Source: http://www.google.com/patents/US4454258?dq=6,250,774
Timestamp: 2017-03-25 13:57:36
Document Index: 32852155

Matched Legal Cases: ['Application No. 54', 'art/100', 'art/100', 'art/200', 'art/200', 'art/200', 'art/200']

Patent US4454258 - Resin-forming material, implant material and compositions for restorative ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsResin-forming material suitable for medical or dental use comprising tetramethylolmethane tri- or tetracrylate or tetramethylolmethane tri- or tetramethacrylate; and implant material suitable for medical or dental use comprising nitride of at least one member of metal selected from the group consisting...http://www.google.com/patents/US4454258?utm_source=gb-gplus-sharePatent US4454258 - Resin-forming material, implant material and compositions for restorative material suitable for medical or dental useAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS4454258 APublication typeGrantApplication numberUS 06/340,689Publication dateJun 12, 1984Filing dateJan 20, 1982Priority dateApr 11, 1979Fee statusPaidAlso published asDE3069819D1, EP0017936A2, EP0017936A3, EP0017936B1, EP0092260A1, EP0092260B1, US4327014, US4440878Publication number06340689, 340689, US 4454258 A, US 4454258A, US-A-4454258, US4454258 A, US4454258AInventorsHaruyuki Kawahara, Teruo Makita, Shozo Kudo, Takashi FunakoshiOriginal AssigneeKanebo Ltd.Export CitationBiBTeX, EndNote, RefManPatent Citations (5), Referenced by (17), Classifications (24), Legal Events (3) External Links: USPTO, USPTO Assignment, EspacenetResin-forming material, implant material and compositions for restorative material suitable for medical or dental use
US 4454258 AAbstract
1. A composition of matter, especially useful as a dental filling material, consisting essentially of:(A) from about 50 to about 95% by weight of finely divided, inorganic filler having a Moh's hardness of at least 5 and which filler is safe and effective for use in a dental filling in the human body, and (B) from about 50 to about 5% by weight of polymerizable monomer component capable of polymerizing to form a binder resin, wherein said monomer component consists essentially of(1) from 60 to 100% by weight of a mixture consisting of (a) from 30 to 95% by weight of first monomer having the formula (II) ##STR11## and (b) from 5 to 70% by weight of second monomer having the formula (III) ##STR12## wherein R1, R2, R3 and R4, which are the same or different, are hydrogen, methyl, ethyl, n-propyl or iso-propyl, and (2) up to 40% by weight of at least one, third polymerizable monomer which is different from said first and second polymerizable monomers and is suitable for use as a resin-forming monomer for dental filling materials. 2. A composition of matter according to claim 1, in which said mixture consists of 40 to 80% by weight of said first monomer and 20 to 60% by weight of said second monomer.
3. A composition of matter according to claim 1, in which said mixture consists of 45-70% by weight of said first monomer and 30-55% by weight of said second monomer.
4. A composition of matter according to claim 1, claim 2 or claim 3, in which R1, R2, R3 and R4 are hydrogen or methyl.
5. A composition of matter according to claim 1, claim 2 or claim 3, in which said first monomer consists essentially of tetramethylolmethane triacrylate, tetramethylolmethane trimethacrylate or a mixture thereof.
6. A composition of matter according to claim 5, in which said second monomer consists essentially of tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate or a mixture thereof.
7. A composition of matter according to claim 1, in which said mixture comprises at least 70% by weight of said monomer component (B).
8. A composition of matter according to claim 1, in the form of two pastes, one paste consisting essentially of a mixture of (A), (B) and an activator for activating polymerization of (B), and the second paste consisting essentially of a mixture of (A), (B) and a catalyst for catalyzing polymerization of (B).
9. A composition of matter according to claim 1, comprising about 70 to about 90% (A) and about 30 to about 10% of (B).
10. A composition of matter according to claim 1 in which said filler has a particle diameter of 50 microns or less and is selected from the group consisting of α-SiO2, Al2 O3, ZrO2 and ZrSiO4.
11. A composition of matter according to claim 10 in which said filler is coated with a keying agent selected from the group consisting of silicon-containing organic compounds having at least three alkoxy groups and having, as a terminal group, a monoolefinic hydrocarbon group, a primary amino group or an epoxy group.
12. A composition of matter according to claim 10 in which said filler is coated with a keying agent selected from the group consisting of α-methacryloxypropyltrimethoxysilane or vinyltriethoxysilane.
