WO1998016187A1

WO1998016187A1 - Curable root canal filling compositions for dental use and kits containing the same

Info

Publication number: WO1998016187A1
Application number: PCT/JP1997/003644
Authority: WO
Inventors: Takashi Yamamoto; Kouichi Tashiro; Hiroshi Henmi
Original assignee: Sun Medical Co., Ltd.
Priority date: 1996-10-11
Filing date: 1997-10-09
Publication date: 1998-04-23
Also published as: JP3638615B2

Abstract

Curable compositions which show a fluidity and thus can be conveniently used as root canal filling materials, remain usable over a prolonged period of time, and are excellent in X-ray contrast and sealing properties. These compositions comprise mono-functional polymerizable monomers (A), boron-containing polymerization initiators (B), thixotropic agents (C), X-ray contrast fillers (D) and polymers (E) which undergo swelling or dissolution in the presence of the component (A). Root canal surface-treating agents suitable for the above-mentioned compositions are also provided.

Description

Description Hardening material for dental root canal filling ttl material and kit containing it Technical field

The present invention relates to a cured product suitable for a root canal filling that is iiffl into the root canal of a tooth ₀ More specifically, it is possible to igffl a ^ # agent or a good material for teeth, bones, ceramics, resins, etc. for B¾ applications Cured tt! Background art

The ideal case of root canal filling was proposed by Grossman as follows (Grossman 丄. I .: Enaodontic practice: 10th ed., Lea & Febiger, Phi la delphia, 296-302, 1981). ₀ : (1) Easy to operate, exhibit »property and have a sufficient pot life (handling time), (2) Good dimensional stability, (3) Root canal It can be sealed in the vertical direction, (4) there is no irritation to the apical periodontal fiber, (5) it does not penetrate moisture, (6) it is insoluble and does not corrode, (7) it does not allow the growth of bacteria, It has been suggested that (8) it has X ¾i ^ properties, (9) it does not discolor the dentin, (10) it is sterile, and (11) it can be removed depending on the machine. Most of the existing materials are thermoplastic resins that have been given X-ray radiation properties by combining an X ^ f property (a property that makes X-rays hard to thigh). It was a material that filled the root canal with properties and solidified in the process of the resin becoming the same temperature. With such a resin, there was no interaction between the resin and the root canal wall, so that the sealing property and adhesion to the root canal wall were not sufficient. The lack of blockage and tightness causes' λ of external foreign matter into the root canal dentin, and it is considered that unhealthyness in the root canal causes collapse of the root and adverse effects on the alveolar bone. Furthermore, since the thermoplastic resin produced by the technology hardly expects contact with the root canal wall, if a mechanical or physical external force is applied to the root canal wall, the sealability and adhesion may be impaired. On the other hand, an adhesive has been proposed that is applied to enamezo and elephants that contain more calcium 5 ^ than in the root canal. In Japanese Patent Application Laid-Open No. 49-51443, a filling material for dental treatment using tributyl borane as a polymerization initiator has been proposed. The cured product has no X-ray: ^ properties and does not contain heavy acid monomers containing acidic groups that should interact with the root canal wall. In the dental material disclosed in Japanese Patent Application Laid-Open No. 52-113809, there is no description of aluminum oxide filler in the root canal. Cannot provide sufficient X-ray properties. Further, the crane disclosed in Japanese Patent Application Laid-Open No. 59-15468 describes various fillers, but does not show sufficient lubricity. The fillers described in the above proposal are capable of imparting 性 ^ 性 property if i¾S2 is incorporated into the composition, but on the other hand, they have the problem that they become poorly filled and cannot fill the root canal < Occurs. Adhesives such as the I ^ plan contain "^" so that they can interact with the tooth surface. However, since it is not the purpose of filling the root canal, the operating force is extremely short, it is not intuitive, and there is not enough straightness.

In addition, for use as a root canal filler, the material must be applied within a properly treated dentin root canal. Usually, the treatment of the root canal is performed with an aqueous solution of hydrogen peroxide or sodium hypochlorite for the purpose of sterilization or disinfection, but this treatment is not suitable for individual root canal materials. hard. There have been many proposals for adhesives for dentin such as composite resin and resin cement, or surface treatment agents for hardening curable materials, but they can be applied to the root canal, which contains a very large amount of protein. It is recommended to select a less decalcified and less invasive process, but there are few specific proposals.

