JP2020100567A - Dental composition - Google Patents

Abstract

To provide a dental composition exhibiting high adhesion even to dentine in which caries parts are present.SOLUTION: The dental composition comprises a phosphate group-containing monomer (A-1) represented by the specified general formula (1), a phosphate group-containing monomer (A-2) represented by the specified general formula (2), water (B), and optionally an acidic group-free, hydrophilic monomer (C), where the mass ratio between the monomer (C) and the water (B) ([monomer (C) content]/[water (B) content]) is less than 1. (In the general formula (1), R1 represents a hydrogen atom or methyl group, and m represents an integer from 6 to 12.) (In the general formula (2), R2 represents a hydrogen atom or methyl group, and n represents an integer from 3 to 5.)SELECTED DRAWING: None

Description

The present invention relates to a dental composition used in the field of dentistry.

When repairing dentin (enamel, dentin, and cementum) damaged by caries, etc., the carious part is usually removed by cutting with a dental cutting tool such as an air turbine, and then exposed to a healthy dentin. On the other hand, filling restoration materials such as filling composite resin and filling compomer, and crown restoration materials such as metal alloy, porcelain, and resin material are used as dental adhesive compositions such as dental bonding materials and dental cement. To be bonded to restore the function of the tooth. Recent advances in the performance of dental adhesive compositions have been significant, improving adhesiveness and simplifying the procedure of use, benefiting both the patient being treated and the treating dentist.

The dental adhesive composition usually contains a polymerizable monomer such as an acidic group-containing monomer, a hydrophilic monomer and a crosslinkable monomer, and as the polymerizable monomer, (Meth)acrylic monomers are commonly used.

The above-mentioned acidic group-containing monomer is a monomer having an acidic group such as a phosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, or a carboxylic acid group, which can chemically bond to the tooth substance to enhance the adhesiveness. Are widely used, and among them, many techniques are known for a monomer having a phosphoric acid group (phosphoric acid group-containing monomer).

For example, in Patent Document 1, as a (meth)acrylic acid ester having a phosphoric acid group, a radical monomer having a water solubility of 5 g/100 g or more and a water solubility of 1 g/100 g or less. A specific dental composition in which water and a photopolymerization initiator are further used in combination with a radically polymerizable monomer is described, and according to the dental composition, before the etching treatment or the primer treatment, etc. It is described that the tooth substance and the dental restoration can be bonded to each other with high bonding strength without any treatment, and the bonding durability is also excellent. In Patent Document 1, 2-methacryloyloxyethyl dihydrogen phosphate, tetraethylene glycol dihydrogen phosphate monomethacrylate, or the like is used as the radical monomer having a water solubility of 5 g/100 g or more. Further, 6-methacryloyloxyhexyl dihydrogen phosphate, 10-methacryloyloxydecyl dihydrogen phosphate or the like is used as the radical polymerizable monomer having a solubility in water of 1 g/100 g or less. Is described.

Further, in Patent Document 2, a specific phosphoric acid group-containing polymerizable monomer (11-methacryloyloxytetraethylene glycol dihydrogen phosphate, 17-methacryloyloxyhexaethylene glycol dihydrogen phosphate, etc.), crosslinkable polymerizable A monomer, a photopolymerization initiator, water, an organic solvent, a penetration enhancer (2-hydroxyethyl methacrylate (HEMA), etc.) and one molecule having a plurality of carboxyl groups in one molecule or reacting with water to form one molecule. According to the dental adhesive composition containing a polymerizable monomer having a plurality of carboxyl groups therein, an adhesive material which is a highly allergenic substance without requiring pretreatment such as deashing treatment and permeation promoting treatment. It is possible to bond the tooth structure and the dental restoration with high adhesive strength while reducing the content of HEMA in the composition, and the adhesive composition forms a uniform composition without phase separation before and after curing. It is described that it becomes possible.

JP, 2007-137798, A International Publication No. 2017/086228

Adhesive Dentistry, Vol. 17, No. 3, pp. 186-191, 1999 Adhesive Dentistry, Vol. 25, No. 1, pp. 12-18, 2007

By the way, in dental treatment, a carious part may be left unintentionally or unintentionally. However, when a carious part is present in the tooth, as shown in Non-Patent Document 1, for example, It is difficult to obtain sufficient adhesiveness. Therefore, it is a problem to obtain a dental composition that exhibits high adhesiveness (initial adhesive strength and adhesive durability) not only to a healthy tooth but also to a tooth having a carious portion, Is a combination of a radical monomer having a water solubility of 5 g/100 g or more and a radical polymerizable monomer having a water solubility of 1 g/100 g or less, as in Patent Document 1, Alternatively, simply using a specific phosphoric acid group-containing polymerizable monomer as in Patent Document 2 cannot sufficiently solve the problem.