13. A composition of matter, especially useful as a dental filling material, consisting essentially of:(A) from about 50 to about 95% by weight of finely divided, inorganic filler having a Moh's hardness of at least 5 and which filler is safe and effective for use in a dental filling in the human body, said filler being selected from the group consisting of α-SiO2, Al2 O3, ZrO2 and ZrSiO4, and (B) from about 50 to about 5% by weight of polymerizable monomer component capable of polymerizing to form a binder resin, wherein said monomer component consists essentially of(1) from 60 to 100% by weight of a mixture consisting of (a) from 30 to 95% by weight of first monomer having the formula (II) ##STR13## and (b) from 5 to 70% by weight of second monomer having the formula (III) ##STR14## wherein R1, R2, R3 and R4, which are the same or different, are hydrogen or methyl, (2) up to 40% by weight of at least one, third polymerizable monomer which is different from said first and second polymerizable monomers and is suitable for use as a resin-forming monomer for dental filling materials, said third polymerizable monomer being selected from the group consisting of bismethacryloxyethoxydiphenylpropane, bisphenol A diglycidyl methacrylate, bisphenol A dimethacrylate, neopentylglycol dimethacrylate, triethyleneglycol dimethacrylate and trimethylolpropane triacrylate. 14. A composition of matter, especially useful as a dental filling material, consisting essentially of:(A) from about 70 to about 95% by weight of finely divided, inorganic filler having a Moh's hardness of at least 5 and which filler is safe and effective for use in a dental filling in the human body, said filler being selected from the group consisting of α-SiO2 and Al2 O3, and (B) from about 30 to about 5% by weight of polymerizable monomer component capable of polymerizing to form a binder resin, wherein said monomer component consists essentially of (a) from 30 to 70% by weight of first monomer selected from the group consisting of tetramethylolmethane triacrylate and tetramethylolmethane trimethacrylate, and (b) from 30 to 70% by weight of second monomer selected from the group consisting of tetramethylolmethane tetraacrylate and tetramethylolmethane tetramethacrylate. 15. A composition of matter according to claim 1 in which said third polymerizable monomer is selected from the group consisting of (1) polycarbinol polymethacrylates, (2) a monomer having the formula ##STR15## wherein R is hydrogen or methyl, X is alkylidene or --SO2 --, and Y is oxyalkylene having from 2 to 5 carbon atoms or alkylidene having 1 to 5 carbon atoms, (3) a monomer having the formula ##STR16## wherein R5 is CH3 --, CH3 CH2 -- or CH3 CH2 CH2 --, and R6 is H or --CH3, (4) a monomer having the formula ##STR17## wherein R7 is hydrogen or methyl, R8 is alkylene and R9 is a divalent hydrocarbon radical, (5) a monomer having the formula ##STR18## (6) neopentylglycol dimethacrylate and (7) triethyleneglycol dimethacrylate.
This is a continuation, division of application Ser. No. 138,814, filed Apr. 9, 1980, now U.S. Pat. No. 4,327,014.
The present invention relates to resin-forming material suitable for medical or dental use, and more particularly, to resin-forming material applicable in the field of repairing bones, and teeth is extremely excellent in physical properties, such as hardness, compressive strength, abrasion resistance and so on, as well as in bonding to the hard tissue of the human body.
As a reason why the Bis-GMA type composite resin is poor in the bonding property to teeth, it can be mentioned that because of the joint use of a great deal of inorganic filler, in addition to the somewhat poor bondability to teeth of Bis-GMA, the viscosity of the composite resin is increased, resulting in a poor wettability on the tooth surface.
Compounds represented by the said formula (I) divide broadly into two classes, one is compounds represented by the following formula (II) and the other is compounds represented by the following formula (III). ##STR3## wherein R1, R2 and R3 are as defined in the formula (I). ##STR4## wherein R1, R2, R3 and R4 are as defined in the formula (I).
(2) O-70% by weight of at least one member of compounds represented by the following formula (III): ##STR6## wherein R1, R2, R3 and R4 are as defined in the formula (I).
The compound of the said formula (II) is excellent in bonding to the hard tissue of the human body caused by the effect of the four methylol groups and by using such compound of the formula (II) and compound of the formula (III). In combination, in particular, a resin for medical or dental use can be advantageously formed which is excellent in bonding to the hard tissue of the human body as well as in the compressive strength.
Furthermore, the compounds of the formula (II) and/or formula (III) can be used in combination with any inorganic fillers for medical or dental use which are non-noxious to the human body and have a great hardness, such as powdered quartz, powdered glass, glass beads, powdered aluminum oxide, borosilicate glass, barium glass, hydroxy apatite and alumino silicate, in addition to the catalyst and activator. These inorganic fillers, although it differs according to use, should preferably have a Mohs' scale of hardness of at least 5 and preferably, at least 6. In this case, however, the physical properties, as a material for medical or dental use, are much better if the resin-forming material is used in combination with the hereinafter-described specified metal nitride discovered anew by the instant inventors. The said inorganic filler should preferably account for 50-95% by weight, preferably 50-90% by weight, and most preferably 70-90% by weight, based on the total amount of the composition of the filler and the resin-forming compound (monomer) such as compound of the formula (II) or (III).
If the inorganic filler is pretreated with a keying agent, such as 7-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane and so forth, the bond between the formed resin and the inorganic filler will be intensified and the physical properties as a material for medical or dental use will be further improved.
The monomer of the present invention can also be polymerized and cured by irradiation of ultraviolet rays. In this case it is not necessary to formulate the composition into the said two-liquid form and it is preferred to use a photosensitizer in the amount of 0.1-10% by weight based on the total weight of the polymerizable monomers. As the photosensitizer, there can be cited, for instance, carbonyl compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, acetoin, benzophenone, p-chlorobenzophenone, p-methoxybenzophenone and so on, sulphur compounds, such as tetramethylthiuranium monosulphide, tetramethylthiuranium disulphide and so on, azo compounds, such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile and so on, peroxides compounds, such as benzoyl peroxide, tertiary butyl peroxide and so on, etc.
In the case of using such material in the restoration of the hard tissue of the human body, such as teeth and bones, the said material possesses sufficient bonding to the hard tissue, but it is also effective to apply the said material after precoating the hard tissue with a bonding agent in ordinary use, such as 2-hydroxyethylmethacrylate and so on, for the purpose of improving the bonding to the hard tissue. As the said bonding agent, the subject matter of another co-pending Patent Application Ser. No. 138,815, filed Apr. 9, 1980, claiming the priority based on Japanese Patent Application No. 54-44751, discovered by the instant inventors, can by very effectively used, which bonding agent consists predominantly of a composition comprising 50-99.5% by weight of polymerizable acrylate esters and/or methacrylate esters having hydrophilic groups comprising carboxyl, epoxy, amino or hydroxyl, and 0.5-50% by weight of at least one member of organic metal compounds selected from the group consisting of alkoxy-containing titanium compounds and silicon compounds.
