JP2007210944A - Packing kit for dentistry - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a packing kit for dentistry, comprising a dental composite resin and an adhesive, capable of obtaining a dental composite resin cured product having sufficient adhesive strength and marginal sealing property even by visible light irradiation of one step. <P>SOLUTION: The packing kit for dentistry is prepared by independently packaging each of the dental composite resin and the adhesive and obtained by combining so that the double bond remaining ratio after 4 s photoirradiation on the dental composite resin is higher than the double bond remaining ratio after 4 s photoirradiation on the adhesive to develop practical marginal sealing property and/or adhesive strength by one step photoirradiation. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a dental filling kit. More specifically, the present invention relates to a dental composite resin having a specific composition used for filling a dental cavity and a dental filling kit including an adhesive in its configuration.

  The performance of dental composite resin (hereinafter sometimes abbreviated as “CR”) as a metal substitute material has evolved rapidly in conjunction with the improvement in performance of dental adhesives, and has been used sufficiently in clinical practice as a molding restoration material. Recognized as tolerable. In addition, since the performance of the adhesive has greatly improved, troubles such as falling off of the CR cured product have been extremely reduced. Among these CRs, in recent years, a large number of photopolymerization type CRs that are polymerized and cured by irradiation with visible light have been occupied.

  This photopolymerization CR generally has (1) First, an adhesive (for example, AQ Bond Plus: manufactured by Sun Medical Co., Ltd.) is applied to the cavity surface, and the adhesive is cured by irradiation with visible light. (2) Next, CR (for example, Metafil Flo: manufactured by Sun Medical Co., Ltd.) is filled in the cavity and irradiated with visible light again to cure the CR itself.

  Therefore, when performing molding restoration using these photopolymerization type CRs, it is necessary to first insert a tip of a light irradiator into the oral cavity in order to cure the adhesive. However, especially when the cavity to be treated is located deep inside the oral cavity, the tip of the light irradiator can be inserted deep inside the oral cavity to ensure that the adhesive applied to the cavity surface is cured. It is necessary and it may be difficult to insert the tip of the light irradiator. Also, patients may be painful because they must open their mouths wide during surgery. Furthermore, when the mouth is opened, saliva overflows and the cavity surface is contaminated. Therefore, it is desirable to avoid light irradiation in the oral cavity as many times as possible for both operators and patients.

  However, when a conventional photopolymerization CR and an adhesive are used in combination, the adhesive is applied to the cavity surface, and the CR is further filled without substantially irradiating visible light. Even when a CR cured product was obtained by irradiation, performances such as adhesion strength to the tooth or its prosthesis and marginal sealing were not sufficient.

  The present invention provides a dental composite resin cured product having sufficient adhesive strength and marginal sealing properties even by one-stage light irradiation, and has an operability comprising a dental composite resin and an adhesive as components. An object is to provide an improved dental filling kit.

The present invention is a dental filling kit having photopolymerizability comprising a dental composite resin and an adhesive as constituents,
The dental filling kit is formed so as to be able to express a practical edge sealing property and / or adhesive strength by one-stage light irradiation,
The residual rate of double bonds remaining in the dental composite resin after light irradiation of the dental composite resin for 4 seconds is the double bond remaining in the adhesive after light irradiation of the adhesive for 4 seconds. The dental filling kit is characterized by being higher than the residual rate.

Further, the present invention is a dental filling kit having photopolymerizability comprising a dental composite resin and an adhesive as constituent elements,
The dental filling kit is formed so as to be able to express a practical edge sealing property and / or adhesive strength by one-stage light irradiation,
The residual ratio of polymerizable double bonds in the adhesive after light irradiation of the adhesive and the dental composite resin for 4 seconds under the same conditions is 30% or less, and the polymerizable double bond in the dental composite resin The dental filling kit is characterized in that the residual rate is 60% or more.

Furthermore, the present invention is a dental filling kit having photopolymerizability comprising a dental composite resin and an adhesive as constituent elements,
The dental filling kit is formed so as to be able to express a practical edge sealing property and / or adhesive strength by one-stage light irradiation,
The dental filling kit is characterized in that the polymerization induction period of the dental composite resin is longer than the polymerization induction period of the adhesive.

  As a result of intensive studies to solve the above problems, the present inventor determined the residual rate of double bonds remaining in the dental composite resin 4 seconds after the start of photocuring in the adhesive 4 seconds after the start of photocuring. If it is higher than the residual rate of the double bond remaining in the kit, it is a kit comprising a dental composite resin and an adhesive having a practical marginal sealing property and / or adhesive strength by one-stage light irradiation. Has been found, and the present invention has been completed.

  The polymerization reaction starts by light irradiation of the photocurable dental composite resin and adhesive. When the polymerization reaction proceeds in this way, volume shrinkage occurs with the polymerization of the dental composite resin. Accordingly, when the polymerization reaction rate of the dental composite resin is faster than the polymerization reaction rate of the adhesive, the polymerization reaction of the dental composite resin proceeds and the volume shrinkage occurs before the adhesive applied to the tooth surface is cured. As a result, the stress accompanying the volume shrinkage of the dental composite resin is applied to the adhesive, and the adhesive peels off from the tooth surface, leading to a decrease in the cavity sealing ability and adhesive strength.

  On the other hand, if the polymerization reaction rate of the adhesive is faster than the polymerization reaction rate of the dental composite resin, the adhesive cures faster than the dental composite resin and adheres firmly to the tooth surface. Can withstand the stress of volume shrinkage that accompanies polymerization. In other words, if the residual rate of the double bonds remaining in the dental composite resin is made higher than the residual rate of the double bonds remaining in the adhesive, a practical marginal blockage can be achieved even by one-step light irradiation. And a dental composite resin and adhesive kit having adhesiveness and adhesive strength can be obtained.

In general, a dental composite resin and an adhesive are blended with a polymerization inhibitor or a polymerization inhibitor so that the polymerization reaction does not proceed during storage. After the light irradiation, before the substantial polymerization reaction starts. In the polymerization induction period, the polymerization inhibitor and polymerization inhibitor added in advance for stabilizing the dental composite resin and the adhesive are consumed, and the polymerization reaction does not proceed simultaneously with the light irradiation. That is, after the light irradiation, the polymerization reaction occurs through a polymerization induction period in which a polymerization inhibitor or a polymerization inhibitor is consumed in a short time (polymerization induction period) but not at the same time as the light irradiation. proceed. Therefore, if the polymerization reaction of the adhesive is allowed to proceed first by making the polymerization induction period of the dental composite resin longer than the polymerization induction period of the adhesive, the adhesive hardens first, Sufficient adhesive strength can be expressed. After the adhesive strength of the adhesive to the tooth surface becomes sufficiently high in this way, the adhesive strength of the adhesive can be resisted by the volume shrinkage stress accompanying the polymerization of the dental composite resin by polymerizing the dental composite resin. it can. That is, by setting the polymerization induction period of the dental composite resin longer than the polymerization induction period of the adhesive, the dental composite resin has practical marginal sealing properties and adhesive strength even by one-step light irradiation. And an adhesive kit can be obtained.

