glass bottle and thoroughly mixed by tumbling i:his for one hour. The powder was then passed twice through a 150 ~ nylon sieve before being transferred into a labeled container.
Method of measuring fluoride release For each material, three cured discs having a diam-eter of 20 mm and a thickness of 1 mm were prepared. Each disc was placed into a bottle containing 25 ml of dis-tilled water, and stored at 37°C. At intervals of one week the water was renewed, and the fluoride content of the old water determinead in the presence of 10% TISAB IV
buffer. The average measurement of the three discs was calculated and expressed in terms of ~g fluoride ion per square cm of surface area o:E the disc (including the sides). Each week a blank was run by storing a bottle containing only water. The fluoride content of this was determined as a control. The electrode was calibrated before use using solutions with a known fluoride content, also in the presence of 10% TISAB IV buffer.
Preparation of But:.ane-1,2,3,4 tetracarboxylic dian-hydride. (BTCA) Butane-1,2,3,4 tetracarboxylic acid (230 g) (Aldrich-..iemie GmbH, catalog No. 8, 402-3, 97%) and acetic anhy-dride (690 ml) (Aldrich-Ghemie GmbH, catalog No. 11,004-3, 99%) were placed in a :L500 ml flask fitted with a distil-lation fraction cutter and reflux condenser and heated with stirring to reflu~; for 3 hours. After this time, 250 ml of a mixture of acetic acid and acetic anhydride were slowly distilled out when the reflux temperature slowly increased from 118°C to 138°C. The mixture was then stirred while it cooled. The crystals were filtered off using a suction funnel, washed twice with 300-400 ml of hexane, and the filt~ar cake sucked dry. The white crystals (185 g) were t'.hen transferred to a desiccator and stored over sodium hydroxide pellets.
Preparation of Monomer A.
Butane-1,2,3,4-tet.racarboxylic acid, bis(2-hydroxy-ethyl methacrylate) ester is prepared as follows:
Butanetetracarboxylic acid dianhydride (34.5 g), 2-hydroxyethyl-methacrylate (HENtA,, 50 g), (Aldrich-Chemi GmbH, catalog No. 12,813-5, 97%) and anhydrous sodium acetate (0.46 g) (Mark" catalog No. 6268), were stirred and heated together at 80°C. The changes in concentra-tions of reactants and products were followed by means of HPLC and IR spectroscopy, and after seven hours it was found that all the anhydride was consumed, and the reac-ion was therefore at an end. The product was a light colored viscous liquid, which was used directly in the formulations given elsewhere.
Powder compositions were prepared from the following two ingredients:
*The Strontium glass was made according to U.S. Patent 4,814,362 and had the following analysis with all elements except fluorine being calculated as the oxide of the element.
The mean particle size was 5.5 microns.
Composition ~rarts SiOZ 32.1 A1z03 24 . 6 Na20 2 , 9 Sr0 2g.~
12.3 PZ~g 4 . 8 polyacrylic acid (PAA) (molecular weight Specification range 30,000 to 45,000 Usual range around 35,000.
The powder was prepared by tumbling the glass and PAA
together in a bottle for one hour, then passing the resultant mixture through a _L50 ~ sieve. Two powder compositions, 3 and 4, were prepared as follows with the proportions given in parts by weight.
Powder compvsition;s 2 3 Strontium Glass 90.9 80 PAA 9 .1. 2 0 E:~AMPLES 5 to 10 Adhesive light cured Composition.
A series of compositions were formulated from the ingredients in the proportions given in Table 1 in parts by weight.
Ingredients in given before camphoroquinone (CQj (Aldrich Chemical,GmbH
catalog No. 23,122'3) dimethaminobenzoic acid, ethyl ester (DMABE) {Aldrich Chemical, GmbH
catalog No. E2,490-5) The compositions were prepared by first mixing monomer A and 2-hydro:~cy ethy:lmethacrylate with stirring and then dissolving th.e camphoroquinone and dimethamino-benzoic acid, ethyl ester in the Monomer mixture with stirring at 50~C: Fina,liy the water was added and stirred until totally dissolved. Roughly equal weights of the liquid and powder were mixed on a paper pad, when a fluid composition was obtained having a visually and tactually observed consistency suitable for use as a dental mater-ial, particularly as a lining material under fillings, as a cement, or as a fissure sealant. This was hardened by application of light from a dental curing light (Pris-metics~ light, Dentsply International Inc.) for 30 seconds. The following properties were measured:
Table 1 Liquid Components [in grams]
Examples 5 6 7 8 9 10 Monomer A 6.25 7.14 6.82 6.00 4.50 8.50 HEMA 2.50 1.90 2.73 :3.20 5.50 1.50 Water 1.25 0.95 0.45 0.80 0.00 0.00 CQ 0.06 0.06 0.06 0.06 0.06 0.06 DMABE 0.08 0.08 0.08 0.08 0.08 0.08 Powder # 2 2 2 2 3 3 The properties listed were evaluated with the results shown.
Barcol Hardness 75 80 89 86 90 90 Compressive Strength MPa 62.1 72.4 91.4 81.2 N/D N/D*
Adhesion to wet Dentin MPa 4.7 5.8 6.6 5.8 N/D N/D
Fluoride Release ~g/cm2 17 31 40 34 92 60 These examples show the utility of the compositions as demonstrated by their strength, rapid polymerization, adhesion to wet dentin, and the ability to release fluoride from the glass component through the polymerized matrix of the compositions described.
*N/D = not determined EXAMPT~E 11 Powder Formulation Strontium Glass g0 F'~ 10 Iaiquid Formulation Monomer A 59.4 2-hydroxyethyl m~ahacrylate 31.8 water 8.0 camphoroquinone 0.38 DMABE 0.44 Butylated hydroxytoluene 0.01 The powder and liquid were mixed 1:1 [By weight] as in Examples 5 to 10. This gave a fluid cement like consist-envy suitable for use as a liner covering the floor of prepared dental cavities. Properties were determined and compared. The properi~ies were compared to a commercial product, Vitra-bond's a product of 3M, sold for the stated purpose and also light polymerized.
Table 2 Example 11 Vitrabond~
Compressive Strength MPa 81 3.2 4g Flexural Strength MPa 17.2 0.5 20.7 + 1 Flexural Modulus MPa 1332 252 1268 115 Diametral Tensile Strength MPa 15.4 0.9 17.6 + 1 Adhesion to wet ntin de MPa 8.4 3.8 6.5 + 1.3 All settings as the standard method.
in ~arcol Hardness measured 60 seconds after irradiation for 30 seconds Specimen Top Surface gp 0 Specimen Bottom Surface 8p 0 Fluoride Release (7 days) ~Cg/cm2 90 (7 days) 114 (3 days) Translucency Ca.T clear opaque <0.35 >0.75 *measured using a Langer photometer model UME3.
Formulations of Monomer A with calcium glass.
Powder Formulation Calcium Glass* 75 Liquid Formulation Monomer A 59.4 2-hydroxyethyl methacrylate 31.8 water 8.0 camphoroquinone 0.38 DMABE 0.44 BHT 0.10 The powder and liquid were mixed 1:1 by weight on a paper pad as before. This gave a visible light curable (VLC) glass ionomer cement h<~ving a creamy consistency suitable for use, for example, as dental cavity liner or cement.
It is believed that t:he glass provides calcium ion by elution which help to crosslink the polymerized mass. The mixture was cured by exposure to a dental curing light for seconds irradiated from one surface only. The Barcol Hardness was 75 at ths: top surface and 70 at the lower surface 1.3' millimeters beneath the exposed surface.
The Calcium glass had a mean particle size of 6.5 microns. , The analysis was carried out at the Dorfner Analysen Zentrum, Hirschan, Germany.
Composition by parts SiOz 27.8 A1203 31. 3 Na20 10 . 6 Ca0 10.8 F' 14.8 PzOs 7 . 0 Formulations of Monomer A with calcium glass.
Another powder wa:~ formulated as follows:
Powder Formulation Calcium Glass g5 The powder was combined with the liquid component of Example 12 at a ratio of 1:1 on a glass pad, and mixed with a dental spatula. As before, it was cured with a Prismetics light; the B~arcol Hardness at the upper surface was 78 and the lower sup.°face, 1.3 millimeters beneath, was 73.
Both Examples 12 and 13 show the ability of the monomers and compositions of the invention to be reactive and polymerize by addition polymerization in the presence of various glasses which provide cations capable of cross-linking the compositions. These sonically crosslinked polymers are useful as :liners, cements and filling mater-a so gals. They have excepi;.ional translucency and may be cured to considerable depth compared to commercially available dental liners and cements. These properties are espe-cially valuable where rapid cure to good depth of inher-ently adhesive ionical7Ly cross.linked restorative materials are desired.
Crosslinking with zinc oxide.
