CA1299311C - Root canal filler for dental use - Google Patents
Root canal filler for dental useInfo
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- CA1299311C CA1299311C CA000532582A CA532582A CA1299311C CA 1299311 C CA1299311 C CA 1299311C CA 000532582 A CA000532582 A CA 000532582A CA 532582 A CA532582 A CA 532582A CA 1299311 C CA1299311 C CA 1299311C
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- powdery
- acid
- weight
- root canal
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Abstract
ABSTRACT OF THE DISCLOSURE
A root canal filling material for dental use compris-ing a powdery agent including.alpha.-TCP (.alpha. -Ca3(P04)2 ; alpha type tricalcium phosphate), hydroxyapatite, X-ray contrast media and at least one of antibacterial agent or pharma-ceutical agent, and a polyacrylic acid type liquld agent capable of reacting with the powdery agent into a coagu-lated hardened product in an oral circumstance.
The new biomaterial can be hardened to an adequate strength in a short but appropriate period of time in oral circumstances while giving no biostimulation and securing biocompatibility when used for root canal filling.
A root canal filling material for dental use compris-ing a powdery agent including.alpha.-TCP (.alpha. -Ca3(P04)2 ; alpha type tricalcium phosphate), hydroxyapatite, X-ray contrast media and at least one of antibacterial agent or pharma-ceutical agent, and a polyacrylic acid type liquld agent capable of reacting with the powdery agent into a coagu-lated hardened product in an oral circumstance.
The new biomaterial can be hardened to an adequate strength in a short but appropriate period of time in oral circumstances while giving no biostimulation and securing biocompatibility when used for root canal filling.
Description
~2~3~
ROOT CANAL FIL.LER FOR DENTAL USE
BACKGROUND OF THE INVENTION
Field of the Invention This invention concerns a root canal filling material for dental useO
Description of the Prior Art So-called powder/liquid type dental compositions using powdery agents and liquid agents have been applied as various kind of products in many application fields such as, for examples, tooth reconstructing material, pulp capping material, root canal filling material and various kinds of dental cements (for joining, filling, capping, lining, backing, etc.).
While these materials are mainly composed Or inorganic or synthetic resin type materials as the main ingredient, there has been a problem that they show deleterious effects on biobodies. That is, conventional dental compositions are more or less stimulative to biobodies and, since they are made Or materials different from those of the biobody, their biocompatibility is poor.
Thus, there has been a difficulty in using conventional dental compositions as root canal filling material because Or their stimula-ting nature to the biobody and, accordingly t 12~31~ 69065-23 it has been desired for the development of such root canal filling material for dental use that has no stimulating nature and can be hardened firmly in a relatively short pexiod of time with an appropriate time margin for the operation.
SU~D~ARY OF THE INVENTION
The object of this invention is to provide root canal filling material for dental use that can be hardened to an adequate strength in a relatively short period of time with an appropriate time margin for the operation, while giving no stimulations and securing biocompatibility.
This invention provides a root canal filling material for dental use, comprising:
(A) a powdery agent consisting essentially of (i) from 10 to 90% by weight (based on the powdery agent) of alpha tricalcium phosphate (~-Ca3(PO4)2), (ii) from 9 to 70% by weight lbased on the powdery agent) of hydroxyapatite and (iii) from 1 to 35% by weight (based on the powdery agent~ of a combination of an X-ray contrast medium and a pharmaceutical agent, and ~B) a liquid agent consisting essentially of (i) from 10 to 40% by weight (based on the liquid agent) of a homo~
polymer of acrylic acid or a copolymer thereof with another unsaturated carboxylic acid copolymerizable with acrylic acid, (ii) from 35 to 88.5% by weight (based on the liquid agent) of purified water, (iii) from 1 to 15% by weight of an organic or inorganic non-toxic acid and (iv) from 0.5 to 10% by weight (based on the liquid agent) of at least one member selected from the .
~9~ 69065~23 group consisting of [a] water-soluble calcium, aluminum, sodium or magnesium salts, [b] surface active agentsl [c~ p~ controllers and [d] viscosity improvers, wherein the liquid agent is capable of reacting with the said powdery agent and forming a coagulated hardened product in an oral circumstance.
~ powdery agent including ~-TCP (~-Ca3(PO4)2):
alpha type tricalcium phosphate), hydroxyapatite, an X-ray con-trast medium and a pharmaceutical agent is kneaded with a poly-acrylic acid type liquid agent capable of reacting with the powdery agent in an oral circumstance to form a coagulated hardened product.
The most prominent feature of this invention is to us~ ~-TCP as an ingredient of the powdery agent.
~s has been well-known, the main constituent ingre-dient for inorganic components such as too-th and bone is HAP (Cal0(PO4)6(OH)2 : hydroxyapatite) and inorganic biomaterails similar thereto have been noted in recent years.