  Using the dental filling kit of the present invention, the adhesive is applied to the cavity surface, and the adhesive is further filled with the dental composite resin CR in the cavity without substantially irradiating visible light. Even when the dental composite resin is cured by irradiation with visible light, it is excellent in performance such as adhesion strength to the tooth or its prosthesis and marginal sealing. In addition, since the cavity is treated with an adhesive and then the dental composite resin is filled, visible light irradiation is performed only once, so that the operation time can be shortened. Furthermore, since the visible light irradiated portion is also a dental composite resin-filled surface, unlike the conventional case, confirmation of light irradiation is easy and clinical operability is extremely excellent.

Hereinafter, the dental filling kit of the present invention will be specifically described.
The dental filling kit of the present invention comprises a dental composite resin and an adhesive, which are packaged separately.

<Dental composite resin constituting the dental filling kit of the present invention>
(A) Dental composite resin (A) Dental composite resin constituting the dental filling kit of the present invention comprises a monomer (a), a photopolymerization initiator (b), a polymerization inhibitor and / or an antioxidant. (C) and a filler (d) are contained. When each compounding amount is 100 parts by weight of (A) dental composite resin, monomer (a), photopolymerization initiator (b), polymerization inhibitor or / and antioxidant (c), and filler ( It mix | blends so that the total weight part of d) may be 100 weight part. Specifically, the monomer (a) is preferably in the range of 5 to 70 parts by weight, more preferably in the range of 7.5 to 60 parts by weight, and still more preferably in the range of 10 to 50 parts by weight. The agent (b) is preferably in the range of 0.01 to 5 parts by weight, the polymerization inhibitor and / or the antioxidant (c) is usually in the range of 0.001 to 10 parts by weight, and the filler (d) is Usually, it is in the range of 50 to 90 parts by weight, and the total is 100 parts by weight.

  Within the above range, (A) a dental composite resin containing (a), a photopolymerization initiator (b), a polymerization inhibitor or / and an antioxidant (c), and a filler (d) is sufficient as a tooth filling material. It is preferable because it has excellent mechanical strength and aesthetic performance.

[Monomer (a)]
(A) As the monomer (a) used in the dental composite resin, a known monofunctional monomer (a1) or polyfunctional monomer (a2) can be used, preferably A radical polymerizable monomer can be used.

Among these monofunctional monomers (a1) or polyfunctional monomers (a2), (meth) acrylate monomers can be preferably used because of their relatively low irritation to the human body.
As the monofunctional (meth) acrylate that can be used as the monofunctional monomer (a1) in the present invention, for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate Alkyl (meth) acrylates such as lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate;
2-hydroxyethyl (meth) acrylate, 2 or 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 1,2 -Or 1,3-dihydroxypropyl mono (meth) acrylate, erythritol mono (meth)
(Meth) acrylic acid hydroxyalkyl esters such as acrylates;
Polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate;
Ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polypropylene glycol monoalkyl (Poly) glycol monoalkyl ether (meth) acrylates such as ether (meth) acrylates;
Fluoroalkyl esters of (meth) acrylic acid such as perfluorooctyl (meth) acrylate and hexafluorobutyl (meth) acrylate;
Silane compounds having a (meth) acryloxyalkyl group such as γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltri (trimethylsiloxy) silane,
And (meth) acrylate having a heterocyclic ring such as tetrafurfuryl (meth) acrylate.

Of these monofunctional (meth) acrylates, alkyl (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate;
Hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 1,3-dihydroxypropyl mono (meth) acrylate, erythritol mono (meth) acrylate;
Particularly preferred are (meth) acrylates having an ethylene glycol chain in the molecule, such as triethylene glycol monomethyl ether (meth) acrylate and triethylene glycol mono (meth) acrylate.

These monofunctional monomers can be used alone or in combination of two or more.
Moreover, these monofunctional monomers can also be used in combination with the polyfunctional monomer described later.

In the present invention, as the polyfunctional (meth) acrylate that can be used as the polyfunctional monomer (a2), for example,
Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Poly (meth) acrylates of alkane polyols such as pentaerythritol tetra (meth) acrylate,
Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, dibutylene glycol di (meth) acrylate, Polyoxyalkane polyol poly (meth) acrylates such as dipentaerythritol hexa (meth) acrylate,
Bis (methacryloxyalkyloxycarbonylamino) alkanes such as 1,6-bis (methacryloxyethyloxycarbonylamino) -2,2,4-trimethylhexane (UDMA);
An aliphatic or aromatic di (meth) acrylate represented by the following formula (1);

(In the formula (1), R is a hydrogen atom or a methyl group, m and n may be the same or different, is an integer of 0. And R ^1,

Either)
An aliphatic or aromatic epoxy di (meth) acrylate represented by the following formula (2);

(In the formula (2), R is a hydrogen atom or a methyl group, n is an integer of 0 to 10, and R ¹ is

It is. );
And a polyfunctional (meth) acrylate having a urethane bond in the molecule represented by the following formula (3).

(In the formula (3), R is a hydrogen atom or a methyl group, and R ² is

It is. )
Among these polyfunctional (meth) acrylates, for example, di (meth) acrylate having an ethylene glycol chain in the molecule such as triethylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate,
A compound represented by the following formula (1) -a;

(Here, the definitions of R, m and n are the same as in formula (1).);
A compound represented by the following formula (2) -a;

(Here, the definition of R is the same as in formula (2).);
A compound represented by the following formula (3) -a;

(Here, the definition of R is the same as in formula (3).),
Etc. are particularly preferably used.
Moreover, the monomer (a3) which has an acidic group and a hydroxyl group can be used. These monomers having an acidic group and a hydroxyl group in the molecule have the effect of improving the compatibility between the adhesive and the dental composite resin, while the monomer (a) is used for the dental composite resin (A). If the amount is too large, the mechanical properties of the dental composite resin may be deteriorated.

As said acidic group contained in a monomer (a3), a carboxyl group or its anhydride group, a phosphoric acid group, a sulfonic acid group etc. can be mentioned.
As the monomer (a3), for example,
A compound in which a carboxyl group is directly bonded to a vinyl (vinylidene) group such as (meth) acrylic acid,
A compound having one or more (meth) acryloxyalkyl groups in a benzene-based compound having a plurality of carboxyl groups such as 1,4-di (meth) acryloxyethylpyromellitic acid,
A compound having one or more (meth) acryloxyalkyl groups in a naphthalene-based compound having a plurality of carboxyl groups such as 6- (meth) acryloxyethylnaphthalene-1,2,6-tricarboxylic acid,
N- (meth) acryloylaminobenzoic acid series such as N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-o-aminobenzoic acid, N- (meth) acryloyl-m-aminobenzoic acid Compound,
Salicylic acid having an N- (meth) acryloylamino group such as N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid,
4- (meth) acryloxyethyl trimellitic acid, 4- (meth) acryloxybutyl trimellitic acid, 4- (meth) acryloxyhexyl trimellitic acid, 4- (meth) acryloxydecyl trimellitic acid ( (Meth) acryloxyalkyl trimellitic acid, and its anhydride,
(Meth) acryloyloxybenzoic acid such as 2- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid,
β- (meth) acryloyloxyethyl hydrogen esters such as β- (meth) acryloyloxyethyl hydrogen succinate, β- (meth) acryloyloxyethyl hydrogen maleate, β- (meth) acryloyloxyethyl hydrogen phthalate Compound,
11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid or the like (
(Meth) acryloyloxy or acryloyloxy, a (meth) acrylic acid (preferably an ester thereof) containing a carboxylic acid group such as a chain aliphatic compound having one or more carboxyl groups at the other end or a partial anhydride thereof body;
vinyl compound monomers containing an aromatic carboxylic acid group such as vinyl benzoic acid such as p-vinylbenzoic acid;
2- (meth) acryloxyethyl phosphoric acid, 2- (meth) acryloxyethyl phenyl phosphoric acid, 10- (meth) acryloxydecyl phosphoric acid, PM-2, 2-acryloxyethyl phosphoric acid, (Meth) acrylic containing a (meth) acryloxy group such as acid phosphooxypolyoxyethylene glycol monomethacrylate, acid phosphooxypolyoxypropylene glycol monomethacrylate or a phosphoric acid group such as a hydrocarbon compound having an acryloxy group and a phosphoric acid group An acid (preferably its ester) monomer;
In addition, a monomer containing a sulfonic acid group such as a styrene sulfonic acid compound such as p-styrene sulfonic acid, a compound having an acrylamide group and a sulfonic acid group such as 2-acrylamido-2-methylpropane sulfonic acid, etc. Can be mentioned.