The liquid composition of Example 12 was combined on a dental mixing pad at a ratio of 1 part to 4.6 parts by weight of zinc oxide containing powder (Poly FTM Plus, DeTrey Dentsply, Konst:anz) to form a stiff paste of a consistency suitable for use as a dental filling material.
The powder contains 83;> by weight of a zinc oxide mixture with minor amounts of the oxides of magnesium, aluminum and silica; 13% powder~_d polyacrylic acid, and 4% of tin fluoride. The surface of a mass of this material could be cured by 30 seconds exposure to a dental curing light to give a tough water resistant surface. Curing by irradiation with visible light was slower with this rather opaque composition than the composition of Example 12.
The following table snows that the composition becomes cured whether or not exposed to light but that when polymerization occurs prior to crosslinking a hard composition results more rapidly, and that reaction with ~inc oxide occurs even without prior polymerization. The composition has dental. applications, for example, as a liner or base under permanent fillings, a temporary fil-ling material, or as a cement.
Table 3 Time (min) Barcol Hardness (test) of Test Lic~ht Cured Not Light Cured 0 Light Cure 30 seconds 52 p Readings were taken sequentially on one light cured and one non light cured specimen.
Tie Coat and Top Coat compositions.
The crown of an e~;tracted human tooth was ground so as to expose a flat area of dentin. This was dried with a paper tissue and the ~.iquid of Example 12 was applied in a thin layer. This was cured for 10 seconds with a Pris-metics~ curing light used in standard clinical manner. A
blob of the powder:liquid mixture of Example 39 was placed on top to cover an area about 4 mm in diameter. This was cured for 30 seconds with the Prismetics~' light used in the standard clinical manner. Five minutes later force was applied ~ to the dent~in composition interface using a metal spatula. It was not possible to dislodge the compo-.~ition from the dentin surface by this means, indicating that its adhesion to dentin is at a high and clinically useful level. In contrast, a mixture of Poly FT" Plus powder (a composition formed by the combination of the same reactive zinc oxide filler and the same polyacrylic acid), and water which is the commercially recommended method for using this material, mixed according to directions and applied to a dentin surface, was easily dislodged.
EXAMPLE 16 to 17 Preparation of bonding agents For Dental composite Filling materials.
Formulations were made up as follows, where quanti-ties are given in parts by weight.
Ex. 16 Monomer A 52.59 HEMA 38.49 water 8,0 0.38 DMABE 0.44 BHT 0.10 Ex. 17 Momomer A 54.58 HEMA 36.39 water 3,gg 25% glutarald~shyde soln* 3.99 CQ 0.36 DMABE 0.45 BHT 0.23 *supplied by Fluka, catalog No. 49630 Adhesion of a composite material (AP.HT", Dentsply International Inc.) to dentine was measured using the above liquid compositions as dentine primer or tie coat.
..he chosen liquid was brushed thinly onto the prepared dentine surface, and cured for ten seconds before applying the composite filled straw. The method was otherwise identical to the general method given before. Results are given below, and compared to those measured in a similar way for a commercially available dentine bonding agent (Prisms Universal Bonds°, Dentsply International Inc.).
Table 4 liquid Ex. 16 adhesion = 6.62 ~ 2.09 MPs liquid Ex. 17 adhesion = 5.12 ~ 1.86 MPs dental bonding adhesion = 4.22 ~ 0.99 MPs agent Both experimental forrraulations therefore gave adhesion values at le~~st as high as obtained with the commercially available material dental bending agent (Prisms Universal Bonds II), thereby demonstrating the usefulness of the monomer A in this application.
Fluoride ion releasing adhesive formulations Adhesive resin formulations were made up with compo-sitions as shown below.
liquid Ex. 18) Monomer A 61.36 2-hydroxyethyrl methacrylate 33.39 ~
water 4.51 camphor quinone 0.34 DMABE 0.40 BHT 0.1 liquid Ex. 19) Monomer A 51.15 2-hydroxyethyl methacrylate 37.43 water g.p camphor quinone 0.38 DMABE 0.44 BHT 0.1 Cetylamin hydrofluoride* 2.5 liquid Ex. 20) Monomer A 51.15 2-hydroxyethyl methacrylate 37.43 camphor quinone 0.38 DMABE 0.44 BHT 0.1 Cetylamin hyd.rofluor:ide* 2.5 liquid Ex. 21) An attempt was made to formulate a composition con-taining an equivalent amount of fluoride ion using the composition of Ex. 18) but replacing the cetylamin fluoride with 0.2 parts of sodium fluoride. However, the sodium fluoride did not dissolve.
*supplied by Merk, Germany, catalog No. 11679.
_able 5 Bondin g ent Adhesion MPa ag Fluoride release ~.ca~cm2 liquid Ex.18) 6.62 2.09 0 liquid Ex.19) 4.39 1.89 gg liquid Ex.20) 2.73 0.86 141 Prisma Universal Bond~ II
(Dentsply) 4.22 0.99 0 The adhesive is interesting in that the fluoride ions are totally dissolved in and dispersed evenly throughout the liquid, which remains glass clear when cured.
EXAMPLE. 2 2 In order to furthsar demonstrate the general useful-ness of monomer A (the reaction product of butanetetra-carboxylic acid dianhydride and 2-hydroxyethyl-meth-acrylate) as an adhesive agent or primer, a liquid compo-sition was made up as follows.
1) Direct preparation of a solution of monomer A in HEMA
Butanetetracarboxylic acid dianhydride (500 g 2.5 moles), 2-hydroxyethylmiethacrylate (1.5 kg 11.5 moles), BHT (1.5 g) and sodium acetate: (5.0 g) were stirred and treated together at 80~C for two hours, after which time a clear viscous liquid wa:~ obtained. The infrared spectrum of this showed that all the anhydride had reacted, and the ..eaction was therefore finished. The liquid, which con-sisted of a mixture of <~pproximately 1500 grams of monomer A in approximately 850 grams of HEMA, was allowed to cool and used in the liquid formulation below.
2) Adhesive Primer composition in darts by weiaht solution of monomer A in HEMA 200 BHT 0.44 camphor quinone 0.84 DMABE p,g7 water 17.58 The mixture was heated to 50°C, stirred until homogenous, then allowed to coal.
3) Use of the liquid composition in 21 as an adhesion primer to a nicke_1 - chrome dental allow.
Blocks of the met<~1 alloy (Wiron 88, BEGD, Bremen, Germany) were prepared by grinding one surface flat on 220 grit silicon carbide paper. The surface was then rinsed under clean water and dried on a paper tissue. The liquid in 2) was brushed on thinly, and cured by exposure for 10 seconds to light from a Prismetics~ dental curing light.
A section of a plastic drinking straw with an internal diameter of 5.25 mm and length of approximately 2 mm, was then held on the surface and i:illed with a commercially available composite material (AP. H. TM, Dentsply) . This was cured by exposure to thsa Prismetics light for 40 seconds, after which the sample was stored in water at 37°C for 24 hours. The shear bond strength was then tested in a Zwick model 1455 using a crosshead speed of 1 mm/min.
Using 6 samples, an average adhesion of 5.7 ~ 2.15 MPa was measured.
4) Adhesion to a coba7.t - chrome alloy The experiment in 3) was repeated using a cobalt -chrome alloy (DentalliumT" Extra hard, Svedia). A average adhesion of 7.3 ~ 1.7 N(Pa was measured for 7 samples.
General. Description By an aspect of the invention new dental/medical restorative/prosthetic compositions are provided. These compositions are the product of the use of a class of com-pounds new to such use. As a liner or bonding agent, especially a dental liner for application to tooth enamel and dentin (meaning~natural tooth structure), the compound can be applied in preferred forms neat or with only poly-merization initiators added to assure quick curing and aid in completion of th,e cure o f the compositions. Of course, 4a 64053-'260 a pending on the application ~.ntended other materials may be added. When dental cements and composites are the intended compositions the compound of the present inven-Lion is used as a complete or a partial substitute for conventional resins.
The Chemical Compound Employed The class of compounds that characterize the inven-tion are those having as a principle functional ingredient polymerizable unsaturated monomers of a substituted butane moiety with acid or reactive acid derivative functionality having the general formula:
(Rp2C) x ._- C4g6 ._- (COZR' ) Y
where R is an acid radical or a reactive acid derivative and R' is a palymerizable unsaturated radical having from 2 to l3 C and x is 2 to 3 and y is 1 to 2. Preferably at least one carbon adjacent tea each carbon carrying a (C02R')y is associated with a (RO2C)~ and the preferred polymerizable unsaturated radical is preferable a (meth) acrylate. (Meth) acrylate means either an acrylate or a methacrylate.
The compounds average molecular weight is preferably about 200 - 600, more preferable 2b0 - 499 and most pre-ferably 290 - 460. The preferred compounds are liquid at room temperature. By liquid it is meant that the material is fluid with viscosities of less than 100,000 cps at 23°C.