In order to solve the above problems, the present invention provides, as a root canal filling material, a curable exfoliated material exhibiting easy-to-operate fluidity, long life, and excellent X * ¾Eif properties and sealing properties. To provide.

Another object of the present invention is to provide a root canal filling kit in combination with a tooth surface treating agent suitable for the curable composition of the present invention.

Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the object and ij point of the present invention are as follows: (A) Single government food ^ W monomer

(B) a polymerization initiator,

(C) a thixotropic agent,

(D) X-ray woven filler and

(E) A polymer that is soluble or soluble depending on the component (A)

A root canal hardening debris containing, or

(A) Single key ^ ft monomer,

(B) a polymerization initiator,

(C) thixotropic agent,

(D) X¾¾ ^

(E) a polymer dissolved or dissolved by the component (A) and

(F) Polyfunctional heavy monomer

A curable fibrous material for root canal fiber containing

Done by

As the monomer (A), specifically, for example, (meth) methyl acrylate, (meth) ethyl acrylate, (meth) propyl acrylate, (meth) butyl acrylate, ( (Meth) Pentyl acrylate, hexyl (meth) acrylate, and the like. Fatty acid esters of (meth) acrynoleic acid 1-arrow esters; aromatic esters such as phenyl (meth) acrynolate; 2-hydroxyethyl (meth) acrylate, 2- or 3-Hydroxybutanol (meth) acrylate, glycerone mono (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, pentaethylene glycol mono (meth) acrylate G, polyethylene glycol mono (meth) acrylate, 2- Hydroxy-containing (meth) acrylates, such as droxy-3-phenoxyprovir (meth) acrylate; hydroxyl-containing (meth) acrylamides, such as methylol (meth) acrylamide; one of which is a methyl group or ethyl Examples thereof include polyethylene glycol mono (meth) acrylates mentioned above.

Each of the above monofunctional heavy monomers can be used alone or in combination I can do it.

When a monofunctional heavy ft monomer is formed into a curable fiber, the weight of the monofunctional heavy ft monomer is slower than that of a polyfunctional heavy ft monomer, so that the curing time can be increased. Therefore, there is an advantage that operating time can be increased.

The play (A) in the present invention can contain a 碰 group in the molecule. Examples of such a group include a carboxylic acid group, a carboxyhydrate group, a phosphoric acid group, a sulfonic acid group, and the like, and further, a thiocarboxylic acid group, a thiophosphate group, and the like. Examples of the heavy functional group in the present invention include an acryloyl group, a methacryloyl group (hereinafter, both may be referred to as a (meth) acryloyl group), a styryl group, a vinyl group, and an aryl group. And unsaturated groups. Here, the monofunctional monomer is a heavy monomer containing one heavy ft group as described above in one molecule.

Of the ft-monomers containing a fiber group, examples of the mono-m-compatible monomers having a carboxyl group in one molecule include monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, and the like. Examples thereof include tetracarboxylic acids and polycarboxylic acids or anhydrides thereof. More specifically, for example, (meth) acrylic acid, maleic acid, p-vinylinobenzoic acid, 11- (meth) acryloyloxy-1,1-didecanedicarboxylic acid (MAC-1 0), 1,4-Di (meth) acryloyloxyshethyl vilomeritic acid, 6- (meth) acryloyloxhetylnaphthalene-1,2,6-tricarboxylic acid, 41 (Meth) acryloyloleoxymethyl trimellitate and its anhydride, 41- (Meth) acryloyloxyshethyltrimellitic acid and its anhydride, 41- (Meth) acryloyloleoxybutyl trimellitate Acid and its anhydride, 4- [2-hydroxy-13- (meth) acryloyloxy] butyltrimellitic acid and its non-K, 2,3-bis (3,4-dicarboxybenzoic acid) Roxy) propyl (meth) acrylate, 2 or 3 or 4 I (Meth) acryloyl reoxybenzoic acid, Ν, Ο (di) acryloyloxytyrosine, 0— (meth) acryloyloxy mouth mouth, Ν— (meth) acryloyl Oxytyrosine, Ν— (meth) acryloyloxyphenylalanine, Ν— (meth) acryloyl ρ-amino Benzoic acid, N- (meth) acryloyl 0-aminobenzoic acid, N-phenylglycine or adduct of N-tolylglycine with glycidyl (meth) acrylate, 4-[(2-hydroxy-3- (meth) a (Cryloyloxypropyl) amino] phthalic acid, 3- or 4- (N-methylN- (2-hydroxy-3- (meth) acryloyloxypropyl) amino) phthalic acid. Of these, 11-methacryloyloxy 1,1-decanedecanedicarboxylic acid (MAC-10) and 4-methacryloyloleoxyethyltrimellitic acid (4-MET) or its anhydride (4-META) is preferably used.

