JP4592302B2 - Dentin regenerated pulp capping agent - Google Patents

Description

  The present invention relates to a dentin regenerating pulp capping agent used for the treatment of carious teeth, and more particularly to a dentin regenerating pulp capping agent in which regeneration of dentin is further promoted.

Conventionally, in the treatment of carious teeth, a method has been used in which caries portions of enamel or dentin are excised and then treated by embedding metal or resin in the portions, but at this time the dentin is deleted. The pulp may be exposed on the part.
In this case, if the dental pulp is directly covered with metal or resin, the adhesion between the dental pulp and the metal or resin may be insufficient. It is desirable that the dental pulp be covered with regenerated dentine because it can also be painful to irritation.

  As a method for regenerating such dentin, a calcium hydroxide preparation is sometimes used as a pulp capping agent for the exposed dental pulp, but a necrotic layer due to strong alkali is formed on the pulp surface in contact with calcium hydroxide, or a lower part thereof. Even if the dentin is regenerated, the regeneration rate is considered to be very low, and the pulp is often retracted downward due to necrosis, which is not preferable.

In recent years, various studies have been conducted on ingredients that are effective as a capping agent for the treatment of promoting dentin regeneration in place of calcium hydroxide preparations. For example, N-acetyl-D-glucosamine and the like Contains a medullary capping agent containing saccharides (for example, see Patent Document 1), a dentin-forming capping agent containing bone morphogenetic protein as an active ingredient (for example, see Patent Document 2), and further a bovine blood extract. A second dentin formation accelerator (see, for example, Patent Document 3) has been proposed.
JP-A-6-256132 JP-A-6-340555 JP 2002-363084 A

  However, with the pulp capping agents and promoters described in the above-mentioned patent documents, although a certain degree of dentine regeneration effect can be expected, a regeneration scaffold that is important during such regeneration, that is, a cell scaffold having the ability to regenerate dentin It is not possible to say that sufficient studies have been made, and one of the reasons for the inadequate regeneration effect is that the cells having the ability to regenerate dentin proliferate because the regeneration of dentin proceeds well. It is thought that there is a lack of adequate scaffolding for this purpose.

Then, as a result of the present inventor's earnest research on a pulp capping agent excellent in dentin regeneration ability, the saponified ethylene-vinyl acetate copolymer (A) fine particles and binder (B) in which collagen is immobilized on the surface The present invention was completed by finding that a dentin regenerating pulp capping agent containing a substance has an excellent function of securing a scaffold for the growth of cells having the ability to regenerate dentin and meets the above-mentioned purpose. It was.
Furthermore, in the present invention, the ethylene-vinyl acetate copolymer saponified product (A) fine particles having the collagen immobilized thereon are fine particles having an average particle size of 0.2 to 30 μm, or further contain a boron compound. Has also been found to be a preferred embodiment.

  The dentin regenerating pulp capping agent of the present invention exhibits an excellent dentine regenerating effect and is very useful in biological direct pulp capping in dental treatment.

The present invention is described in detail below.
As the collagen used for the dentin regenerating pulp capping agent of the present invention, any of commercially available types I to V can be used.

  The saponified ethylene-vinyl acetate copolymer (A) for immobilizing the collagen is not particularly limited, but the ethylene content is 5 to 60 mol% (more preferably 10 to 50 mol%, particularly 20 to 45). Mol%, particularly 25 to 40 mol%) is preferred. When the ethylene content is less than 5 mol%, the in vivo stability is deteriorated. On the other hand, when it exceeds 60 mol%, the collagen immobilization rate is deteriorated. Absent.

  The saponification degree of the vinyl acetate component is preferably 85 mol% or more (more preferably 90 mol% or more, particularly 95 mol% or more, particularly 99 mol% or more). When the saponification degree is less than 85 mol%, collagen is used. The immobilization rate of is deteriorated and is not preferable.

  Furthermore, the average degree of polymerization of the saponified ethylene-vinyl acetate copolymer (A) [number-average molecular weight as measured by GPC using the ethylene-vinyl acetate copolymer after reacetylation as an eluent (equivalent to polystyrene) ) Is preferably 100 to 1000 (more preferably 200 to 800, particularly 300 to 700). When the average degree of polymerization is less than 100, the in vivo stability is deteriorated. It is not preferable because the formation of fine particles becomes difficult.