Therefore, an object of the present invention is to provide a dental composition that exhibits high adhesiveness (initial adhesive strength and adhesive durability) not only to a healthy tooth structure but also to a tooth structure having a carious portion. ..

As a result of intensive studies to achieve the above object, the inventors of the present invention have used two kinds of specific phosphoric acid group-containing monomers having different structures in combination and, in addition, have hydrophilicity not having water and an acidic group. Density composition showing high adhesiveness (initial adhesive strength and adhesive durability) not only to healthy dentin but also to dentin with carious parts when the ratio of the monomer to The present invention has been completed, and the present invention has been completed through further studies based on the findings.

That is, the present invention relates to the following.
[1] Phosphoric acid group-containing monomer (A-1) represented by the following general formula (1), phosphoric acid group-containing monomer (A-2) represented by the following general formula (2), and water (B ), and a hydrophilic monomer (C) having no acidic group as an optional component, and the mass ratio of the monomer (C) and water (B) ([containing monomer (C). Amount]/[content of water (B)]) is less than 1.

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 6 to 12.)

(In the general formula (2), R ² represents a hydrogen atom or a methyl group, and n represents an integer of 3 to 5.)
[2] Mass ratio of the phosphoric acid group-containing monomer (A-1) and the phosphoric acid group-containing monomer (A-2) ([containing phosphoric acid group-containing monomer (A-1) [Amount]/[content of phosphoric acid group-containing monomer (A-2)]) is 20/80 to 90/10, The dental composition according to [1].
[3] In the content of [1] or [2], the content of the water (B) is 1 to 900 parts by mass based on 100 parts by mass of the total amount of polymerizable monomers contained in the dental composition. The described dental composition.
[4] The dental composition according to any one of [1] to [3], further including a hydrophobic monomer (D) having no acidic group.
[5] The dental composition according to any one of [1] to [4], which further contains a polymerization initiator (E).
[6] The dental composition according to any one of [1] to [5], which is a dental bonding material.

ADVANTAGE OF THE INVENTION According to this invention, the dental composition which shows high adhesiveness (initial adhesive force and adhesive durability) not only to a healthy tooth substance but also to the tooth substance in which a carious part exists is provided.

<Dental composition>
The dental composition of the present invention comprises a phosphoric acid group-containing monomer (A-1) represented by the following general formula (1) and a phosphoric acid group-containing monomer (A-) represented by the following general formula (2). 2) (Hereinafter, the phosphoric acid group-containing monomer (A-1) and the phosphoric acid group-containing monomer (A-2) are collectively referred to as "phosphoric acid group-containing monomer (A)". A), water (B), and, as an optional component, a hydrophilic monomer (C) having no acidic group. That is, the dental composition of the present invention may or may not contain the monomer (C). Then, in the dental composition of the present invention, the mass ratio of the monomer (C) and water (B) ([content of monomer (C)]/[content of water (B)]. ) Is less than 1.

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 6 to 12.)

(In the general formula (2), R ² represents a hydrogen atom or a methyl group, and n represents an integer of 3 to 5.)

In the present specification, the expression “(meth)acrylic” is used to include both methacrylic and acrylic, and the same applies to similar expressions. Further, in the present specification, the upper limit value and the lower limit value of the numerical range (content of each component, value calculated from each component, each physical property, etc.) can be appropriately combined.

[Phosphoric acid group-containing monomer (A)]
-Phosphoric acid group-containing monomer (A-1)
The dental composition of the present invention contains a phosphate group-containing monomer (A-1). The phosphoric acid group-containing monomer (A-1) can contribute to deashing action, penetrating action and hardening action, and has an acid etching function, a primer treatment function and a dental composition for the dental composition of the present invention. A polymerization and curing function can be imparted. In particular, the phosphate group-containing monomer (A-1) has a highly hydrophobic alkylene chain in its molecule, and therefore contributes to water resistance (particularly adhesion durability) after curing the dental composition. Is also big.