Heavy 14 monomers having a phosphoric acid group or a thiophosphoric acid group in one molecule include, for example, 2- (meth) acryloyloxyshethyl sacyl phosphate, 2 and 3— (meth) acryloino Leoxyprovir acid phosphate, 4- (meth) acryloyloxybutyl acid phosphate, 6- (meth) acryloyloxyhexyl acid phosphate, 8- (meth) acryloyl zoleoxy Ctylacidophosphate, 10- (Meth) acryloyloxydecylacidophosphate, 121- (Meth) acryloyloxydodecylacidophosphate, 2— (Meth) acryloylinoreoxyche Tilphenyl phosphide phosphate, 2- (meth) acryloyl oxexetil p-methoxyphenyl phosphide phosphate and the like can be mentioned. The phosphate groups in these compounds can be replaced with thiophosphate groups. Of these, 2-((meth) acryloyloleoxyshetylphenylacyside phosphate and 10- (meth) acryloyloleoxydecyl acid phosphate are preferably used.

Examples of the heavy monomer having a sulfonic acid group in one molecule include 2-sulfoethyl (meth) acrylate, 2- or 1-sulfo 1 or 2-propyl (meth) acrylate, and 1- or 3-sulfo 2-butyl ( (Meth) acrylate, 3-butamate 2-sulfo-1-propyl (meth) acrylate, 3-methoxy-1-sulfo 2-provyl (meth) acrylate, 1,1-dimethyl-12-sulfoethyl (meth) acrylamide And the like. Of these, 2-methyl-2- (meth) acrylamide propanesulfonic acid is preferably used. Here, a monofunctional heavy monomer having an acidic group in one molecule may be substituted with other substituents such as an amino group, an amide group, a cyano group, a ditrinole group, a hydroxyl group, a thiolae group and a nodogen atom. May be provided. Further, a part or all of the ■ group may form a metal salt or a complex, or may form a complex with an ammonium salt or an ammonium salt. Further, a compound with another aminated ^ I may be formed.

The monomer having an acidic group in one molecule is preferably 0.1 to 30% by weight of the monomer.

(B) is the ^^ ffl coalescence initiator. Examples of such a polymerization initiator include organic borides and extinct materials containing the same. ^ Boron compounds include, for example, triethyl boron, tripropyl boron, triisopropyl boron, tributyl boron, tri-sec-butyl boron, triisobutyl boron, tripentyl boron, trihexyl boron, trioctyl boron, tridecyl boron, Trialkylboranes such as tridodecylboron, tricyclopentylboron, and tricyclohexylboron; alkoxyalkylborons such as butoxydibutylboron; butyldicyclohexylborane, diisoamylborane, 9-borabicyclo [3.3.1] nonane, and the like Examples include dialkylboranes and partially oxidized compounds of the above compounds. Furthermore, these compounds can be used in combination. Of these, triplyl boron or partially oxidized tributyl boron is preferably used. As the partially oxidized tributylboron, for example, those obtained by adding 0.3 to 0.9 mol of benzene to 1 mol of triptyl hydrogen are preferably used.

^ (C) is a thixotropic agent. This thixotropy-imparting agent is formulated to control the thixotropy of the composition, and provides an appropriate viscosity and pavement for root canal filling when preparing a cured composition. It plays a role in shortening the time to gain sex.

Although not limiting the scope of the present invention, thixotropy is generally non-spherical particles having a larger axial ratio than spherical particles, and particles less than 100 nm, where the effect of the particle surface becomes important, are considered significant. (“Elucidation of dispersion and coagulation and applied technology” supervision :; ibrn sentence Yu, published by Techno System Co., Ltd. J o Examples of such fillers include pot oxides such as acid i ^, aluminum oxide and vanadium pentoxide, ^ 塩 salts such as canolecidum (gypsum), and oxides such as silica. I can name gay elements. Here, it is preferable to ffl the silica filler. The particle size of the silica filter can be selected according to the purpose, but the average particle size is preferably 0.001 to 100 m, more preferably 0.001 to 50 // m, and still more preferably 0.001 to 10 // m. It is a finely divided silica filler. In particular, when it is used as a root canal filler, it is preferable that the average particle diameter is in the range of 0.001 to 1 since the length can be increased. The content of SiO ₂ is usually 60% J¾ ±, but is preferably 80% or more when used as a root canal filler. Examples of other metals that may be contained in silica include sodium, balium, aluminum, zirconium, strontium, titanium, and fluorine. We can raise the power.