Such inorganic biomaterials are favorable because oE
their compatibility with biobody tissues such as induction of formation and binding of newly formed bones at the interface with hard tissues in addition to their in-vivo stability. They are classified into bioinert materials such as A12O3 and bioactive materials such as HAP depending on the activity with the biobody tissue interface. ~-TCP used in this invention is a HAP precur-sor having a feature of biodegradability like that of low crystal-line HAP, but it is a biocompatible inorganic material which '' - . ~
~Zg~3~ 69065-23 has chemical activity as well and can be expected to be con-verted into HAP in the presence of water. The ~-TCP can be converted into a firm coagulated hardened product in a short period of time withi.n an oral cavity when kneaded with a poly-acrylic acid type liquid agent. It is widely known that the polyacrylic type copolymer has generally been used as the liquid ingredient for dental cement compositions.
While biocompatible inorganic materials include HAP, 3a -, . v ~
~L29~3~1 ~-TCP and the like in addition to ~ -TCP used in this invention, but both of HAP and ~-TCP are poor in the chemical activity and di~icult to be hardened ln the oral circumstance. C~-TCP is used as the ingredient in -this sense and a novel root canal filling material not found in the prior art can be obtained by blending~-TCP with HAP
into and adequate composition.
By using a polyacrylic acid type aqueous solution as the liquid agent, it is possible to provide a kneaded slurry with an appropriate viscosity and attain firm har-dening in an oral circumstance in a relatively short period of time while giving an appropriate time margin for the operation.
Root canal filling material is used for supplementing and~illing material defect of pulp cavities formed after the pulpectomic operation or therapy for infected root canal. The root canal therapy is completed after the canal has been filled exactly.
The object of the root canal therapy is to completely close the space in the root canal, e.g., for interrupting the route of infection between the root canal and the peridental tissues, between the root canal and the oral cavity and the like and protecting the wound at the apical portion to form granulat,ion tissues to heal bone scars, thereby preserving pulpless tooth in the state not delete-rious to human body and maintaining -the function of the 3~gL
69065~23 tooth.
While Ca(OH)2 type root canal filling materials have exclusively been used in this field, their primary object resides in obtaining therapeutic ef-Eects and most o~
them are not hardenable. Further, conventional root canal filling materials are filled to the root canal together with gutta-percha, but this operation is troublesome~
Accordingly, the root canal filling material for dental use according to this invention is an extremely advantageous material that can complete airtigh-t canal fill-ing by the operation for once, and can be coagulated ~irmly to harden in a short period of time in the root canal with an appropriat~ time margin for the operation. It is of course possible to use the material in combination with conventional solid material.
The root canal filling material according to this invention is prepared from the powdery agent and the liquid agent shown in Table-l.
Explanation is at first made to the powdery agent.
The powdery agent comprises ~-TCP, HAP, X-ray contrast media and a pharmaceutical agent.
~-TCP is contained in the powdery agent by from 10 to 90 %, pre~erably 15 to 40 % by weight based on the powdery agent. If ~-TCP is less than 10 %, biocompatibility is reduced to increase the hardening time and, in addition, coagulation does not proceed completely.
~2~t~3~
While on the other hand, if ~-TCP is more than 90%, it is difficult to obtain an appropriate time margin for the operation since the hardening reaction proceeds too rapidly ancl the strength of the coagulated hardened product becomes exces~
sively high in view of the physical properties, although it is advantageous in view o~ the biocompatibility.
It is sufficient that the root canal filling material can fill the space in the root canal and, if the strength upon hardening is too high, it can not be taken out upon re-operation.
Then, ~AP is used primarily for the improvement of the biocompatibility and also for adjusting (retarding) the reaction of ~-TCP and polyacrylic acid and adjusting (lowering) the strength o the coagulated hardened product. HAP is con-tained in the powdery agent by from 9 to 70 %, preferably 20 to 55 % by weight based on the powdery agent, depending on the content of ~-TCP. If HAP is less than 9 %, the foregoing object can not be attained and, particularly, the strength of the powdery agent becomes excessive failing to impro~e the biocom-patibility. While on the other hand, if HAP is more than 70 %, it is difficult to react the coagulated hardened product with the liquid agent in a short period of time although the bio-compatibility is impro~ed.
Substances that can be used as the X-ray contrast medium and/or pharmaceutical agent include iodoform, barium sulfate, tantalum powder, silver powder, bismuth subcarbonate , . ~
~ 69065-23 (i.e., bismus oxycarbonate (BiO)2CO3), various salts of chloro-hexidine, calcium fluoride and sodium monofluoro phosphate.
Among them, iodoform is most appropriate, which has -the func-tions both of X-ray contrast medium and antibacterial effect.
Although barium phosphate can be used as an X-ray contrast medium, it is necessary to additionally use another ingredient, for e~ample, chlorohexidine hydrochloride as an antibacterial agent. Sodium monofluoro phosphate can be used as the pharmaceu-tical agent.
The total amount of the X-ray contrast medium and the pharmaceutical agent in the powdery agent is from 1 to 35 %, preferably 10 to 35 % by weight, depending on the con-dition of use.
If the amount of the X-ray contrast medium and the pharmaceutical agent is less than 1 %, X-ray impermeabil-ity becomes poor making it difficult to check the filled state in the root canal after application, as well as it is no more possible to maintain the aseptic state in the root canal after the therapy. Image pick-up is impossible and bacterial infection is caused. Further, if the amount of the X-ray contrast media antibacterial agent or pharmaceutical agent is increased more than 30 %, no other effects than their inherent function can be attained and, in addition, the con-tent of ~-TCP is relatively decreased undesirably.