  The saponified ethylene-vinyl acetate copolymer (A) may be copolymerized with a copolymerizable ethylenically unsaturated monomer without departing from the object of the present invention. As olefins such as propylene, 1-butene and isobutene, unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, or salts thereof, or Mono- or dialkyl esters having 1 to 18 carbon atoms, acrylamide, N-alkyl acrylamides having 1 to 18 carbon atoms, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or salts thereof, acrylamidopropyldimethylamine or acid salts thereof Alternatively, acrylamides such as quaternary salts, methacrylamide, N having 1 to 18 carbon atoms Alkylmethacrylamide, N, N-dimethylmethacrylamide, 2-methacrylamideamidopropanesulfonic acid or its salt, methacrylamide such as methacrylamideamidopropylamine or its acid salt or its quaternary salt, N-vinylpyrrolidone, N- N-vinylamides such as vinylformamide and N-vinylacetamide, vinyl cyanides such as acrylonitrile and methacrylonitrile, vinyl ethers such as alkyl vinyl ether having 1 to 18 carbon atoms, hydroxyalkyl vinyl ether and alkoxyalkyl vinyl ether, vinyl chloride, Vinyl halides such as vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl bromide, allyl acetate, allyl chloride, allyl alcohol, dimethylallyl alcohol, trimethyl- ( - acrylamide 3- dimethylpropyl) - ammonium chloride, and the like acrylamido-2-methylpropanesulfonic acid.

  Further, it may be post-modified such as urethanization, acetalization, cyanoethylation, etc. within the range not impairing the gist of the present invention. Further, a saponified ethylene-vinyl acetate copolymer containing silicon as described in JP-A-60-144304 can also be used.

The saponified ethylene-vinyl acetate copolymer (A) is preferably a fine particle having an average particle size of 0.2 to 30 μm (more preferably 0.5 to 10 μm, particularly 0.8 to 5 μm). If the particle size is less than 0.2 μm, the collagen immobilization rate decreases, and if it exceeds 30 μm, uniform cell growth may not be performed.
In order to obtain the finely divided ethylene-vinyl acetate copolymer saponified product (A), industrially produced pellets and granules are spray-dried after low-temperature pulverization or wet pulverization, water-alcohol It can be obtained by a method of cooling into a solution or adding a poor solvent to form an emulsion and spray drying.

  Collagen is immobilized on the fine particles of the saponified ethylene-vinyl acetate copolymer (A) obtained as described above. First, the saponified ethylene-vinyl acetate copolymer ( It is necessary to oxidize the surface of A) to introduce carboxyl groups on the surface of the saponified ethylene-vinyl acetate copolymer.

In such introduction, an oxidation method using ozone can be adopted, and the oxidation method does not leave the oxidizing agent in the saponified ethylene-vinyl acetate copolymer (A) or in the living body as impurities or foreign matters. It is simple in that it is excellent in that it can oxidize a three-dimensional object evenly. Specifically, using an ozone generator, the fine particles of ethylene-vinyl acetate copolymer saponified product (A) can be introduced by gas treatment in a hot water bath. The amount of carboxyl group introduced is preferably about 0.3 to 2 (more preferably 0.5 to 1.5) μmol · cm ⁻² .

  Next, collagen is immobilized on the saponified ethylene-vinyl acetate copolymer (A) having a carboxyl group introduced on its surface. Such immobilization involves immersing the fine particles in (A) in a phosphoric acid solution of collagen. It can be immobilized on the surface of fine particles of the saponified ethylene-vinyl acetate copolymer (A) by ion adsorption.

The amount of collagen immobilized at this time is not particularly limited, but is preferably 5 μg · cm ⁻² or more (more preferably 10 μg · cm ⁻² or more, particularly 16 μg · cm ⁻² or more). If it is less than cm ⁻² , the adhesion efficiency of cells having the ability to regenerate dentin is lowered and the effect of regenerating dentin may be poor, which is not preferable. The upper limit of the amount of collagen immobilized is not particularly defined, but the amount of collagen immobilized is proportional to the amount of carboxyl groups introduced onto the surface of the ethylene-vinyl acetate copolymer saponified product (A) fine particles. If the introduction amount of the group is too large, (A) the durability of the fine particles may be impaired, so the upper limit of the amount of collagen immobilized is about 40 μg · cm ⁻² (moreover 35 μg · cm ⁻² ).

