WO2000009030A1 - Dental treatment methods - Google Patents

Abstract

Disclosed are two methods for coating teeth so as to protect the tooth surfaces from caries and periodontal diseases and optionally paints teeth at a desired color. The anti-caries protection is due to the blocking of the enamel minerals that exit the enamel in order to balance the acidic environment that is created by the bacteria acids. The periodontal diseases protection is due to the low surface tension that is created after the application of specific substances on the enamel, i.e., makes the enamel more slippery. The painting effect comes from the colors that the applied substances have. One embodiment includes three steps: etching of the teeth, application of the protective and painting substance and sealing of the teeth (optional). Another embodiment relates to the implantation of a material in the outer layer of the tooth enamel or dentin or cementum and involves an implantable material, polymer or ceramic, fixed in place by use of a dental laser or a flame. This method also includes three steps: the dental tissue is etched and dried, the material is applied into the tissue, the laser beam or the flame melts the material into the tissue and finally the irradiated spot is air dried.

Description

DENTAL TREATMENT METHODS

BACKGROUND OF THE INVENTION

Two related methods of treating the teeth are presented herein. The first embodiment of the present invention relates to a teeth-coating method that protects teeth from caries and periodontal diseases along with giving color to them. The method includes three steps: create space into the teeth by etching them, apply the protecting and coloring substances and sealing of the teeth (optional). The protection is due to the blocking of the dental enamel minerals that exit from teeth in order to balance the pH of the tooth environment (anti- caries) and due to the low surface tension that these substances create in the enamel surface which make the enamel practically uncollonizable by the bacteria (anti-periodontal diseases). The coloring is due to the colors that these substances can have. By applying these substances, the teeth are practically painted in a desired color, at the same time that they are protected.

The second embodiment of the present invention relates to the implantation of a material in the outer layer of the tooth enamel or dentin or cementum and involves an implantable material, polymer or ceramic, fixed in place by use of a dental laser or a flame. This method also includes three steps: the dental tissue is etched and dried, the material is applied into the tissue, the laser beam or the flame melts the material into the tissue and finally the irradiated spot is air dried. This method protects the teeth from dental caries and periodontal diseases, paints the teeth at a desired shade and the implantable material can be used as a filling material itself.

The protection of the teeth from caries is due to the blocking of the dental minerals that exit the tooth in order to balance the pH of the tooth environment. The protection from periodontal diseases is due to the low surface tension that the implantable materials create in the enamel surface which make the enamel practically uncolonizable to the bacteria. The painting of the teeth is due to the shades that the implantable materials have and can be used to give the teeth a desired tint. A material with properties similar to the enamel or dentin or cementum can be used as a filling material itself in dental cavities.

Defining the etiology of dental caries and periodontal diseases is the primary purpose. Dental research has proved the significance of the microflora and its causation to dental caries and periodontal diseases. Bacteria populations first colonize the teeth's surfaces and then they produce acids. Due to these acids, the new environment between enamel and bacteria has a newly formed lower pH, which causes the enamel to lose mineral content. This interaction takes place from the enamel to the bacteria and starts from the intraprismatic area, between the rods of the hydroxyapatite. The continuous loss of the enamel minerals leads eventually to a decayed or carious tooth. These same acids also interact with periodontal tissues. If the colonies are not mechanically removed by a toothbrush or a dentist, they become bigger, more organized and gram negative, making the acids which they produce, stronger. As a result, these acids enter the gums causing inflammation, which can lead to bone loss and / or eventually to tooth loss.

The shade of the teeth is a very important esthetic factor. Liquids like coffee and cola, use of tetracycline in pregnancy and in early childhood, aging, endodontic treatment and many other staining factors darken the teeth. To this problem, dental bleaching gives an answer. This technique, though, has several defects. Rebound of the shade, sensitivity of the tooth, existing bleaching materials do not bleach composite restorations or, in some cases they have no results at all.

The interface between the restorative material and the tooth is a well studied field. Many compounds like composites, ceramics or even amalgam are in use today having the same problems: the microleakage and the wear of the restoration. These problems arise from the difference of the properties between the tooth tissues and the restorative materials. Different coefficient of linear thermal expansion, different hardness, different tear strength are some of the most important factors that lead the restoration to failure.

In order to prevent dental caries and periodontal diseases scientists had previously followed two directions:

1. The co-operation with the patient,

2. The intervention in oral health of the individuals without co-operation.

The co-operation with the patient includes oral hygiene for the plaque control (brushing, flossing, fluoride rinses, gels) and dietary control. Sometimes it is necessary to change the whole nutritional habits of a certain population.

The scientifically based intervention in oral health submits plaque control, fluoridation of the water, dental-induced application of fluoride and sealants for the enhancement of the enamel.

Fluoride prevents dental caries in two ways:

1 : When applied to the enamel, it is believed that fluoride makes the enamel less soluble to bacteria acids, by penetrating the enamel and changing hydroxyapatite to fluoroapatite.

2: Blocks the enolase, an enzyme that enhances the metabolic activity of the bacteria.

Oral hygiene prevents dental caries and periodontal diseases by removing the dental plaque. No bacteria populations means no damage to the tooth. It is important to brush teeth after every meal in order to remove especially the sugars of the food, that are one of the most important factor for the adherence of the bacteria to the enamel. This is due to sugars high-energy chemical bond (Gh=- 6600cal/mole) which is used form the bacteria to their multiplicity, and due also to the capability of the sugars to adhere smooth-like surfaces, like enamel surface.

According to these directions caries and periodontal diseases should have been eliminated. It is a fact that the prevalence of these diseases has been decreased, especially in children, but we are far from postulating that there is no caries or periodontal diseases any more.

The reasons are the ineffectiveness of the fluoride-oriented preventive treatment and the unwillingness of the individual to follow an everyday oral hygiene. Practically, decayed teeth or periodontal diseases do appear in very clean oral cavities.

The results of fluoride application are not only the enhanced fluorided hydroxy apatite of the enamel but also CaF₂ and 6(CaHPO₄) which are very soluble to saliva. This explains why most of the fluoride dissolves in minutes after its application to teeth. On the other hand, the fluoride blocks the enolase when it is in an ionic phase, something which rarely happens, because most of the fluoride immediately bonds with the minerals of the plaque and become inactive. These are mainly the reasons why most of today's teeth protective techniques are eventually ineffective.

Sealants have used to prevent pit and fissures caries in children. The preventive value of sealant have been thoroughly examined and proved. The problem, though, of caries and periodontal diseases still exists, especially in adult population.

On the other hand nobody can force a patient to comply with the oral hygiene methods. This unλvillingness of the individuals leads to longer exposure of the enamel to the bacteria acids and respectively to caries and periodontal diseases. The critical pH (5.3-5.5) of the dental plaque and the enamel surface must not be decreased for long time. When this happens, minerals from the enamel move towards the dental plaque to balance the new environment's conditions. After 20-40 minutes this pH returns to its previous number. That means that the enamel starts to be remineralized again from the saliva adjustment mechanisms. This remineralization takes 3-5 hours to be completed. If between these hours, a second decrease of the pH occurs -due to food- the enamel doesn't have time to complete remineralization. This results in a second minerals offering, which finally weakens the enamel and create caries.

SUMMARY OF THE INVENTION

The present invention eliminates all these problems because the protective substance is embedded into the teeth and sealed there. It changes the environmental conditions by making the enamel practically unsoluble to the bacteria acids (blocking the enamel minerals) and making the colonization of the teeth nearly impossible (low surface tension).

In the first prefened embodiment, the present invention is a teeth-coating method that protects teeth from caries and periodontal diseases and at the same time paints the teeth. There are three steps:

a. Etching of the teeth. There are already known etching techniques that dentists use in today's dentistry. Etching gels or etching liquids including phosphoric and citric acids or others that can be easily applied to the teeth. Laser induced etching can be also used with various types of laser beams. The teeth are all over etched in all their surfaces especially the more sensitive ones like interproxLmal and in pits and fissures. If there is periodontitis involved in a certain tooth, even cementum must be etched in order to be later coated and protected. The depth of the etching is closely related to the penetration ability of the application technique (step #2) and the penetration ability of the substance that will be used in the second step. That depth varies from a few microns to half a millimeter.

b. Application of the substance. This substance can be a polymer or a salt that contains fluoride or metals. The application technique is electrophoresis, spraying or just application of the substance to the teeth. The application technique is related to the nature of the substance, i.e. to the penetration ability of the specific substance into the enamel. If a substance can give a polar solution, electrophoresis is the best application technique. If a substance can be sprayed, spraying is the best solution. Every technique is accepted if can result in a minimum penetration into the enamel. After the application of the particular substance, a second light etching is needed, in order to create some space for the sealing. This step is not necessary if there is space left. In case the used substance has sealing or glazing characteristics the following step is not necessary.

c. Sealing of the teeth. After the application of the protective and coloring substance the teeth must be sealed. Various glazes, curable or not, can be used, in order to seal the teeth.

The protective substances may advantageously also have color additives, so that their application into the teeth leads to the cosmetic painting of the teeth. Various types of white color or other colors can be used to add a new tint to the teeth.