Explanation will then be made to the polyacrylic acid type liquid agent referring to Table-l.
~2~g3~
The liquid agent includes an acrylic acid polymer, purified water, an organic acid or inorganic acid, as well as one or more other ingredients that are conventionally used in a root canal filling material.
The acrylic acid polymer may be a homopolymer of acrylic acid or a copolymer of acrylic acid and another unsaturated carboxylic acid copolymerizable with acryli~ acid, such as itaconic acid, fumaric acid and maleic acid.
The acrylic acid polymer is contained in the liquid agent in an amount of from 10 to 40 %. If the acrylic acid polymer is less than 10 %, hardening reaction with the powdery agent does not proceed sufficiently. While on the other hand, if it is more than 40 ~, ~iscosity of the liquid agent is increased and the kneaded slurry becomes too hard thereby reducing the operationability and bringing about a difficulty of use upon filling the root canal.
If purified water is less than 35 %, the viscosity Qf the kneaded slurry becomes too high bringing about a diffi-culty in use, and conversion of ~-TCP into HAP can no more be expected. Whereas, if the purified water is more than 88.5 %
the viscosity is too low bringing abcut a difficulty in use.
Organic acid or inorganic acid includes mainly monobasic or polybasic carboxylic acids such as glycolic acid, lactic acid, citric acid, acetic acid and tartaric acid, or inorganic acids such as phosphoric acid, hydrochloric acid and nitric acid and they are contained by from 1 to 15 ~ in the : ij 8 :
12~ 69065~23 liquid agent. They are used for adjusting the hardening time, sharpness for the hardening and the strength upon hardening.
The sharpness of the hardening means the rate of rising speed of rapid hardening of the kneading slurry from the powdery agent and the liquid agent after the elapse of a predetermined time margin for the operation.
If the organic acid or inorganic acid is less than 1 %, the foregoing object can not be attained. While on the other hand, if it is more than 15 %, the time margin for the operation becomes extremely shortened making it impossible for sufficient kneading and, as a result, the hardened product can not completely be converted into a coagulated state thereby tending to cause embrittline destruction or the like.
Other ingredients that can be included in the liquid agent are for example water soluble calcium salt, aluminum salt, sodium salt or magnesium salts; sur~ace active agents such as cationic surface active agent, anionic surface active agent and nonionic surface active agent, pH controllers such as sodium hydroxide and potassium hydroxide; and viscosity improvers such as carboxymethylcellulose, hydroxypropyl-cellulose, polyoxyethylene high polymer, polyethylene glycol and water soluble silicon, and they are contained in an amount of from 0.5 to 10 ~ of the liquid agentu As the water soluble calcium salt, phosphate is preferable and, for example, calcium dihydrogenphosphate monohydrate is used for adjusting the hardening time, sharpness of the hardening and the mechanical g _ ~ 2~311 69065-23 strength. The surface acti~e agent is used for securing the wettability of the kneading slurry, the pH controller is used for adjusting the pH value and the viscosity improver is used for adjusting the viscosity.
In any of the cases, the amount o~ each of the ingredients in the powdery agent and the amount of each of the ingredients in the liquid agent may properly be adjusted depend-ing on the purpose. The powder/liquid weight ratio is preferably 2:1 to 1:2, more preferably about 1:1. The powdery agent and the liquid agent are normally separated from each other until shortly before use.
Example Table 2 shows examples for root canal filling mate-rials.
In Example 1, the powder/liquid ratio is 1.0, the hardening time is 45 minutes, and the compression strength is 75 kg/f/cm2. In Example 2, the powder/liquid ratio is 1.0, the hardening time is 35 minutes and the compression strength is 93 kg/f/cm2. In Example 3, the powderlliquid ratio is 1.0, the hardening time is 60 minutes and the compression strength is 88 kgf/cm2.
In Examples 1, 2 and 3, hardening time is appropriate as the time margin for the handling of root canal ~illing materials, to obtain adequate compression strength.
In the actual use of the root canal ~illing material, the powdery agent and the polyacrylic type liquid agent are , ~ . ~
, ~9311 69065-23 kneaded at a predetermined powder/liquid ratio, for example, 1.0 into a slurry to provide an appropriate - lOa -~2~3~
viscosity. Then, when the kneaded slurry i9 filled, for example, to the root canal after the pulpectomic operation, coagulated hardened product of an adequate compression strength is obtained after the elapse Or a predetermined of hardening time.
Since the coagulated hardened product contains ~ -TCP
and HAP, it is biocompatible and causes no stimulations.
By the way, the polyacrylic acid type liquid agent is used in this invention. It has been found tha-t if the lactic polymer type liquid agent were used instead of the polyacrylic acid type agent, the compression strength of the coagulated hardened product would be lowered and the hardening time be increased and, accordingly, the lactic polymer type liquid agent is not suitable to such a use.