Further, the resin-forming material of the present invention can be advantageously used, in medical or dental use, not only as material for bone cement and artificial bones in the orthopedic surgery and restorative surgery field, but also as a restorative material for crown bridges, core material for crowns, dental cement, filling material, cavity lining material, root canal filling material and so on, in the operative dentistry and prosthetic dentistry field in particular.
As typical examples of composite resin-forming material obtained from a combination of conventional resin-forming material and inorgaic filler, there can be cited, for instance, bone cement and artificial bone material in the orthopedic surgery and restorative surgery field or restorative material for crown bridges, core material for crowns, dental cement, filling material, cavity lining material, root canal filling material and so forth in the operative dentistry and prosthetic dentistry field.
In the case of curing by applying the conventional composite resin-forming material for dental use to molars in the operative dentistry and prosthetic dentistry field, for instance, clinical examples show that the form is lost in a short period of time because of the markedly high occlusal pressure and frictional force in the molar and that it is difficult to use it stably over a long period of time. In order to make it applicable to molars, there is demanded a composite resin for dental use having higher mechanical strengths, such as compressive strength, abrasion resistance, impact resistant function and so on. Conventionally, metal material and dental amalgam are mainly used in the molars, but the metal material presents a problem in the point of convenience, whereas the dental amalgam, on the other hand, leaves a problem to solve in the point of toxicity and of recurrent caries caused from the property inherent in the amalgam and, for these reasons, it is not satisfactory material.
Of conventionally known fillers, however, powdered alumina filler shows exceptionally high hardness and abrasion resistance. Alumina is a material which is excellent in abrasion resistance having a Mohs' hardness of 9, but because of inferior bonding to the resin for medical or dental use a, satisfactory resin-forming material for medical or dental use cannot be obtained, even if it is subjected to various surface treatments.
The said metal nitride of the present invention can fully exhibit this effect even if it is used in combination with materials applicable to the orthopedic surgery and restorative surgery field or the operative dentistry and prosthetic dentistry field, other than the resin-forming material, such as conventionally known zinc phosphate cement, and silicate cement.
The restorative implant material for the human body of the present invention should preferably be in powder form, in particular, and its particle diameter should preferably fall in the range of 50 microns or less and 0.1-50 microns, in particular. If the particle size is less than 0.1 micron, in some cases, the paste comprising the composite resin-forming material in an uncured condition may overly increase in viscosity. If it is in excess of 50 microns, on the contrary, the resin and filler tend to readily separate from each other after being mixed together. In some cases, it is practically rendered difficult to operate. The implant material material of the present invention should have Mohs' hardness of 7 or more, but preferably it should have Mohs' hardness of 9 or more. If the hardness is less than 7, the purpose of the present invention cannot be achieved in the aspect of physical properties obtained when using it as composite substance mixed with the resin. In this connection, of implant materials of the present invention, as those which have a Mohs' hardness of 9 or more there can be cited BN, Si3 N4 and VN. Further, aluminum nitride is somewhat lower in Mohs' hardness than the said nitrides, but those with Mohs' hardness of about 8 can be obtained with relative ease and hence, aluminum nitride is preferable.
In the case of using the filler for medical of dental use belonging to the present invention by mixing same with the resin-forming material (monomer) for medical or dental use to form composite resin-forming material for medical or dental use, for proportions in which it is incorporated, the said filler should preferably be set at 50-95% by weight, and 70-90% by weight, in particular, and the resin-forming material for medical or dental use at 5-40% by weight, and 10-25% by weight, in particular. If the filler is used in an amount of less than 50% by weight, the composite resin obtained will be lowered in physical property values, such as compressive strength, abrasion strength and so on, whereas if it is in excess of 95% by weight, the composite resin paste in an uncured condition will be higher in viscosity and inferior in operation.
(4) Urethane diacrylate type monomers represented by the following formula (6) as disclosed in U.S. Pat. Nos., 3,825,518; 3,862,920, etc.: ##STR9## wherein R1 is a hydrogen atom or a methyl group, R2 is an alkylene group and R3 is a divalent hydrocarbon radical.
(5) Monomers of the type represented by the following formula (7) as disclosed in the U.S. Pat. Nos. 3,853,962, etc.: ##STR10##
(6) Neopentylglycol dimethacrylate (NPG) type monomers as disclosed in Japanese Laid-Open Patent Application (JAPAN KOKAI) No. 48-90332.
The method of compounding of at least one member of compounds (monomer) of the present invention represented by the formulae (I), (II) and (III) and the said metal nitride filler as well as the preparation and curing of their paste, it is the same as described for the case of compounding the said compound (monomer) and conventional inorganic filler.
For a method for use of such composite resin-forming material based on practical use, for instance, a paste-like substance (paste A) comprising the filler belonging to the present invention, preferably said powdery filler, resin-forming material (monomer) and an activator and a paste-like substance (paste B) comprising the filler belonging to the present invention, resin-forming material (monomer) and a catalyst could be prepared in advance to, and these two pastes can be mixed together when used by doctors or dentists. It can be used with good efficiency since the resin is cured with the polymerization initiated upon their mixing.