Today's whitening methods are based in the hydroxy peroxide that oxidizes the enamel minerals resulting in the bleaching of the teeth. This bleaching method is not sufficient because the teeth turn dark again in a few weeks, due to the color of the coffee, the food, or the cigarette.

The present invention is not based on the oxidation of the enamel minerals but practically paints the tooth in the desired color. The same substances that are used for the protection of the teeth can be used to give a desired color to the teeth. The new color lasts longer than the simple bleaching because the discoloration of the food and the drinks cannot be attached to the teeth due to the newly formed low surface tension.

The second preferred embodiment of the present invention relates to the implantation of a thermoplastic polymer or a ceramic into the outer layer of the dental enamel, dentin or cementum. This method includes three steps:

1. The dental tissue is etched and dried. The part of the tooth that is etched depends on the application. For caries and periodontal diseases protection, the whole tooth must be etched especially interproximally and in pits and fissures. For the painting of the teeth the etched space relies on the esthetic ideal, because the etched space will accept the desired shade. For the use of a ceramic or a specific polymer as a filling material the etched part is defined by the margins of the restoration. The drying of the etched tooth is performed after the etching and can be done by air or a lower wattage laser beam.

2. The application of the specific material for the specific application is performed by air spraying the material into the etched dental tissue. The material must be in fine powder so that it can permeate the etched tooth especially between the hydroxyapatite rods.

3. The proper laser beam, adjusted in the proper settings for every application, scans the tooth and melts the material instantaneously into the tooth. Right after the melting, the lased part of the tooth is air dried. The flame must reach the melting point of each material and must not damage the material or the tissue from overheating.

In the second preferred embodiment of the present invention, the problems of the past are eliminated because:

a. the implanted material blocks the exit of the dental minerals from the enamel and especially the intraprismatic space of the enamel -anti caries protection;

b. the implanted material has very high chemical resistance and creates a very low surface tension to the tooth tissues which make the tooth uncolonizable to the bacteria -anti periodontal diseases protection;

c. the implanted materials have a broad range in colors and can be used to give the teeth the desired shade-painting method;

d. the implanted material creates an alloy with the tooth tissues as it is co-melted with them, making the restoration, a part of the tooth -restorative material.

In the second preferred embodiment, the implantable material is a polymer or a ceramic that can be melted into the tooth. For caries and perio protection the polymers are preferable because of the excellent chemical resistance and the low surface tension that create to the tooth enamel, making it uncolonizable to bacteria. For the painting of the teeth the polymers are preferable again because of the versatility of their use and the wide shade range that they have. For dental restorations the ceramics are preferable because of the non-existence of microleakage -due to the co-melting of the ceramic and the tissue- and the vicinity of properties between dental tissues and ceramics.

The laser beam must be adjusted to the properties of every dental tissue to which it refers. The wavelength of the laser must be the same that every dental tissue absorbs (i.e., 9.3 - 9.6 μm for the enamel or 6-7.5 μm for the dentin). This fact gives the dentist the opportunity to heat the dental tissue to that point where each material melts. The specific wavelength which every dental tissue fully absorbs makes that specific tissue unable to transmit the laser wave deeper into the tooth and consequently hurt the pulp of the tooth.

Every dental tissue has a specific thermal damage envelope. The melting of the implantable material -polymer or ceramic- must coordinate with this envelope. That means that the melting of the material must happen instantaneously in order to avoid the damage of the tissue which can arise from prolonged time of irradiation.

The thermal relaxation time of every tissue must be followed too. Therefore, the laser beam, can be either pulsed or continuous. That depends on the application. For laser melting the pulsed mode is preferable because it gives the tooth time to coo, especially in the restorative application. For laser drying after etching even continuous mode can be used because of the low wattage of the laser.

The flame must reach the melting point of each material and must not char or damage the implantable material or the tissue.

DETAILED DESCRIPTION OF THE INVENTION

As described above, the first preferred embodiment of the present invention is a teeth-coating method that protects teeth from dental caries and periodontal diseases and optionally also paints teeth at a desired color. This coating method consists of the following steps:

a. etching the teeth, for example by acid, laser, or other methods available to dentists;

b. application of the protective substance and any optionally desired coloring substance to the etched teeth, by any of the methods available to dentists.

c. sealing the teeth, by any of the methods available to dentists. This step depends on the nature of the protective and coloring substance because many substances have sealing characteristics. If that happens, additional sealing is not necessary.

The etching of the teeth can be performed by the already known techniques, e.g., acid or laser induced. The etching step is essential because there must be enough space for the second step, the application of the protective substances. The entire exposed surface of the teeth must be etched, in order to provide adequate protection. Another etching procedure that can be employed herein is the "air abrasion" option. These techniques are discussed in detail in the dental literature, and several references are recited below.

For acid etching, commonly employed materials include phosphoric acid, maleic acid, citric acid, pyruvic acid, and the like. For laser etching, common lasers used are the C0₂, Nd/Yag, Ar:F and others.

Advantageously, known techniques are used for an overall etching, at a sufficient depth that will accommodate the protective substances and any optional colorants. Special care should also be given to those places that are more prone to develop caries like interproximately and in pits and fissures, or in the places that already have or are more prone to develop periodontitis (in some cases even cementum must be protected). The etching depth is closely related to the penetration ability and the application technique of the protective substances which will be applied after the etching step. Finally, the quality of the tooth enamel is another factor, which will vary on a patient by patient basis. Usually, an etching depth of about 50 microns (μ ) is adequate for most aspects of the present invention.

The application of the protective substance (and optional coloring substances) can be performed by various techniques depending on the nature of the substance used. Electrophoresis, spraying, or any other technique that results in the penetration of the substance into the enamel. This penetration can vary from a few microns to half a millimeter depending on the etching technique that is previously used and the penetration ability that every substance has. The total depth of the penetration is closely related to the protection degree that every substance has. More protective characteristics mean less depth and vice versa.

Commonly employed protective substances include the water soluble polymers (xanthan and others), other polymers, salts (e.g., ZnF, CaF, NaF and others), oxides (ZrO₂, TiO₂ and others), cellulose products (cellulose acetate and others), proteins, polyurethane solid coatings, composites (Bisphenol A-Glycidyl Methacrylate and others), resins (Bis-GMA and others).

The final step is the sealing of the teeth. This step is necessary when protective substances with no sealing characteristics were previously used, and not necessary in case of protective substances with self-sealing characteristics. The sealing materials generally require some space in order to be applied, so if the protective (and optional colorant) substance has filled every space in the teeth, a second light etching will be required before the sealing. The sealing can be curable, like the already known glazes in dentistry or not. The sealing must hermetically seal the tooth's surface. One commonly employed sealer is available under the brand name "Fortify." Other sealers are also known and commercially available.

In the second prefened embodiment of the invention, a thermoplastic polymer or a meltable ceramic material is implanted into the tooth. The implantable polymer or ceramic, in fine powder, is air sprayed into the acid etched and laser dried tooth. A specific laser or a flame, adjusted in the proper settings, scans the tooth and instantaneously melts the polymer or the ceramic. The application ends with the air drying of the lased part of the tooth right after the melting.

The etching of the dental enamel, dentin or cementum is performed by acid or laser. Already used etching acids like phosphoric acid, maleic acid, citric acid, pyruvic acid can be used for this step. The laser etching can also be used, although not preferably, because of the melting that creates to the dental tissues. After the etching the etched dental tissue is dried by air or by laser. The laser is preferable because it does not create the piston phenomenon. In this case the air that flows into the intraprismatic area cannot reach and dry the bottom part of the tags because of the existing amount of air that is already pressed there in a higher pressure than the pressure of the air spray. The drying laser follows the same rules with the melting laser in a lower wattage.

The application of the implantable polymer or ceramic is performed by air spraying the material into the etched part of the tooth. The polymer or the ceramic is in fine powder so that it can permeate the tooth and rest into the tooth, especially between the rods of the apatite. The polymers that can be used must be thermoplastic in order to be melted using the laser or the flame. The melting point of the polymers and the ceramics must not exceed the melting point of the dental tissue that will be implanted in. The maximum melting point that any implantable material can have is the melting point of the dental tissue that will be implanted in. The material that is used every time, after the laser and the air drying, does not override the level of the tooth structure except the special polymer or the ceramic that is used as a restorative material and involves the co-melting of the material and the dental tissue. That includes mostly polymers that will be melted into the dental tissue -and their properties, especially wear resistance and tear strength are not close to the dental tissue's. In case of using this method for restorative purposes, the final level of the newly formed alloy (the dental tissue and the ceramic or some polymers) is the same. In this case the amount of the dental tissue that is removed from the etching corresponds to the amount of the material that is deposited and the result after the laser irradiation is an alloy of dental tissue and implanted material (ceramic or special polymer) that has the same dimensions with the part of the tooth where the application took place.