As is apparent from the foregoings, the root canal filling material according to this invention can be har-dened to an adequate strength in a relatively short period of time with an appropriate time margin for the operation in an oral circumstance when used as a root canal filling material, while giving no stimulating nature to a biobody and securing biocompatibility~
~2~ 69065-23 Table 1 . _ Ingredient ratio(~) _ _ _ .
Powdery ~ -TCp 10 - 90 agent (~ -Ca3(PO4) 2~ alpha type tricalcium phosphate) HAP _ (Cal0(P4)6(OH)2~ hydroxyapatite) 9 - 70 X-ray contrast media, antibacterial agent or pharmaceutical agent Ebarium sulfate(BaSO4), iodoform(CHI3)] 1 - 35 . .
liquid acrylic acid polymer l0 - 40 agent (copolymer of acrylic acid and itacor.ic acid) (copolymer of acrylic acid and fumaric acid) .
(copolymer of acrylic acid and maleic acid) .
_~
purified water 35 - 88.5 _ organic or inorganic acid 1 - 15 Etartaric acid, glycolic acid, phosphoric acid, hydrochloric acid, nitric acid] _ ¦
other ingredient Ewater-soluble calcium salt, surface active o.S - 10 agent, pH conroller, viscosity improverl ~2~ 1 69065-23 Table 2 Exa- powdery agent liquid agent powder/ hardening compres-mple liquid time[min] sion ratio strength [kgf/cm2 ~ _ 1 ~-TCP 25% acrylic acid HAP 45% polymer 23 iodoform 30% purified water 72%
glycolic acid 3.0% 1.0 45 75 cationic surface active agent 0.4 sodium __ hydroxide 1.6%
2 ~-TCP 30% acrylic acid HAP 39% polymer 25.0%
barium purified sulfate 14.9% water 69.9~ 1.0 35 93 sodium mono- phosphoric fluoro phos- acid 2.7%
phate 0.4~ cationic bismuth surface subcarbonate active agent 15.0~ 0.4%
chlorohexi- polyethylene dine hydro~ glycol 2.0%
chloride 0~7% _ : _ _ ~ 2~
Exa- powdery agent liquid agent powder/ hardening compres-mple liquid time[min] sion ratio strength _ : [kgf/cm 3 C~TCP 20% acrylic acid 1.0 60 88 HAP 45% polymer 25.0~
iodoform 35~ purified water 2.4%
hydroxypropyl-cellulose 1.3%
sodium hydroger . . phosphate 2.3%1 . .
,~ ~,.. .
ROOT CANAL FIL.LER FOR DENTAL USE
BACKGROUND OF THE INVENTION
Field of the Invention This invention concerns a root canal filling material for dental useO
Description of the Prior Art So-called powder/liquid type dental compositions using powdery agents and liquid agents have been applied as various kind of products in many application fields such as, for examples, tooth reconstructing material, pulp capping material, root canal filling material and various kinds of dental cements (for joining, filling, capping, lining, backing, etc.).
While these materials are mainly composed Or inorganic or synthetic resin type materials as the main ingredient, there has been a problem that they show deleterious effects on biobodies. That is, conventional dental compositions are more or less stimulative to biobodies and, since they are made Or materials different from those of the biobody, their biocompatibility is poor.
Thus, there has been a difficulty in using conventional dental compositions as root canal filling material because Or their stimula-ting nature to the biobody and, accordingly t 12~31~ 69065-23 it has been desired for the development of such root canal filling material for dental use that has no stimulating nature and can be hardened firmly in a relatively short pexiod of time with an appropriate time margin for the operation.
SU~D~ARY OF THE INVENTION
The object of this invention is to provide root canal filling material for dental use that can be hardened to an adequate strength in a relatively short period of time with an appropriate time margin for the operation, while giving no stimulations and securing biocompatibility.
This invention provides a root canal filling material for dental use, comprising:
(A) a powdery agent consisting essentially of (i) from 10 to 90% by weight (based on the powdery agent) of alpha tricalcium phosphate (~-Ca3(PO4)2), (ii) from 9 to 70% by weight lbased on the powdery agent) of hydroxyapatite and (iii) from 1 to 35% by weight (based on the powdery agent~ of a combination of an X-ray contrast medium and a pharmaceutical agent, and ~B) a liquid agent consisting essentially of (i) from 10 to 40% by weight (based on the liquid agent) of a homo~
polymer of acrylic acid or a copolymer thereof with another unsaturated carboxylic acid copolymerizable with acrylic acid, (ii) from 35 to 88.5% by weight (based on the liquid agent) of purified water, (iii) from 1 to 15% by weight of an organic or inorganic non-toxic acid and (iv) from 0.5 to 10% by weight (based on the liquid agent) of at least one member selected from the .
~9~ 69065~23 group consisting of [a] water-soluble calcium, aluminum, sodium or magnesium salts, [b] surface active agentsl [c~ p~ controllers and [d] viscosity improvers, wherein the liquid agent is capable of reacting with the said powdery agent and forming a coagulated hardened product in an oral circumstance.
~ powdery agent including ~-TCP (~-Ca3(PO4)2):
alpha type tricalcium phosphate), hydroxyapatite, an X-ray con-trast medium and a pharmaceutical agent is kneaded with a poly-acrylic acid type liquid agent capable of reacting with the powdery agent in an oral circumstance to form a coagulated hardened product.