  Among these monomers having an acidic group, 4- (meth) acryloxyethyl trimellitic acid, 4- (meth) acryloxydecyl trimellitic acid, 2- (meth) acryloxyethyl phosphoric acid, 2- ( (Meth) acryloxyethyl phenylphosphoric acid, 10- (meth) acryloxydecylphosphoric acid, or a compound represented by the following formula (4) is preferred.

(In the formula, n is 0 or 1, a is 1 or 2, and b is an integer that satisfies the relationship b = (3-a).)
These monomers containing an acidic group can be used alone or in combination of two or more.

Moreover, as a monomer which has a hydroxyl group, 2-hydroxy-3-2-naphthoxypropyl methacrylate can be mentioned, for example.
Other examples of the monomer (a) that can be used include vinyl acetate, vinyl pyrrolidone, and maleic acid alkyl esters. These can be used alone or in combination of two or more.

The total weight of the monomer (a3) relative to the total weight of the monomers (a1), (a2) and (a3) is usually 15% by weight or less, preferably 10% by weight or less.
[Photopolymerization initiator (b)]
The polymerization initiator blended in the dental composite resin of the present invention is a photopolymerization initiator.

Examples of the photopolymerization initiator include (b1) α-ketocarbonyl compounds and (b2) acylphosphine oxide compounds.
As the α-ketocarbonyl compound (b1) blended as a photopolymerization initiator in the present invention,
For example, α-diketone, α-ketoaldehyde, α-ketocarboxylic acid, α-ketocarboxylic acid ester and the like can be mentioned. Specifically, diacetyl, 2,3-pentadione,
2,3-hexadione, benzyl, 4,4′-dimethoxybenzyl, 4,4′-diethoxybenzyl, 4,4′-oxybenzyl, 4,4′-dichlorobenzyl, 4-nitrobenzyl, α-naphthyl , Β-naphthyl, camphorquinone, camphorquinonesulfonic acid, camphorquinonecarboxylic acid, α-diketones such as 1,2-cyclohexanedione;
Α-ketoaldehydes such as methylglyoxal and phenylglyoxal;
Examples include pyruvic acid, benzoylformic acid, phenylpyruvic acid, methyl pyruvate, ethyl benzoylformate, methyl phenylpyruvate, and butyl phenylpyruvate.

  Among these α-ketocarbonyl compounds, α-diketones are preferably used from the viewpoint of stability and the like, and among α-diketones, diacetyl, benzyl and camphorquinone are particularly preferable.

Examples of the acylphosphine oxide compound (b2) blended as a photopolymerization initiator in the present invention include benzoyldimethoxyphosphine oxide, benzoylethoxyphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2-methylbenzoyldiphenylphosphine oxide, and 2,4. , 6-trimethylbenzoyldiphenylphosphine oxide and the like. The component (b1) and the component (b2) can be used alone or in combination.

Furthermore, in order to improve the polymerization initiation effect of the photopolymerization initiator, a reducing compound that does not adversely affect the catalytic effect of the compound can be used in combination. As these reducing compounds,
For example, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-diethanol-p-toluidine, N, N-dimethyl-p
-Tert-butylaniline, N, N-dimethylanisidine, N, N-dimethyl-p-chloroaniline, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminobenzoic acid, and
For example, ester compounds such as methyl N, N-dimethylaminobenzoate, ethyl N, N-dimethylaminobenzoate, 2-n-butoxyethyl N, N-dimethylaminobenzoate, N, N-diethylaminobenzoic acid, and Ester compounds such as methyl N, N-diethylaminobenzoate, ethyl N, N-diethylaminobenzoate, butoxyethyl N, N-diethylaminobenzoate, N, N-dimethylaminobenzaldehyde, N-phenylglycine, N-phenylglycine Alkali metal salt, N-tolylglycine, alkali metal salt of N-tolylglycine, N, N- (3-methacryloyloxy-2-hydroxypropyl) phenylglycine, triethanolamine, N-ethyldiethanolamine, N-methyldiethanolamine , Triallylamine, N, N-dimethyl Le aminoethyl methacrylate, N, N-diethylethanolamine, and organic reducing compound triethylamine, etc.. In addition, examples of the reducing compound other than the above include organic sulfinic acid or a salt thereof. Of these, organic sulfinic acid, or alkali metal salts, alkaline earth metal salts, amine salts, and ammonium salts of organic sulfinic acids can be preferably used.

  Examples of the alkali metal salt include lithium salt, sodium salt, potassium salt and the like, and examples of the alkaline earth metal salt include magnesium salt, calcium salt, strontium salt and barium salt. .

Examples of the amine salts include salts of primary amines such as methylamine, ethylamine, propylamine, butylamine, aniline, toluidine, phenylenediamine, and xylylenediamine;
Salts of secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, pepyridine, N-methylaniline, N-ethylaniline, diphenylamine, N-methyltoluidine;
Trimethylamine, triethylamine, pyridine, N, N-dimethylaniline, N, N-di (β-hydroxyethyl) aniline, N, N-diethylamine, N, N-dimethyltoluidine, N, N-diethyltoluidine, N, N- Mention may be made of salts of tertiary amines such as (β-hydroxyethyl) toluidine.

  Examples of the salt of the ammonium compound include ammonium salt, tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, and trimethylbenzylammonium salt.

  Examples of the above organic sulfinic acid include ethane sulfinic acid, propane sulfinic acid, hexane sulfinic acid, octane sulfinic acid, decane sulfinic acid, dodecane sulfinic acid and other alkane sulfinic acids, cyclohexane sulfinic acid, cyclooctane sulfinic acid and other alicyclic rings. Aromatic sulfinic acids such as benzenesulfinic acid, o-toluenesulfinic acid, p-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, chlorobenzenesulfinic acid and naphthalenesulfinic acid be able to.