The laser or the flame is used actually to instantaneously heat the dental tissue or the implantable material (depends on the application) to a specific point where the melting point of the implantable material stands. The flame must not exceed the melting point of the implantable material. The laser -preferably used for restorative reasons- follows the thermal damage envelope of every dental tissue that will be used on. The wavelength of the laser that will be applied in any dental tissue must be fully absorbed by the specific dental tissue so that the laser energy is not transmitted into the pulp of the tooth. For example the wavelength that is fully absorbed by the enamel is 9.3-9.6 μm and can be delivered by a CQ dental laser. The wattage of the laser relates to the energy that the implantable material needs to be melted into the dental tissue or maximum needs the dental tissue along with the ceramic or the polymer to be melted together. The mode of the laser - continuous or pulsed- depends on the implantable materials and the thermal relaxation time of every dental tissue. For laser drying, continuous mode is preferable because the wattage is very low. For laser melting, pulsed mode is preferable because it gives the tooth time to cool. The spot diameter of the laser beam or the flame plays an important role in the amount of energy that is deposited into the dental tissue and can vary from 0.1 mm (for pits and fissures) to 1.5 mm for the wider areas of the tooth.

The drying of the melted material into the tooth is performed by air spraying. Right after the laser beam melts the polymer or the ceramic into the tooth, an air spray follows to cool down the tooth area that has accepted the implantation. This cooling down turns -progressively- the temperature of the irradiated spot back to the normal level.

The thermoplastic polymers that can be used in this invention are all the polymers that can be melted by a laser or a flame and their melting point does not exceed the melting point of the dental tissue that will receive this implantation. The ceramics follow the same rule. Every ceramic compound can be used if it can be melted by a laser or a flame and its melting point does not exceed the melting point of the dental tissue that will receive the implantation.

The following references are provided as additional information to assist the skilled artisan in further understanding and utilizing the present invention. The documents cited below are hereby incorporated herein by reference.

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51. Bader JD. Sams DH. O'Neil EH. Estimates of the effects of a statewide sealant initiative on dentists' knowledge and attitudes. Journal of Public Health Dentistry. 47(4): 186-92, 1987 Fall. Health Sciences Library (Boston).

52. Whyte RJ. Leake JL. Howley TP. Two-year follow-up of 11,000 dental sealants in first permanent molars in the Saskatchewan Health Dental Plan. Journal of Public Health Dentistry. 47(4): 177-81, 1987 Fall. Health Sciences Library (Boston).

53. Faine RC. The use of dental sealants in the Washington State Medical Assistance Program: a one-year report. ASDC Journal of Dentistry for Children. 54(6) :451-3, 1987 Nov-Dec. Health Sciences Library (Boston).

54. Duffy MB. Bernet JK. Chovanec GK. Majerus GJ. Frazier PJ. Newell KJ. Dental hygienists' knowledge, opinions, and use of pit and fissure sealants: a comparison of two states. Journal of Public Health Dentistry. 47(3): 121-33, 1987 Summer. Health Sciences Library (Boston).

55. Flanders RA. Effectiveness of dental health educational programs in schools. Journal of the American Dental Association. 114(2):239-42, 1987 Feb. Health Sciences Library (Boston).

56. DiLeone CM. Dental sealants: information and guidelines for insurance carriers. Dental Hygiene. 61(1): 18-23, 1987 Jan. Health Sciences Library (Boston).

57. Isman R. Kizer KW. Preventive dentistry update—dental sealants. Western Journal of Medicine. 146(5):631-2, 1987 May. Health Sciences Library (Boston).

58. Rubenstein LK. Dinius A. Dental sealant usage in Virginia. Journal of Public Health Dentistry. 46(3): 147-51, 1986 Summer. Health Sciences Library (Boston).

59. Faine RC. Dennen T. A survey of private dental practitioners' utilization of dental sealants in Washington state. ASDC Journal of Dentistry for Children. 53(5):337-42, 1986 Sep-Oct. Health Sciences Library (Boston).

60. Glasrud PH. Insuring preventive dental care: are sealants included?. American Journal of Public Health. 75(3):285-6, 1985 Mar.

61. Anonymous. Dental sealants in the prevention of tooth decay. NIH Consensus Development Conference summary. British Dental Journal. 156(8):295- 8, 1984 Apr 21. Health Sciences Library (Boston).

62. Anonymous. Dental sealants in the prevention of tooth decay. National Institutes of Health Consensus Development Conference statement. Journal - Connecticut State Dental Association. 58(2):62-9, 1984 May. Health Sciences Library (Boston).

63. Anonymous. Dental sealants in the prevention of tooth decay. [Review] [0 refs] National Institutes of Health Consensus Development Conference Summary. 4(11):9 p., 1984. Health Sciences Library (Boston).

64. Koop CE. Dental sealants. Journal of Public Health Dentistry. 44(3): 126, 1984 Summer. Health Sciences Library (Boston).

65. Anonymous. Consensus development conference statement on dental sealants in the prevention of tooth decay. National Institutes of Health. Journal of the American Dental Association. 108(2):233-6, 1984 Feb. Health Sciences Library (Boston).

66. Stamm JW. Is there a need for dental sealants? Epidemiological indications in the 1980s. Journal of Dental Education. 48(2 Suppl):9-17, 1984 Feb. Health Sciences Library (Boston).

67. Anonymous. National Institutes of Health Consensus Development conference Statement. Dental sealants in the prevention of tooth decay. Journal of Dental Education. 48(2 Suppl): 126-31, 1984 Feb. Health Sciences Library (Boston).

68. Jeronimus DJ Jr. Till MJ. Sveen OB. Reduced viability of microorganisms under dental sealants. ASDC Journal of Dentistry for Children. 42(4):275-80, 1975 Jul-Aug. Health Sciences Library (Boston).

69. A. Munro GA. Hilton TJ. Hermesch CB. In vitro microleakage of etched and rebonded Class 5 composite resin restorations. Operative Dentistry. 21(5):203-8, 1996 Sep-Oct. Health Sciences Library (Boston).

70. B. May KN Jr. Swift EJ Jr. Wilder AD Jr. Futrell SC. Effect of a surface sealant on microleakage of Class V restorations. American Journal of Dentistry. 9(3): 133-6, 1996 Jun.

71. C. Finger W. Dreyer Jorgensen K. [Inhibition of polymerization by oxygen in composite filling materials and enamel sealers]. [German] SSO: Schweizerische Monatsschrift fur Zahnheilkunde. 86(8):812-24, 1976 Aug.

References for laser etching

1. Vaarkamp J. ten Bosch JJ. Verdonschot EH. Propagation of light through human dental enamel and dentine. Caries Research. 29(1):8-13, 1995. Health Sciences Library (Boston).

2. Varma B. Tandon S. Enamel etching by carbon dioxide laser. An in- vitro comparative evaluation. Indian Journal of Dental Research. 8(1): 19-25, 1997 Jan-Mar.

3. el-Karaksi AO. Influence of laser enamel and dentine etching on marginal integrity of porcelain laminate veneers. Egyptian Dental Journal. 41(2): 1095- 103, 1995 Apr.

4. Young A. Smistad G. Karlsen J. Rolla G. Rykke M. Zeta potentials of human enamel and hydroxyapatite as measured by the Coulter DELSA 440. Advances in Dental Research. l l(4):560-5, 1997 Nov. Health Sciences Library (Boston).

5. Sonju Clasen AB. Ogaard B. Duschner H. Ruben J. Arends J. Sonju T. Caries development in fluoridated and non-fluoridated deciduous and permanent enamel in situ examined by microradiography and confocal laser scanning microscopy. Advances in Dental Research. l l(4):442-7, 1997 Nov. Health Sciences Library (Boston).

6. Moritz A. Gutknecht N. Schoop U. Goharkhay K. Wernisch J. Sperr W. Alternatives in enamel conditioning: a comparison of conventional and innovative methods. Journal of Clinical Laser Medicine & Surgery. 14(3): 133-6, 1996 Jun.

7. Ariyaratnam MT. Wilson MA. Mackie IC. Blinkhorn AS. A comparison of surface roughness and composite/ enamel bond strength of human enamel following the application of the Nd:YAG laser and etching with phosphoric acid. Dental Materials. 13(l):51-5, 1997 Jan. Health Sciences Library (Boston).

8. Lian HJ. Lan WH. Lin CP. The effects of cooling systems on CO2-lased human enamel. Journal of Clinical Laser Medicine & Surgery. 14(6):381-4, 1996 Dec.

9. Duschner H. Gotz H. Ogaard B. Fluoride-induced precipitates on enamel surface and subsurface areas visualised by electron microscopy and confocal laser scanning microscopy. European Journal of Oral Sciences. 105(5 Pt 2):466- 72, 1997 Oct. Health Sciences Library (Boston). 10. Hess JA. Subsurface morphologic changes of ND:YAG laser-etched enamel. Lasers in Surgery & Medicine. 21(2): 193-7, 1997. Health Sciences Library (Boston).

11. Patel BC. Rickwood KR. Morphological changes induced by short pulse hydrogen fluoride laser radiation on dental hard tissue and restorative materials. Lasers in Surgery & Medicine. 21(1): 1-6, 1997. Health Sciences Library (Boston).

12. Fried D. Glena RE. Featherstone JD. Seka W. Permanent and transient changes in the reflectance of CO2 laser-inadiated dental hard tissues at lambda = 9.3, 9.6, 10.3, and 10.6 microns and at fluences of 1-20 J/cm2. Lasers in Surgery & Medicine. 20(1):22-31, 1997. Health Sciences Library (Boston).