The most prominent feature of this invention is to us~ ~-TCP as an ingredient of the powdery agent.
~s has been well-known, the main constituent ingre-dient for inorganic components such as too-th and bone is HAP (Cal0(PO4)6(OH)2 : hydroxyapatite) and inorganic biomaterails similar thereto have been noted in recent years.
Such inorganic biomaterials are favorable because oE
their compatibility with biobody tissues such as induction of formation and binding of newly formed bones at the interface with hard tissues in addition to their in-vivo stability. They are classified into bioinert materials such as A12O3 and bioactive materials such as HAP depending on the activity with the biobody tissue interface. ~-TCP used in this invention is a HAP precur-sor having a feature of biodegradability like that of low crystal-line HAP, but it is a biocompatible inorganic material which '' - . ~
~Zg~3~ 69065-23 has chemical activity as well and can be expected to be con-verted into HAP in the presence of water. The ~-TCP can be converted into a firm coagulated hardened product in a short period of time withi.n an oral cavity when kneaded with a poly-acrylic acid type liquid agent. It is widely known that the polyacrylic type copolymer has generally been used as the liquid ingredient for dental cement compositions.
While biocompatible inorganic materials include HAP, 3a -, . v ~
~L29~3~1 ~-TCP and the like in addition to ~ -TCP used in this invention, but both of HAP and ~-TCP are poor in the chemical activity and di~icult to be hardened ln the oral circumstance. C~-TCP is used as the ingredient in -this sense and a novel root canal filling material not found in the prior art can be obtained by blending~-TCP with HAP
into and adequate composition.
By using a polyacrylic acid type aqueous solution as the liquid agent, it is possible to provide a kneaded slurry with an appropriate viscosity and attain firm har-dening in an oral circumstance in a relatively short period of time while giving an appropriate time margin for the operation.
Root canal filling material is used for supplementing and~illing material defect of pulp cavities formed after the pulpectomic operation or therapy for infected root canal. The root canal therapy is completed after the canal has been filled exactly.
The object of the root canal therapy is to completely close the space in the root canal, e.g., for interrupting the route of infection between the root canal and the peridental tissues, between the root canal and the oral cavity and the like and protecting the wound at the apical portion to form granulat,ion tissues to heal bone scars, thereby preserving pulpless tooth in the state not delete-rious to human body and maintaining -the function of the 3~gL
69065~23 tooth.
While Ca(OH)2 type root canal filling materials have exclusively been used in this field, their primary object resides in obtaining therapeutic ef-Eects and most o~
them are not hardenable. Further, conventional root canal filling materials are filled to the root canal together with gutta-percha, but this operation is troublesome~
Accordingly, the root canal filling material for dental use according to this invention is an extremely advantageous material that can complete airtigh-t canal fill-ing by the operation for once, and can be coagulated ~irmly to harden in a short period of time in the root canal with an appropriat~ time margin for the operation. It is of course possible to use the material in combination with conventional solid material.
The root canal filling material according to this invention is prepared from the powdery agent and the liquid agent shown in Table-l.
Explanation is at first made to the powdery agent.
The powdery agent comprises ~-TCP, HAP, X-ray contrast media and a pharmaceutical agent.
~-TCP is contained in the powdery agent by from 10 to 90 %, pre~erably 15 to 40 % by weight based on the powdery agent. If ~-TCP is less than 10 %, biocompatibility is reduced to increase the hardening time and, in addition, coagulation does not proceed completely.
~2~t~3~
While on the other hand, if ~-TCP is more than 90%, it is difficult to obtain an appropriate time margin for the operation since the hardening reaction proceeds too rapidly ancl the strength of the coagulated hardened product becomes exces~
sively high in view of the physical properties, although it is advantageous in view o~ the biocompatibility.
It is sufficient that the root canal filling material can fill the space in the root canal and, if the strength upon hardening is too high, it can not be taken out upon re-operation.
Then, ~AP is used primarily for the improvement of the biocompatibility and also for adjusting (retarding) the reaction of ~-TCP and polyacrylic acid and adjusting (lowering) the strength o the coagulated hardened product. HAP is con-tained in the powdery agent by from 9 to 70 %, preferably 20 to 55 % by weight based on the powdery agent, depending on the content of ~-TCP. If HAP is less than 9 %, the foregoing object can not be attained and, particularly, the strength of the powdery agent becomes excessive failing to impro~e the biocom-patibility. While on the other hand, if HAP is more than 70 %, it is difficult to react the coagulated hardened product with the liquid agent in a short period of time although the bio-compatibility is impro~ed.
Substances that can be used as the X-ray contrast medium and/or pharmaceutical agent include iodoform, barium sulfate, tantalum powder, silver powder, bismuth subcarbonate , . ~
~ 69065-23 (i.e., bismus oxycarbonate (BiO)2CO3), various salts of chloro-hexidine, calcium fluoride and sodium monofluoro phosphate.
Among them, iodoform is most appropriate, which has -the func-tions both of X-ray contrast medium and antibacterial effect.