In such cases, it is advantageous to use, as the filler for the paste A, the metal nitride of the present invention and to use as the filler for the paste B an inorganic filler capable of forming a stable paste even if it is maintained in contact with a conventional known catalyst, such as powdered α-quartz, in such a manner that the metal nitride in the paste A should account for at least 50% by weight, preferably at least 70% by weight, and more preferably at least 80% by weight, based on the total amount of fillers including the inorganic filler in the paste B. By combining together both pastes in such a manner, a cured composite resin composition is formed therefrom which is stable to storage and extremely excellent in mechanical characteristics.
The composite resin composition which underwent a curing treatment, using the filler for medical or dental use belonging to the present invention shows excellent mechanical strengths, such as extremely high compressive strength, abrasion resistance, impact resistance and so on, and it is readily applicable according to usage to every field of medical use, such as the orthopedic surgery and restorative surgery field or the operative dentistry and prosthetic dentistry field and so on.
In this connection, in the examples the method for the preparation of composite resin and methods for the measurement of compressive strength, abrasion, water sorption, hardness, toothbrush abrasion, coloring, linear thermal expansion coefficient, and tensile strength follow the hereinafter-described procedures.
(1)-2. Preparative of monomer paste:
Cured composite resin loaded in and taken out from the mould by following the procedures set forth in section of "(2) Measurement of compressive strength" was used as specimens for measurement of abrasion loss. The specimens were dried in a hot air dryer held at 100° C. for 24 hours and then cooled in a desiccator for one hour and weighed. The specimens were placed in a cylindrical metal ball mill with an inner capacity of 500 ml and inner diameter of 10 cm and simultaneously, 20 stainless steel balls of 1 mm diameter and 200 ml of polishing paste prepared by adding 900 parts by weight of distilled water to 200 parts by weight of powdered Si3 N4 passing through a 325 mesh sieve, as a polishing material, were loaded, the ball mill was sealed and then rotated at a rate of 100 r.p.m. for 78 hours. After it was finished, the specimens were washed with water, dried in the hot air dryer held at 100° C. for 24 hours and cooled in the desiccator for another one hour and weighed. Abrasion loss was calculated according to the following equation: ##EQU1##
Composite resin was cured to prepare a disk specimen 20 mm across and 1 mm thick. The specimen was left to stand in a constant temperature dryer held at 37° C., then placed in the desiccator, cooled for one hour and weighed. Value when a constant quantity was reached with repetition of this operation was set as dry weight. Then, the specimen was immersed in water held at 37° C. for 7 days, then taken out, the water on the surface was wiped off with soft gauze and the specimen was weighed to determine the weight of water absorbed. The amount of water absorbed was calculated by the following equation: ##EQU2##
Composite resin was cured to prepare and fix a columnar specimen 13 mm across and 4 mm high. A commercially available toothbrush with a load of 200 g was applied to the flat portion of the specimen and this toothbrush was reciprocated at a stroke of 2 reciprocations/second to polish the specimen surface. In the meantime a solution prepared by diluting 150 g of commercially available toothpaste to 1/2 with water was continuously added dropwise. After 8 hours the specimen was washed with water, dried and weighed. Rate of toothbrush abrasion loss was calculated by the following equation. ##EQU3##
Disk test pieces 13 mm across and 4 mm high were surface-polished with No. 800 emery paper and then immersed in commercially available aqueous coffee solution (solution obtained by dissolving 2.5 g of powdered coffee in 100 ml of water) at 37° C. for 4 days. The specimens were washed with water, dried and then their color was measured by means of a colorimeter, a product of Nippon Denshoku Kogyo company, to read the values L, a and b. Likewise, the values LO, aO and bO, which were the measured color values of the specimen surfaces prior to immersing into the coffee solution, were read, the degree of discoloration ΔE was calculated by the following equation and ΔE was set as a basis for coloring. The greater the ΔE, the greater is is the value of the degree of discoloration. This test was also effected on the surface of the unpolished specimen. ##EQU4##
(8) Measurement of linear thermal expansion coefficient:
Measurement was made of the linear thermal expansion coefficient of the specimens so prepared by means of linear thermal expansion measuring instrument, a product of Rigsku Denki company. In making the measurements the heating and temperature raising rate was set at 5° C./min.
Silane-treated α-SiO2 was prepared following the procedure for the preparation of filler in section (1)-1. Then, using mixed monomers, as the monomer component, prepared by mixing tetramethylolmethane triacrylate (TMM-3A) and tetramethylolmethane tetracrylate (TMM-4A) in proportions of 55:45 (by weight ratio), silane-treated α-SiO2, catalyst and activator, the mixed monomer was divided into two equal parts for the preparation of Paste Al-1 and Paste Bl-1 of the following compositions according to the procedure for the preparation of monomer paste in section (1)-2.
Paste Al-1 and Paste Bl-1 so prepared were taken each in equal amounts, mixed and kneaded together or kneading paper at room temperature for 30 seconds whereby a composite resin was prepared.