  As the binder (B) used in the pulp capping agent of the present invention, a dental polymerizable monomer (preferably a photocurable monomer) can be used. For example, it is a polymerizable monomer having a (meth) acryloyl group. Includes monofunctional vinyl monomers such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, methacrylates such as glycidyl methacrylate, and acrylates corresponding to these methacrylates; or acrylic acid, methacrylic acid, p-methacryloyloxybenzoic acid, N-2-hydroxy-3-methacryloyloxypropyl-N-phenylglycine, 4-methacryloyloxyethyl trimellitic acid, and its anhydride, 6- Tacryloyloxyhexamethylenemalonic acid, 10-methacryloyloxydecamethylenemalonic acid, 2-methacryloyloxyethyl dihydrogen phosphate, 10-methacryloyloxydecyl dihydrogen phosphate, 2-hydroxyethyl hydrogen phenyl phosphate, etc. Is mentioned.

  Examples of the bifunctional vinyl monomer include aromatic 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane), 2,2 -Bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2 (4-methacryloyl) Oxydiethoxyphenyl) -2 ( -Methacryloyloxydiethoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxyditriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxy) Triethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane and acrylates corresponding to these methacrylates; 2-hydroxyethyl Methacrylate such as methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, or acrylates corresponding to these methacrylates A vinyl monomer having a UNA -OH group, diisocyanate methyl benzene, etc. diadduct obtained from the addition of the diisocyanate compound having an aromatic group such as 4,4'-diphenylmethane diisocyanate (such as urethane diacrylate) and the like.

  Furthermore, aliphatic ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4 -Butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and acrylates corresponding to these methacrylates; methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate or the like A vinyl monomer having an —OH group such as acrylate corresponding to methacrylate, Diadducts obtained from addition with diisocyanate compounds such as diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate); acrylic anhydride, methacrylic anhydride, 1,2-bis ( 3-methacryloyloxy-2-hydroxypropoxy) ethyl, di (2-methacryloyloxypropyl) phosphate and the like.

  Examples of the trifunctional vinyl monomer include methacrylates such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, and acrylates corresponding to these methacrylates. As functional vinyl monomers, pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate and diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylenebis (4-cyclohexylisocyanate), 4,4-diphenylmethane Diisocyanate, It can be exemplified obtained diadduct like from the addition of the diisocyanate compound and the glycidol dimethacrylate as rylene-2,4-diisocyanate.

  These polymerizable monomers may be used alone or in combination of two or more.

  Further, if necessary, a polymerization initiator that functions by heat or light can be used in combination, and as a thermal polymerization initiator, for example, benzoyl peroxide, p-chlorobenzoyl peroxide, tert-butylperoxy- Peroxides such as 2-ethylhexanoate, tert-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, azo compounds such as azobisisobutyronitrile, tributylborane, tributylborane partial oxide, tetraphenylboric acid Boron compounds such as sodium, sodium tetrakis (p-fluorophenyl) borate, tetraphenylborate triethanolamine salt, barbituric acids such as 5-butyl barbituric acid, 1-benzyl-5-phenylbarbituric acid, Sodium benzenesulfinate Sulfinic acid salts such as sodium p- toluenesulfinate acid.

  Photopolymerization initiators include benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, benzyl ketals such as benzyl dimethyl ketal and benzyl diethyl ketal, benzophenone, and 4,4′-dimethylbenzophenone. Benzophenones such as 4-methacryloxybenzophenone, diacetyl, 2,3-pentadionebenzyl, camphorquinone, 9,10-phenanthraquinone, α-diketones such as 9,10-anthraquinone, 2,4-dike Thioxanthone compounds such as ethoxythioxanthone, 2-chlorothioxanthone, methylthioxanthone, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoy ) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2 , 4,6-trimethylbenzoyl) -phenylphosphine oxide and the like.