The phosphoric acid group-containing monomer (A-1) is represented by the above general formula (1). Here, R ¹ represents a hydrogen atom or a methyl group, and is preferably a methyl group. Further, m represents an integer of 6 to 12, preferably an integer of 7 or more, more preferably an integer of 8 or more, further preferably an integer of 9 or more, and an integer of 11 or less. Is preferred.

Specific examples of the phosphoric acid group-containing monomer (A-1) include, for example, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 12-(meth ) Acryloyl oxide decyl dihydrogen phosphate and the like. As the phosphoric acid group-containing monomer (A-1), one type may be used alone, or two or more types may be used in combination.

Among these phosphoric acid group-containing monomers (A-1), 10-(meth)acryloyloxydecyl dihydrogen phosphate is preferable from the viewpoint of adhesiveness to tooth structure, and 10-methacryloyloxydecyl dihydrogen phosphate is preferable. Is more preferable.

-Phosphoric acid group-containing monomer (A-2)
The dental composition of the present invention contains a phosphate group-containing monomer (A-2). Like the phosphate group-containing monomer (A-1), the phosphate group-containing monomer (A-2) can also contribute to the deashing action, the penetrating action, and the curing action, and thus the dental use of the present invention The composition can be imparted with an acid etching function, a primer treatment function and a polymerization curing function. In particular, since the above-mentioned phosphate group-containing monomer (A-2) has a highly hydrophilic polyethylene glycol chain in the molecule, the dental composition is more likely to effectively penetrate into the dentin tissue containing a lot of water. ..

The phosphoric acid group-containing monomer (A-2) is represented by the above general formula (2). Here, R ² represents a hydrogen atom or a methyl group, and is preferably a methyl group. N represents an integer of 3 to 5, is preferably 3 or 4, and is more preferably 4.

Specific examples of the phosphoric acid group-containing monomer (A-2) include 8-(meth)acryloyloxytriethylene glycol dihydrogen phosphate (a compound in which n is 3 in the general formula (2)), 11- (Meth)acryloyloxytetraethylene glycol dihydrogen phosphate (a compound in which n is 4 in the above general formula (2)), 14-(meth)acryloyloxypentaethylene glycol dihydrogen phosphate (in the above general formula (2)) and a compound in which n is 5. The phosphoric acid group-containing monomer (A-2) may be used alone or in combination of two or more.

Among these phosphoric acid group-containing monomers (A-2), 11-(meth)acryloyloxytetraethylene glycol dihydrogen phosphate is preferable from the viewpoint of adhesion to the tooth structure, and 11-methacryloyloxytetraethylene glycol is preferable. Dihydrogen phosphate is more preferred.

In the dental composition of the present invention, the mass ratio of the phosphoric acid group-containing monomer (A-1) and the phosphoric acid group-containing monomer (A-2) is not particularly limited, but there is a carious portion. From the viewpoint of adhesiveness to the tooth substance, the ratio of the content of the phosphate group-containing monomer (A-1) to the content of the phosphate group-containing monomer (A-2) ([phosphate group-containing monomer [Content of monomer (A-1)]/[content of phosphate group-containing monomer (A-2)] is preferably 20/80 or more, and 25/75 or more. More preferably, it is more preferably 30/70 or more, particularly preferably 40/60 or more, preferably 90/10 or less, more preferably 85/15 or less, 80/ It is more preferably 20 or less, and particularly preferably 75/25 or less.

In the dental composition of the present invention, the total content of the phosphoric acid group-containing monomer (A-1) and the phosphoric acid group-containing monomer (A-2) is not particularly limited, but the effect of the present invention Therefore, 1 part by mass or more is preferable, and 3 parts by mass or more is preferable for 100 parts by mass in total of the polymerizable monomers contained in the dental composition. It is more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, and can be, for example, 90 parts by mass or less, further 80 parts by mass or less, and 50 parts by mass or less. The amount is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 25 parts by mass or less. When the content is at least the above lower limit, the adhesiveness to dentin is further improved, and when the content is at most the above upper limit, the mechanical strength of the cured product is improved and the adhesiveness is also improved.

In addition, all the polymerizable monomers contained in the dental composition of the present invention (the above-mentioned phosphoric acid group-containing monomer (A), acidic group-containing monomer (A′) described later, and acidic group There is no particular limitation on the total content of hydrophilic monomers (C) that do not have, hydrophobic monomers (D) that do not have acidic groups, etc. Since the adhesiveness to both the restorative material and the tooth substance is further improved, the content can be, for example, 10% by mass or more based on the mass of the dental composition of the present invention, and 20% by mass. % Or more, more preferably 30% by mass or more, further preferably 40% by mass or more, particularly preferably 50% by mass or more, and for example 99% by mass or less. The amount is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less.