______________________________________                    Part                    by weight______________________________________Paste A1-2Bisphenol A diglycidyl methacrylate (Bis-GMA)                      80Triethyleneglycol dimethacrylate (TEGDMA)                      20Silane treated &#945;-SiO2                      300N,N--bis(2-hydroxyethyl)-4-methylaniline                      0.8Paste B1-2Bisphenol A diglycidyl methacrylate (Bis-GMA)                      80Triethyleneglycol dimethacrylate (TEGDMA)                      20Silane treated &#945;-SiO2                      300Benzoyl peroxide           0.8Paste A1-3Bismethacryloxyethoxydiphenylpropane (Bis-MEPP)                      100Silane treated &#945;-SiO2                      300N,N--bis(2-hydroxyethyl)-4-methylaniline                      1.0Paste B1-3Bismethacryloxyethoxydiphenylpropane (Bis-MEPP)                      100Silane treated &#945;-SiO2                      300Benzoyl peroxide           1.0Paste A1-4Neopentylglycol dimethacrylate (NPGDMA)                      100Silane treated &#945;-SiO2                      300N,N--bis(2-hydroxyethyl)-4-methylaniline                      2.0Paste B1-4Neopentylglycol dimethacrylate (NPG-DMA)                      100Silane treated &#945;-SiO2                      300Benzoyl peroxide           2.0Paste A1-5Trimethylolpropane triacrylate (TMPT)                      100Silane treated &#945;-SiO2                      300N,N--bis(2-hydroxyethyl)-4-methylaniline                      1.5Paste B1-5Trimethylolpropane triacrylate (TMPT)                      100Silane treated &#945;-SiO2                      300Benzoyl peroxide           1.5______________________________________
TABLE 1__________________________________________________________________________                               Bonding strength            Amount of                   Compressive                          Abrasion                               (kg/cm2)            filler used*2                   strength                          loss Bovine                                   BovineMonomer composition tested*1            (&#945;-SiO2)                   (kg/cm2)                          (cm3)                               enamel                                   dentin__________________________________________________________________________1 TMM-3A(55)/TMM-4A(45)            75 wt. %                   2,570  0.49 60-70                                   15-202*  Bis-GMA(80)/TEG(20)            "      2,100  0.62 30-40                                   0-53*  Bis-MEPP       "      2,290  0.59 --  --4*  MPGDMA         "      2,180  0.57 --  --5*  TMPT           "      2,440  0.62  5-10                                   0__________________________________________________________________________ (NOTE) *1 In the case of mixed monomer, parentheses () following upon a short form for each monomer indicates a weight ratio of the monomer. (The same will apply to the respective tables in the hereinafterdescribed Examples.) *2 The amount of filler used indicates a percentage by weight of the filler based on the total amount of the monomer and the filler. (The same will apply to the respective tables in the hereinafterdescribed Examples. *Indicates Control and the same will apply to the respective tables in th hereinafterdescribed Examples.
It follows from the above table that the composite resin (Run No. 1) comprising the monomer composition of TMM-3A(55)/TMM-4(45) belonging to the present invention should be excellent in compressive strength, abrasion loss and bonding strength as compared to the composite resins of Run Nos. 2-5 comprising the monomer compositions of Bis-GMA/TEG, Bis-MEPP, MPGDMA or TMPT conventionally known as resin-forming monomers for medical or dental use.
A fresh anterior bovine tooth implanted in a square rod made of acryl resin was polished and leveled with emery paper, and further polished and finished with No. 800 emery paper for the formation of a bonding surface whereby there was prepared a testpiece of material for the bonding test with the bovine enamel. This bonding testpiece was stored in water. It was taken out from the water immediately before the measurement was made. The surface of the testpiece was well wiped off and etched with 50% aqueous phosphate solution for one minute. It was successfully washed with water and air dried using a weak air stream. Using the testpiece of material for the bonding test with the bovine enamel so prepared, its bonding strength was measured following the same procedure as in the case of the measurement of the bonding strength with the bovine dentin and the measured values were indicated in the same manner.
Using, as the monomer, mixed monomers prepared by mixing TMM-3A, and TMM-4A in various such proportions as indicated in Table 2, Paste A 2 and Paste B 2 of following compositions were prepared. Paste A 2 and Paste B 2 were mixed and kneaded together following the same procedure as set forth in Example 1 whereby composite resins were prepared.
______________________________________               Part by weight______________________________________Paste A 2TMM-3A                      100    in totalTMM-4ASilane treated &#945;-SiO2                  300N,N--bis(2-hydroxyethyl)-4-methylaniline                  0.1Paste B 2TMM-3A                      100    in totalTMM-4ASilane treated &#945;-SiO2                  300Benzoyl peroxide       1.0______________________________________
TABLE 2__________________________________________________________________________Monomer     Amount of             Compressive                    Abrasion                         Amount of                                 Bonding strength composition       filler used             strength                    loss water sorption                                 (kg/cm2)TMM-3A TMM-4A       (&#945;-SiO2)             (kg/cm2)                    (cm3)                         (mg/cm2)                                 (to bovine dentin)__________________________________________________________________________1 100   0   75 wt. %             2,410  0.55 0.38    15-202 90   10   "     2,480  0.54 0.36    15-203 70   30   "     2,490  0.50 0.30    10-154 50   50   "     2,520  0.48 0.30    10-155 30   70   "     2,550  0.48 0.33     5-106 10   90   "     2,500  0.52 0.33     5-107  0   100  "     2,450  0.53 0.37    0-5__________________________________________________________________________
TABLE 3__________________________________________________________________________                    Amount of                          Amount of                    activator                          catalyst           Filler   (part/100                          (part/100                                Compressive                                       Abrasion               Amount                    parts of                          parts of                                strength                                       lossMonomer composition           Kind               (wt %)                    monomer)                          monomer)                                (kg/cm2)                                       (cm3)__________________________________________________________________________1 TMM-3A(55)/TMM-4A(45)           Al2 O3               75   0.8   1.0   2,570  0.472 "             ZrO2               70   1.0   1.5   2,500  0.473 "             ZrSiO4               75               2,700  0.434*  Bis-GMA(80)/TEG(20)           Al2 O3               75   0.8   1.0   2,100  0.605*  "             ZrO2               70               2,040  0.586*  "             ZrSiO4               75               2,200  0.55__________________________________________________________________________ *indicates Control.