  Photopolymerization initiators include tertiary amines such as 2- (dimethylamino) ethyl methacrylate, ethyl 4-dimethylaminobenzoate and N-methyldiethanolamine, lauryl aldehyde, dimethylaminobenzaldehyde, terephthalaldehyde and the like. Reducing agents such as sulfur-containing compounds such as aldehydes, 2-mercaptobenzoxazole, 1-decanethiol, thiosalicylic acid, and thiobenzoic acid may be used in combination.

The binder (B) may contain a filler. Examples of the filler include silica, silica alumina, alumina, alumina quartz, glass, zirconia, kaolin, clay, synthetic zeolite, calcium phosphate, and barium sulfate. And inorganic fillers such as titanium oxide, and organic fillers such as polymethyl methacrylate powder. Furthermore, an organic-inorganic composite filler obtained by polymerizing and coating the surface of the above-mentioned inorganic filler with a polymerizable monomer, or suspension polymerizing a polymerizable monomer in the presence of the inorganic filler is also used. The particle size of these fillers is 100 μm or less, usually 30 μm or less, and fine fillers having a particle size of 10 to 50 μm are also used. The inorganic filler may be surface-treated with a silane coupling agent or the like in advance to be hydrophilized or hydrophobized.
Specific examples of the binder (B) used in the present invention include “Clear Fill Mega Bond” manufactured by Kuraray Medical Co., Ltd., “AQ Bond” manufactured by Sun Medical Co., Ltd., and 3M Healthcare Co., Ltd. ) "Single bond" manufactured by the company.

  Although the content ratio of the saponified ethylene-vinyl acetate copolymer (A) and the binder (B) in the dentin regenerating pulp capping agent of the present invention is not particularly limited, 100 parts by weight of the binder (B) in the pulp capping agent The ethylene-vinyl acetate copolymer saponified product (A) is preferably contained in an amount of 1 to 100 parts by weight (more preferably 5 to 50 parts by weight, particularly 8 to 30 parts by weight). If the amount is less than parts by weight, the action and effect of the present invention is poor. On the other hand, if the amount exceeds 50 parts by weight, the adhesive force and strength of the pulp capping agent are undesirably lowered.

In the present invention, the above-mentioned ethylene - pre boron compound vinyl acetate copolymer saponified (A) (C) Contact Ku be contained. Examples of the boron compound (C) include boric acid, calcium borate, cobalt borate, zinc borate (zinc tetraborate, zinc metaborate, etc.), aluminum borate / potassium borate, ammonium borate (ammonium metaborate, tetra Ammonium borate, ammonium pentaborate, ammonium octaborate, etc.), cadmium borate (cadmium orthoborate, cadmium tetraborate, etc.), potassium borate (potassium metaborate, potassium tetraborate, potassium pentaborate, six Potassium borate, potassium octaborate, etc.), silver borate (silver metaborate, silver tetraborate, etc.), copper borate (cupric borate, copper metaborate, copper tetraborate, etc.), sodium borate (Sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, octaborate Thorium, etc.), lead borate (lead metaborate, lead hexaborate, etc.), nickel borate (nickel orthoborate, nickel diborate, nickel tetraborate, nickel octaborate, etc.), barium borate (orthoboric acid) Barium, barium metaborate, barium diborate, barium tetraborate, etc.), bismuth borate, magnesium borate (magnesium orthoborate, magnesium diborate, magnesium metaborate, trimagnesium tetraborate, pentamagnesium tetraborate) ), Manganese borate (manganese borate, manganese metaborate, manganese tetraborate, etc.), lithium borate (lithium metaborate, lithium tetraborate, lithium pentaborate, etc.), borax, Listed are borate minerals such as carnite, inyoite, agate stone, suian stone, and zyberite. It is, preferably borax, boric acid, sodium borate (sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate acid, eight sodium borate) may be used.

The content of the boron compound (C) is an ethylene -. 0.001 parts by weight of boron converted based on vinyl acetate copolymer saponified 100 parts by weight (more from 0.01 to 0 07 parts by weight ) Is preferably contained, and when the content is less than 0.001 part by weight, the durability of the pulp capping agent may decrease, and conversely, when the content is more than 0.1 part by weight The effect of the present invention may not be sufficiently exhibited, which is not preferable.