Examples of the organic sulfinates include lithium benzenesulfinate, sodium benzenesulfinate, potassium benzenesulfinate, magnesium benzenesulfinate, calcium benzenesulfinate, strontium benzenesulfinate, barium benzenesulfinate, and benzenesulfinate. Butylamine salt, benzenesulfinic acid aniline salt, benzenesulfinic acid toluidine salt, benzenesulfinic acid phenylenediamine salt, benzenesulfinic acid diethylamine salt, benzenesulfinic acid diphenylamine salt, benzenesulfinic acid triethylamine salt, benzenesulfinic acid ammonium salt, benzenesulfinic acid tetra salt Examples include methylammonium and trimethylbenzylammonium benzenesulfinate. It is possible. Furthermore, o-toluenesulfinate lithium, o-toluenesulfinate sodium, o-toluenesulfinate potassium, o-toluenesulfinate calcium, o-toluenesulfinate cyclohexylamine salt, o-toluenesulfinate aniline salt, o-toluene Ammonium sulfinate, tetraethylammonium o-toluenesulfinate, lithium p-toluenesulfinate, sodium p-toluenesulfinate, potassium p-toluenesulfinate, p-toluenesulfinate, barium p-toluenesulfinate, p- Toluenesulfinic acid ethylamine salt, p-toluenesulfinic acid toluidine salt, p-toluenesulfinic acid N-methylaniline salt, p-toluenesulfinic acid pyridine salt, p-toluenesulfinic acid Ammonium salt, tetramethylammonium p-toluenesulfinate, sodium β-naphthalenesulfinate, strontium β-naphthalenesulfinate, β-naphthalenesulfinate triethylamine, β-naphthalenesulfinate N-methyltoluidine, β-naphthalenesulfinate ammonium, Examples thereof include trimethylbenzylammonium β-naphthalenesulfinate.

Other examples of reducible compounds that can be used include barbituric acid and barbituric acid derivatives. Specifically, 1,3,5-trimethylbarbituric acid, 1,3,
5-triethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,5-
Dimethyl barbituric acid, 1-methyl-5-ethyl barbituric acid, 1-methyl-5-propyl barbituric acid, 5-ethyl barbituric acid, 5-propyl barbituric acid, 5-butyl barbituric acid, 5- Methyl-1-butyl barbituric acid, 1-benzyl-5-phenylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid or alkali metal salts thereof can be preferably used.

  Among these reducing compounds, organic sulfinic acid or a salt thereof can be preferably used. The compounding quantity of the said reducing compound exists in the range of 0.3-5 times normally with respect to the photoinitiator amount to be used.

[Polymerization inhibitor, antioxidant (c)]
The polymerization inhibitor and / or antioxidant used in the present invention can be appropriately selected from known ones.

Examples of the polymerization inhibitor used in the present invention include compounds such as 4-methoxyphenol, hydroquinone, and phenothiazine. Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant, and more specifically 2,6-di-t-butyl-p. -Cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propinate, 2,2'- Methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4 , 4 '
-Butylidenebis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, tetras [methylene-3- (3 ', 5 '-Di-t-butyl, hydroxyphenol) propionate] methane, 1,3,5-tris (3', 5'-di-t-butyl-4-hydroxybenzyl) -sec-triazine-2, 4,6- (1H, 3H, 5H) trione, dilauryl 3,3-thiodipropionate, triphenyl phosphite, diphenylisodecyl phosphite, diphenyldiisodecyl phosphite, tris (nonylphenyl) phosphite, etc. can be used .

These polymerization inhibitors and antioxidants can be used alone or in combination of two or more thereof, and may be used in combination with a polymerization inhibitor and / or an antioxidant.
[Filler (d)]
The filler (d) is appropriately selected from an inorganic filler, an organic filler, and an organic-inorganic composite filler.

The shape of the inorganic filler used in the present invention may be spherical or irregular. In addition, known types of inorganic fillers can be appropriately selected and used, for example, periodic groups I, II, III, IV, transition metals and oxides, hydroxides, chlorides, sulfates thereof. , Sulfites, carbonates, phosphates, silicates, and mixtures and composite salts thereof.

Specifically, glass powder such as silicon dioxide, strontium glass, lanthanum glass, barium glass,
Inorganic compound powder such as barium sulfate, aluminum oxide, titanium oxide, barium salt, barium fluoride, lead salt,
Ceramic powder made of zirconium oxide, tin oxide, other ceramics,
Quartz powder, glass beads, glass fiber, glass filler containing talc, colloidal silica, silica gel and the like can be used.

  The particle diameter of the inorganic filler is appropriately selected and used, but the average particle diameter is usually 0.001 to 50 μm, preferably 0.001 to 10 μm. These inorganic fillers can be used alone or in combination of two or more thereof, and may be used in combination with an organic filler and / or an organic-inorganic composite filler.

  Examples of organic fillers include polymethyl (meth) acrylate, polyethyl (meth) acrylate, methyl (meth) acrylate / ethyl (meth) acrylate copolymer, methyl (meth) acrylate / butyl (meth) acrylate copolymer, methyl Non-crosslinkable polymer such as (meth) acrylate / styrene copolymer, methyl (meth) acrylate / ethylene glycol di (meth) acrylate copolymer, methyl (meth) acrylate / triethylene glycol di (meth) acrylate copolymer And (meth) acrylate polymers such as a copolymer of methyl (meth) acrylate and a butadiene monomer. The shape of the organic filler is not particularly limited, and the filler particle diameter is also appropriately selected and used, but the average particle diameter is usually 0.001 to 50 μm, preferably 0.001 to 10 μm. .

  Examples of the organic-inorganic composite filler include TMPT filler (trimethylolpropane methacrylate and silica filler mixed and polymerized and then pulverized). There is no restriction | limiting in particular about the shape of an organic inorganic composite filler, Moreover, although a filler particle diameter is also selected and used suitably, an average particle diameter is 0.001-50 micrometers normally, and it may be 0.001-10 micrometers. preferable.

[Other additives]
To the dental composite resin (A) used in the present invention, additives such as a colorant may be added and used as long as the effects of the present invention are not impaired.

  As the coloring agent, known dental pigments and dyes can be used. For example, known inorganic pigments such as black iron oxide, yellow iron oxide, dial, titanium yellow, titanium white, and bromophthalal red, bromo Organic pigments such as phthalic yellow can be used.

  The blending amount of the colorant is the (a) polymerizable monomer, (b) photopolymerization initiator, (c) polymerization inhibitor and antioxidant, and filler (included in the dental composite resin (A)). The amount is usually 0.01 to 3 parts by weight based on 100 parts by weight of d).

  Further, the dental composite resin (A) may contain water as a hydrophilic solvent, if necessary. In addition to the water, solvents such as acetone, ethanol, isopropyl alcohol, etc. may be included as hydrophilic solvents. The amount of these solvents is preferably 5 parts by weight or less, more preferably 1 part by weight or less, still more preferably 0.1 parts by weight or less with respect to 100 parts by weight of the total weight of the polymerizable monomers (a). It is.

Examples of other additives include bactericides and stabilizers.
(B) Dental adhesive The adhesive which comprises the dental filling kit of this invention is a monomer (A) containing an acidic group in the dental adhesive (B) used for the modification | reformation process of an adhesive surface. e), a monomer (f) not containing an acidic group, a photopolymerization initiator (g), and water (h).