Using, as the composite resin-forming monomer, TMM-3A(55)/TMM-4A(45) or tetramethylolmethane trimethacrylate (TMM-3M)/(55)/tetramethylolmethane tetramethacrylate (45) Paste A 4-1, B 4-1 and Paste A 4-2 and B 4-2 of following compositions were prepared. Following the same procedure as that of Example 1 these pastes were mixed for the preparation of composite resins.
______________________________________                    Part                    by weight______________________________________Paste A 4-1TMM-3A                     55TMM-4A                     45Silane treated &#945;-SiO2                      456N,N--bis(2-hydroxyethyl)-4-methylaniline                      0.8Paste B 4-1TMM-3A                     55TMM-4A                     45Silane treated &#945;-SiO2                      456Benzoyl peroxide           1.0Paste A 4-2Tetramethylolmethane trimethacrylate (TMM-3M)                      55Tetramethylolmethane tetramethacrylate (TMM-4M)                      45Silane treated &#945;-SiO2                      456N,N--bis(2-hydroxyethyl)-4-methylaniline                      0.8Paste B 4-2Tetramethylolmethane trimethacrylate (TMM-3M)                      55Tetramethylolmethane tetramethacrylate (TMM-4M)                      45Silane treated &#945;-SiO2                      456Benzoyl peroxide           1.0______________________________________
Using, as the composite resin-forming monomer, mixed monomer comprising a combination of TMM-3A and TMM-4A belonging to the present invention and conventionally known dental resin-forming monomers Paste A 5-1, B 5-1 and Paste A 5-2 and B 5-2 were prepared. Following the same procedure as that of Example 1 these pastes were mixed for the preparation of composite resins.
TABLE 5______________________________________                       Com-     Ab-             Amount of pressive rasion             filler used                       strength lossMonomer composition             (&#945;-SiO2)                       (kg/cm2)                                (cm3)______________________________________1   TMM-3A(50)/TMM-4A(30)/                 82 wt %   2,860  0.43    Bis-MEPP(13)/NPG(7)2   TMM-4A(80)/Bis-GMA(10)/                 "         2,840  0.41    NPG(10)______________________________________
It is noticed from the above table that the cured composite resins using mixed monomers prepared by mixing about 20% by weight of conventionally known dental resin-forming monomers, such as Bis-MEPP, NPG, Bis-GMA and so on, to the composite resin-forming monomer belonging to the present invention should also be valuable as dental material in terms of their physical property values. They did not give rise to any compatability problem.
______________________________________               Part by weight______________________________________Paste ABis-GMA(80)/TEGDMA(20)                 100N,N--bis-(2-hydroxyethyl)-4-methylaniline                 2Silane treated inorganic filler                 400Paste BBis-GMA(80)/TEGDMA(20)                 100Benzoyl peroxide      2.5BHT                   0.25Silane treated inorganic filler                 400______________________________________
TABLE 6__________________________________________________________________________         Filler            Compressive                                  Abrasion                     Amount*2                           strength                                  lossMonomer composition*1         Kind             Mohs' hardness                     (wt %)                           (kg/cm2)                                  (cm3)__________________________________________________________________________1 Bis-GMA(80)/TEG(20)         Si3 N4              9&lt;     80    2,750  0.272 "           AlN 7-8     "     2,570  0.333 "           BN   9&lt;     "     2,800  0.264 "           VN  9       "     2,660  0.285*  "           &#945;-SiO2             7       "     2,260  0.606*  "           Al2 O3             9       "     2,260  0.56__________________________________________________________________________ *indicates Control. (NOTE) *1 In the case of mixed monomer parentheses () following upon a shor form for each monomer indicates a weight ratio of the monomer. *2 The amount of filler used indicates a weight percentage of filler based on the total amount of the monomer and the filler.
______________________________________               Part by weight______________________________________Paste A 7-1Silane treated filler 400Bis-MEPP              100N,N--bis-(2-hydroxyethyl)-4-methylaniline                 1.0Paste B 7-1Silane treated filler 400Bis-MEPP              100Benzoyl peroxide      2.0BHT                   0.15Paste A 7-2Silane treated filler 400NPGDMA                100N,N--bis-(2-hydroxyethyl)-4-methylaniline                 2.0Paste B 7-2Silane treated filler 400NPGDMA                100Benzoyl peroxide      2.5BHT                   0.10Paste A 7-3Silane treated inorganic filler                 400TMPT                  100N,N--bis-(2-hydroxylethyl)-4-methylaniline                 1.5Paste B 7-3Silane treated inorganic filler                 400TMPT                  100Benzoyl peroxide      2.5BHT                   0.15______________________________________
TABLE 7______________________________________    Filler     Compressive                          Abrasion              Amount   strength lossMonomer    Kind    (wt %)   (kg/cm2)                                (cm3)______________________________________1   Bis-MEPP   Si3 N4                  80     2,890    0.242   NPGDMA     "       "      2,930    0.253   TMPT       "       "      3,000    0.234*  Bis-MEPP   &#945;-SiO2                  "      2,410    0.585*  NPGDMA     "       "      2,450    0.576*  TMPT       "       "      2,470    0.57______________________________________
______________________________________               Part by weight______________________________________Paste A 8Various powdery fillers                 in given amounts                 as indicated                 in Table 8TMM-3A(55)/TMM-4A(45) 100N,N--bis-(2-hydroxyethyl)-4-methylaniline                  2Paste B 8Various powdery fillers                 in given amounts                 as indicated in                 Table 8TMM-3A(55)/TMM-4A(45) 100Benzoyl peroxide      2.5BHT                   0.15______________________________________
TABLE 8__________________________________________________________________________            Filler            Compressive                                     Abrasion                        Amount                              strength                                     lossMonomer composition            Kind                Mohs' hardness                        (wt %)                              (kg/cm2)                                     (cm3)__________________________________________________________________________1  TMM-3A(55)/TMM-4A(45)            Si3 N4                 9&lt;     75    3,080  0.222  "             &#945;-SiO2                7       "     2,570  0.493  "             Al2 O3                9       "     2,570  0.474  "             Si3 N4                 9&lt;     80    3,200  0.195  "             AlN 7-8     "     2,980  0.256  "             ZrN 8-9     "     3,010  0.237  "             NbN 8       "     2,860  0.258  "             TiN 8-9     "     3,020  0.249  "             BN   9&lt;     "     3,280  0.1610 "             VN  9       "     3,140  0.20SiO2        &#945;   7             "   2,720   0.4612 "             Al2 O3                9       "     2,720  0.45__________________________________________________________________________
It is also noted there that with the cured composite resins using, as the filler, the metal nitride beloning to the present invention BN, VN and Si3 N4 with a Mohs' scale of hardness of 9 or more show exceptionally high compressive strength and abrasion resistance and that they should be suited to use as crown bridge restoratives or filling materials in molars.