  When the boron compound (C) is contained in the saponified ethylene-vinyl acetate copolymer, the saponified ethylene-vinyl acetate copolymer can be contained in an aqueous solution of the boron compound (C).

  The method for bringing the saponified ethylene-vinyl acetate copolymer into contact with such an aqueous solution is not particularly limited. Usually, the saponified ethylene-vinyl acetate copolymer formed into a pellet is put into the aqueous solution while stirring. The boron compound (C) is preferably contained.

  In applying the dentin regenerating pulp capping agent of the present invention to caries dental treatment, after the caries portion is excised, the surface of the excised portion is sterilized and disinfected with sodium hypochlorite, hydrogen peroxide solution, etc. The primer can be treated with a primer, and the spinal cord can be applied and then cured by irradiating UV light from a high pressure, Nakasho, low pressure mercury lamp, visible light from a halogen lamp, xenon lamp, metal halide lamp, or the like.

Thus, a pulp capping agent for dentin regeneration is formed according to the present invention. Usually, a composite resin is filled on the pulp capping agent and repaired. Such composite resin is blended with a filler for the purpose of improving mechanical strength. Examples of the filler include silica, silica alumina, alumina, alumina quartz, glass, zirconia, kaolin, clay, synthetic zeolite, calcium phosphate, sulfuric acid. Examples thereof include inorganic fillers such as barium and titanium oxide, and organic fillers such as polymethyl methacrylate powder. Furthermore, an organic-inorganic composite filler obtained by polymerizing and coating the surface of the above-mentioned inorganic filler with a polymerizable monomer, or suspension polymerizing a polymerizable monomer in the presence of the inorganic filler is also used. The particle size of these fillers is 100 μm or less, usually 30 μm or less, and fine fillers having a particle size of 10 to 50 μm are also used. The inorganic filler may be surface-treated with a silane coupling agent or the like in advance to be hydrophilized or hydrophobized.
In addition, as the polymerizable monomer used as the composite resin, known monomers generally used for dental composite materials can be used. The most representative examples of the polymerizable monomer are polymerizable monomers having a meta (acryloyl) group. Specifically, bisphenol A-glucidyl methacrylate adduct, 2,2-bis (4- (methacryloxyethoxy) phenyl) propane, 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane, Examples include ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, urethane dimethacrylate, tetrafunctional urethane methacrylate, hexafunctional urethane methacrylate, trimethylolpropane trimethacrylate, methyl methacrylate, and lauryl methacrylate.

  The filler is usually blended in an amount of about 100 to 900 parts by weight with respect to 100 parts by weight of the polymerizable monomer in the composite resin.

Moreover, well-known additives, such as a pigment and a polymerization inhibitor, can be mix | blended with a composite resin other than said filler.
The composite resin can also be cured by irradiating UV light from a high pressure, medium pressure, low pressure mercury lamp, visible light from a halogen lamp, xenon lamp, or metal halide lamp.

Hereinafter, the present invention will be specifically described with reference to examples.
In the examples, “parts” and “%” are based on weight unless otherwise specified.

Reference example 1
Saponified ethylene-vinyl acetate copolymer having an average particle size of 1 μm [ethylene content 29 mol%, saponification degree 99.7 mol%, average polymerization degree 450, boric acid not added] (A) Ozone irradiation to fine particles Carboxyl groups were introduced on the surface (introduction amount 0.86 μmol · cm ⁻² ). On the other hand, commercially available bovine-derived type I atelocollagen [0.94% containing 5 mM phosphoric acid solution, pH 3.7, manufactured by Nitta Gelatin Co., Ltd.] was added to a 5 mM phosphoric acid aqueous solution [pH 3.7, Nacalai Tesque, Inc.] The surface of the saponified ethylene-vinyl acetate copolymer (A) is prepared by immersing and stirring the fine particles at 25 ° C. for 16 hours. Collagen was immobilized on. The amount of collagen immobilized was 20 μg · cm ⁻² .

  Next, 10 parts of saponified ethylene-vinyl acetate copolymer with the collagen immobilized above and an adhesive [Kuraray Medical Co., Ltd. “Clearfil Megabond”] (B) 100 parts Were mixed to obtain a dentin regenerating pulp capping agent of the present invention.