~~
The compounds essentially contain or include in a single chemical compour,~d at least two different functional substituent groups, one of which is capable of addition polymerization and the other of which is carboxyl or other acid or reactive acid derivative. Tt is important that there be at least one such addition polymerizable group, but not more than two ;end there must be two or more acid or reactive acid derivative groups but in the most pre-ferred compound there .are no more than three, The pre-ferred chemical compounds are in a preferred aspect derived from the reaction of butanetetracarboxylic acid or its anhydride with a hydroxyl or polyhydric compound to form esters and diesters.
The new dental/medical compositions of matter are capable of being polymerized to form linear or crosslinked polymers which contain multiple acid groups or reactive acid derivative groups that may be further reacted with rations, especially tho:~e of valence 2 or greater, to form poly-salts relatively :insoluble in water. Because the compounds are monomers of relatively low molecular weight with a high density of both ethylenic unsaturation and carboxylic reactive acid derivative sites, excellent curing with superior integrity occurs. The rations may be supplied by ingredients or components of the given formulation or they may be supplied from a solution of rations supplied from a second component of the formu-tion, or they may be supplied from the substrate against which the formulation is polymerized especially the tooth in the preferred dental compositions where this provides an especially good bond in the preferred applications. In such a case the carboxyl ions, other acid ions or reactive acid derivative ions may be chelated with surface cations of the substrate to provide an adhesive bond. In a pre-ferred dental composition not only is this substrate bonding available but bonding with an ion contributing inorganic filler aids in binding the entirety together.
It will be understood that. the term reactive acid derivative ions as used here includes the water soluble salts of cations, especially the monovalent species of cations, for example t:he sodium, ammonium and potassium salts, which are displaced by cations of greater valency by metathesis. However, the carboxyl group itself is most preferred over other acid groups or the reactive acid derivative ions. Especially appropriate acid groups are all those that can react with. oxidic, mineral, ceramic, vitreous, or metallic killers.
Examples of other acid radicals, the radicals in-clude:
O O C> O
II I~ il! 11 -P-OH, -P-OR, -O-P-OH, and -O-P-OR, i ( 1 OH OH OH OH
of phosphorus acids wherein R i.s alkyl, aryl, or vinyl for :ample, the radicals --S02H, S03H, OR --O-- S03H of sul-furic acids, and the radicals -i-OH, -~-OR. -O-'-OH, and -O-~-OR, OH OH 'OH OH
of boron acids wherein R is alkyl, aryl, or vinyl.
Cationic acid radicals like --NR2H+ or --PRZH+
(wherein R is H or alkyl) are also appropriate.
The reactive acid derivatives can be substituted with acid halides with acid anhydrides, and with acid amides, nitriles, and esters, i;,hat readily hydrolyze into acid, such can enter into ion-exchange, neutralization, salt formation, or chelation reactions with the reactive filler. Preferred acre acid groups or reactive acid derivatives in the form of carboxylate, phosphate, phos-phonate, sulfonate, or borate acid radicals or of their reactive derivatives.
Preferred polymerizable unsaturated radicals are alkenyl, alkenoxy, cyc:loalkenyl, radicals, with acryl, methacryl, vinyl, and ef these, the olefins are preferred with the acrylic and met:hacrylic radicals being especially preferred.
For a better under:~tanding of the characteristics and method of producing the preferred ethylenically unsatu-rated carboxylic acid compounds of the present invention the production of a most preferred series of the butane based compounds is described as follows showing a prefer-_.d method of their production:
For starting materials, Butane 1,2,3,4-tetracar-boxylic acid is refluxcad with acetic anhydride.
HO C--- i ~ ------C-,---C---C OH
H C=O C=O H
O O
H H
O O
/\/
Butane 1,2,3,4 tetracarboxylic acid acetic anhydride.
The reaction yields butane tetracarboxylic acid di anhydride and acetic acid.
HZ H H Hz O = C C---C C---C C = 4 _O-C C--O' il II
il Butane tetracarboxylic acid anhydride acetic acid.
One mole butane t:etracarboxylic acid anhydride is then reacted with two moles 2-hydroxyethyl methacrylate (HEMA) in the presence o~f HZS04 or other suitable catalyst.
~ H3 (I
CH2 = C ~ - C - O - C;Hz - CHI - OH
2-hydroxyethyl meithacrylate (HEMA) The reaction yields a liquid product, believed to be a mixture of isomer monomers of Butane tetracarboxylic acid bis (2-hydroxyethyl metha<:rylate) ester. The isomers differ in the positioning of the hydroxyethyl methacrylate moiety on the carboxylate groups.
~I If II ~I II II
~ ~'~ ~ iG
HO OH RO OR HO OR
R ~ ~ ~ R H ~ I I ~ H R ~ ~ % H
\, il ~ II i~ II
Butane tetracarbo~:ylic acid bis (2-Hydroxyethyl methacrylate) esters.
In this example, R is the hydroxyethyl methacrylate moiety. Thus, the second isomer above would be structur-ally diagrammed as follows.
H~~ /G ' ~ ~ H3 CHZ=C-C-O-CHz-CH2-O O-~CH2-CH2-O-~-C=GHZ
H ~ ~ H
I
O
Butanetetracarboxylic acid bis (2-hydroxyethyl meth-acrylate) ester.
The Butane tetraca~~boxylic acid bis (2-hydroxyethyl ahacrylate) esters a:re referred to by the initials BCA.
The above reaction gives a monomer molecule having two reacted carboxylic acid groups and two unreacted car-boxylic acid groups. In an analogous manner 1 mole of butane-dicarboxylic-acid-anhydride may be reacted with 1 mole of hydroxy ethyl. methac:rylate to similarly yield isomers of butane tetracarboxylic acid mono (2-hydroxy-ethyl methacrylate). Different combinations of reactive esters may be formed by different concentrations of reactants; but according to the invention there must be at least two unreacted carboxylic acid group in the monomer.
The number of reacted or unreacted carboxylic acid groups in the monomer is controlled by varying the reaction conditions.
The (meth)acrylate radical may be joined on in a number of ways, for example:
Exemplary radical: would be ethoxy acrylate -O-CfI2-CH2-O-C-CH=CHZ
iH3 ethoxy methacrylate -~O-CHZ-CHZ-O-~-C-=CHZ
H3 ~~ f H3 (iso) propoxy (meth)acrylate ~-O-CHZ-CH-O-C-C=CHZ
polyglycol methacrylate -O-CH2-CHz- (O-CHz-CH2) ~-O-~-C=CHZ
where n is preferably from 1 to 10.
amide -HN-CHZ-CHZ-O-C-C=CHZ
The preferred radicals would be the (meth) acrylates and especially the eth~oxy (meth)acrylate radicals.
The Denta:L/Medical Compositions The compounds of this invention can desirably be used as primers in some pre~Eerred aspects with only initiators present or initiators and accelerators or only accele-rators present. In some instances the butane compounds may be used neat or with only curing agents and ingred-Tents that would be considered incidental and thus not counted when considering "co:nsistency essentially of".
Such incidental ingredients would be anti-oxidants, stabi-liters and pigments and the like which may be included in proper instances.
The monomers of the present invention polymerize by well known addition polymerization procedures through the ethylenically unsaturated group by a variety of means.
Most often curing agents, catalysts and initiators and accelerators, are used to expedite and control the poly-merization. It is known in the dental art to practice addition polymerization by employing a peroxide, for example benzoyl peroxide, and heat to initiate the reac-tion. It is also known that accelerators enhance the reaction so that it may proceed more expeditiously at room temperature. Accelerators are reducing amines or sulfi-iz tes for example. It: is also known to polymerize such compounds by ultraviolet and visible light using initi-ators and accelerators known to the art. Visible light curing is preferred. 1.~'or preformed objects, or those cured outside the body, other forms of radiation, for example ionizing radiai~ion is known.
It will be appreciated that in-vivo polymerization must take into account the suitability of the method and composition so as not to harm the patient within whom polymerization of the monomer or oligomer compound and the curing of the composition occurs. Thus the elements of a polymerization system, for example a peroxide and an amine, may be components of a two part formulation in which polymerization i;s delayed until the two parts are combined and react to polymerize the monomer. Or all the necessary chemical components may be combined within a -single composition which is induced to polymerize by the application of heat or light or other initiating action.
It is known for example to initiate by irradiation with 'ultraviolet or visible light in which case the initiator, often a benzophenone o:r camphoroquinone may be combined within a single, premixed, ready to use shelf-stable composition. A particular ;polymerization method and system may be preferred depending on the application requirements of the material. Whatever the mode of poly-merization, or "cure" of the composition including the . homer or monomers an important characteristic of the polymers which form ar<, that they are capable of further reaction with di- or polyvalent cations through their acid or reactive acid derivative functionality. A further important aspect of the compounds and compositions of the invention is that they exhibit adhesion between the mono-mer compound and a cation containing surface, metal, metal oxide, tooth bone and the like, against which they are polymerized.