TABLE 9__________________________________________________________________________                             Amount of                                   Amount of                             activator                                   catalyst                   Filler    (part/200                                   (part/200                                         Compressive                                                Abrasion                       Amount                             parts of                                   parts of                                         strength                                                lossMonomer composition     Kind                       (wt %)                             monomer)                                   monomer)                                         (kg/cm2)                                                (cm3)__________________________________________________________________________1  TMM-3A(55)/TMM-4A(45)                   SiN4                       85    2.0   2.5   3,350  0.162    "                  "   90    "     "     3,520  0.143    "                  ZrH 80    "     "     3,010  0.234    "                  TiN "     "     "     3,020  0.245  TMM-3A(44)/TMM-4A(36)/Bis-MEPP(20)                   SiN4                       "     1.0   2.0   3,220  0.17 6*   Bis-GMA(80)/TEG(20)  &#945;-SiO2                       "     2.0   2.5   2,260  0.60__________________________________________________________________________ *BHT was used in the amount of 0.15 (part/200 parts of monomer) in Run Nos. 1-5 and in the amount of 0.25 (part/200 parts of monomer) in Run No. 6.
In the comparisons of the compressive strength as well as the abrasion loss with the cured composite resin (Run No. 6) with a combination of conventionally known monomer Bis-GMA)80)/TEG(20) and known filler α-SiO2 a first glance at the above table shows that by making the composite resin-forming material by combining the monomer containing 80% or more of TMM-3A(55)/TMM-4A(45), the monomer of the present invention, with SiN4, ZrN or TiN, the metal nitride, the composite resin formed should have specifically excellent compressive strength and abrasion resistance.
When comparing the amounts in which the filler can be combined with the composite resin-forming monomer in such a range as not to give rise to the operation problem of the composite resin paste, the monomer containing 80% or more of TMM-3A(55)/TMM-4A(45), the monomer of the present invention, could be incorporated with the filler in greater amounts than the Bis-GMA(80)/TEG(20). This is conceived to be attributed to the difference in the fluid characteristics of the monomer. As is clear from a comparison between Run No. 1 and Run No. 2, because the compressive strength and abrasion resistance increase in proportion to the amount of filler used, obviously the composite resin having a higher compressive strength and abrasion resistance could be obtained when using, as the composite resin-forming material, the monomer of the present invention capable of incorporating a great deal of filler without causing trouble in the operation.
______________________________________               Part by weight______________________________________Paste A 10-1TMM-3A(55)/TMM-4A(45) 100Si3 N4      400N,N--bis-(2-hydroxyethyl)-4-methylaniline                 2Paste A 10-2TMM-3A(55)/TMM-4A(45) 100Si3 N4      400N,N--bis-(2-hydroxyethyl)-4-methylaniline                 2Paste A 10-3TMM-3A(55)/TMM-4A(45) 100Si3 N4      400N,N--bis-(2-hydroxyethyl)-4-methylaniline                 2Paste A 10-4Bis-GMA(80)/TEGDMA(20)                 100Si3 N4      400N,N--bis-(2-hydroxyethyl)-4-methylaniline                 2Paste A 10-5Bis-GMA(80)/TEGDMA(20)                 100&#945;-SiO2     400N,N--bis-(2-hydroxyethyl)-4-methylaniline                 2Paste B 10-1TMM-3A(55)/TMM-4A(45) 100&#945;-SiO2     400Benzoyl peroxide      2.5BHT                   0.15Paste B 10-2TMM-3A(55)/TMM-4A(45) 100Al2 O3      400Benzoyl peroxide      2.5BHT                   0.15Paste B 10-3TMM-3A(55)/TMM-4A(45) 100Si3 N4      400Benzoyl peroxide      2.5BHT                   0.15Paste B 10-4Bis-GMA(80)/TEGDMA(20)                 100&#945;-SiO2     400Benzoyl peroxide      2.5BHT                   0.25Paste B 10-5Bis-GMA(80)/TEGDMA(20)                 100&#945;-SiO2     400Benzoyl peroxide      2.5BHT                   0.25______________________________________
TABLE 10__________________________________________________________________________             Filler    Compressive                              Abrasion                 Amount                       strength                              lossMonomer composition             Kind                 (wt %)                       (kg/cm2)                              (cm3)__________________________________________________________________________1  TMM-3A(55)/TMM-4A(45)             Si3 N4                 40    2,960  0.33             &#945;-SiO2                 402  "              Si3 N4                 40    2,975  0.32             Al2 O3                 403  "              Si3 N4                 80    3,200  0.194  Bis-GMA(80)/TEGDMA(20)             Si3 N4                 40    2,505  0.44             &#945;-SiO2                 40 5*   "              &#945;-SiO2                 80    2,260  0.60__________________________________________________________________________
It is noted from the above table that in comparison of the composite resin (Run No. 5) with a combination of Bis-GMA(80)/TEGMA(20), the conventionally known composite resin (Run No. 4) comprising the said monomer and the known filler α-SiO2 of which one half the amount was replaced by Si3 N4, the filler of the present invention, with the cured composite resin formed by use of only a small amount of the filler of the present invention the filler is very great in the extent to which it contributes to the improvements of the compressive strength and abrasion resistance.