Although barium phosphate can be used as an X-ray contrast medium, it is necessary to additionally use another ingredient, for e~ample, chlorohexidine hydrochloride as an antibacterial agent. Sodium monofluoro phosphate can be used as the pharmaceu-tical agent.
The total amount of the X-ray contrast medium and the pharmaceutical agent in the powdery agent is from 1 to 35 %, preferably 10 to 35 % by weight, depending on the con-dition of use.
If the amount of the X-ray contrast medium and the pharmaceutical agent is less than 1 %, X-ray impermeabil-ity becomes poor making it difficult to check the filled state in the root canal after application, as well as it is no more possible to maintain the aseptic state in the root canal after the therapy. Image pick-up is impossible and bacterial infection is caused. Further, if the amount of the X-ray contrast media antibacterial agent or pharmaceutical agent is increased more than 30 %, no other effects than their inherent function can be attained and, in addition, the con-tent of ~-TCP is relatively decreased undesirably.
Explanation will then be made to the polyacrylic acid type liquid agent referring to Table-l.
~2~g3~
The liquid agent includes an acrylic acid polymer, purified water, an organic acid or inorganic acid, as well as one or more other ingredients that are conventionally used in a root canal filling material.
The acrylic acid polymer may be a homopolymer of acrylic acid or a copolymer of acrylic acid and another unsaturated carboxylic acid copolymerizable with acryli~ acid, such as itaconic acid, fumaric acid and maleic acid.
The acrylic acid polymer is contained in the liquid agent in an amount of from 10 to 40 %. If the acrylic acid polymer is less than 10 %, hardening reaction with the powdery agent does not proceed sufficiently. While on the other hand, if it is more than 40 ~, ~iscosity of the liquid agent is increased and the kneaded slurry becomes too hard thereby reducing the operationability and bringing about a difficulty of use upon filling the root canal.
If purified water is less than 35 %, the viscosity Qf the kneaded slurry becomes too high bringing about a diffi-culty in use, and conversion of ~-TCP into HAP can no more be expected. Whereas, if the purified water is more than 88.5 %
the viscosity is too low bringing abcut a difficulty in use.
Organic acid or inorganic acid includes mainly monobasic or polybasic carboxylic acids such as glycolic acid, lactic acid, citric acid, acetic acid and tartaric acid, or inorganic acids such as phosphoric acid, hydrochloric acid and nitric acid and they are contained by from 1 to 15 ~ in the : ij 8 :
12~ 69065~23 liquid agent. They are used for adjusting the hardening time, sharpness for the hardening and the strength upon hardening.
The sharpness of the hardening means the rate of rising speed of rapid hardening of the kneading slurry from the powdery agent and the liquid agent after the elapse of a predetermined time margin for the operation.
If the organic acid or inorganic acid is less than 1 %, the foregoing object can not be attained. While on the other hand, if it is more than 15 %, the time margin for the operation becomes extremely shortened making it impossible for sufficient kneading and, as a result, the hardened product can not completely be converted into a coagulated state thereby tending to cause embrittline destruction or the like.
Other ingredients that can be included in the liquid agent are for example water soluble calcium salt, aluminum salt, sodium salt or magnesium salts; sur~ace active agents such as cationic surface active agent, anionic surface active agent and nonionic surface active agent, pH controllers such as sodium hydroxide and potassium hydroxide; and viscosity improvers such as carboxymethylcellulose, hydroxypropyl-cellulose, polyoxyethylene high polymer, polyethylene glycol and water soluble silicon, and they are contained in an amount of from 0.5 to 10 ~ of the liquid agentu As the water soluble calcium salt, phosphate is preferable and, for example, calcium dihydrogenphosphate monohydrate is used for adjusting the hardening time, sharpness of the hardening and the mechanical g _ ~ 2~311 69065-23 strength. The surface acti~e agent is used for securing the wettability of the kneading slurry, the pH controller is used for adjusting the pH value and the viscosity improver is used for adjusting the viscosity.
In any of the cases, the amount o~ each of the ingredients in the powdery agent and the amount of each of the ingredients in the liquid agent may properly be adjusted depend-ing on the purpose. The powder/liquid weight ratio is preferably 2:1 to 1:2, more preferably about 1:1. The powdery agent and the liquid agent are normally separated from each other until shortly before use.
Example Table 2 shows examples for root canal filling mate-rials.
In Example 1, the powder/liquid ratio is 1.0, the hardening time is 45 minutes, and the compression strength is 75 kg/f/cm2. In Example 2, the powder/liquid ratio is 1.0, the hardening time is 35 minutes and the compression strength is 93 kg/f/cm2. In Example 3, the powderlliquid ratio is 1.0, the hardening time is 60 minutes and the compression strength is 88 kgf/cm2.
In Examples 1, 2 and 3, hardening time is appropriate as the time margin for the handling of root canal ~illing materials, to obtain adequate compression strength.
In the actual use of the root canal ~illing material, the powdery agent and the polyacrylic type liquid agent are , ~ . ~
, ~9311 69065-23 kneaded at a predetermined powder/liquid ratio, for example, 1.0 into a slurry to provide an appropriate - lOa -~2~3~
viscosity. Then, when the kneaded slurry i9 filled, for example, to the root canal after the pulpectomic operation, coagulated hardened product of an adequate compression strength is obtained after the elapse Or a predetermined of hardening time.