The following dentin regeneration experiment was performed using the dentin regeneration pulp capping agent obtained above.
Under general anesthesia, 5 V 1-year-old vehicle dogs were subjected to black V-class cavity in the upper and lower canines and molars, and an exposed surface with a diameter of 2 mm was formed at the center bottom. Then, the exposed cave was divided into two groups (for the example and the comparative example), and one (for the example) was exposed to a primer [Kuraray Medical Co., Ltd. “Clearfil Megabond”. ] Is further applied onto the spinal cord preparation of the present invention obtained above, cured using a metal halide lamp, and then composite resin [Clearfil AP manufactured by Kuraray Medical Co., Ltd. -X "] was charged and cured in the same manner. The same treatment was applied to the other (comparative example) exposed cave group except that a commercially available adhesive ("Clearfil Megabond" manufactured by Kuraray Medical Co., Ltd.) was used instead of the capping agent. .
Three months later, the beagle dog was euthanized, the extracted tooth was decalcified (4 ° C), and a thin slice was prepared. When the amount of regeneration was evaluated with a scanning electron microscope, it was confirmed that there was almost no inflammation in the dental pulp and the thickness of the regenerated dentin layer was 500 μm.

Comparative Example 1
In Reference Example 1 , as a result of evaluation of the exposed sinus cave group for comparative example (using only the adhesive without adding the saponified ethylene-vinyl acetate copolymer to which collagen was immobilized), regenerated ivory The thickness of the stratum corneum was confirmed to be 360 μm, but inflammation was seen in the pulp.

Example 1
In Reference Example 1 , an ethylene-vinyl acetate copolymer saponified product having an ethylene content of 29 mol%, a saponification degree of 99.7 mol%, an average polymerization degree of 450, and a boric acid addition amount of 0.03 parts was used. As a result of evaluation in the same manner, almost no inflammation was observed in the dental pulp portion of the detrusor sinus group for Examples, and the thickness of the regenerated dentin layer was 520 μm.
The introduced amount of carboxyl groups at this time was 1.30 μmol · cm ⁻² , and the amount of collagen immobilized was 30 μg · cm ⁻² .

Example 2
In Reference Example 1 , an ethylene-vinyl acetate copolymer saponified product having an ethylene content of 29 mol%, a saponification degree of 99.7 mol%, an average polymerization degree of 450, and a boric acid addition amount of 0.03 parts, and As a result of evaluating in the same manner except that the addition amount was 20 parts, there was almost no inflammation in the pulp part of the detrusor sinus group for Example, and the thickness of the regenerated dentin layer was 550 μm.

  The dentin regeneration pulp capping agent of the present invention is very useful in biological direct pulp capping in dental treatment.

Claims (6)

Collagen is immobilized on the surface of a saponified ethylene-vinyl acetate copolymer containing a boron compound (C), saponified ethylene-vinyl acetate copolymer (A) particles having an average particle size of 0.2 to 30 μm , 0.001 parts by weight der in terms of boron based on the vinyl acetate copolymer saponified 100 parts by weight - binder (B) and Ri greens contain, content of ethylene of the boron compound (C) Dentin regenerating pulp capping agent characterized by that. Collagen immobilized ethylene - dentine according to claim 1, wherein the content is characterized in that the binder (B) 1 to 100 parts by weight per 100 parts by weight of vinyl acetate copolymer saponified (A) Regenerated pulp capping agent. The dentine regeneration pulp capping agent according to claim 1 or 2, wherein the binder (B) contains a photocurable monomer. The amount of collagen immobilized is 5 to 40 μg · cm ^-2 The dentin regeneration pulp capping agent according to any one of claims 1 to 3, wherein After the collagen-immobilized ethylene-vinyl acetate copolymer saponified product (A) fine particles oxidize the surface of the ethylene-vinyl acetate copolymer saponified product (A) fine particles to introduce carboxyl groups, collagen phosphoric acid The dentin regeneration pulp capping agent according to any one of claims 1 to 4, wherein collagen is immobilized on the surface of saponified ethylene-vinyl acetate copolymer (A) particles by dipping in a solution. . The introduction amount of the carboxyl group is 0.3-2 μmol · cm ^-2 The dentin regenerating pulp capping agent according to claim 5, wherein