______________________________________               Part by weight______________________________________Paste A 11-1TMM-3A                55TMM-4A                45N,N--bis-(2-hydroxyethyl)-4-methylaniline                 0.6Silane treated Si3 N4                 400Paste B 11-1TMM-3A                55TMM-4A                45Benzoyl peroxide      0.8Silane treated Si3 N4                 400Paste A 11-2TMM-3A                55TMM-4A                45N,N--bis-(2-hydroxyethyl)-4-methylaniline                 0.6Silane treated &#945;-SiO2                 400Paste B 11-2TMM-3A                55TMM-4A                45Benzoyl peroxide      0.8Silane treated &#945;-SiO2                 400Paste A 11-3Bis-GMA               80TEGDMA                20N,N--bis(2-hydroxyethyl)-4-methylaniline                 0.6Silane treated Si3 N4                 400Paste B 11-3Bis-GMA               80TEGDMA                20Benzoyl peroxide      0.8Silane treated Si3 N4                 400Paste A 11-4Bis-GMA               80TEGDMA                20N,N--bis-(2-hydroxyethyl)-4-methylaniline                 0.6Silane treated &#945;-SiO2                 400Paste B 11-4Bis-GMA               80TEGDMA                20Benzoyl peroxide      0.8Silane treated &#945;-SiO2                 400______________________________________
TABLE 11(1)__________________________________________________________________________                                    Toothbrush                                           Amount of                                                 Linear thermal             Filler    Compressive                               Abrasion                                    abrasion                                           water expansion                 Amount                       strength                               loss loss   sorption                                                 coefficientMonomer composition             Kind                 (wt %)                       (kg/cm2)                               (cm3)                                    (wt %) (mg/cm2)                                                 (× 10-6                                                 /°C.)__________________________________________________________________________1  TMM-3A(55)/TMM-4A(45)             Si3 N4                 80    3,200   0.19 0.054  0.30  20.52  "              &#945;-SiO2                 "     2,780   0.40 0.100  0.28  26.53  Bis-GMA(80)/TEG(20)             Si3 N4                 "     2,530   0.31 0.120  0.42  26.1 4*   "              &#945;-SiO2                 "     2,260   0.60 0.215  0.42  30.0__________________________________________________________________________ *indicates Control.
TABLE 11(2)__________________________________________________________________________                                Coloring property                                           Bonding strength           Filler         Tensile                                (&#916;E) (kg/cm2)               Amount                     Knoop                          strength    Un-  Bovine enamel                                                     BovineMonomer composition           Kind               (wt %)                     hardness                          (kg/cm2)                                Polished                                      polished                                           (1) (2)   dentin__________________________________________________________________________1  TMM-3A(55)/  Si3 N4               80    81   490   2.68  4.73 60-70                                               --    10-15   TMM-4A(45)2  TMM-3A(55)/  &#945;-SiO2               "     70   470   2.21  4.92 60-70                                               100-105                                                     10-15   TMM-4A(45)3  Bis-GMA(80)/TEG(20)           Si3 N4               "     74   410   2.35  4.90 30-40                                               --    0-5 4*SiO2       &#945;   "            54  360   3.88 10.23 30-40 --   0-5__________________________________________________________________________ *indicates Control.
______________________________________                  Part by weight______________________________________Bonding agent ATMM-3A                   98Tetraisopropyltitanate   2N,N--bis-(2-hydroxyethyl)-4-methylaniline                    2Bonding agent BTMM-3A                   98Tetraisopropyltitanate   2Benzoyl peroxide         22,5-di-tert. butyl-4-methylphenol                    0.15______________________________________
TABLE 12__________________________________________________________________________                        Cell numbers              Filler    in 1 ml                  Amount                        After                             AfterMonomer composition              Kind                  (wt %)                        2 days                             4 days__________________________________________________________________________Blank --           --  --    4.6 × 104                             56 × 1041   TMM-3A(55)/TMM-4A(45)              Si3 N4                  80    3.0 × 104                             24 × 104SiO2          &#945;    "              3.2 × 104                  22 × 104 3* Bis-GMA(80)/TEGDMA(20)              &#945;-SiO2                  75    2.3 × 104                             19 × 104__________________________________________________________________________ *indicates Control.
Clinical observations were conducted by the following procedure. Caries of a patient was removed by a dental drill and it was cleansed with water and the enamel of the caries was immediately coated by a brush with 40% phasphate etching solution. After one minute it was cleansed with water and further dried in an air stream for the formation of a clean enamel surface.
It follows from these clinical test results that the composite resin with a combination of the composite resin-forming monomer belonging to the present invention and the metal nitride powdery filler of the present invention can fully withstand practical use even if it is applied to molars and it is superior in performance to the widely used dental amalgam restoratives as the conventional molar restorative filling material.
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