One preferred cla:as of compositions of the present invention are shelf-sizable compositions that initiate curing in response to visible light. By shelf-stable it is meant the composit:i.on retains good application and curing characteristic when stored in a visible light opaque container at room temperature for one year or more.
Curing by visible light refers to actinic light initiated compositions curing within the visible light range of approximately 360 to 600 nanometers.
In many dental and medical applications it is desir-able to include fillers supplying reactive cations, and optionally non reactive fillers or mixtures thereof in the compositions of the present invention in preferred aspects thereof. Among those fa.llers which are especially suited for use in this invention are inorganic glasses such as are presently known in the art to form glass ionomer cement compositions. Exemplary of such fillers are those of U.S. Patent 4,814,362.
Preferred species of glasses include, for example, barium. aluminosilicate, calcium aluminosilicate, and strontium, lanthanum, tantalum, tung-sten, etc. glasses. Silica, including submicron silica, or quartz may also be used. Ceramic fillers, for example, calcium hydroxy apatite: may also be used to good advant-age. The fillers used in the invention may be reduced in particle size and them preferably silanated by methods known in the art before they are incorporated into such compositions. Preferred levels of filler material are from about 20% to about: 80% based on the total weight of the adhesive composition, with from about 40% to about 70%
being more preferable and about 45 to 60% being most pre-ferred. If a more finely particulated filler is used, amounts of filler may be decreased due to the relative increase in surface area which attends the smaller sizes of particles. Preferred particle size distributions are from 0.02 to 50 microns, more preferably 0.1 to 10 microns, and most preferably 1 to 6 microns.
Other ingredients that may be present are, for example, solvents, plast,icizers, pigments, anti microbials and therapeutics which may be time released from the composition and oxi-dat.ion inhibitors such as butylated hydroxytoluene. The mixtures in accordance with the invention can also contain other polymerizable unsaturated .nomers and/or oligomers and/or prepolymers that do not contain any acid group, and/or salts thereof and/or reac-tive readily hydrolyzing acid-derivative groups thereof.
Particularly appropriate are monomers that are consti-tuents of conventional composites such as for example hydroxy alkyl methacr;tlate. The mixtures can also if necessary contain other compounds that, although they contain acid groups and/or their salts and/or their reactive readily hydr~alyzing derivative groups do not contain any groups that are unsaturated and polymerizable.
preferred in this case are multi-basic acids or their reactive, readily hyd~:olyzing~ derivatives. Especially preferred multibasic ;kids are hydroxy acids such as tartaric or citirc acid, but also polyacids such as poly-carboxylic, polyphosph~oric, polyphosphonic, or polysul-fonic acids.
Compounds that have chelating graups taut do not contain acid groups or readily hydrolyzing acid-derivative groups can be employed. Examp:Les of this type are vanil-eates, syringates, and salicylates.
While one of the special advantages of the use of the class of compounds of the present invention in treating mammals, especially humans and especially in the maxio-.facial, mouth area, in dentistry is the fact that the com-pounds are relatively fluid monomers and large amounts of diluents are not required, there are instances where .luents may be desiraxrle. For example, in bonding agent adhesive compositions to aid in more completely and quickly wetting the substrate. Suitable diluents would be, for example, ethanol, water, and less viscous reactive monomers.
Mixing of the compositions of the present invention may be achieved using standard compounding techniques.
for example, liquids, photoinitiator(s), and accele-rator s) are blended first, and then when fillers are to be included they are added incrementally thereafter. When blending light sensitive compositions, however, a photo-safe light, i.e., one that does not contain substantial amounts of wavelengths of electromagnetic radiation that would activate the photoinitiating system used, should be employed to avoid initiating polymerization prematurely.
The butane (based) compounds of the present invention also have medical applications, especially preferred would be the bone cements and adhesives. But the application of the present invention t:o dental treatment by application to a tooth or a number of teeth in viva, in the mouth of a live patient by a dentist or dental practitioner, is a most preferred use.
One preferred dental treatment is the application of the composition as a dental liner. The dental liner composition may in one most preferred embodiment consist essentially of the butane compound and other active o' .gredients chosen from the group consisting of none, curing catalysts, initiators, accelerators, and mixtures thereof. In other preferred compositions diluents may be present or other ingredients may be present.
The composition is applied as a liner using conven-tional techniques and preferably cured with application of visible light in conventional manner. In other preferred embodiments the composition is a two-part system and the curing agent is spatu~:ed in prior to placement and the placement is by standard technique. Yet another preferred embodiment is a comingation of the other two where there is a two-part system but after mixing the system is cured with visible light with substantial self-curing occurring.
Another preferred dental treatment is the application of the composition as a dental composite filling. The dental composite filling composition may in one most preferred embodiment consist essentially of the butane compound and other active ingredients chosen from the group consisting of finely divided reactive filler that can react sonically with the acids or acid derivative of said butane compound, curing agent and mixtures thereof.
In other preferred compositions diluents may be present or other ingredients may be present.
The composition is applied as a composite filling using conventional techniques and preferably is a one-component composite filling material cured with appli-~tion of visible light in conventional manner. In other preferred embodiments the composition is a two-part system and the curing agent is spatuled in prior to place-ment and the placement is by standard technique. Yet another preferred embodiment is a combination of the other two, where there is a t:wo-part system but after mixing the system is cured with visible 7.ight with substantial self-curing occurring.
Having generally described the invention, a more com-plete understanding can be obtained with reference to cer-tain specific examples, which are included for purposes of illustration only. 7~t should be understood that the invention is not limited to the specific details of the Examples.
EXAMPT~ES
Throughout the Examples once a material, procedure or test procedure has been described, the description will not be repeated in subsequent Examples in most instances 'where the description remains the same, it being under-stood that the description applies in subsequent Examples.
~~11 ingredients are by weight unless otherwise specified.
Method for measurement of compressive strength For each material to be tested, cylinders 4 mm diam-eter and 6 mm long were prepared by filling the mixed material into stainless steel molds and light curing from ,ach end for 40 seconds using a PrismeticsT" light. The cylinders were removed from the molds and stored in water at 37~C for 24 hours prior to testing. The force needed to load the specimens t:o breaking point was measured using a Zwick model 2455 set to a c~__~osshead speed of 1 mm/min.
Method of transverse flexural strength, The uncured material was filled into a split stain-less steel mold with internal dimensions 25 mm x 2 mm x 2 mm. The exposed faces were then covered with polyester foil and clamped between transparent plastic blocks approximately 5 mm thick. The material was light cured for a total of 120 seconds by moving a dental curing light evenly backwards and forwards along the mold with the wand of the light in contact with the plastic blocks. After curing, the hardened :specimens were stored in water at 37~C for 24 hours. Before being tested, any remaining flash along the edges of the specimens was carefully removed and the exact dimensions of each specimen measured. The specimens were then tested in three point bending made using a Zwick model 1455 set to a crosshead speed of 1 mm/min, with the sample resting on supports 20 mm apart and being loaded at the mid paint. The trans-verse bending strength was calculated from the standard formula in Mega Pascals (MPs).
ahod for measurement of diametral strencxth For each material to be tested, cylinders approxi-mately 6 mm diameter and 3 mm long were prepared by fill-ing the mixed material into stainless steel molds and light curing from each end for 40 seconds using a Pris-meticsTM light. The cylinders were removed from the molds and stored in water at 37°C for 24 hours prior to testing.
Immediately before testing, the exact dimensions of each cylinder was measured with a micrometer, for use Later in calculating the diametral strength. The force needed to load the specimens across the diameter to breaking point was measured using a Zwick model 1455 set to a crosshead speed of 10 mm/min.
~arcol hardness measurements The Barcol hardne:as tester model GYZJ 935 was used for all measurements.
To avoid errors and effects due to changes in ambient lighting, these tests were carried out in a room with yellow lighting to which the photoinitiators systems are not sensitive. A circular brass mold having an internal diameter of 8 mm and a thickness of 1.3 mm was used. This was placed on a white surface and filled with the material to be tested. The surface was then covered with a small piece of transparent polyester film and the sample cured from above for the required time (usually 30 seconds), ~~olding the end of the light guide lightly in contact with the foil. At the end of the craring time a stop watch was started and the hardness measured after 60 seconds.
It is necessary to wait ~0 seconds.after curing the materials and before measuring the hardness, since light cured compounds show a rapid .increase in hardness during the first few seconds after curing, and attempts to measure during this time can lead to unnecessary vari-ations and errors. A waiting period of sixty seconds was chosen since this could be reliably and reproducibly carried out, and the hardness of the compound is increas-ing relatively slowly at this time.