Further, as the (C) in the present invention, a particularly preferable filler is a filler which, when mixed with a heavy ^ ft monomer, turns into a yarn having a thixotropic property in a short time such as JlJ ifiK material. Can be determined as follows: That is, add 0.014 g of filler to 0.18 g of ΜΜΑ and mix for 30 seconds. Immediately, apply about 0.01 g of this mixture to the center of a slide glass (Micro slide glass S-1111, MAT SUNAMI GLASS I ND..LTD). Then, stand upright and immediately measure the movement gg of the mixture at 30 seconds, and measure the dripping. The smaller the value, the shorter the waiting time and the better the operability. Judgment bends are almost not drooping (0-5mm), slightly drooping (5-15mm), dripping well (15-40mm), and very dripping (40-50mm). "^ Has a different thixotropy depending on the particle size and amount of the filler and the type of monomer used. ^ It can be selected according to the purpose and application. Therefore, the experiment is one of the most favorable (C) It is merely a method and is not intended to limit the scope of the invention.

The β¾ component (D) is an X ^ i¾ filler. Such a filler is added to confirm an X-ray opaque image of the cured product. One of the fillers contains a metal element. The average particle diameter is preferably in the range of 1 to 50 microns. In the present invention, since it is preferable to show the X¾ property at a small amount of the monomer relative to the monomer, elements such as aluminum, parium, zirconium, strontium, titanium, iron, copper, and cobalt are contained. Preferably, it is included. The present invention is particularly preferred as (D) in view of its use as a medical material, and examples thereof include a filler containing cerium, zirconium, and strontium. Examples of the zirconium-containing filler include fillers such as zirconium oxide, silica zirconium, silica aluminum zirconium, and zirconium phosphate. These fillers can be used alone or in combination to ffl. Further, the surface of these fillers may be treated with a surface treatment such as silanization ^ ゃ titanation ^! Or the like, or may be coated or embedded with a polymer in advance.

m) is a polymerization mentioned or dissolved in (A), preferably having an average particle size of 1 to 300 microns, more preferably 10 to: LOO O microns. Such a polymer is (A)! It is a polymer that has the property of dissolving or dissolving to increase the viscosity of the fi¾- (A) liquid and to shorten the curing time. For example

A monofunctional M monomer or copolymer of the monofunctional heavy monomer represented by (Α) can be mentioned. Specific examples include polymethyl (meth) acrylate, polyethyl (meth) acrylate, polypropyl (meth) acrylate, polybutyl (meth) acrylate, and a copolymer of methyl (meth) acrylate and ethyl (meth) acrylate. I can do it.

m (F) is the Tankankura 量 simple quantity. ^ (F) is used as needed. The purpose of (F) is mainly for the purpose of adjusting the cured fiber of the cured object and improving the mechanical properties of the cured product. Specifically, for example, aliphatic esters of (meth) acrylic acid such as neopentyl glycol di (meth) acrylate and trimethylolpropanetri (meth) acrylate; 1 mole of bisphenol A and 2 moles of glycidyl ( (Meth) Aroma of acrylates, etc .; ^ (Meth) acrylates; Ethylene glycol di (meth) acrylate, diethylene dali Cold (meth) acrylate, triethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, tetradecaethylene glycol (meth) acrylate, etc. Polyethylene propylene glycol (meth) acrylates; propylene diol glycol (meth) acrylate, dibrovirene glycol di (meth) acrylate, tripropylene glycol (meth) acrylate, nonapropylene glycol (meta) Polypropylene glycol di (meth) acrylates such as acrylates; 2- (meth) acryloyloxyshethyl isocyanate or 2,2,4-trimethylhexamethylene diisocyanate or 1,3.5— Trimethyl (Meth) acrylates having a urethane bond such as those of hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate; (meth) acrylic acid added to the product of bisphenol A with oxyethylene 2,4-bis (4- (meth) acryloyloxypolyethoxyphenyl) propanes and the like.