[Acidic group-containing monomer (A') other than phosphoric acid group-containing monomer (A)]
The dental composition of the present invention may further contain an acidic group-containing monomer (A′) other than the phosphoric acid group-containing monomer (A). The acidic group-containing monomer (A′) has, for example, at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group, In addition, a polymerizable monomer having at least one polymerizable group such as an acryloyl group, a methacryloyl group, a vinyl group and a styrene group, which does not correspond to the above-mentioned phosphoric acid group-containing monomer (A) can be mentioned. .. The acidic group-containing monomer (A′) is preferably a (meth)acrylic monomer having an acidic group such as (meth)acrylic acid ester having an acidic group and (meth)acrylamide having an acidic group. A (meth)acrylic acid ester having an acidic group is more preferable, and a methacrylic acid ester having an acidic group is further preferable. The acidic group-containing monomer (A′) may be used alone or in combination of two or more. Specific examples of monomers having various acidic groups that can be preferably used as the acidic group-containing monomer (A′) are shown below.

Examples of the monomer having a phosphoric acid group include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, and 4-(meth)acryloyloxybutyl dihydrogen. Dihydrogen phosphate monoesters such as phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyeicosyl dihydrogen phosphate Group-containing monomer; bis[2-(meth)acryloyloxyethyl] hydrogen phosphate, bis[4-(meth)acryloyloxybutyl] hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl] hydrogen Phosphate, 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl phenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis[ Monomers having a hydrogen phosphate diester group such as 2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl] hydrogen phosphate; and acid anhydrides, acid halides (acid chlorides, etc.), alkalis thereof. Examples thereof include metal salts and ammonium salts.

Examples of the monomer having a pyrophosphate group include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl]pyrophosphate, and bis[6-(meth)pyrophosphate. Acryloyloxyhexyl], bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate, and acid anhydrides thereof, acid halides (acid chlorides, etc.), Examples thereof include alkali metal salts and ammonium salts.

Examples of the monomer having a thiophosphoric acid group include 2-(meth)acryloyloxyethyl dihydrogen thiophosphate, 3-(meth)acryloyloxypropyl dihydrogen thiophosphate, and 4-(meth)acryloyloxybutyl diphosphate. Hydrogen thiophosphate, 5-(meth)acryloyloxypentyl dihydrogenthiophosphate, 6-(meth)acryloyloxyhexyl dihydrogenthiophosphate, 7-(meth)acryloyloxyheptyl dihydrogenthiophosphate, 8-( (Meth)acryloyloxyoctyl dihydrogen thiophosphate, 9-(meth)acryloyloxynonyl dihydrogen thiophosphate, 10-(meth)acryloyloxydecyl dihydrogen thiophosphate, 11-(meth)acryloyloxyundecyl dihydro Genthiophosphate, 12-(meth)acryloyloxidedecyldihydrogenthiophosphate, 16-(meth)acryloyloxyhexadecyldihydrogenthiophosphate, 20-(meth)acryloyloxyeicosyldihydrogenthiophosphate, and these Acid anhydrides, acid halides (acid chlorides, etc.), alkali metal salts, ammonium salts and the like.

Examples of the phosphonic acid group-containing monomer include 2-(meth)acryloyloxyethylphenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl- 3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexylphosphonoacetate, 10-(meth)acryloyloxydecylphosphonoacetate, and Examples thereof include acid anhydrides, acid halides (acid chlorides, etc.), alkali metal salts, ammonium salts and the like.

Examples of the monomer having a sulfonic acid group include 2-(meth)acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, 2-sulfoethyl(meth)acrylate, and their acid anhydrides and acid halides ( Acid chlorides, etc.), alkali metal salts, ammonium salts and the like.

Examples of the monomer having a carboxylic acid group include a monomer having one carboxyl group in the molecule and a monomer having a plurality of carboxyl groups in the molecule.

Examples of the monomer having one carboxyl group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, O-(meth)acryloyltyrosine, N- (Meth)acryloyl tyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth) ) Acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen malate, and their acid anhydrides and acid halides (acid chlorides Substances), alkali metal salts, ammonium salts and the like.