Measurement of Adhesioru to dentine Preparation of the teeth Extracted human teeth were cleaned and sterilized in 1% sodium hypochlorite solution. The teeth were then stored in fresh la sodium hypochlorite solution at 4°C
until needed. Both antearior and posterior teeth were used at random. Before use a dentine surface was exposed on each tooth by grinding an area of the crown flat with 300 grit abrasive paper, and then polishing this with 600 grit paper. All this work ways carried out under water to avoid desiccation of the dentine.
reparation of adhesion samples Immediately before use, t:he prepared dentine surface was quickly blotted with a paper tissue. This removes excess surface water without drying out the tubules and the dentine retains its translucent appearance, rather than the white opaque <~ppearance which occurs when exces-sive drying has taken place. A length of a plastic drink-ing straw approximately 4 mm long and 3 mm in diameter was then filled with the m<~terial to be tested, pressed lightly onto the dentine surface, and the material light cured through the straw for 4o seconds using a PrismeticsTM
curing light. The prepared samples were normally tested after storage in water at 37~c: for 24 hours, though some were tested after only to minutes.
Testinq_the prepared sam les After storage for the required time, the samples were set in plaster so that the dentine surface was vertical.
The samples were kept covered with a damp paper tissue during this time to avoid their desiccation. The force needed to shear the cylinders from the dentine was then measured using a Zwick model 1455 set to a crosshead speed of 1 mm/min, and the adhesion calculated in Mega Pascals.
Samples which were to be tested after 10 minutes were set in plaster before use.
reparation of pow er samples The ingredients were weighed into a glass bottle and thoroughly mixed by tumbling i:his for one hour. The powder was then passed twice through a 150 ~ nylon sieve before being transferred into a labeled container.
Method of measuring fluoride release For each material, three cured discs having a diam-eter of 20 mm and a thickness of 1 mm were prepared. Each disc was placed into a bottle containing 25 ml of dis-tilled water, and stored at 37°C. At intervals of one week the water was renewed, and the fluoride content of the old water determinead in the presence of 10% TISAB IV
buffer. The average measurement of the three discs was calculated and expressed in terms of ~g fluoride ion per square cm of surface area o:E the disc (including the sides). Each week a blank was run by storing a bottle containing only water. The fluoride content of this was determined as a control. The electrode was calibrated before use using solutions with a known fluoride content, also in the presence of 10% TISAB IV buffer.
Preparation of But:.ane-1,2,3,4 tetracarboxylic dian-hydride. (BTCA) Butane-1,2,3,4 tetracarboxylic acid (230 g) (Aldrich-..iemie GmbH, catalog No. 8, 402-3, 97%) and acetic anhy-dride (690 ml) (Aldrich-Ghemie GmbH, catalog No. 11,004-3, 99%) were placed in a :L500 ml flask fitted with a distil-lation fraction cutter and reflux condenser and heated with stirring to reflu~; for 3 hours. After this time, 250 ml of a mixture of acetic acid and acetic anhydride were slowly distilled out when the reflux temperature slowly increased from 118°C to 138°C. The mixture was then stirred while it cooled. The crystals were filtered off using a suction funnel, washed twice with 300-400 ml of hexane, and the filt~ar cake sucked dry. The white crystals (185 g) were t'.hen transferred to a desiccator and stored over sodium hydroxide pellets.
Preparation of Monomer A.
Butane-1,2,3,4-tet.racarboxylic acid, bis(2-hydroxy-ethyl methacrylate) ester is prepared as follows:
Butanetetracarboxylic acid dianhydride (34.5 g), 2-hydroxyethyl-methacrylate (HENtA,, 50 g), (Aldrich-Chemi GmbH, catalog No. 12,813-5, 97%) and anhydrous sodium acetate (0.46 g) (Mark" catalog No. 6268), were stirred and heated together at 80°C. The changes in concentra-tions of reactants and products were followed by means of HPLC and IR spectroscopy, and after seven hours it was found that all the anhydride was consumed, and the reac-ion was therefore at an end. The product was a light colored viscous liquid, which was used directly in the formulations given elsewhere.
Powder compositions were prepared from the following two ingredients:
*The Strontium glass was made according to U.S. Patent 4,814,362 and had the following analysis with all elements except fluorine being calculated as the oxide of the element.
The mean particle size was 5.5 microns.
Composition ~rarts SiOZ 32.1 A1z03 24 . 6 Na20 2 , 9 Sr0 2g.~
12.3 PZ~g 4 . 8 polyacrylic acid (PAA) (molecular weight Specification range 30,000 to 45,000 Usual range around 35,000.
The powder was prepared by tumbling the glass and PAA
together in a bottle for one hour, then passing the resultant mixture through a _L50 ~ sieve. Two powder compositions, 3 and 4, were prepared as follows with the proportions given in parts by weight.
Powder compvsition;s 2 3 Strontium Glass 90.9 80 PAA 9 .1. 2 0 E:~AMPLES 5 to 10 Adhesive light cured Composition.
A series of compositions were formulated from the ingredients in the proportions given in Table 1 in parts by weight.
Ingredients in given before camphoroquinone (CQj (Aldrich Chemical,GmbH
catalog No. 23,122'3) dimethaminobenzoic acid, ethyl ester (DMABE) {Aldrich Chemical, GmbH
catalog No. E2,490-5) The compositions were prepared by first mixing monomer A and 2-hydro:~cy ethy:lmethacrylate with stirring and then dissolving th.e camphoroquinone and dimethamino-benzoic acid, ethyl ester in the Monomer mixture with stirring at 50~C: Fina,liy the water was added and stirred until totally dissolved. Roughly equal weights of the liquid and powder were mixed on a paper pad, when a fluid composition was obtained having a visually and tactually observed consistency suitable for use as a dental mater-ial, particularly as a lining material under fillings, as a cement, or as a fissure sealant. This was hardened by application of light from a dental curing light (Pris-metics~ light, Dentsply International Inc.) for 30 seconds. The following properties were measured:
Table 1 Liquid Components [in grams]
Examples 5 6 7 8 9 10 Monomer A 6.25 7.14 6.82 6.00 4.50 8.50 HEMA 2.50 1.90 2.73 :3.20 5.50 1.50 Water 1.25 0.95 0.45 0.80 0.00 0.00 CQ 0.06 0.06 0.06 0.06 0.06 0.06 DMABE 0.08 0.08 0.08 0.08 0.08 0.08 Powder # 2 2 2 2 3 3 The properties listed were evaluated with the results shown.
Barcol Hardness 75 80 89 86 90 90 Compressive Strength MPa 62.1 72.4 91.4 81.2 N/D N/D*
Adhesion to wet Dentin MPa 4.7 5.8 6.6 5.8 N/D N/D
Fluoride Release ~g/cm2 17 31 40 34 92 60 These examples show the utility of the compositions as demonstrated by their strength, rapid polymerization, adhesion to wet dentin, and the ability to release fluoride from the glass component through the polymerized matrix of the compositions described.
*N/D = not determined EXAMPT~E 11 Powder Formulation Strontium Glass g0 F'~ 10 Iaiquid Formulation Monomer A 59.4 2-hydroxyethyl m~ahacrylate 31.8 water 8.0 camphoroquinone 0.38 DMABE 0.44 Butylated hydroxytoluene 0.01 The powder and liquid were mixed 1:1 [By weight] as in Examples 5 to 10. This gave a fluid cement like consist-envy suitable for use as a liner covering the floor of prepared dental cavities. Properties were determined and compared. The properi~ies were compared to a commercial product, Vitra-bond's a product of 3M, sold for the stated purpose and also light polymerized.
Table 2 Example 11 Vitrabond~
Compressive Strength MPa 81 3.2 4g Flexural Strength MPa 17.2 0.5 20.7 + 1 Flexural Modulus MPa 1332 252 1268 115 Diametral Tensile Strength MPa 15.4 0.9 17.6 + 1 Adhesion to wet ntin de MPa 8.4 3.8 6.5 + 1.3 All settings as the standard method.
in ~arcol Hardness measured 60 seconds after irradiation for 30 seconds Specimen Top Surface gp 0 Specimen Bottom Surface 8p 0 Fluoride Release (7 days) ~Cg/cm2 90 (7 days) 114 (3 days) Translucency Ca.T clear opaque <0.35 >0.75 *measured using a Langer photometer model UME3.
Formulations of Monomer A with calcium glass.
Powder Formulation Calcium Glass* 75 Liquid Formulation Monomer A 59.4 2-hydroxyethyl methacrylate 31.8 water 8.0 camphoroquinone 0.38 DMABE 0.44 BHT 0.10 The powder and liquid were mixed 1:1 by weight on a paper pad as before. This gave a visible light curable (VLC) glass ionomer cement h<~ving a creamy consistency suitable for use, for example, as dental cavity liner or cement.
It is believed that t:he glass provides calcium ion by elution which help to crosslink the polymerized mass. The mixture was cured by exposure to a dental curing light for seconds irradiated from one surface only. The Barcol Hardness was 75 at ths: top surface and 70 at the lower surface 1.3' millimeters beneath the exposed surface.