  Here, as the kind of the monomer (e) containing an acidic group constituting the dental adhesive (B), the same monomer as the monomer (a3) can be preferably used. Moreover, as a kind of monomer (f) which does not contain an acidic group, the thing similar to the said monomer (a1) and (a2) can be used suitably. Furthermore, as a photoinitiator (g), the thing similar to the said photoinitiator (b) can be used conveniently. Each blending amount is (B) when the dental adhesive is 100 parts by weight, the monomer (e) containing an acidic group, the monomer (f) not containing an acidic group, a photopolymerization initiator (g) And the total weight part of water (h) is 100 parts by weight. Specifically, the monomer (e) containing an acidic group is preferably in the range of 3 to 40 parts by weight, more preferably in the range of 5 to 35 parts by weight, and the monomer (f) containing no acidic group. Is preferably in the range of 5 to 50 parts by weight, the photopolymerization initiator (g) is usually in the range of 0.01 to 10 parts by weight, and the water (h) is usually in the range of 1 to 50 parts by weight. , Preferably, it exists in the range of 5-40 weight part, and it mix | blends so that a sum total may be 100 weight part.

Within the above range, the monomer (e), the monomer (f) not containing an acidic group, the photopolymerization initiator (g), and water (h) (A) a dental composite resin is applied to the teeth. Since it has high adhesive strength, it is preferable.
[Relationship between compounding amount of dental composite resin and dental adhesive]
The dental filling kit of the present invention has sufficient adhesive strength and marginal sealing properties even if the adhesive applied to the tooth surface and the dental composite resin placed thereon are polymerized and cured simultaneously.

  As a means for allowing the dental filling kit of the present invention to have such characteristics, the residual ratio of polymerizable double bonds remaining in the dental composite resin 4 seconds after the start of photocuring is the photocuring start 4. A dental composite resin and an adhesive prepared so as to be higher than the residual ratio of polymerizable double bonds remaining in the adhesive after 2 seconds are selected and used in combination.

The polymerizable double bond as used herein is, for example, in a mild physical environment at normal temperature and pressure, such as in the oral cavity, under mild chemical conditions that are neither extremely acidic nor basic. Thus, it is a double bond that can be polymerized at a reaction rate sufficient to achieve strong adhesive strength and the like within a sufficiently practical time in normal dental treatment. More specifically, an ethylenic double bond such as a (meth) acrylic monomer may be mentioned. On the other hand, those that do not correspond to this are markedly sterically hindered even if they are double bonds of aromatic rings such as benzene rings or ethylenic double bonds, and these remain permanently after the curing is completed. Therefore, it is not a so-called polymerizable double bond in the present invention. In the case of a polyfunctional monomer having two or more ethylenic double bonds in one molecule, even if at least one of the double bonds is polymerized, one or more other double bonds are not present. It can be left behind in the cured polymer. For example, there is an ethylenic double bond that remains unreacted even after a light irradiation treatment of 90 seconds or longer in a light irradiation device for curing reaction, especially in a dental composite resin suitably used in the dental field. In addition, it is known that about 40% of the ethylenic double bonds remain and remain almost permanently, and if it is 50% or less, there is no practical problem. Therefore, even if the ethylenic double bond that remains after the light irradiation treatment for 90 seconds or more is not particularly sterically hindered, this is an indication of the polymerizable double bond remaining rate. It is reasonable not to count. Accordingly, in the present invention, the polymerizable double bond is a polymerizable double bond that undergoes a polymerization reaction when light irradiation is performed for 90 seconds using a light irradiation device for curing reaction.

  The residual ratio of polymerizable double bonds in the component is the amount of polymerizable double bonds after a predetermined time (t) from the start of polymerization based on the amount of polymerizable double bonds (Q0) before the start of polymerization. It is the ratio (Q1 / Q0) of (Q1). This is essentially a molar ratio. As a specific measurement method, a chemical quantification method using a saturation reaction is possible, but more simply, a physical or optical measurement means is preferable, and examples thereof include infrared spectroscopy.

When measuring the residual ratio of the polymerizable double bond using infrared spectroscopy, the infrared spectroscopic measurement is performed on the sample to be measured, and a peak derived from the polymerizable double bond, for example, triethylene glycol dimer having a methacrylic structure is obtained. In the case of methacrylate, about 1636 cm ⁻¹ , the height h _A 0 before the start of polymerization of the peak from the baseline, and a predetermined t time (= 4) from the start of polymerization.
Second) after height h _A 1 and after completion of curing (after 90 seconds), height h _A 2 is obtained, and each value (h _A 0
, H _A 1, h _A 2), the residual rate R can be obtained by the following equation.
R = (h _A 1-h _A 2) / (h _A 0-h _A 2)

However, when it is difficult to continuously perform infrared spectroscopic measurement on the same sample, it may be impossible to measure accurately due to differences in the concentration and amount of the sample due to sample preparation at the time of measurement. Alternatively, an error may occur due to characteristics unique to the measurement system. In such cases, a peak derived from a structure in which the infrared spectral peak height and wave number do not vary substantially due to the polymerization reaction in the sample, for example, a certain amount of a (meth) acrylic carbonyl group such as triethylene glycol dimethacrylate can be determined 1710 cm ^-1 or longitudinal, correcting the polymerizable double bond of the residual ratio of the quantity of the peak 1608 cm ^-1 heights benzene ring, as an internal standard in. If necessary, an internal standard may be added by adding a component that is difficult to evaporate, such as toluene, and is difficult to chemically react by polymerization reaction. Now, with respect to the infrared spectroscopic peak derived from the internal standard, the peak height from the baseline is obtained before the start of polymerization, after a predetermined t time (= 4 seconds) from the start of polymerization, and after the end of curing. _{Assuming B} 0, h _B 1 and h _B 2, the corrected remaining rate R ′ is obtained by the following equation.
R ′ = (h _A 1 / h _B 1−h _A 2 / h _B 2) / (h _A 0 / h _B 0−h _A 2 / h _B 2)

  In the present invention, the one-step light irradiation is not particularly limited. For example, after applying an adhesive to the tooth to be treated, the application layer is immediately subjected to dental treatment without requiring substantial light irradiation. It is the first time that light is irradiated at the stage of laminating and forming a composite resin. Alternatively, other operations such as applying a dental composite resin in the middle of light irradiation are not required. However, during the light irradiation operation such as pulsed light emission, it is not necessary to insert other operations in particular, and it is possible to consider that light irradiation is interrupted for a short time instead of multiple steps.

  Of course, the light irradiation is mainly intended to promote the photopolymerization of the monomer, and naturally, an electric lamp for illumination does not usually correspond to the light irradiation of the present invention. The light irradiation requires a strong energy density and the shape of the tooth to be treated is not simple. Therefore, when the light irradiation device is inserted into the patient's oral cavity, it needs to be very close.

The light irradiation is not particularly limited, but the wavelength is preferably 350 to 550 nm, more preferably 400 to 520 nm, and the output is preferably 100 to 2500 mW / cm ² .
More preferably, light irradiation is performed with a light irradiator of 200 to 2000 mW / cm ² , preferably with a distance of 1 to 50 mm, more preferably 1 to 30 mm. The light source is not particularly limited, and a dental halogen light irradiator, a dental LED light irradiator, a dental plasma arc light irradiator, or the like can be used.

In the present invention, the light irradiation condition for measuring the characteristics is that light irradiation is performed with a light irradiator having a wavelength of 400 to 520 nm and an output of 250 mW / cm < ² > provided with a distance of 10 mm. In addition, the light irradiation is continued at least until a time (90 seconds) when it is considered that the curing has been completed.

If the residual ratio of polymerizable double bonds (R) in the components of the dental composite resin and the adhesive 4 seconds after the start of photocuring is Rc and _Rb , respectively, the ratio r (= R _c / R _b )> 1, the object of the present invention can be achieved, but r is preferably 1.1 or more, more preferably 1.2 or more, and still more preferably 1.3 or more. Below the lower limit, the marginal blockage is undesirably lowered. There is no particular upper limit for r, and there is no problem as long as the dental composite resin is finally cured.