The multifunctional key-forming monomer that can be used as a game (F) can contain a fiber group in the molecule. Examples of the polyfunctional monomer having at least one carboxyl group in one molecule include monocarboxylic acid, dicarboxylic acid, tricarboxylic acid, and tetracarboxylic acid, and derivatives thereof. More specifically, for example, an adduct (PMDM) of 2-hydroxyethyl (meth) acrylate and viromellitic acid dihydrate, 2 moles of 2-hydroxyethyl (meth) acrylate and 1 mole of anhydrous maleic acid Acid or 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA) or 3,3'.4,4'-biphenyltetracarboxylic dianhydride etc .: Examples thereof include 2- (3,4-dicarboxybenzoyloxy) 1, 3-di (meth) acryloyloleoxypropane.

As a polyfunctional polymerizable monomer represented by (F), a polyfunctional heavy ft monomer having at least one phosphate group or thiophosphate group in one molecule includes, for example, bis (2) — (Meth) acryloyloxietyl} acid phosphate, bis {2 or 3— (meth) acryloyloxyprovir} Examples include acid phosphate. The phosphate group in these compounds can be replaced by a thiophosphate group.

The above-mentioned multi-phasic monomer (F) can be used in insects or in combination.

The amount of each component is in the range of 10 to 60 dragon parts, preferably 10 to 50 parts by weight, more preferably 15 to 40 parts by weight, based on 100 parts by weight of (A) to (E) in total. fi¾9- (B) force ~ 20M »part, preferably 1 ~: LO parts by weight, more preferably l ~ 5Si part, (C) force 1 ~ 50 parts by weight, preferably l ~ 40Sft part, Preferably in the range of 1 to 30 parts by weight, (D) force << 10 to 85 parts by weight, preferably 20 to 80 Sa parts, more preferably in the range of 30 to 50 parts by weight, and ^ (E) force 1 to 50 M¾ parts, preferably It is preferably in the range of 1 to 40 parts by weight, more preferably 1 to 3 OSM parts.

When the polyfunctional polymerizable monomer (F) is further contained, in the total of 1 OOM * parts of the components (A) to (F), (A) is 10 to 60 parts by mass, preferably 10 5050 parts by weight, more preferably 15 to 40 Mfi parts, component (B) is 1 to 20 parts by weight, preferably 1 to: L OSM part, more preferably 1 to 5 S¾ part, ^ (C) force << l-50 fiM parts, preferably l-40 mft parts, more preferably 1-30 parts, (D) 10-85 parts by weight, preferably 20-80 parts by weight, more preferably 30-75 parts by weight (E) is 1 to 50 parts by weight, preferably 1 to 4 OMM parts, more preferably 1 to 30 parts by weight, and (F) is 0.1 to 20 parts by weight, preferably 0.1 to: L0M * part. More preferably, it is in the range of 0.1 to 5 M parts.

In preparing the cured product of the present invention, the material can be turned directly into the thigh and turned. Further, depending on the situation, the inside of the root canal may be washed in advance with a liquid containing peroxygen-containing water or an aqueous solution of sodium hypochlorite. In applying this hardening material, it is preferable to pretreat the tooth surface with an etching agent and a tooth surface treatment agent such as Z or a primer. As such an etching agent, For example, a hydrochloride having a pH of 5 or less containing hydrochloric acid, nitric acid, phosphoric acid, citric acid, oxalic acid, and the like, as well as JP-A-61-183203 and Patent 63 In the molecule, such as ethylenediaminetetraacetic acid or a salt thereof (EDTA) having a pH of 9 or less in Sl¾, and diethylenetriamine or a salt thereof (DTPA) described in JP-A No. 1-253010 ^ Fat! ^ Or / and ^ = aromatic amines and acetic acid, etc. ^ ft functional groups ^! Sexualization such as ^! We can raise the power. In addition, it is preferable that these etchant 1 compositions contain metal ions such as canolasite ion, iron ion, copper ion and covanoleion. Examples of the primer include water, Z and an organic sea that can be mixed with water, and other substances containing (A) and / or (B) fi ^ of the present invention. In addition, pirates containing polymerization initiators such as ^ ions such as calcium ions, iron ions, copper ions, and cobalt ions, organic or non-oxide amine compounds, and photosensitizers such as potassium quinaquinone. We can raise the power.