The Calcium glass had a mean particle size of 6.5 microns. , The analysis was carried out at the Dorfner Analysen Zentrum, Hirschan, Germany.
Composition by parts SiOz 27.8 A1203 31. 3 Na20 10 . 6 Ca0 10.8 F' 14.8 PzOs 7 . 0 Formulations of Monomer A with calcium glass.
Another powder wa:~ formulated as follows:
Powder Formulation Calcium Glass g5 The powder was combined with the liquid component of Example 12 at a ratio of 1:1 on a glass pad, and mixed with a dental spatula. As before, it was cured with a Prismetics light; the B~arcol Hardness at the upper surface was 78 and the lower sup.°face, 1.3 millimeters beneath, was 73.
Both Examples 12 and 13 show the ability of the monomers and compositions of the invention to be reactive and polymerize by addition polymerization in the presence of various glasses which provide cations capable of cross-linking the compositions. These sonically crosslinked polymers are useful as :liners, cements and filling mater-a so gals. They have excepi;.ional translucency and may be cured to considerable depth compared to commercially available dental liners and cements. These properties are espe-cially valuable where rapid cure to good depth of inher-ently adhesive ionical7Ly cross.linked restorative materials are desired.
Crosslinking with zinc oxide.
The liquid composition of Example 12 was combined on a dental mixing pad at a ratio of 1 part to 4.6 parts by weight of zinc oxide containing powder (Poly FTM Plus, DeTrey Dentsply, Konst:anz) to form a stiff paste of a consistency suitable for use as a dental filling material.
The powder contains 83;> by weight of a zinc oxide mixture with minor amounts of the oxides of magnesium, aluminum and silica; 13% powder~_d polyacrylic acid, and 4% of tin fluoride. The surface of a mass of this material could be cured by 30 seconds exposure to a dental curing light to give a tough water resistant surface. Curing by irradiation with visible light was slower with this rather opaque composition than the composition of Example 12.
The following table snows that the composition becomes cured whether or not exposed to light but that when polymerization occurs prior to crosslinking a hard composition results more rapidly, and that reaction with ~inc oxide occurs even without prior polymerization. The composition has dental. applications, for example, as a liner or base under permanent fillings, a temporary fil-ling material, or as a cement.
Table 3 Time (min) Barcol Hardness (test) of Test Lic~ht Cured Not Light Cured 0 Light Cure 30 seconds 52 p Readings were taken sequentially on one light cured and one non light cured specimen.
Tie Coat and Top Coat compositions.
The crown of an e~;tracted human tooth was ground so as to expose a flat area of dentin. This was dried with a paper tissue and the ~.iquid of Example 12 was applied in a thin layer. This was cured for 10 seconds with a Pris-metics~ curing light used in standard clinical manner. A
blob of the powder:liquid mixture of Example 39 was placed on top to cover an area about 4 mm in diameter. This was cured for 30 seconds with the Prismetics~' light used in the standard clinical manner. Five minutes later force was applied ~ to the dent~in composition interface using a metal spatula. It was not possible to dislodge the compo-.~ition from the dentin surface by this means, indicating that its adhesion to dentin is at a high and clinically useful level. In contrast, a mixture of Poly FT" Plus powder (a composition formed by the combination of the same reactive zinc oxide filler and the same polyacrylic acid), and water which is the commercially recommended method for using this material, mixed according to directions and applied to a dentin surface, was easily dislodged.
EXAMPLE 16 to 17 Preparation of bonding agents For Dental composite Filling materials.
Formulations were made up as follows, where quanti-ties are given in parts by weight.
Ex. 16 Monomer A 52.59 HEMA 38.49 water 8,0 0.38 DMABE 0.44 BHT 0.10 Ex. 17 Momomer A 54.58 HEMA 36.39 water 3,gg 25% glutarald~shyde soln* 3.99 CQ 0.36 DMABE 0.45 BHT 0.23 *supplied by Fluka, catalog No. 49630 Adhesion of a composite material (AP.HT", Dentsply International Inc.) to dentine was measured using the above liquid compositions as dentine primer or tie coat.
..he chosen liquid was brushed thinly onto the prepared dentine surface, and cured for ten seconds before applying the composite filled straw. The method was otherwise identical to the general method given before. Results are given below, and compared to those measured in a similar way for a commercially available dentine bonding agent (Prisms Universal Bonds°, Dentsply International Inc.).
Table 4 liquid Ex. 16 adhesion = 6.62 ~ 2.09 MPs liquid Ex. 17 adhesion = 5.12 ~ 1.86 MPs dental bonding adhesion = 4.22 ~ 0.99 MPs agent Both experimental forrraulations therefore gave adhesion values at le~~st as high as obtained with the commercially available material dental bending agent (Prisms Universal Bonds II), thereby demonstrating the usefulness of the monomer A in this application.
Fluoride ion releasing adhesive formulations Adhesive resin formulations were made up with compo-sitions as shown below.
liquid Ex. 18) Monomer A 61.36 2-hydroxyethyrl methacrylate 33.39 ~
water 4.51 camphor quinone 0.34 DMABE 0.40 BHT 0.1 liquid Ex. 19) Monomer A 51.15 2-hydroxyethyl methacrylate 37.43 water g.p camphor quinone 0.38 DMABE 0.44 BHT 0.1 Cetylamin hydrofluoride* 2.5 liquid Ex. 20) Monomer A 51.15 2-hydroxyethyl methacrylate 37.43 camphor quinone 0.38 DMABE 0.44 BHT 0.1 Cetylamin hyd.rofluor:ide* 2.5 liquid Ex. 21) An attempt was made to formulate a composition con-taining an equivalent amount of fluoride ion using the composition of Ex. 18) but replacing the cetylamin fluoride with 0.2 parts of sodium fluoride. However, the sodium fluoride did not dissolve.
*supplied by Merk, Germany, catalog No. 11679.
_able 5 Bondin g ent Adhesion MPa ag Fluoride release ~.ca~cm2 liquid Ex.18) 6.62 2.09 0 liquid Ex.19) 4.39 1.89 gg liquid Ex.20) 2.73 0.86 141 Prisma Universal Bond~ II
(Dentsply) 4.22 0.99 0 The adhesive is interesting in that the fluoride ions are totally dissolved in and dispersed evenly throughout the liquid, which remains glass clear when cured.
EXAMPLE. 2 2 In order to furthsar demonstrate the general useful-ness of monomer A (the reaction product of butanetetra-carboxylic acid dianhydride and 2-hydroxyethyl-meth-acrylate) as an adhesive agent or primer, a liquid compo-sition was made up as follows.
1) Direct preparation of a solution of monomer A in HEMA
Butanetetracarboxylic acid dianhydride (500 g 2.5 moles), 2-hydroxyethylmiethacrylate (1.5 kg 11.5 moles), BHT (1.5 g) and sodium acetate: (5.0 g) were stirred and treated together at 80~C for two hours, after which time a clear viscous liquid wa:~ obtained. The infrared spectrum of this showed that all the anhydride had reacted, and the ..eaction was therefore finished. The liquid, which con-sisted of a mixture of <~pproximately 1500 grams of monomer A in approximately 850 grams of HEMA, was allowed to cool and used in the liquid formulation below.
2) Adhesive Primer composition in darts by weiaht solution of monomer A in HEMA 200 BHT 0.44 camphor quinone 0.84 DMABE p,g7 water 17.58 The mixture was heated to 50°C, stirred until homogenous, then allowed to coal.
3) Use of the liquid composition in 21 as an adhesion primer to a nicke_1 - chrome dental allow.
Blocks of the met<~1 alloy (Wiron 88, BEGD, Bremen, Germany) were prepared by grinding one surface flat on 220 grit silicon carbide paper. The surface was then rinsed under clean water and dried on a paper tissue. The liquid in 2) was brushed on thinly, and cured by exposure for 10 seconds to light from a Prismetics~ dental curing light.
A section of a plastic drinking straw with an internal diameter of 5.25 mm and length of approximately 2 mm, was then held on the surface and i:illed with a commercially available composite material (AP. H. TM, Dentsply) . This was cured by exposure to thsa Prismetics light for 40 seconds, after which the sample was stored in water at 37°C for 24 hours. The shear bond strength was then tested in a Zwick model 1455 using a crosshead speed of 1 mm/min.
Using 6 samples, an average adhesion of 5.7 ~ 2.15 MPa was measured.
4) Adhesion to a coba7.t - chrome alloy The experiment in 3) was repeated using a cobalt -chrome alloy (DentalliumT" Extra hard, Svedia). A average adhesion of 7.3 ~ 1.7 N(Pa was measured for 7 samples.
5) Adhesion to Gold A reclaimed gold crown was mounted on a steel post so that two faces could be held vertically in a clamp in the Zwick testing machine. The crown was cleaned well with a pumica/detergent mixture, rinsed well, and dried. The liquid from 2 ) was then brushed on in a thin layer, and cured for 10 seconds using a prismetics~ light. AP.H.T"
composite material was .applied in a straw in the same way as for the previous examples, and cured for 40 seconds.