It is an object of the present invention to have a polymerizable double bond residual ratio at the same light irradiation, when _Rb is 30% or less for the adhesive, _Rc is 60% for the dental composite resin, Is 65%, more preferably 70% or more, and can also be achieved by a configuration in which R _c is 50% or less by performing light irradiation as described above for 90 seconds.

In the present invention, the object of the present invention can also be achieved by making the polymerization reaction induction period of the dental composite resin longer than the polymerization reaction induction period of the adhesive.
The polymerization reaction induction period is a period until the steady polymerization is performed and a period in which the polymerization does not substantially occur. Immediately after the polymerization reaction is started, a polymerization initiator such as a radical is consumed by a polymerization inhibitor or the like. It is in a state. During the polymerization reaction induction period, the double bond reduction rate ((1-R) / hour) is 0.1 [mol / (mol · second)] or less.

  In the present invention, if the time of the induction period of polymerization reaction between the dental composite resin and the adhesive is Ic and Ib, respectively, if the difference ΔI (= Ic−Ib)> 0, the object of the present invention can be achieved. ΔI is preferably 0.1 seconds or longer, more preferably 0.5 seconds or longer, and even more preferably 1.0 seconds or longer. Below the lower limit, the marginal blockage is undesirably lowered.

  1.01 to 100 times the total weight of the polymerization inhibitor and / or antioxidant compounded in the adhesive of the same weight as the polymerization inhibitor and / or antioxidant compounded in the dental composite resin , Preferably 2 to 80 times, more preferably 2 to 50 times.

  The total weight of the polymerization initiator and the photosensitizer blended in the adhesive is 1.01 to 100 times the total weight of the polymerization initiator and the photosensitizer blended in the dental composite resin of the same weight, preferably Is blended so as to be 2 to 80 times, more preferably 2 to 50 times.

  Alternatively, the methoxyphenol blended in the dental composite resin is 1.01 to 100 times, preferably 2 to 80 times, more preferably 2 to 50 times the methoxyphenol blended in the adhesive of the same weight. It is blended to become.

  Or, the camphorquinone compounded in the adhesive is 1.01 to 100 times, preferably 2 to 80 times, more preferably 2 to 50 times the camphorquinone compounded in the same weight of the dental composite resin. It is blended to become.

[Other ingredients]
Furthermore, a solvent such as acetone, ethanol, isopropyl alcohol or the like can be used for the dental adhesive (B) used in the present invention.

  The amount of the solvent is preferably in the range of 80 parts by weight or less, more preferably 0.1 to 70 parts by weight with respect to 100 parts by weight of the total weight of the monomer (e) and the monomer (f). Can be used in the range of 1 to 60 parts by weight.

When the solvent is used within the above range, it becomes a uniform solution with the monomer as the oil component, a reliable coating property can be obtained, and the adhesive layer can be made thin.
Moreover, the adhesive (B) used for this invention can also mix | blend another additive in the range which does not impair the objective of this invention. Examples of the additives include inorganic fillers, organic fillers, thickeners, bactericides, stabilizers, colorants such as pigments and dyes. These additives are preferably contained in an amount of 0.01 to 10 parts by weight. Further, it is more preferably 0.01 parts by weight or more and 5 parts by weight or less. When these additives are added, the thickness of the adhesive layer can be made uniform even under various conditions, and the storage stability can be improved.

Furthermore, you may mix | blend a fluorine ion releasing substance with the adhesive agent (B) used for this invention. By blending a fluorine ion-releasing substance, acid resistance can be imparted to the tooth layer and the coating layer composed of the adhesive (B) and the tooth material used in the present invention. Such fluorine ion releasing substances include fluorine glasses such as fluoroaluminosilicate glass, metal fluorides such as sodium fluoride and potassium fluoride, and fluorine ion releasing properties such as a copolymer of methyl methacrylate and methacrylate methacrylate. Mention may be made of fluorine ion releasing substances such as polymers and cetylamine hydrofluorate.

<Configuration of Dental Filling Kit of the Present Invention>
The dental filling kit of the present invention has the above-mentioned dental composite resin (A) and adhesive (B) as constituent elements and is usually filled in independent containers.
The dental filling kit of the present invention may be further combined with (C) an etching agent, (D) a primer, and the like.

<Specific application method and procedure>
The dental filling kit of the present invention can be used as follows.

First, the tooth surface to be filled with the dental composite resin (A) is treated with the adhesive (B). After removing the excess adhesive (B) with a dental air gun or the like, the dental composite resin (A) is filled. The adhesive (B) can be applied any number of times.

After the surface of the filled dental composite resin (A) is prepared, light irradiation is performed with a dental light irradiation machine to cure. The dental filling kit of the present invention is treated with an adhesive (B),
The dental composite resin (A) is filled, and the adhesive (B) and the dental composite resin (A) are cured by a single light irradiation using the difference in polymerizability. It does not exclude one or more light irradiations. When using an etching agent to enhance durability, it is applied before using the adhesive (B).

Furthermore, when using a primer in order to improve durability, it applies after an etching process.
In addition, the practical marginal sealability achieved when using the dental filling kit of the present invention is preferably 70 to 100%, more preferably 80 to 100%, Is preferably about 3 to 30 MPa, more preferably about 5 to 15 MPa.

〔Example〕
EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited by these.

[Abbreviation of compound]
MMA: Methyl methacrylate 4-META: 4-Methacryloyloxyethyl trimellitic anhydride PM-2: (Bis) methacryloxyethylated phosphoric acid ((CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ O) _a PO (OH) _3-a , equimolar mixture of compounds of a = 1 and 2)
A-9300: 2-propenoic acid (2,4,6-trioxo-1,3,5-triazine-1,3,5- (2H, 4H, 6H) tolyl) tri-2,1-ethanediyl ester DTMPO : Diphenyl (2,4,6-trimethylbenzoylphosphine oxide)
1. UDMA: 1,6 bis (methacryloxyethyloxycarbonylamino) -2,2,4-trimethylhexane TEGDMA: triethylene glycol dimethacrylate HEMA: 2-hydroxyethyl methacrylate RDMA: 1,3-dimethacryloxyethoxybenzene 6E: 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane CQ: camphorquinone The structural monomers used in the examples are RDMA, TEGDMA, 2.6E and UDMA are RDMA: TEGDMA: 2. 6E: UDMA = 23: 15: 56: 6 mixed at a weight ratio.

[Example 1]
(Preparation of materials)
By weight, barium glass filler: structural monomer: 4-methoxyphenol: 2,6-di-t-butyl-p-cresol: CQ: butoxyethyl 4-dimethylaminobenzoate: PM-2 = 65. A dental composite resin (CR1) was prepared so as to be 0: 34.39: 0.1: 0.01: 0.1: 0.1: 0.3. This formulation is shown in Table 1.

(Measurement of polymerization rate)
A diamond micro ATR machine (Dura Scope ST Japan) was installed in an FT-IR measuring machine (Paragon 1,000 Perkin Elmer), and the polymerization rate of the composite resin (CR1) was used for measurement.