Since the coagulated hardened product contains ~ -TCP
and HAP, it is biocompatible and causes no stimulations.
By the way, the polyacrylic acid type liquid agent is used in this invention. It has been found tha-t if the lactic polymer type liquid agent were used instead of the polyacrylic acid type agent, the compression strength of the coagulated hardened product would be lowered and the hardening time be increased and, accordingly, the lactic polymer type liquid agent is not suitable to such a use.
As is apparent from the foregoings, the root canal filling material according to this invention can be har-dened to an adequate strength in a relatively short period of time with an appropriate time margin for the operation in an oral circumstance when used as a root canal filling material, while giving no stimulating nature to a biobody and securing biocompatibility~
~2~ 69065-23 Table 1 . _ Ingredient ratio(~) _ _ _ .
Powdery ~ -TCp 10 - 90 agent (~ -Ca3(PO4) 2~ alpha type tricalcium phosphate) HAP _ (Cal0(P4)6(OH)2~ hydroxyapatite) 9 - 70 X-ray contrast media, antibacterial agent or pharmaceutical agent Ebarium sulfate(BaSO4), iodoform(CHI3)] 1 - 35 . .
liquid acrylic acid polymer l0 - 40 agent (copolymer of acrylic acid and itacor.ic acid) (copolymer of acrylic acid and fumaric acid) .
(copolymer of acrylic acid and maleic acid) .
_~
purified water 35 - 88.5 _ organic or inorganic acid 1 - 15 Etartaric acid, glycolic acid, phosphoric acid, hydrochloric acid, nitric acid] _ ¦
other ingredient Ewater-soluble calcium salt, surface active o.S - 10 agent, pH conroller, viscosity improverl ~2~ 1 69065-23 Table 2 Exa- powdery agent liquid agent powder/ hardening compres-mple liquid time[min] sion ratio strength [kgf/cm2 ~ _ 1 ~-TCP 25% acrylic acid HAP 45% polymer 23 iodoform 30% purified water 72%
glycolic acid 3.0% 1.0 45 75 cationic surface active agent 0.4 sodium __ hydroxide 1.6%
2 ~-TCP 30% acrylic acid HAP 39% polymer 25.0%
barium purified sulfate 14.9% water 69.9~ 1.0 35 93 sodium mono- phosphoric fluoro phos- acid 2.7%
phate 0.4~ cationic bismuth surface subcarbonate active agent 15.0~ 0.4%
chlorohexi- polyethylene dine hydro~ glycol 2.0%
chloride 0~7% _ : _ _ ~ 2~
Exa- powdery agent liquid agent powder/ hardening compres-mple liquid time[min] sion ratio strength _ : [kgf/cm 3 C~TCP 20% acrylic acid 1.0 60 88 HAP 45% polymer 25.0~
iodoform 35~ purified water 2.4%
hydroxypropyl-cellulose 1.3%
sodium hydroger . . phosphate 2.3%1 . .
,~ ~,.. .
Claims (5)
1. A root canal filling material for dental use, comprising:
(A) a powdery agent consisting essentially of (i) from 10 to 90% by weight (based on the powdery agent) of alpha tricalcium phosphate (.alpha.-Ca3(PO4)2), (ii) from 9 to 70% by weight (based on the powdery agent) of hydroxyapatite and (iii) from 1 to 35% by weight (based on the powdery agent) of a combination of an X-ray contrast medium and a pharmaceutical agent, and (B) a liquid agent consisting essentially of (i) from 10 to 40% by weight (based on the liquid agent) of a homopolymer of acrylic acid or a copolymer thereof with another unsaturated carboxylic acid copolymerizable with acrylic acid, (ii) from 35 to 88.5% by weight (based on the liquid agent) of purified water, (iii) from 1 to 15% by weight of an organic or inorganic non-toxic acid and (iv) from 0.5 to 10% by weight (based on the liquid agent) of at least one member selected from the group consisting of Ca] water-soluble calcium, aluminum, sodium or magnesium salts, [b] surface active agents, [c] pH controllers and [d] viscosity improvers, wherein the liquid agent is capable of reacting with the said powdery agent and forming a coagulated hardened product in an oral circumstance.
(A) a powdery agent consisting essentially of (i) from 10 to 90% by weight (based on the powdery agent) of alpha tricalcium phosphate (.alpha.-Ca3(PO4)2), (ii) from 9 to 70% by weight (based on the powdery agent) of hydroxyapatite and (iii) from 1 to 35% by weight (based on the powdery agent) of a combination of an X-ray contrast medium and a pharmaceutical agent, and (B) a liquid agent consisting essentially of (i) from 10 to 40% by weight (based on the liquid agent) of a homopolymer of acrylic acid or a copolymer thereof with another unsaturated carboxylic acid copolymerizable with acrylic acid, (ii) from 35 to 88.5% by weight (based on the liquid agent) of purified water, (iii) from 1 to 15% by weight of an organic or inorganic non-toxic acid and (iv) from 0.5 to 10% by weight (based on the liquid agent) of at least one member selected from the group consisting of Ca] water-soluble calcium, aluminum, sodium or magnesium salts, [b] surface active agents, [c] pH controllers and [d] viscosity improvers, wherein the liquid agent is capable of reacting with the said powdery agent and forming a coagulated hardened product in an oral circumstance.