The procedure was repeated for the other chosen face, and the crown stored in wager at 37~C for 15 minutes before the shear bond strength was tested in the Zwick machine at a crosshead speed of 1 mm/min.
For eight samples, an average shear bond strength of 6.2 ~ 2.6 MPa was measured.
6) Adhesion to ceramic material Ceramic teeth (Dentsply GmbH, Dreieich, Germany) were ~s . anded under water on 220 grit SiC paper to give a flat surface. The liquid from 2) was applied and cured, and AP.H.TM composite applied as in the previous examples. The prepared samples were 'then stored in water for 24 hours before being tested, again as in the previous examples.
In all samples failure was within the ceramic, so that after breakage large pieces of ceramic remained attached to the compos:i.te button. The true adhesion to ceramic was therefore not measured and the value of 8.53 ~ 3.93 MPa obtained is a measure of the strength of the ceramic teeth. However the highest value obtained was 15.2 MPa, indicating that adhesion is at a high and useful level, usually only obt:ai:ned by silane treatment of the ceramic.
The foregoing description illustrates preferred embodiments of the invention. However, concepts employed may, based upon such description, be employed in other embodiments without departing from the scope of the inven-tion. Accordingly, the following claims are intended to protect the invention broadly, as well as in the specific forms shown herein.
composite material was .applied in a straw in the same way as for the previous examples, and cured for 40 seconds.
The procedure was repeated for the other chosen face, and the crown stored in wager at 37~C for 15 minutes before the shear bond strength was tested in the Zwick machine at a crosshead speed of 1 mm/min.
For eight samples, an average shear bond strength of 6.2 ~ 2.6 MPa was measured.
6) Adhesion to ceramic material Ceramic teeth (Dentsply GmbH, Dreieich, Germany) were ~s . anded under water on 220 grit SiC paper to give a flat surface. The liquid from 2) was applied and cured, and AP.H.TM composite applied as in the previous examples. The prepared samples were 'then stored in water for 24 hours before being tested, again as in the previous examples.
In all samples failure was within the ceramic, so that after breakage large pieces of ceramic remained attached to the compos:i.te button. The true adhesion to ceramic was therefore not measured and the value of 8.53 ~ 3.93 MPa obtained is a measure of the strength of the ceramic teeth. However the highest value obtained was 15.2 MPa, indicating that adhesion is at a high and useful level, usually only obt:ai:ned by silane treatment of the ceramic.
The foregoing description illustrates preferred embodiments of the invention. However, concepts employed may, based upon such description, be employed in other embodiments without departing from the scope of the inven-tion. Accordingly, the following claims are intended to protect the invention broadly, as well as in the specific forms shown herein.
Claims (30)
1. A dental/medical restorative/prosthetic polymerizable unsaturated substituted butane compound with acid or reactive acid derivative functionality having the general formula:
(RO2C)x - C4H6 - (CO2R')y where R is hydrogen, an acid radical containing moiety or a moiety containing a reactive acid derivative and R' is a polymerizable unsaturated ester-containing radical having from
(RO2C)x - C4H6 - (CO2R')y where R is hydrogen, an acid radical containing moiety or a moiety containing a reactive acid derivative and R' is a polymerizable unsaturated ester-containing radical having from
2 to 13 C and x is 2 to 3 and y is 1 to 2.
2. A dental/medical restorative/prosthetic composition in the form of a dental liner or bonding agent consisting essentially of a butane compound according to claim 1 and at least one other active ingredient selected from the group consisting of curing catalysts, initiators, accelerators and mixtures thereof.
2. A dental/medical restorative/prosthetic composition in the form of a dental liner or bonding agent consisting essentially of a butane compound according to claim 1 and at least one other active ingredient selected from the group consisting of curing catalysts, initiators, accelerators and mixtures thereof.
3. The dental/medical restorative/prosthetic composition of claim 2 wherein said composition is in the form of a single, premixed, ready-to-use shelf-stable composition.
4. A dental/medical restorative/prosthetic composition in the form of a dental liner or bonding agent comprising a compound according to claim 1 in association with curing agents and aldehyde.
5. The dental/medical restorative/prosthetic composition of claim 4 wherein said aldehyde is glutaraldehyde and said composition is in the form of a single, premixed, ready-to-use shelf-stable composition.
6. A dental/medical restorative/prosthetic composition in the form of a dental composite comprising a butane compound according to claim 1, at least one finely divided reactive filler that can react ionically with an acid or acid derivative of said butane compound and curing agent.
7. A dental/medical restorative/prosthetic composition in the form of a dental composite consisting essentially of a butane compound according to claim 1 and other active ingredients chosen from the group consisting of finely divided reactive filler which is ionically active with an acid or acid derivative of said butane compound, curing agent and mixtures thereof.
8. A dental/medical restorative/prosthetic composition in the form of a dental cement comprising a butane compound according to claim 1, curing agent and other ingredients chosen from the group consisting o~ finely divided reactive filler which is ionically active with an acid or acid derivative of said butane compound, non reactive filler, reactive diluent and mixtures thereof.
9. A dental/medical restorative/prosthetic composition comprising a butane compound according to claim 1 and dentally or medically acceptable diluent wherein said composition is in the form of a single, premixed, ready-to-use shelf-stable composition.
10. The dental/medical restorative/prosthetic compound of claim 1 wherein R is H providing an acid radical CO(OH).
11. The dental/medical restorative/prosthetic compound of claim 1 wherein R is H and R' is a 2-hydroxyethyl-methacrylate radical and x is 2 and y is 2.
12. A dental/medical restorative/prosthetic composition comprising a butane compound according to claim 1 and a filler chosen from the group of reactive glasses, non reactive glass, and inorganic particulate that consist essentially of metal oxides, hydroxides or salts and mixtures thereof.
13. The dental/medical restorative/prosthetic composition of clainn 12 wherein said filler is zinc oxide.
14. A dental/medical restorative/prosthetic composition comprising a butane compound according to claim 1 further comprising a fluoride ion soluble in said composition.
15. The dental/medical restorative/prosthetic composition of claim 14 wherein said fluoride ions are amine fluorides.
16. A dental/medical restorative/prosthetic composition comprising a butane compound according to claim 1 and a fluoride ion eluting filler that is a source of cations reactive with said compound.
17. Butane tetracarboxylic acid bis-(2-hydroxyethyl-methacrylate) ester.
18. The compound of claim 1 wherein R is a hydroxyethyl methacrylate moiety.
19. The compound of claim 1 wherein R is ethoxy acrylate, ethoay methacrylate, (iso) propoxy (meth) acrylate, or polyglycol methacrylate.
20. A dental/medical restorative/prosthetic polymerizable unsaturated substituted butane compound with acid or reactive acid derivative functionality having the general formula wherein R1 and R'1 each independently is a moiety containing a reactive acid derivative which is polymerizable, unsaturated and has from 2 to 13 carbon atoms.
21. The compound of claim 20, wherein R1 is
22. A dental/medical restorative/prosthetic compound of the formula (RO2C)x ~ C4H6 ~ (CO2R ' )y where R is hydrogen, an acid radical containing moiety or a moiety containing a reactive acid derivative and R' is a group of the formula:
where n is 1 to 10, x is 2 to 3 and y is 1 to 2.
where n is 1 to 10, x is 2 to 3 and y is 1 to 2.
23. The compound of claim 22, wherein R is hydrogen.
24. A dental/medical restorative/prosthetic compound of the formula (HO2C) 2 ~ C4H6 ~ (CO2R) 2 which is in the form of one or more of the isomers of the formula (A) , (B) , or (C):
where R is and n is 1 to 10.
where R is and n is 1 to 10.
25. The compound of claim 24, where R is
26. Use of a compound according to any one of claims 1, 10, 11 and 17 to 25 for dental treatment in a mammal.
27. Use of a dental/medical restorative/prosthetic composition according to any one of claims 2 to 9 and 12 to 16 for dental treatment in a mammal.
28. Use according to claim 27 wherein said composition is in a form suitable for direct application without mixing and for curing with the application of visible light.
29. A commercial package comprising a compound according to any one of claims 1, 10, 11 and 17 to 25 together with instructions for use thereof for dental treatment of a mammal.