13. Wilder-Smith P. Lin S. Nguyen A. Liaw LH. Arrastia AM. Lee JP. Berns MW. Morphological effects of ArF excimer laser irradiation on enamel and dentin. Lasers in Surgery & Medicine. 20(2): 142-8, 1997. Health Sciences Library (Boston).

14. Shahabi S. Brockhurst PJ. Walsh LJ. Effect of tooth-related factors on the shear bond strengths obtained with CO2 laser conditioning of enamel. Australian Dental Journal. 42(2):81-4, 1997 Apr. Health Sciences Library (Boston).

15. Angmar-Mansson B. al-Khateeb S. Tranaeus S. Monitoring the caries process. Optical methods for clinical d agnosis and quantification of enamel caries. European Journal of Oral Sciences. 104(4 ( Pt 2)):480-5, 1996 Aug. Health Sciences Library (Boston).

16. Ogaard B. Duschner H. Ruben J. Arends J. Microradiography and confocal laser scanning microscopy applied to enamel lesions formed in vivo with and without fluoride varnish treatment. European Journal of Oral Sciences. 104(4 ( Pt l)):378-83, 1996 Aug. Health Sciences Library (Boston).

17. Odor TM. Watson TF. Pitt Ford TR. McDonald F. Pattern of transmission of laser light in teeth. International Endodontic Journal. 29(4):228-34, 1996 Jul. Health Sciences Library (Boston).

18. Frentzen M. Winkelstrater C. van Benthem H. Koort HJ. The effects of pulsed ultraviolet and infra-red lasers on dental enamel. European Journal of Prosthodontics & Restorative Dentistry. 4(3):99-104, 1996 Sep.

19. Westerman GH. Hicks MJ. Flaitz CM. Powell GL. Blankenau RJ. Surface morphology of sound enamel after argon laser inadiation: an in vitro scanning electron microscopic study. Journal of Clinical Pediatric Dentistry. 21(l):55-9, 1996 Fall. Health Sciences Library (Boston). 20. Zentner A. Duschner H. Structural changes of acid etched enamel examined under confocal laser scanning microscope. Journal of Orofacial Orthopedics. 57(4):202-9, 1996 Aug. 96345793

21. Mercer CE. Anderson P. X-ray microtomography: a novel technique for the quantification of effects in enamel following CO2 laser application. British Dental Journal. 180(12):451-5, 1996 Jun 22. Health Sciences Library (Boston).

22. Emami Z. al-Khateeb S. de Josselin de Jong E. Sundstrom F. Trollsas K. Angmar-Mansson B. Mineral loss in incipient caries lesions quantified with laser fluorescence and longitudinal microradiography. A methodologic study. Acta Odontologica Scandinavica. 54(1):8-13, 1996 Feb. Health Sciences Library (Boston).

23. Tagomori S. Iwase T. Ultrastructural change of enamel exposed to a normal pulsed Nd-YAG laser. Caries Research. 29(6):513-20, 1995. Health Sciences Library (Boston).

24. Stratmann U. Schaarschmidt K. Schurenberg M. Ehmer U. The effect of ArF-excimer laser irradiation of the human enamel surface on the bond strength of orthodontic appliances. Scanning Microscopy. 9(2):469-76; discussion 476-8, 1995 Jun.

25. Zijp JR. ten Bosch JJ. Groenhuis RA. HeNe-laser light scattering by human dental enamel. Journal of Dental Research. 74(12): 1891-8, 1995 Dec. Health Sciences Lib

26. McCormack SM. Fried D. Featherstone JD. Glena RE. Seka W. Scanning electron microscope observations of CQ laser effects on dental enamel. Journal of Dental

27. Arrastia AM. Wilder-Smith P. Berns MW. Thermal effects of CQ laser on the pulpal chamber and enamel of human primary teeth: an in vitro investigation. Lasers in Surgery & Medicine. 16(4):343-50, 1995. Health Sciences Lib

28. Cernavin I. A comparison of the effects of Nd:YAG and Ho:YAG laser irrad ation on dentine and enamel. Australian Dental Journal. 40(2):79-84, 1995 Apr. Health Sciences Library (Boston).

29. Seka W. Fried D. Featherstone JD. Borzillary SF. Light deposition in dental hard tissue and simulated thermal response. Journal of Dental Research. 74(4): 1086-92, 1995 Apr. Health Sciences Library (Boston).

References for air abrasion 1. Awliya W. Oden A. Yaman P. Dennison JB. Razzoog ME. Shear bond strength of a resin cement to densely sintered high-purity alumina with various surface conditions. Acta Odontologica Scandinavica. 56(1):9-13, 1998 Feb. Health Sciences Library (Boston).

2. Mayes J. Porth R. Air abrasion: the new "drill-less" dentistry [interview by Phillip Bonner]. Dentistry Today. 16(9):58, 60, 62-5, 1997 Sep.

3. Feigenbaum N. Adhesives and air abrasion. [Review] [6 refs] Dentistry Today. 14(4):98, 100-1, 1995 Apr.

4. Zyskind D. Zyskind K. Hirschfeld Z. Fuks AB. Effect of etching on leakage

of sealants placed after air abrasion. Pediatric Dentistry. 20(l):25-7, 1998 Jan- Feb. Health Sciences Library (Boston).

5. Christensen GJ. Air abrasion tooth cutting: state of the art 1998. Journal of the American Dental Association. 129(4):484-5, 1998 Apr. Health Sciences Library (Boston).

6. Boston DW. Alperstein KS. Boberick K. Cavosurface margin geometry in conventional and air abrasion Class V cavity preparations. American Journal of Dentistry. 10(2):97-101, 1997 Apr.

7. Radz GM. Air abrasion: the future of restorative microdentistry. Compendium of Continuing Education in Dentistry. 18(6):534-8, 540, 1997 Jun. Health Sciences Library (Boston).

8. Olsen ME. Bishara SE. Damon P. Jakobsen JR. Comparison of shear bond strength and surface structure between conventional acid etching and air- abrasion of human enamel. American Journal of Orthodontics & Dentofacial Orthopedics. 112(5):502-6^ 1997 Nov. Health Sciences Library (Boston).

9. Kanellis MJ. Warren JJ. Levy SM. Comparison of air abrasion versus acid etch sealant techniques: six-month retention. Pediatric Dentistry. 19(4):258-61, 1997 May-Jun. Health Sciences Library (Boston).

10. Willems G. Carels CE. Verbeke G. In vitro peel/shear bond strength evaluation of orthodontic bracket base design. Journal of Dentistry. 25(3-4):271- 8, 1997 May-Jul. Health Sciences Library (Boston).

11. Kotlow LA. New technology in pediatric dentistry. New York State Dental Journal. 62(2):26-30, 1996 Feb. Health Sciences Library (Boston).

12. Kupiec KA. Barkmeier WW. Laboratory evaluation of surface treatments for composite repair. Operative Dentistry. 21(2):59-62, 1996 Mar-Apr. Health Sciences Library (Boston).

13. Sonis AL. Air abrasion of failed bonded metal brackets: a study of shear bond strength and surface characteristics as deteπriined by scanning electron microscopy. American Journal of Orthodontics & Dentofacial Orthopedics. 110(l):96-8, 1996 Jul. Health Sciences Library (Boston).

14. Brown JR. Barkmeier WW. A comparison of six enamel treatment procedures for sealant bonding. Pediatric Dentistry. 18(1):29-31, 1996 Jan-Feb. Health Sciences Library (Boston).

15. Roeder LB. Berry EA 3rd. You C. Powers JM. Bond strength of composite to air-abraded enamel and dentin. Operative Dentistry. 20(5): 186-90, 1995 Sep- Oct. Health Sciences Library (Boston). 16. Berry EA 3rd. Ward M. Bond strength of resin composite to air-abraded enamel. Quintessence International. 26(8):559-62, 1995 Aug. Health Sciences Library (Boston).

17. Laurell KA. Hess JA. Scanning electron micrographic effects of air- abrasion cavity preparation on human enamel and dentin. Quintessence International. 26(2): 139-44, 1995 Feb. Health Sciences Library (Boston).

18. Los SA. Barkmeier WW. Effects of dentin air abrasion with aluminum oxide and hydroxyapatite on adhesive bond strength. Operative Dentistry. 19(5): 169-75, 1994 Sep-Oct. Health Sciences Library (Boston).

19. Latta MA. Barkmeier WW. Bond strength of a resin cement to a cured composite inlay material. Journal of Prosthetic Dentistry. 72(2): 189-93, 1994 Aug. Health Sciences Library (Boston).

20. Swift EJ Jr. Brodeur C. Cvitko E. Pires JA. Treatment of composite surfaces for indirect bonding. Dental Materials. 8(3): 193-6, 1992 May. Health Sciences Library (Boston).

21. Huennekens SC. Daniel SJ. Bayne SC. Effects of air polishing on the abrasion of occlusal sealants. Quintessence International. 22(7):581-5, 1991 Jul. Health Sciences Library (Boston).