2. The material as defined in claim 1, wherein the powdery agent and the liquid agent are separated from each other until shortly before use.
3. The material as defined in claim 1 or 2, wherein iodoform is employed as the X-ray contrast as well as an anti-bacterial agent.
4. The material as defined in claim 1 or 2, wherein the ingredient (i) in the liquid agent (A) is an acrylic acid homopolymer or a copolymer of acrylic acid with another monomer selected from the group consisting of itaconic acid, fumaric acid and maleic acid.
5. The material as defined in claim 1 or 2, wherein the ingredient (iii) of the powdery agent comprises a combination of [a] an X-ray contrast agent selected from the group consisting of barium sulfate, barium phosphate, tantalum powder, silver powder and bismus bicarbonate and [b] a pharmaceutical agent selected from the group consisting of a chlorohexidine salt, calcium fluoride and sodium monofluoro phosphate.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60157044A JPS6219508A (en) | 1985-07-18 | 1985-07-18 | Root canal filling material for dental use |
| CA000532582A CA1299311C (en) | 1985-07-18 | 1987-03-20 | Root canal filler for dental use |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60157044A JPS6219508A (en) | 1985-07-18 | 1985-07-18 | Root canal filling material for dental use |
| CA000532582A CA1299311C (en) | 1985-07-18 | 1987-03-20 | Root canal filler for dental use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1299311C true CA1299311C (en) | 1992-04-21 |
Family
ID=25671271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000532582A Expired - Fee Related CA1299311C (en) | 1985-07-18 | 1987-03-20 | Root canal filler for dental use |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS6219508A (en) |
| CA (1) | CA1299311C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10307344B2 (en) | 2016-02-15 | 2019-06-04 | Shofu Inc. | Two-paste type sealer composition for root canal filling |
| US10463581B2 (en) | 2016-02-15 | 2019-11-05 | Shofu Inc. | Sealer composition for root canal filling |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH062152B2 (en) * | 1987-05-28 | 1994-01-12 | 三菱マテリアル株式会社 | Bone defect and bone void filling material |
| JPH0662379B2 (en) * | 1988-03-16 | 1994-08-17 | デンタル化学株式会社 | Dental material composition |
| JP2512324B2 (en) * | 1988-11-24 | 1996-07-03 | 株式会社ジーシーデンタルプロダクツ | Dental resin composition |
| JPH0360451A (en) * | 1989-07-25 | 1991-03-15 | Natl Inst For Res In Inorg Mater | Calcium phosphate hydraulic cement composition |
| JPH03112843A (en) * | 1989-09-25 | 1991-05-14 | Mitsubishi Materials Corp | Hydraulic calcium phosphate cement composition |
| JPH03128063A (en) * | 1989-10-16 | 1991-05-31 | Natl Inst For Res In Inorg Mater | Water-curable type calcium phosphate cement composition |
| JPH03128062A (en) * | 1989-10-16 | 1991-05-31 | Natl Inst For Res In Inorg Mater | Water-curable type calcium phosphate cement composition |
| JPH0669480B2 (en) * | 1990-03-17 | 1994-09-07 | 三菱マテリアル株式会社 | Hydraulic calcium phosphate cement hardening liquid |
| JPH0429907A (en) * | 1990-05-24 | 1992-01-31 | Showa Denko Kk | Root canal filling composition |
| JPH0734816B2 (en) * | 1991-06-26 | 1995-04-19 | 新田ゼラチン株式会社 | Medical and dental curable materials |
| US7455805B2 (en) * | 2003-10-28 | 2008-11-25 | Hewlett-Packard Development Company, L.P. | Resin-modified inorganic phosphate cement for solid freeform fabrication |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5883605A (en) * | 1981-11-13 | 1983-05-19 | Takuro Ishibashi | Dental cement composition and its preparation |
| JPS5988351A (en) * | 1982-11-10 | 1984-05-22 | 科学技術庁無機材質研究所長 | Production of apatite cement hardened body |
| JPS59188263A (en) * | 1983-04-08 | 1984-10-25 | Nec Corp | Key telephone set with dial pulse confirmation display |
| JPS60253454A (en) * | 1984-03-24 | 1985-12-14 | 大日本塗料株式会社 | Bone lack part and gap part filler composition |
-
1985
- 1985-07-18 JP JP60157044A patent/JPS6219508A/en active Pending
-
1987
- 1987-03-20 CA CA000532582A patent/CA1299311C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10307344B2 (en) | 2016-02-15 | 2019-06-04 | Shofu Inc. | Two-paste type sealer composition for root canal filling |
| US10463581B2 (en) | 2016-02-15 | 2019-11-05 | Shofu Inc. | Sealer composition for root canal filling |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6219508A (en) | 1987-01-28 |
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