30. A commercial package comprising a dental/medical restorative/prosthetic composition according to any one of claims 2 to 9 and 12 to 16 together with instructions for use thereof for dental treatment in a mammal.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US654,135 | 1991-02-11 | ||
| US07/654,135 US5218070A (en) | 1991-02-11 | 1991-02-11 | Dental/medical composition and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2060928A1 CA2060928A1 (en) | 1992-08-12 |
| CA2060928C true CA2060928C (en) | 2002-04-30 |
Family
ID=24623570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002060928A Expired - Lifetime CA2060928C (en) | 1991-02-11 | 1992-02-10 | Dental/medical composition and use |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5218070A (en) |
| EP (1) | EP0499180B1 (en) |
| JP (1) | JP3609432B2 (en) |
| AT (1) | ATE137954T1 (en) |
| AU (1) | AU653980B2 (en) |
| CA (1) | CA2060928C (en) |
| DE (1) | DE69210640T2 (en) |
| ES (1) | ES2081269T3 (en) |
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| US6093084A (en) * | 1988-08-01 | 2000-07-25 | Dentsply Research & Development Corp. | Device and method for dispensing polymerizable compositions |
| US5756559A (en) * | 1992-02-06 | 1998-05-26 | Dentsply Research & Development | Method and composition for adhering to tooth structure |
| US6191190B1 (en) | 1993-04-19 | 2001-02-20 | Dentsply Research & Development Corp. | Method and composition for adhering to tooth structure |
| US6391940B1 (en) | 1993-04-19 | 2002-05-21 | Dentsply Research & Development Corp. | Method and composition for adhering to metal dental structure |
| US6500879B1 (en) * | 1993-04-19 | 2002-12-31 | Dentsply Research & Development Corp. | Dental composition and method |
| US5385727A (en) * | 1993-05-19 | 1995-01-31 | Church & Dwight Co., Inc. | Dentifrices containing zinc oxide particles and sodium bicarbonate |
| US5502087A (en) * | 1993-06-23 | 1996-03-26 | Dentsply Research & Development Corp. | Dental composition, prosthesis, and method for making dental prosthesis |
| DE4400073C3 (en) † | 1994-01-04 | 2002-02-28 | Burghardt Krebber | Dentures made of fiber-reinforced composite materials and their use |
| TW414713B (en) | 1994-05-12 | 2000-12-11 | Dentsply Gmbh | Fluoride releasing liquid dental primer product and method |
| US6313191B1 (en) | 1994-08-22 | 2001-11-06 | Dentsply Gmbh | Method and composition for priming and adhering to tooth structure |
| US5645429A (en) * | 1994-08-22 | 1997-07-08 | Dentsply Research & Development Corp. | Method for adhering to tooth structure |
| US6391286B1 (en) | 1995-11-17 | 2002-05-21 | 3M Innovative Properties Company | Use of metallofluorocomplexes for dental compositions |
| US6262142B1 (en) | 1997-04-02 | 2001-07-17 | Dentsply Research & Development | Translucent wear resistant dental enamel material and method |
| US6353040B1 (en) * | 1997-04-02 | 2002-03-05 | Dentsply Research & Development Corp. | Dental composite restorative material and method of restoring a tooth |
| US20040209975A1 (en) * | 1997-04-02 | 2004-10-21 | Subelka John C. | Dental composite restorative material and method of restoring a tooth |
| US5859089A (en) * | 1997-07-01 | 1999-01-12 | The Kerr Corporation | Dental restorative compositions |
| US6300390B1 (en) | 1998-06-09 | 2001-10-09 | Kerr Corporation | Dental restorative composite |
| US6121344A (en) * | 1998-06-19 | 2000-09-19 | Kerr Corporation | Optimum particle sized hybrid composite |
| US6605651B1 (en) | 1998-09-09 | 2003-08-12 | Biomat Sciences, Inc. | Curing methods and material compositions having dental and other applications |
| WO2000018191A1 (en) | 1998-09-18 | 2000-03-30 | Marc Seghatol | Microwave polymerization system for dentistry |
| US6254389B1 (en) | 1999-09-20 | 2001-07-03 | Marc Seghatol | Hand-held microwave intra-oral dental system |
| US6133339A (en) * | 1998-09-24 | 2000-10-17 | Kerr Corporation | Dental cement for a temporary dental prosthesis or appliance and method of use |
| US6143919A (en) * | 1999-05-18 | 2000-11-07 | 3M Innovative Properties Company | Polymerizable acidic compounds and methods of preparation |
| US6315566B1 (en) | 1999-05-18 | 2001-11-13 | 3M Innovative Properties Company | Dental materials |
| US6326417B1 (en) | 1999-10-21 | 2001-12-04 | Jeneric/Pentron Incorporated | Anti-microbial dental compositions and method |
| KR100367567B1 (en) * | 2000-10-25 | 2003-01-10 | 주식회사 덴키스트 | Photo-Cured Dental Pit and Fissure Sealant Compositions for Caries Prevention |
| US20090048367A1 (en) | 2004-04-26 | 2009-02-19 | Klee Joachim E | Dental adhesive |
| US7326759B2 (en) * | 2004-04-02 | 2008-02-05 | Hewlett-Packard Development Company, L.P. | Compositions for solid freeform fabrication |
| EP1771141B1 (en) * | 2004-07-27 | 2009-03-25 | DENTSPLY DETREY GmbH | Dental adhesive composition |
| EP1776943B1 (en) | 2005-10-20 | 2011-12-14 | Dentsply DeTrey GmbH | Dental adhesive |
| US9308058B2 (en) * | 2006-09-13 | 2016-04-12 | David J. Clark | Devices and a seamless, single load, injection molded cavity preparation and filling technique |
| US9289358B2 (en) | 2007-02-28 | 2016-03-22 | Ultradent Products, Inc. | Resin reinforced zinc polycarboxylate temporary cement compositions and related kits and methods |
| US20100018641A1 (en) * | 2007-06-08 | 2010-01-28 | Kimberly-Clark Worldwide, Inc. | Methods of Applying Skin Wellness Agents to a Nonwoven Web Through Electrospinning Nanofibers |
| EP2335668A1 (en) * | 2009-12-15 | 2011-06-22 | Dentsply DeTrey GmbH | Dental composition |
| CN101804012B (en) * | 2010-03-25 | 2012-02-22 | 东华大学 | Photo-curing compound resin used for dental repair and using diatomite as stuffing and preparation method thereof |
| EP2949782B1 (en) * | 2013-10-18 | 2019-12-11 | Sumitomo Rubber Industries, Ltd. | Surface-modified metal and method for modifying metal surface |
| JP6154370B2 (en) | 2014-12-26 | 2017-06-28 | 住友ゴム工業株式会社 | Surface-modified metal and method for modifying metal surface |
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| CA571111A (en) * | 1959-02-24 | Shell Development Company | Unsaturated esters of 1,2,4-alkane tricarboxylic acids and polymers thereof | |
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| US4514527A (en) * | 1983-01-10 | 1985-04-30 | American Dental Association Health Foundation | Method for obtaining strong adhesive bonding of composites to dentin enamel and other substrates |
| US4521550A (en) * | 1983-01-10 | 1985-06-04 | American Dental Association Health Foundation | Method for obtaining strong adhesive bonding of composites to dentin, enamel and other substrates |
| DE3536076A1 (en) * | 1985-10-09 | 1987-04-09 | Muehlbauer Ernst Kg | POLYMERIZABLE CEMENT MIXTURES |
| US4964911A (en) * | 1987-10-13 | 1990-10-23 | Den-Mat Corporation | Adhesive bonding of acrylic resins, especially in dentistry |
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| JP2690138B2 (en) * | 1988-03-28 | 1997-12-10 | 株式会社トクヤマ | Adhesive composition |
| JPH1123805A (en) * | 1997-07-03 | 1999-01-29 | Rohm Co Ltd | Optical lens of image reader and image reader |
-
1991
- 1991-02-11 US US07/654,135 patent/US5218070A/en not_active Expired - Lifetime
-
1992
- 1992-01-14 AU AU10228/92A patent/AU653980B2/en not_active Expired
- 1992-02-10 CA CA002060928A patent/CA2060928C/en not_active Expired - Lifetime
- 1992-02-10 AT AT92102200T patent/ATE137954T1/en not_active IP Right Cessation
- 1992-02-10 DE DE69210640T patent/DE69210640T2/en not_active Expired - Lifetime
- 1992-02-10 EP EP92102200A patent/EP0499180B1/en not_active Expired - Lifetime
- 1992-02-10 ES ES92102200T patent/ES2081269T3/en not_active Expired - Lifetime
- 1992-02-12 JP JP02505692A patent/JP3609432B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| AU1022892A (en) | 1992-08-13 |
| ES2081269T1 (en) | 1996-03-01 |
| AU653980B2 (en) | 1994-10-20 |
| ES2081269T3 (en) | 1996-08-01 |
| JPH05139927A (en) | 1993-06-08 |
| EP0499180A2 (en) | 1992-08-19 |
| DE69210640D1 (en) | 1996-06-20 |
| EP0499180B1 (en) | 1996-05-15 |
| ATE137954T1 (en) | 1996-06-15 |
| JP3609432B2 (en) | 2005-01-12 |
| US5218070A (en) | 1993-06-08 |
| CA2060928A1 (en) | 1992-08-12 |
| EP0499180A3 (en) | 1993-10-13 |
| DE69210640T2 (en) | 1996-10-31 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| MKEX | Expiry |