22. Ferrari M. Cagidiaco MC. Breschi R. Evaluation of resin-bonded retainers with the scanning electron microscope. Journal of Prosthetic Dentistry. 59(2): 160-5, 1988 Feb. Health Sciences Library (Boston).

References for acid-etching

1. A. Buonocore MG. A simple method of increasing the adhesion of acrylic filling materials to enamel surfaces. J. Dent. Res 1955; 34:849-853.

2. B. Gwinnett AJ. Matsui A. A study of enamel adhesives. The physical relationship between enamel and adhesive. Arch. Oral Biol 1967; 12: 1615-1620

3. C. Relief DH. Effect of conditioning the enamel surface with phosphoric acid. J. Dent. Res. 1973; 52:333-341

4. D. Gwinnett AJ. Histologic changes in human enamel following treatment with acidic adhesive conditioning agents. Arch Oral Biol 1971; 16:731-738

5. E. Silverstone LM, Saxton CA, Dogon IL, Fejerskov O. Variation in the pattern of acid etching of human dental enamel examined by scanning electron microscopy. Caries Res 1975; 9:373-387

6. F. Seow WK. Amaratunge A. The effects of acid-etching on enamel from different clinical variants of amelogenesis imperfecta: an SEM study. Pediatric Dentistry. 20(l):37-42, 1998 Jan-Feb. Health Sciences Library (Boston).

7. Seow WK. Amaratunge A. The effects of acid-etching on enamel from different clinical variants of amelogenesis imperfecta: an SEM study. Pediatric Dentistry. 20(l):37-42, 1998 Jan-Feb. Health Sciences Library (Boston).

8. Zyskind D. Zyskind K. Hirschfeld Z. Fuks AB. Effect of etching on leakage of sealants placed after air abrasion. Pediatric Dentistry. 20(l):25-7, 1998 Jan- Feb. Health Sciences Library (Boston).

9. Moritz A. Gutknecht N. Schoop U. Goharkhay K. Wernisch J. Sperr W. Alternatives in enamel conditioning: a comparison of conventional and innovative methods. Journal of Clinical Laser Medicine & Surgery. 14(3): 133-6,

1996 Jun.

10. Gunadi G. Nakabayashi N. Preparation of an effective light-cured bonding agent for orthodontic application. Dental Materials. 13(1):7-12, 1997 Jan. Health Sciences Library (Boston).

11. Ariyaratnam MT. Wilson MA. Mackie IC. Blinkhorn AS. A comparison of surface roughness and composite/ enamel bond strength of human enamel following the application of the Nd:YAG laser and etching with phosphoric acid. Dental Materials. 13(l):51-5, 1997 Jan. Health Sciences Library (Boston).

12. Chan AR. Titley KC. Chernecky R. Smith DC. A short- and long-term shear bond strength study using acids of varying dilutions on bovine dentine. Journal of Dentistry. 25(2): 145-52, 1997 Mar. Health Sciences Library (Boston).

13. Reisner KR. Levitt HL. Mante F. Enamel preparation for orthodontic bonding: a comparison between the use of a sandblaster and cunent techniques. American Journal of Orthodontics & Dentofacial Orthopedics. l l l(4):366-73, 1997 Apr. Health Sciences Library (Boston).

14. Chung KH. Hwang YC. Bonding strengths of porcelain repair systems with various surface treatments. Journal of Prosthetic Dentistry. 78(3):267-74,

1997 Sep. Health Sciences Library (Boston).

15. Cagidiaco MC. Fercari M. Vichi A. Davidson CL. Mapping of tubule and intertubule surface areas available for bonding in Class V and Class II preparations. Journal of Dentistry. 25(5):379-89, 1997 Sep. Health Sciences Library (Boston).

16. Kuhar M. Cevc P. Schara M. Funduk N. Enhanced permeability of acid- etched or ground dental enamel. Journal of Prosthetic Dentistry. 77(6):578-82, 1997 Jun. Health Sciences Library (Boston). 17. Hummel SK. Marker V. Pace L. Goldfogle M. Surface treatment of indirect resin composite surfaces before cementation. Journal of Prosthetic Dentistry. 77(6): 568-72, 1997 Jun. Health Sciences Library (Boston).

18. Meredith N. Setchell DJ. In vitro measurement of cuspal strain and displacement in composite restored teeth. Journal of Dentistry. 25(3-4):331-7, 1997 May- Jul. Health Sciences Library (Boston).

19. Perdigao J. Lambrechts P. van Meerbeek B. Tome AR. Vanherle G. Lopes AB. Morphological field emission-SEM study of the effect of six phosphoric acid etching agents on human dentin. Dental Materials. 12(4):262-71, 1996 Jul. Health Sciences Library (Boston).

20. Cowan AJ. Wilson NH. Wilson MA. Watts DC. The application of ESEM in dental materials research. Journal of Dentistry. 24(5):375-7, 1996 Sep. Health Sciences Library (Boston).

21. Wong M. Eulenberger J. Schenk R. Hunziker E. Effect of surface topology on the osseointegration of implant materials in trabecular bone. Journal of Biomedical Materials Research. 29(12): 1567-75, 1995 Dec. Health Sciences Library (Boston).

22. Uno S. Finger WJ. Phosphoric acid as a conditioning agent in the Gluma bonding system. American Journal of Dentistry. 8(5):236-41, 1995 Oct.

23. Goracci G. Mori G. Bazzucchi M. Marginal seal and biocompatibility of a fourth-generation bonding agent. DentalMaterials. l l(6):343-7, 1995 Nov. Health Sciences Library (Boston).

24. van Gogswaardt DC. Behrens VG. The effectiveness of an indicator gel in the detection of exposed dentine. Journal of Dentistry. 23(6):375-6, 1995 Dec. Health Sciences Library (Boston).

25. Richards A. Coote GE. Pearce El. Proton probe and acid etching for determining fluoride profiles in porous porcine enamel. Journal of Dental Research. 73(3):644-51, 1994 Mar. Health Sciences Library (Boston).

26. Walsh LJ. Abood D. Brockhurst PJ. Bonding of resin composite to carbon dioxide laser-modified human enamel. Dental Materials. 10(3): 162-6, 1994 May. Health Sciences Library (Boston).

27. Oikarinen KS. Nieminen TM. Influence of acid-etched splinting methods on discoloration of dental enamel in four media: an in vitro study. Scandinavian Journal of Dental Research. 102(6):313-8, 1994 Dec. Health Sciences Library (Boston).

28. Meechan JG. McCabe JF. Beynon AD. Adhesion of composite resin to bone— a pilot study. British Journal of Oral & Maxillofacial Surgery. 32(2):91-3, 1994 Apr. Health Sciences Library (Boston).

29. Suliman AH. Swift EJ Jr. Perdigao J. Effects of surface treatment and bonding agents on bond strength of composite resin to porcelain. Journal of Prosthetic Dentistry. 70(2): 118-20, 1993 Aug. Health Sciences Library (Boston).

30. Swift EJ Jr. Brodeur C. Cvitko E. Pires JA. Treatment of composite surfaces for indirect bonding. Dental Materials. 8(3): 193-6, 1992 May. Health Sciences Library (Boston).

31. Yiu CK. Wei SH. Management of rampant caries in children. [Review] [47 refs] Quintessence International. 23(3): 159-68, 1992 Mar. Health Sciences Library (Boston).

32. Smales RJ. Effects of enamel-bonding, type of restoration, patient age and operator on the longevity of an anterior composite resin. American Journal of Dentistry. 4(3): 130-3, 1991 Jun.

33. Soderholm KJ. Roberts MJ. Variables influencing the repair strength of dental composites. Scandinavian Journal of Dental Research. 99(2): 173-80, 1991 Apr. Health Sciences Library (Boston).

34. Hosoya Y. Goto G. Effects of cleaning, polishing pretreatments and acid etching times on unground primary enamel. Journal of Pedodontics. 14(2):84- 92, 1990 Winter. Health Sciences Library (Boston).

35. Frentzen M. Koort HJ. Kermani O. Dardenne MU. [Preparation of hard tooth structure w ith Excimer lasers]. [German] Deutsche Zahnarztliche Zeitschrift. 44(6):454-7, 1989 Jun. Health Sciences Library (Boston).

36. Iijima Y. Koulourides T. Mineral density and fluoride content of in vitro remineralized lesions. Journal of Dental Research. 67(3):577-81, 1988 Mar. Health Sciences Library (Boston).

37. Ishikiriama A. Oliveira J de F. Vieira DF. Mondelli J. Influence of some factors on the fit of cemented crowns. Journal of Prosthetic Dentistry. 45(4) :400- 4, 1981 Apr. Health Sciences Library (Boston).

38. Vainio J. Kilpikari J. Tormala P. Rokkanen P. Experimental fixation of bone cement and composite resins to bone. Archives of Orthopaedic & Traumatic Surgery. 94(3): 191-5, 1979 Aug.

39. Tsvetkova G. [Dental acid etching methods— theoretical premises and practical application]. [Review] [48 refs] [Bulgarian] Stomatologiia. 60(2): 152-8, 1978 Mar-Apr. 40. Gwinnett AJ. Status report on acid etching procedures. Council on Dental Materials and Devices. Journal of the American Dental Association. 97(3):505-8, 1978 Sep. Health Sciences Library (Boston).