A 1 mm thick Teflon (registered trademark) plate having a 6 mm diameter hole was placed on the sample stage of the diamond micro ATR machine.
A specimen was put in a hole in a Teflon (registered trademark) plate, and a slide glass was placed thereon.
A rubber plate having a thickness of 10 mm with a hole having a diameter of 8 mm was placed on the slide glass.
The tip of a dental light irradiator (JETLITE 1,000, Morita) was set in the hole of the rubber plate, and the light irradiation conditions at the time of measurement were a wavelength of 400 to 520 nm, an output of 250 mW / cm ^2.
The light irradiation was performed at a distance of 10 mm. Light irradiation was performed for 2, 4, 7, 10, 15, 20, 30, and 90 seconds, and IR measurement was performed each time.
After performing light irradiation for 30 seconds, the light irradiation device was set to zero distance, and light irradiation was further performed for 60 seconds (end of curing).

Measurement conditions, the measurement range 4,000cm ^-1 ~650cm ^-1, scan number 4 times, was carried out at a resolution 4 cm ^-1.
Analysis conditions, sets the baseline between 1659 cm ^-1 in 1550 cm ^-1, the height and internal indicators peak 1637 cm ^-1 (h1) from the structural monomers of CR1 from the baseline RDMA, The ratio to the height of the peak 1608 cm ⁻¹ (h2) derived from 2.6E is obtained,
The residual ratio of the double bond amount was calculated based on the ratio.

Double bond relative ratio = h1 / h2
Double bond residual index a = h1 / h2-h1 ^max / h2 ^max
Where h1 ^max / h2 ^max = h1 / h2 at the end of curing
Double bond residual ratio (%) A = (a / a0) × 100: a0 = a value at 0 seconds of irradiation The results are shown in Table 3a.

[Example 2]
(Preparation of materials)
Barium glass filler: structural monomer: 4-methoxyphenol: 2,6-di-t-butyl-p-cresol: CQ: 4-dimethylaminobutoxyethyl: 4-META = 65. A dental composite resin (CR2) was prepared so as to be 0: 34.39: 0.01: 0.1: 0.1: 0.1: 0.3. This formulation is shown in Table 1.
(Measurement of polymerization rate)
The same operation as in Example 1 was performed. The results are shown in Table 3b.

Example 3
(Preparation of materials)
Barium glass filler: structural monomer: 4-methoxyphenol: 2,6-di-t-butyl-p-cresol: CQ: 4-dimethylaminobutoxyethyl: 4-META = 65. A dental composite resin (CR3) was prepared so as to be 0: 34.3: 0.1: 0.1: 0.1: 0.1: 0.3. This formulation is shown in Table 1.

(Measurement of polymerization rate)
The analysis conditions, sets the baseline between 1647cm ^-1 of 1618Cm ^-1, and the height of the peak derived from CR3 structural monomers from the baseline 1636 cm ^-1 (h1), the analysis condition, 1800 cm ^- The same conditions as in Example 1 except that the ratio to the height of the peak 1718 cm ⁻¹ (h2) derived from the CR3 structural monomer, which is an internal index having a baseline set between ¹ and 1565 cm ⁻¹ , was obtained. It was done.
The results are shown in Table 3c.

Example 4
(Preparation of materials)
By weight, barium glass filler: structural monomer: 4-methoxyphenol: 2,6-di-t-butyl-p-cresol: CQ: butoxyethyl 4-dimethylaminobenzoate = 65.0: 34. A dental composite resin (CR4) was prepared so as to be 6: 0.1: 0.1: 0.1: 0.1. This formulation is shown in Table 1.
(Measurement of polymerization rate)
The same operation as in Example 1 was performed. The results are shown in Table 3d.

Example 5
〔material〕
Metafil Flo (manufactured by Sun Medical Co., Ltd.), which is one of dental composite resins, was used.
(Measurement of polymerization rate)
The analysis conditions, sets the baseline between 1659 cm ^-1 in 1562 cm ^-1, structural monomers from the baseline (RDMA, 2.6E, TEGDMA, ODMA ) peak from 1637 cm ^-1 (h1) The ratio between the height of the RDMA and the height of the peak 1607 cm ⁻¹ (h2) derived from the internal index RDMA 2.6E, and the conditions other than the IR measurement at the time of 1 second of light irradiation The same operation as in Example 1 was performed. The results are shown in Table 3e.

Example 6
〔material〕
Unifil Low Flow Plus (GC Corporation), one of the dental composite resins, was used.
(Measurement of polymerization rate)
The analysis conditions, from 1800 cm ^-1 to set the baseline between 1565cm ^-1, and the peak height 1637cm urethane dimethacrylate derived from the baseline ^-1 (h1), from urethane dimethacrylate is an internal index The conditions were the same as in Example 1 except that the ratio with respect to the height of the peak 1714 cm ⁻¹ (h2) was obtained and IR measurement was performed at the time of 1 second of light irradiation. The results are shown in Table 3f.

Example 7
(Preparation of materials)
By weight, acetone: water: 4-META: TEGDMA: HEMA: UDMA: DTMPO: CQ: dimethyl-p-toluidine: silica filler = 37.5: 21.0: 13.0: 10.0: 1.0 An adhesive (P1) was prepared so as to have a ratio of 10.0: 2.5: 1.0: 1.0: 3.0. This formulation is shown in Table 2.

(Measurement of polymerization rate)
The analysis conditions, sets the baseline between 1647cm ^-1 of 1618cm ^-1, 4-META from the baseline, TEGDMA, HEMA, and the height of the peak derived from UDMA 1636cm ^-1 (h1), the analysis conditions an internal indicator is set the baseline between 1800 cm ^-1 of the 1565cm ^-1 4-META, a peak derived from DTMPO 1718cm ^-1
The conditions other than the determination of the ratio of (h2) to the height were the same as in Example 1.
The results are shown in Table 4a.

Example 8
(Preparation of materials)
Acetone: water: 4-META: MMA: HEMA: UDMA: DTMPO: CQ: dimethyl-p-toluidine: silica filler = 37.5: 21.0: 13.0: 10.0: 1.0 An adhesive (P2) was prepared so as to have a ratio of 10.0: 2.5: 1.0: 1.0: 3.0. This formulation is shown in Table 2.

(Measurement of polymerization rate)
The analysis conditions, sets the baseline between 1647cm ^-1 of 1618cm ^-1, 4-META from the baseline, MMA, HEMA, and the height of the peak derived from UDMA 1636cm ^-1 (h1), the analysis conditions Example 1 except that the ratio between the height of the peak 1718 cm ⁻¹ (h2) derived from 4-META and DTMPO, which is an internal index having a baseline set between 1800 cm ⁻¹ and 1565 cm ⁻¹ , was obtained. It carried out like.
The results are shown in Table 4b.

Example 9
(Preparation of materials)
By weight, acetone: water: 4-META: TEGDMA: UDMA: DTMPO: CQ: dimethyl-p-toluidine: silica filler = 38.5: 21.0: 13.0: 10.0: 10.0: 2 An adhesive (P3) was prepared so as to have a ratio of 5: 1.0: 1.0: 3.0. This formulation is shown in Table 2.

(Measurement of polymerization rate)
The analysis conditions, sets the baseline between 1647cm ^-1 of 1618cm ^-1, 4-META from the baseline, TEGDMA, and the height of the peak derived from UDMA 1636cm ^-1 (h1), the analysis condition, 1800 cm The same conditions as in Example 1 except that the ratio between the height of the peak 1710 cm ⁻¹ (h2) derived from 4-META and DTMPO, which is an internal index having a baseline set between ⁻¹ and 1565 cm ⁻¹ , was obtained. It was done.
The results are shown in Table 4c.