Examples of water-miscible organic solvents include alcohols such as methanol, ethanol, propanol, and isobrovir alcohol; ketones such as acetone and methylethyl ketone; ethers such as tetrahydrofuran (THF); Amides such as dimethylformamide; dimethyl sulfoxide (DMSO); and the like. Among them, ethanol, acetone and DMSO are preferably used. The "solvent" usable here plays an important role as a carrier for diffusing the cured product of the present invention into a living body having a high water content.

Before ilffling the root canal ttl material, it is usually difficult to clean it, but it may be washed by a method such as, especially, an aqueous solution containing citric acid and chloride: ^, or an etchant containing EDTA or DTPA * ¾. It is preferred to etch the tooth surface with, preferably, (A) or to flip the primer which contains both nos and ions. In particular, it is preferable to form resin dentin near the contact between the curable yarn and the root canal wall in order to exhibit and maintain a good sealing property.

When the cured product of the present invention is introduced into the root canal, another heat source having X-ray insight It is possible to use a commonly known root canal filler such as a gutta-pouch containing a plastic resin material. Use of a relatively soft M ゝ material such as gutta-pouch is particularly convenient when the curable composition of the present invention is removed outside the root canal. That is, first, after the gutta bar is mechanically or chemically removed according to a method, the cured product of the present invention can be mechanically exposed. As above, hardening for root canal tt Essence or / and dentin surface treatment or

The object of the present invention can be solved.

Hereinafter, the present invention will be described in detail with examples. Example

Difficult cases 1-3 and 赚 example 1

, Examples and Comparative Examples were performed under the following conditions, and the results are shown in Table 1.

(Measurement of operation time)

1 S 0 — 6 8 7 6 (Dental root canal fee)

(Measurement of waiting time)

After mixing the monomer and catalyst in the specified temperature range within 2 3 C, immediately add powder to remove the curable material, and use a spatula (supplied with Super Bond C & B) for 30 seconds. Mixed. Shows the time from the end of mixing until the hardened material becomes ready to be filled by the screw root canal filling. (The waiting time is after filling the hardened material into the root canal. Indicates the time it takes to be able to

, Good body.

(Measurement of pot life)

After the waiting time has elapsed, the time from when the cured ft material reaches a state where it can be removed by the vulva-filled root canal filler until the prepared cured ft! Show. The stringing was confirmed using a spiral root canal filler while occasionally stirring the curable composition.

(Dropping) Add 0.14 g of filler to 0.18 g of MMA, mix for 30 seconds, and immediately place about 0.01 g of this mixture in the center of a glass slide (Microslide S-1111, MAT SUN AMI GLASS I ND..LTD). Stand upright right away and mix for 30 seconds! The movement gg was I † ^, and the dripping distance was taken.

The smaller this value is, the shorter the waiting time and the better the operability is.

Judgment ¾ ^ Almost no dripping 0 ~ 5mm

5 to 15 mm

15 ~ 4 Omm

Very dripping 0 ~ 5 Omm

Gender: flow measurement)

Performed according to ISO 6876 (Dental root canal filling fee).

(Measurement of X-ray cucumber)

Performed according to ISO-6876 (Dental root canal filling material).

G2 ¾M property measurement)

Using a root canal fiber device, the hardened i ^ product of the present invention or a commercially available acid h-lead Eugenol-based root canal ¾¾

(Canal's), then immersed in a methylene punolay water dish, 37. C Stored in a thermostat for up to 30 days, and dyed ^ Ιί ^ into the root canal. Where ¾ ^ is as follows. Enlarged; «Dye from the apical part« toward the inside of the root canal ¾I »L: L≤0.5mm (◎), 0.5 <L≤1.0mm (〇), 1.0 <L≤1.5mm (△), L> 1.5 mm (X) Or Ryuhi Difficulty 1 Male 2 Difficult 3 Comparative 1

M A 32 (.g) Same as left Same as left

4-META 1 Same as left Same as left

B TBB-0 2 Same as left Same as left

C (S i 0 ₂ ) R812 3 R972 3

D ZC 57 Same as left Same as left

E PM A 5 Same as left Same as left

F-0 Same as left Same as left Operation time m 11.5 ― 13.5 Wait time (330 0 0 4.0

Pot life m 7.5 9.5 7.5 Leakage (F-: ΜΙ) 46 47 50 34

X-ray swelling (% Α1) 690 690 690 585 mm m ◎ ◎ ◎ △

* Thermoplastic resin composition: Showa ¾3 Chemical Co., Ltd. The symbol shown in Table 1 indicates the following chemical formula ^).