41. Koch G. Paulander J. [Clinical evaluation of composite restorations made with acid etching methods]. [Swedish] Svensk Tandlakaretidskrift. 69(6): 191-6, 1976.

42. Rowe AH. A modification of the acid-etching technique for restoring fractured incisors. Journal of Dentistry. 2(l):35-6, 1973 Oct. Health Sciences Library (Boston).

Miscellaneous References

1. Lyons KM. Rodda JC. Hood JA. Use of a pressure chamber to compare microleakage of three luting agents. International Journal of Prosthodontics. 10(5):426-33, 1997 Sep-Oct.

2. Kydd WL. Nicholls JL Harrington G. Freeman M. Marginal leakage of cast gold crowns luted with zinc phosphate cement: an in vivo study. Journal of Prosthetic Dentistry. 75(1):9-13, 1996 Jan. Health Sciences Library (Boston).

3. White SN. Yu Z. Tom JF. Sangsurasak S. In vivo microleakage of luting cements for cast crowns. Journal of Prosthetic Dentistry. 71(4):333-8, 1994 Apr. Health Sciences Library (Boston).

4. Prati C. Fava F. Di Gioia D. Selighini M. Pashley DH. Antibacterial effectiveness of dentin bonding systems. Dental Materials. 9(6):338-43, 1993 Nov. Health Sciences Library (Boston).

5. Blair KF. Koeppen RG. Schwartz RS. Davis RD. Microleakage associated with resin composite-cemented, cast glass ceramic restoration. International Journal of Prosthodontics. 6(6):579-84, 1993 Nov-Dec.

6. Zaimoglu A. Karaagaclioglu L. Uctasli. Influence of porcelain material and composite luting resin on microleakage of porcelain laminate veneers. Journal of Oral Rehabilitation. 19(4):319-27, 1992 Jul. Health Sciences Library (Boston).

7. White SN. Sorensen JA. Kang SK. Caputo AA. Microleakage of new crown and fixed partial denture luting agents. Journal of Prosthetic Dentistry.

67(2): 156-61, 1992 Feb. Health Sciences Library (Boston).

8. Berg JH. Pettey DE. Hutchins MO. Microleakage of three luting agents used with stainless steel crowns. Pediatric Dentistry. 10(3): 195-8, 1988 Sep. Health Sciences Library (Boston).

The following is a list of polymers which will be useful as a protective O 00/09030

- 30

substance in the present invention.

POLYMER LIST

Tradenames, Generic Polymers, and Suppliers

Tradename Material Manufacturer

A

Acctuf PP copolymer Amoco Polymers

Acetron Acetal DSM

Aclon fluoropolymer Allied Signal

ACP PVC Alpha Gary

Acrylite acrylic Cyro Industries

Acryrex acrylic Chi Mei Industrial

Adell thermoplastic resin Adell

Adflex Montell

Adpro polypropylene Huntsman

Adstif Montell

Affinity plastomer Dow Plastics

Aim PS Dow Plastics

Akulon nylon 6,66 DSM

Akuloy nylon 6,66 alloys DSM

Alathon HDPE, HDPE copolymer Lyondell Polymers

Albis nylon 6, 66 Albis Canada

Alcryn TP elastomer DuPont Algoflon fluoropolymer Auismont

Alphatec TP elastomer Alpha Gary

Amilan nylon Toray Industries

Amoco thermoplastic resin Amoco

Amodel PPA (polyphthalamide) Amoco Polymers

Apec PC (high temperature) Bayer

API polystyrene American Polymers

Aqualoy nylon 6/ 12, 66, PP ComAlloy

Aquathene polyethylene Quantum

Alcryn TP elastomer DuPont

Arcel styrene / ethylene copolymer Nova Chemicals

Ardel polyarylate Amoco Polymers

Arnitel TP elastomer DSM

Aropol thermoset resin Ashland

Arpro expandable PP bead JSP

Arpak expandable PP bead JSP

Ashlene nylon 6, 66, 6/ 12 Ashley Polymers

Astryn PP alloy, co- and Montell homopolymer, TPO

Attane ULDPE Dow Plastics

AurumTP polyimide Mitsui Toatsu

AVP (various) Polymerland

Azdel thermoplastic resin Azdel

B Bapolene polyethylene Bamberger

Barex acrylonitrile copolymer BP Chemicals

Bayblend polycarbonate/ABS Bayer

Baydur structural foam PUR RIM Bayer

Baylon nylon 6/6 Bay Resins

Beetle urea formaldehyde Cytec Industries

Benvic PVC Solvay

Beta Beta Polymers

Bexloy ionomer DuPont

Boltaron FR PP GenCorp

C

Cabot thermoplastic resin Cabot

Cadon SMA copolymer Bayer

Calibre polycarbonate Dow Plastics

Capron nylon 6, 66, 66/6 Allied Signal

Carilon aliphatic PK Shell

Cefor polypropylene Shell

Celanese nylon 6, nylon 6/6 Hoechst-Celanese

Celanex polyester (PBT) Hoechst-Celanese

Celcon acetal copolymer Hoechst-Celanese

Celstran long fiber reinforced Hoechst-Celanese

Centrex ASA, ASA+AES Bayer

Cevian ABS, ABS+PBT,SAN Daicel C-flex SBS, SEBS Concept Polymer

Chemigum TP elastomer Goodyear

Chemlon Nylon 6,66 Chem Polymer

Claradex ABS Shin-A

Compodic DIC Trading

Comshield PP ComAlloy

Comtuf impact resistant resins ComAlloy

Cosmic Cosmic

Corton mineral filled material PolyPacific

Crastin PBT DuPont

Crystalor polymethylpentene (PMP) Phillips Chemical

CTI Nylon 66 M.A.Hanna

Cycogel ABS Nova Polymers

Cycolac ABS, ABS+PBT GE Plastics

Cycolin ABS/PBT GE Plastics

Cycoloy polycarbonate/ABS GE Plastics

Cyglas TS polyester Cytec Industries

Cymel melamine formaldehyde Cytec Industries

Cyrex acrylic / poly carbonate Alloy Cyro Industries

Cyrolite acrylic Cyro Industries

D

Delrin acetal DuPont

Desmopan TP polyurethane Bayer Dexplex TPO D&S Polymers

Diamon Diamond Polymers

Dimension Nylon 6 alloy Allied Signal

Dowlex HDPE, LLDPE Dow Plastics

Drexflex TP elastomer D&S Plastics

Duraflex polybutylene Shell

Dural PVC Alpha Gary

Durel polyarylate Hoechst-Celanese

Durethan nylon 6 Bayer

Durez thermoset resins Occidental

Dylark SMA copolymer Nova Chemicals

Dylene polystyrene Nova Chemicals

Dylite expandable polystyrene Nova Chemicals

Dynaflex SBS, SEBS GLS Plastics

E

Eastabond PET Eastman Chemical

Eastalloy PC+Polyester Eastman Chemical

Eastapak PET Eastman Chemical

Eastar (various polyesters) Eastman Chemical

Eastman thermoplastic resin Eastman Chemical

Ecdel TP elastomer Eastman Chemical

Ecoprene TP Elastomer Rubber & Plastics Solutions

Edistir polystyrene Enichem Ektar PET, PBT, P T po lyester Eastman Chemical

Ektar FB TP elastomer Eastman Chemical

Elastalloy TP elastomer GLS corp

Elastollan polyurethane TPE BASF

Electrafil electrically conductive DSM polymers

Elexar TP Elastomer Teknor Apex

Elvamide nylon copolymer DuPont

Eltex HDPE Solvay

Eltex P PP Solvay

Elvax EVA copolymer DuPont

Emac EMA copolymer Chevron Chemical

Emiclear Toshiba

Emi-X (various) LNP

Empee polyethylene, polypropylene Monmouth

Enathene ethylene butyl acrylate Quantum

Engage TP elastomer Dow Plastics

Epalex PolyPacific

Eref PA/PP alloy Solvay

Escalloy PP (stress crack resist) ComAlloy

Escoracid terpolymer Exxon Chemical

Escorene polypropylene Exxon Chemical

Estaloc polyurethane BF Goodrich

Estane polyurethane TPEBF Goodrich Evalca EVA copolymer Eval

Exact plastomer Exxon Chemical

Extron glass filled material PolyPacific

Exxtral TP elastomer Exxon Chemical

F

Faradex conductive wire filled DSM

Ferrene polyethylene Ferro

Fenex polypropylene Feno

Feno Ferro

Fenocon Polyolefin Ferro

Fenoflo polystyrene Feno

Fenopak PP/PE alloy Ferro

Fiberfil fiber reinforced material DSM

Fiberloc fiber reinforced PVC Geon

Fiberstran long fiber reinforced DSM material

Fina polyolefin Fina Oil

Finaclear polystyrene, SBS Fina Oil

Finaprene TP elastomer Fina Oil

Flexalloy PVC Teknor Apex

Flexomer polyethylene (ULDPE) Union Carbide

Flexprene TP elastomer Teknor Apex

Fluorocomp reinforced fluoropolymer LNP

Foamspan thermoplastic foam ComAlloy Foraflon PVDF Atochem

Formion ionomer A. Schulman

Fortiflex polyethylene Solvay

Fortilene polypropylene Solvay

Fortron PPS Hoechst-Celanese

FR-P CPC Lucky

FTPE Fluorelastomer 3M Performance Polymers

G

Gapex nylon Ferro

Geloy ASA, ASA+PC, ASA+PVC GE Plastics

Geolast TP elastomer Advanced Elastomer

Sys.