Example 10
[Adhesion test]
An adhesive sample was prepared by the method described below, and the adhesive strength was measured.

  Under water injection, the front forehead of the bull was polished with 180 # water-resistant abrasive paper, and the flat dentin surface for bonding was cut out. A double-sided tape with a hole having a diameter of 4.8 mm was attached to the dentin surface, and then a 2 mm thick cardboard with a hole with a diameter of 4.8 mm was attached to the double-sided tape.

Adhesive (P1) was included in the sponge, applied to the above-mentioned dentin surface, and air was blown and dried.
On this adhesive layer, the composite resin composition (CR1) was filled and cured by light irradiation with a dental halogen irradiator for 20 seconds.

An adhesive rod was adhered and planted on the composite resin using Superbond (manufactured by Sun Medical Co., Ltd.).
The bonded sample was placed in a constant temperature bath at 37 ° C. and 100% humidity, and after 24 hours, the tensile adhesive strength was measured. AGS-1000D (Shimadzu) was used as a testing machine, and the crosshead speed was 2 mm / min.

(Border sealing test)
A sample was prepared by the method described below, and the edge sealing property was measured.
Under water injection, the forehead forehead of the cow was polished with # 180 water-resistant polishing paper, and the flat dentin surface was cut out. A cylindrical cavity having a diameter of 3.0 mm and a depth of 1.5 mm was formed in the dentin.
Adhesive (P1) was included in the sponge, applied to the dentin surface of the cavity, and dried by blowing air.

On this adhesive layer, the composite resin composition (CR1) was filled and cured by light irradiation with a dental halogen irradiator for 30 seconds.
The above sample was placed in a constant temperature bath at 37 ° C. and 100% humidity, and after 24 hours, the teeth were cut so as to pass through the center of the cylindrical cavity.
The cut surface was tested for marginal sealing using a laser microscope (VK-9510 Keyence).

The evaluation of the edge sealing performance was performed according to the following formula.
Peripheral blockage rate = (length of the portion where there is no gap between the tooth and the composite resin / length around the cavity) × 100
The results of adhesion strength and marginal sealing are shown in Table 5.

[Examples 11 to 27]
The combination of the dental composite resin and the adhesive was changed as follows, and the adhesion test and the edge sealing test were conducted.
CR1 and P2 (Example 11), CR1 and P3 (Example 12), CR2 and P1 (Example 13), CR2 and P2 (Example 14), CR2 and P3 (Example 15), CR3 and P1 (Example) Example 16), CR3 and P2 (Example 17), CR3 and P3 (Example 18), CR4 and P1 (Example 19), CR4 and P2 (Example 20), CR4 and P3 (Example 21), Metafil Flo and P1 (Example 22), Metafil Flo and P2 (Example 23), Metafil Flo and P3 (Example 24), Unifil Low Flow Plus and P1 (Example 25), Unifil Low Flow Plus and P2 (Example) 26), Unifil Low Flow Plus and P3 (Example 27),
The results are shown in Table 5.

* 1) Barium glass filler (average particle size 1μm) is used as the filler.
* 2) As a structural monomer
* 3) Monomers mixed at a weight ratio of 4-methoxypheno RDMA / TEGDMA / 2.6E / UDMA = 23/15/56/6 are used as a polymerization inhibitor. Use
* 4) 2,6-Di-t-butyl-p-cresol is used as a polymerization inhibitor.
* 5) CQ is used as polymerization initiator 1.
* 6) Butoxyethyl 4-dimethylaminobenzoate was used as polymerization initiator 2.

* 1) Aerosil R972 (Nippon Aerosil)

* a) Thickness 1mm, light glass, irradiation from 10mm (JETLITE 1000: wavelength 400-520nm
Output 250W)
* b) Light irradiation is set at zero distance for the last 60 seconds, and the IR peak height h ₁ (h ₂ ) immediately after this is h ₁ ^max (h ₂ ^max )
* c) Baseline set to 1659-1550cm ^-1
* d) Baseline set to 1647-1618cm ^-1
* e) Baseline set to 1800-1565cm ^-1
* f) Baseline set to 1659 ~ 1562cm ^-1
* g) Baseline set to 1800-1565cm ^-1
* h) The a value at 0 seconds after irradiation is a ₀
* a to * h are common to Table 3 and Table 4.

Claims (8)

A dental filling kit having a photopolymerizability comprising a dental composite resin and an adhesive as constituents,
The dental filling kit is formed so as to be able to express a practical edge sealing property and / or adhesive strength by one-stage light irradiation,
The residual ratio of double bonds remaining in the dental composite resin after irradiating the dental composite resin for 4 seconds is the double bond remaining in the adhesive after irradiating the adhesive for 4 seconds. A dental filling kit characterized by a higher survival rate. A dental filling kit having a photopolymerizability comprising a dental composite resin and an adhesive as constituents,
The dental filling kit is formed so as to be able to express a practical edge sealing property and / or adhesive strength by one-stage light irradiation,
The residual ratio of polymerizable double bonds in the adhesive after light irradiation of the adhesive and the dental composite resin for 4 seconds under the same conditions is 30% or less, and the polymerizable double bond in the dental composite resin The dental filling kit according to claim 1, wherein the residual ratio is 60% or more. A dental filling kit having a photopolymerizability comprising a dental composite resin and an adhesive as constituents,
The dental filling kit is formed so as to be able to express a practical edge sealing property and / or adhesive strength by one-stage light irradiation,
The dental filling kit according to claim 1 or 2, wherein the polymerization induction period of the dental composite resin is longer than the polymerization induction period of the adhesive. Both the dental composite resin and the adhesive constituting the dental filling kit contain a polymerization inhibitor and / or an antioxidant,
Ratio of the content of the polymerization inhibitor and / or antioxidant contained in the dental composite resin to the content of the polymerization inhibitor and / or antioxidant contained in the adhesive (dental composite resin / adhesion The dental filling kit according to claim 1 or 3, wherein the agent is in the range of 100 to 1.01. Both the dental component resin and the adhesive constituting the dental filling kit contain a photopolymerization initiator,
Ratio of content of photopolymerization initiator and photosensitizer contained in dental composite resin to content of photopolymerization initiator and photosensitizer contained in adhesive (dental composite resin / adhesion The dental filling kit according to claim 1 or 2, wherein the agent is in the range of 100 to 1.01. Both the dental composite resin and the adhesive constituting the dental filling kit contain methoxyphenol,
The ratio (dental composite resin / adhesive) between the content of methoxyphenol contained in the dental composite resin and the content of methoxyphenol contained in the adhesive is in the range of 100 to 1.01. The dental filling kit according to claim 1 or 3, wherein Both the dental composite resin and the adhesive constituting the dental filling kit contain camphorquinone,
Ratio of the content of camphorquinone contained in the dental composite resin and the content of camphorquinone contained in the adhesive (the dental composite resin / adhesive is within the range of 100 to 1.01. The dental filling kit according to claim 1 or 2, characterized in that   The dental sealant according to any one of claims 1 to 7, wherein when the dental filling kit is used, the marginal sealing property is 70 to 100% and the adhesive strength is 3 to 30 MPa. Filling kit.