Examples of the monomer having a plurality of carboxyl groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10- (Meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxidedecane-1,1-dicarboxylic acid, 13-(meth ) Acryloyloxytridecane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyethyl trimellitate, 4-(meth)acryloyloxybutyl trimellitate, 4-(meth)acryloyloxyhexyl trimellitate, 4 -(Meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate, and these acids Examples thereof include anhydrides, acid halides (acid chlorides, etc.), alkali metal salts, ammonium salts and the like.

Among the above acidic group-containing monomers (A′), the monomer having a phosphoric acid group and the monomer having a carboxylic acid group are preferable, since the effects of the present invention are more remarkably achieved. 2-(meth)acryloyloxyethyl dihydrogen phosphate, bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 4-(meth)acryloyl Oxyethyl trimellitate and 4-(meth)acryloyloxyethyl trimellitate acid anhydride are more preferable, and 2-(meth)acryloyloxyethyl dihydrogen phosphate is further preferable.

When the dental composition of the present invention contains the acidic group-containing monomer (A′), the content thereof is not particularly limited, but the effect of the present invention is more remarkably exhibited, and therefore the dental composition. It is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 20 parts by mass or less, with respect to 100 parts by mass in total of the polymerizable monomers contained in the product. It is particularly preferably 10 parts by mass or less, and may be 5 parts by mass or less, 3 parts by mass or less, and further 1 part by mass or less.

[Water (B)]
The dental composition of the present invention contains water (B). When the dental composition contains water (B), hydrogen ions of the phosphate group contained in the phosphate group-containing monomer (A) are easily dissociated, the acidity is increased, and the demineralization function for the tooth structure is obtained. Is effectively expressed. As the water used for preparing the dental composition of the present invention, distilled water or ion-exchanged water is preferable from the viewpoint of not introducing impurities that adversely affect the adhesiveness.

The content of water (B) in the dental composition of the present invention is not particularly limited, but the adhesiveness to both dental restorative material such as filling restorative material and crown restorative material and tooth is further improved. Therefore, it is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and more preferably 10 parts by mass or more with respect to 100 parts by mass in total of the polymerizable monomers contained in the dental composition. More preferably, it is particularly preferably 20 parts by mass or more, 25 parts by mass or more, further 30 parts by mass or more, 900 parts by mass or less, preferably 500 parts by mass or less. The amount is more preferably 100 parts by mass or less, further preferably 100 parts by mass or less, particularly preferably 80 parts by mass or less, and may be 50 parts by mass or less, and further may be 35 parts by mass or less.

[Hydrophilic monomer having no acidic group (C)]
The dental composition of the present invention may contain a hydrophilic monomer (C) having no acidic group as an optional component. When the dental composition of the present invention contains a hydrophilic monomer (C) having no acidic group, a mixture of the hydrophilic monomer (C) having no acidic group and water (B) becomes It is considered that the dentin collagen fiber can be modified into a structure in which the polymerizable monomer easily penetrates, and the adhesiveness is improved.

In the dental composition of the present invention, the mass ratio of the hydrophilic monomer (C) having no acidic group to water (B) ([content of monomer (C)]/[water (B The content])]) is required to be less than 1. As a result, not only a healthy tooth structure, but also a dental composition having a carious portion is highly adhesive to a dental composition. From the viewpoint of adhesiveness of the resulting dental composition, the mass ratio is preferably 0.1 or more, more preferably 0.2 or more, and further preferably 0.3 or more. , 0.4 or more, 0.5 or more, and even 0.6 or more, and preferably 0.95 or less, more preferably 0.9 or less, and 0.85 or less. Is more preferable, and 0.8 or less is particularly preferable. The content of the hydrophilic monomer (C) having no acidic group in the dental composition of the present invention is the same as the hydrophilic monomer (C) having no acidic group and water (B). ) Is not particularly limited as long as it satisfies the mass ratio, but since the effect of the present invention is more remarkably exhibited, with respect to a total of 100 parts by mass of the polymerizable monomer contained in the dental composition, It is preferably 0.5 part by mass or more, more preferably 1 part by mass or more, further preferably 5 parts by mass or more, particularly preferably 10 parts by mass or more, and 15 parts by mass or more, The amount may be 18 parts by mass or more, further 20 parts by mass or more, preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 25 parts by mass or less. ..