Geon PVC Geon

Glaskyd alkyd CYTEC

Glastic thermost resin Glastic

Goldrex acrylic Hanyang Chemical

Grilamid nylon 12 EMS-American

Grilon

Grilon nylon 6, 66 EMS-American

Grilon

Grilpet PET EMS-American

Grilon

Grivory nylon EMS-American

Grilon

H

Halar fluoropolymer Ausimont Halon fluoropolymer Ausimont

Hanalac ABS Miwon

Haysite thermoset resin Haysite

Hercuprene TP elastomer J-Von

Hetron thermoset resin Ashland

Hifax PP, TPE, TPO Montell

HiGlass glass filled polypropylene Himont

Hiloy high strength resin ComAlloy

Histat electrically conductive United Composite:

HiVal polyethylene (HDPE) General Pol

Hivalloy PP alloy Montell

Hostacen metallocene PP Hoechst-Celanese

Hostacom reinforced PP Hoechst-Celanese

Hostaflon fluoropolymers Hoechst-Celanese

Hostaform acetal copolymer Hoechst-Celanese

Hostalen PE Hoechst-Celanese

Hostalen-GUR UHMW PE Hoechst-Celanese

Hostalen PP polypropylene Hoechst-Celanese

Hostalloy polyolefin alloy Hoechst-Celanese

Huntsman thermoplastic Huntsman

Hyflon fluoropolymer Auismont

Hylar PVDF Auismont

Hylon nylon 6, 66 Hale

Hytrel TP elastomer DuPont O 00/09030

- 39 -

Impetpolyester (PET) Hoechst-Celanese

Interpol polyurethane Cook Composites

Iotek ionomer Exxon

Isoplast TPU Dow Plastics

Iupiace PPO/PPE Mitsubishi

Iupilon polycarbonate Mitsubishi

Iupital acetal Mitsubishi

Ixan PVDF Solvay

Ixef polyarylamide Solvay Polymers J

J-Plast TP elastomer J-Von

K

Kadel PAEK Amoco Polymers

Kamax acrylic copolymer AtoHaas

Kemcor LDPE, HDPE Kemcor Australia

Kematal acetal copolymer Hoechst-Celanese

Kibisan SAN Chi Mei Industrial

Kibiton SBS Chi Mei Industrial

Koblend polycarbonate/ABS EniChem America

Kodapak PET polyester Eastman

Kodar PETG polyester Eastman

Kohinor vinyl Rimtec

Kopa Nylon 6,66 Kolon America Kraton styrenic TPE Shell Chemical

K-Resin styrene/butadiene Phillips Chemical copolymer

Kynar PVDF Atochem

L

Ladene polystyrene SABIC

Lexan polycarbonate GE Plastics

Lomod TP elastomer GE Plastics

Lubricomp wear resistant material LNP

Lubrilon nylon 6,66,6/ 12,PBT Comalloy

Lubriloy internally lubricated LNP material

Lucel acetal copolymer Lucky

Lucet acetal copolymer Lucky

Lumax PBT alloy Lucky

Lupan SAN Lucky

Lupol polyolefin Lucky

Lupon nylon 66 Lucky

Lupos ABS Lucky

Lupox PBT Lucky

Lupoy ABS+PBT Lucky

Luran SAN.ASA BASF

Lusep PPS Lucky

Lustran ABS, SAN, ABS+Acrylic Bayer

Luxis nylon 6/6 Westover Lytex epoxy Quantum Compo!

M

Magnacomp Nylon 6, 6/ 10, PP LNP

Magnum ABS Dow Plastics

Makrolon polycarbonate, PC blend Bayer

Makroblend polycarbonate blend Bayer

Malecca styrenic copolymer Denki Kagaku

Maranyl nylon ICI Americas

Marlex polyethylene, polypropylene Phillips Chemical

Mater-Bi biodegradeable polymer Novamont

Microthene PE Quantum

Milastomer TP elastomer Mitsui

Mindel PSU, PSU alloy Amoco Polymers

Minion mineral filled nylon 6/6, DuPont 6/6/6

Morthane TPU Morton

Multibase ABS Multibase

Multi-Flam polypropylene Multibase

Multi-Flex TP elastomer Multibase

Multi-Hips polystyrene Multibase

Multi-Pro polypropylene Multibase

Multi-San SAN copolymer Multibase

N

NASSMMA acrylic Nova Chemicals Naxell polycarbonate (recycled) MRC Polymers

Norsophen Phenolic Norold Composites

Nortuff HDPE, polypropylene Polymerland

Noryl PPO, PPO alloy GE Plastics

Novalast TP elastomer Nova Polymers

Novalene TP elastomer Nova Polymers

Novamid nylon Mitsubishi

Novapol LLDPE,LDPE,HDPE Nova Chemicals

Novatemp PVC Novatec

Novon starch based polymer Novon

NSC Nylon, PS Thermofil

Nucrel EMAA copolymer DuPont

Nybex nylon 6/ 12 Nova

Nydur nylon 6 Bayer (now called Durethan)

Nylafil nylon 66 DSM

Nylamid nylon Polymer Service

Nylast TP elastomer Allied Signal

Nylatron glass reinforced nylon DSM

Nylene nylon Custom Resins

Nylind nylon 66 DuPont

Nyloy nylon 66, PC, PP Nytex Composites

Nypel nylon 6 Allied Signal

Nytron nylon 66 Nytex Composites o

Olehard filled polypropylene Chiso America

Ontex TP elastomer D&S Plastics

Optema EMA copolymer Exxon Chemical

Optix acrylic Plaskolite

Oxy vinyl Occidental

Oxyblend vinyl Occidental

Oxyclear PVC Occidental

P

Panlite polycarbonate Teijin Chemical

Paxon HDPE Paxon

Pebax PEBA Atochem

Pellethane polyurethane TP elastomer Dow Plastics

PermaStat (various) RTP

Perspex acrylic ICI Acrylics

Petlon PBT Albis

Petra polyester (PET) Allied Signal

Petrothene polyethylene, polypropylene, Quantum

TPO

Pibiter polyester (PBT) EniChem

Plaslok thermoset resins Plaslok

Plaslube lubricated materials DSM

Plenco thermoset resins Plastics Engineering Plexiglas acrylic AtoHaas (Rohm & Haas)

Pliovic vinyl Goodyear

PMC melamine formaldehyde Sun Coast

Pocan polyester (PBT) Albis

Polifil reinforced polyolefins Polifil

Polyfabs ABS A. Schulman

Polyfil Polyfil

Polyfine Tokutama Soda

Polyflam flame retardant thermoplastic A. Schulman

Polyflon fluoropolymer Dailtin

Polyfort polypropylene, polyethylene A. Schulman

Polylac ABS Chi Mei Industrial

Polyman ABS Alloy A. Schulman

Polypur reinforced or alloyed TPE A. Schulman

Polytron PVC alloy Geon

Polytrope TP elastomer A. Schulman

Polyvin PVC A. Schulman

Porene ABS Thai Petrochemical

Premi-glas glass reinforced SMC Premix

Premi-ject thick molding compound Premix (thermoset)

Prevail ABS/polyurethane Dow Plastics

Prevex PPE GE Plastics Primef PPS Solvay

Prism polyurethane RIM Bayer

Polyvin PVC A. Schulman

Primacor EAA copolymer Dow Plastics

Pro-Fax polyolefins Montell

Propak polypropylene PolyPacific

Pulse polycarbonate/ABS Dow Plastics

R

RTP RTP

Radel polyether sulfone Amoco Performance Products

Radiflam nylon FR Radicinovacips

Radilon nylon 6 Radicinovacips

Radipol nylon 6/6 Radicinovacips

Reny nylon 6/6 Mitsubishi

Replay polystyrene Huntsman

Reprean ethylene copolymer Discas

Resinoid thermoset resins Resinoid

Retain PE Dow Plastics

Rexene thermoplastic resin Rexene

Rexfiex polypropylene Rexene

Rilsan rotational molding resins Atochem

Rimplast TP elastomer Huls

Rimtec vinyl Rimtec Riteflex TP elastomer Hoechst-Celanese

Rogers thermoset resins Rogers

Ronfalin ABS DSM

Rynite polyester (PET.PBT) DuPont

Ryton PPS Phillips Chemical

S

Sabre PC+PET Dow Plastics

Santoprene TPE, TPO Advanced Elastomer Sys.