ZC: Nippon Metal Chemical Co., Ltd., zirconium oxide ZC :, average particle size 6.1 m

Z r0 ₂ W * 99.5%

R812: Nippon Aerojiru Corporation silica R812, average particle size 7X10- ³ m S i 0 ₂ content of 99.8%; drool 12gil = 0mm (little sag) RX200: Nippon Aerosil Co., Ltd., Silica RX200, average particle size 12X10-3 m,

S i 0 ₂ content 99.8%; dripping g separation = Omm (almost no dripping)

R972: Nippon Aerojiru Corporation, silica R 972, average particle size 16 X 10 - ³ zm,

S i 0 ₂ content of 99.8%; vertical Chi βΒϋ = 47 mm (very drooping)

SB: Super Bond C & B, clear polymer powder, average particle size 30 m

4-META: 4-Methacrylonioleoxyshetyl Trimerit

MMA: methyl methacrylate

TBB-0: partially oxidized tributylborane, oxygen about 0.3 mol Z mol ¾Π thigh: polymethyl methacrylate, number average molecular weight 400,000, average particle size 3 Oum

Claims

The scope of the claims

1. (A) Single key ^ ft monomer,

(B) a mortar combination initiator,

(C) a thixotropic agent,

(D) Χ ¾ϋ ^

(Ε) Polymer dissolved or dissolved by component (Α)

«Hardened ttl for root canal products.

2. The cured product as claimed in claim 1, wherein the monofunctional polymerizable monomer (A) contains 0.1 to 30% by weight of a monofunctional monomer having a group.

3. (A) 10-60 parts by weight, component (B) force l-20Mfi part, fij ^ (C) force 1-50 parts by weight, per 1 OOm * part of total (A)-(E) The cured product according to claim 1, wherein the component (D) is 10 to 85 parts by weight and the component (E) is 1 to 50 parts by weight.

4. (A) Monofunctional heavy monomer,

(B) Hoyu insertion initiator,

(C) thixotropic agent,

(D) X ^ i ^

(E) a polymer dissolved or dissolved by the component (A) and

(F) Multi-level β monomer

A root canal hardening product containing 0

5. (A) is 10 to 60 parts by weight, component (B) is 1 to 20 m * parts, β¾3 · (C) force << 1 to 50 parts per OOfi * part of components (A) to (F) 5. The curable composition according to claim 4, wherein the component (D) is 10 to 85 parts by weight, the component (E) is 1 to 50 parts and the component (F) is 0.1 to 20 parts.

6. If component (A) is

The cured tta product according to claim 1 or 4, wherein R ¹ represents H or a CH ₃ group, and R ² is a hydrocarbon group having β number of 1 to 6.

7. The curable S product according to claim 1 or 4, which is (Β) or a trialkylborane which may be partially oxidized.

8. Component (C) is Shirikafuira one is且Tsu 3 i0 ₂ content of 80% or more in average particle size 0.001~1 111, (D) oxidizing the average particle size of l~50 / zm 5. The polymer of claim 1, wherein (E) is a polymer of a monofunctional alkyl (meth) acrylate having a number average molecular weight of 5,000 or more and an average particle size in the range of 1 to 100 m. The hardening snout of 2¾.

9. Containing a dentin surface treatment a ^ comprising an aqueous exfoliated substance having a pH in the range of 0.1 to 5.0 containing a fibrillated ^ 多 or polyvalent ^ cation and a cured ma ^ product according to claim 1 or ⁴ Root canal kit.

10. A dentin surface treatment comprising an aqueous thread material having a pH in the range of 5.0 to 9.0 containing a sex compound I or Z and a polyvalent carbon and the hardening tt! ¾ίroot canal¾¾ kit 0

11. The kit according to claim 9 or 10, wherein the polyvalent metal cation is a transgene cation.

12. The kit of claim 10, wherein the sexualizing ^! Is at least 1S selected from the group consisting of ethylenediaminetetraacetic acid and salts thereof, dimethylenamine triamine pentaacid and salts thereof.

13. A dental root canal kit comprising the curable composition according to claim 1 or 4 and another ffifiX thermoplastic resin having X-ray weaving properties.

14. A root canal comprising a tooth surface treatment S described in claim 9 or 10 and a thread and a thermoplastic resin having X ^ ii ^ property described in claim 1 or 4. Refill nffl kit.