Saran vinylidine chloride Dow Plastics

Sarlink TPE, TPO DSM

Satinflex PVC Alpha Gary

Schulaflex flexible elastomers A. Schulman

Schulamid nylon 6, 66 A. Schulman

Schulink cross-linkable HDPE A. Schulman

Sclair polyethylene Nova Chemicals

Selar nylon, PET DuPont

Shell polyolefins Shell

Shinite PBT Shinkong

Sinkral ABS EniChem

Sinvet polycarbonate EniChem

Soarnol EVA copolymer Nichimen

Solef PVDF Solvay Polymers

Solvic PVC Solvay Polymers Spectar polyester copolymer Eastman

Stanyl nylon 46 DSM

Stanuloy PC.PET blend (recycled) MRC Polymers

Stapron ABS+PC, SMA DSM

Stat-Kon static dissipative material LNP

Stat-Loy static dissipative material LNP

Stereon styrene/butadiene bl. Firestone copolymer

Stypol thermoset resin Cook Composites

Styrafil filled styrenes DSM

Styron PS Dow Plastics

Styropor PS BASF

Sumiplex acrylic Sumitomo

Sunprene PVC elastomer A. Schulman

Suntra PPS Sunkyong Industries

Supec PPS GE Plastics

Superkleen PVC Alpha Gary

Suprel ABS/PVC Vista Chemical

Surlyn Ionomer DuPont

Synprene TP elastomer Synergistics Industries

T

Technyl nylon 66 Rhone-Poulenc

Tecoflex PUR Thermidics Tecothane PUR Thermidics

Tedur PPS Albis

Teflon fluoropolymer DuPont

Tefzel PE-TFE fluoropolymerDuPont

Tekron TP elastomer Teknor Apex

Telcar TP elastomer Teknor Apex

Telcar TP elastomer Teknor Apex

Tempalloy high temperature resin ComAlloy

TempRite CPVCBF Goodrich

Tenac acetal Ashai

Tenite polyolefin, cellulosic, CAB Eastman

Terluran ABS BASF

Terlux MABS BASF

Texalon nylon Texapol

Texapol Texapol

Texin polyurethane Bayer

Thermex heat dissipative materials ComAlloy

Thermocomp glass, carbon fiber LNP reinforced

Thermx copolyester Eastman

Tone PCL Union Carbide

Tonen TCA Plastics

Topalloy TCA Plastics

Topas cycloolefin copolymer Hoechst-Celanese Topex PBT Tong Yang Nylon

Toplex polycarbonate/ABS Multibase

Toray PBT Toray Industries

Torlon polyamide-imide Amoco Polymers

Toyolac ABS, polycarbonate /ABS Toray Industries

TPX polymethylpentene (PMP) Mitsui

Trefsin TP elastomer Advanced Elastomer Sys.

Triax polycarbonate/ABS, ANS/ Nylon Bayer

Tribit PBT Sam Yang

Triloy PC+PBT, ABS+PC Sam Yang

Trirex PC Sam Yang

Tufrex ABS Bayer

Typlax Typlax

Tyril SAN Dow Plastics

U

Ube Ube Industries

Udel PSO Amoco Performance Products

Ultem polyetherimide GE Plastics

Ultradur polyester (PBT) BASF

Ultraform acetal BASF

Ultramid nylon BASF

Ultrapek PAEK BASF Industries

T

Technyl nylon 66 Rhone-Poulenc

Tecoflex PUR Thermidics

Tecothane PUR Thermidics

Tedur PPS Albis

Teflon fluoropolymer DuPont

Tefzel PE-TFE fluoropolymerDuPont

Tekron TP elastomer Teknor Apex

Telcar TP elastomer Teknor Apex

Telcar TP elastomer Teknor Apex

Tempalloy high temperature resin ComAlloy

TempRite CPVCBF Goodrich

Tenac acetal Ashai

Tenite polyolefin, cellulosic, CAB Eastman

Terluran ABS BASF

Terlux MABS BASF

Texalon nylon Texapol

Texapol Texapol

Texin polyurethane Bayer

Thermex heat dissipative materials ComAlloy

Thermocomp glass, carbon fiber LNP reinforced Thermx copolyester Eastman

Tone PCL Union Carbide

Tonen TCA Plastics

Topalloy TCA Plastics

Topas cycloolefin copolymer Hoechst-Celanese

Topex PBT Tong Yang Nylon

Toplex polycarbonate/ABS Multibase

Toray PBT Toray Industries

Torlon polyamide-imide Amoco Polymers

Toyolac ABS, polycarbonate

/ABS Toray Industries

TPX polymethylpentene (PMP) Mitsui Trefsin TP elastomer Advanced Elastomer

Sys.

Triax polycarbonate / ABS ,

ANS/ Nylon Bayer

Tribit PBT Sam Yang

Triloy PC+PBT, ABS+PC Sam Yang

Trirex PC Sam Yang

Tufrex ABS Bayer

Typlax Typlax

Tyril SAN Dow Plastics

U

Ube Ube Industries Udel PSO Amoco Performance Products

Ultem polyetherimide GE Plastics

Ultradur polyester (PBT) BASF

Ultraform acetal BASF

Ultramid nylon BASF

Ultrapek PAEK BASF

Ultrason - E polyether sulfone (PES) BASF

Ultrason - S polysulfone (PSO) BASF

Ultrastyr ABS Enichem America

Ultrathene EVA copolymer Quantum

Unichem PVC Color ite Plastics

Unival polyethylene Union Carbide

V

Valox polyester (PBT, PET, PCT) GE Plastics

Valtec Montell

Valtra polystyrene Chevron Chemical

Vandar polyester alloy Hoechst-Celanese

Vector SBS, SIS Dexco Polymers

Vectra liquid crystal polymer Hoechst-Celanese

Verton long fiber reinforced LNP

Vespel polyimide DuPont

Vestamid nylon Huls Victrex PEEKICI Advanced Materials

Vista vinyl Vista Chemical

VistaFlex TP elastomer Advanced Elastomer Sys.

Vistel PVC Vista Chemical

Vitax ASA Hitachi Chemical

Voloy flame retardant materials ComAlloy

Vybex polyester Ferro

Vydyne nylon Monsanto

Vyram TP elastomer Advanced Elastomer Sys.

Vythene PVC+PUR Alpha Gary

Wellamid nylon Wellman

WPP PP Washington Penn

X

Xenoy polycarbonate /polyester GE Plastics

XT-Polymer acrylic copolymer Cyro Industries

Xydar liquid crystal polymer Amoco Polymers

Z

Zemid PE, HDPE DuPont Canada

Zenite LCP DuPont

Zeonex polymethylpentene (PMP) Nippon Zeon Zylar acrylic copolymer Novacor

Zytel nylon DuPont

The present invention has been described in detail, including the preferred embodiments thereof. However, it will be appreciated that those skilled in the art, upon consideration of the present disclosure, may make modifications and/ or improvements on this invention and still be within the scope and spirit of this invention as set forth in the following claims.

Claims

WHAT IS CLAIMED IS:

1. A method of protecting teeth from decay comprising the steps of: a. etching the teeth; b. applying one or more protective substances to the etched teeth; and c. sealing the protected teeth.

2. A method of protecting teeth from decay comprising the steps of: a. etching the teeth; and b. applying one or more self-sealing protective substances to the etched teeth.

3. The method of claims 1 or 2, wherein the protective substance further includes at least one colorant material for changing the color of the teeth.

4. The method of Claim 1 or 2, wherein the protective substance comprises a polymer material.

5. The method of Claim 1 or 2, wherein the protective substance comprises a ceramic material.

6. A method of protecting teeth from decay comprising the steps of: a. the dental tissue is etched and dried; b. a protective polymer or ceramic material is applied to the etched dental tissue; and c. a laser beam or flame is used to melt the protective material into each tooth. AMENDED CLAIMS [received by the International Bureau on 9 December 1999 (09.12.99); original claims 1-6 replaced by new claims 1-7 (1 page)]

1. A method of protecting a tooth from decay_/ restoring a tooth or painting a tooth, comprising the steps of:

a. etching at least one section of said tooth; b. drying said etched tooth? c. coating said etched and dried tooth sections with one or more protective and/or restorative preformed polymeric or nαn-hydroxyapatite ceramic substances, wherein said substances may alβo contain a colorant material; and, d. sealing said etched, dried and coated tooth.

2. The method of claim 1, wherein said preformed polymeric substance is a thermoplastic.

3. The method of claim 1, wherein said coating substance is in the form of a powder.

4. The method of claim 1, wherein said coating is applied by spraying or electrophoresis.

5. The method of claim 1, wherein said sealing is produced by a heat source.

6. The method of claim 4, wherein said heat source is selected from the group consisting of a laser, a flame and a hot air stream.

7. The method of claim 1, wherein said coating is self- sealing. STATEMENT UNDER ARTICLE 19 (1)

Th^e elements in substitute claim 1 that distinguish over the Ferrace reference are: ⁽i) the claimed invention uses a preformed polymeric coating ⁽Ferrace produces a polymer only in situ _; and (ii⁾ the claimed invention has an option of a colorant in the coating, whereas Ferrace does not mention coloring.

The ^elements in substitute claim 1 that diεtinguishe over the ^St^ewart reference are: ⁽i) the claimed invention specifically excludes hydroxyapatite, whereas Stewart's coating is limited to hydroxyapatite^; and ⁽ii⁾ Stewart also does not mention a colorant.