As the hydrophilic monomer (C) having no acidic group, a polymerizable monomer having no acidic group and having at least one polymerizable group such as acryloyl group, methacryloyl group, vinyl group and styrene group. The body (particularly the radical polymerizable monomer) can be preferably used. As the polymerizable group, a (meth)acryloyloxy group and a (meth)acrylamide group are preferable, and a methacryloyloxy group and a methacrylamido group are more preferable, because radical polymerization is easy. As the hydrophilic monomer (C) having no acidic group, those having a solubility in water (pure water) at 25° C. of 10% by mass or more can be used, and those having a solubility of 30% by mass or more can be used. Those which can be dissolved in water at an arbitrary ratio at 25° C. are more preferable.

As the hydrophilic monomer (C) having no acidic group, those having a hydrophilic group such as a hydroxyl group, an oxymethylene group, an oxyethylene group, an oxypropylene group and an amide group are preferable, and for example, 2-hydroxyethyl. (Meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 1,3-dihydroxy-2-propyl(meth)acrylate, 2,3-dihydroxypropyl(meth)acrylate, 2- (Meth)acryloyloxyethyltrimethylammonium chloride, (meth)acrylic acid ester such as polyethylene glycol di(meth)acrylate (having 9 or more oxyethylene groups); N-monosubstituted (meth)acrylamide (for example, N -Methylol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, diacetone (meth)acrylamide, etc.), 4-(meth)acryloylmorpholine, Examples include monofunctional (meth)acrylamides such as N,N-disubstituted (meth)acrylamides represented by the following general formula (3).

In the general formula (3), R ³ and R ⁴ are each independently an alkyl group having 1 to 3 carbon atoms which may have a substituent (eg, a hydroxyl group) (eg, a methyl group, an ethyl group, n-propyl group, isopropyl group, etc.), and R ⁵ is a hydrogen atom or a methyl group.

Examples of the N,N-disubstituted (meth)acrylamide represented by the above general formula (3) include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-bis( Examples thereof include hydroxyethyl)(meth)acrylamide, and from the viewpoint of storage stability and the like, N,N-dimethylacrylamide and N,N-diethylacrylamide are preferable, and N,N-diethylacrylamide is more preferable.

Among these hydrophilic monomers (C) having no acidic group, 2-hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, monofunctional, from the viewpoint of adhesiveness to tooth structure. (Meth)acrylamide, which is a carboxylic acid, and is preferably 2-hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, diacetone (meth)acrylamide, or N,N-disubstituted represented by the general formula (3). (Meth)acrylamide is more preferable, 2-hydroxyethyl (meth)acrylate and N,N-disubstituted (meth)acrylamide represented by the above general formula (3) are further preferable, 2-hydroxyethyl methacrylate and N,N-. Diethyl acrylamide is particularly preferred. The hydrophilic monomer (C) having no acidic group may be used alone or in combination of two or more.

[Hydrophobic monomer (D) having no acidic group]
The dental composition of the present invention may further contain a hydrophobic monomer (D) having no acidic group. When the dental composition of the present invention contains a hydrophobic monomer (D) having no acidic group, the dental composition is copolymerized with the phosphoric acid group-containing monomer (A) at the time of curing so that the adhesive and cured product can be obtained. The mechanical strength of the dental composition is improved, and the handleability of the dental composition is also improved.

As the hydrophobic monomer (D) having no acidic group, a polymerizable monomer having no acidic group and having at least one polymerizable group such as acryloyl group, methacryloyl group, vinyl group and styrene group. The body (particularly the radical polymerizable monomer) can be preferably used. As the polymerizable group, a (meth)acryloyloxy group and a (meth)acrylamide group are preferable, and a methacryloyloxy group and a methacrylamido group are more preferable, because radical polymerization is easy. As the hydrophobic monomer (D) having no acidic group, those having a solubility in water (pure water) at 25° C. of less than 10% by mass can be used. For example, an aromatic bifunctional monofunctional monomer can be used. A crosslinkable monomer such as a monomer, an aliphatic bifunctional monomer, or a trifunctional or higher functional monomer can be preferably used.

Examples of the aromatic bifunctional monomer include 2,2-bis((meth)acryloyloxyphenyl)propane and 2,2-bis[4-(3-(meth)acryloyloxy-2-hydroxy]. Propoxy)phenyl]propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane,2,2-bis(4 -(Meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxy Phenyl)-2-(4-(meth)acryloyloxyethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2 -(4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2, 2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane and the like can be mentioned. Among these, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (commonly referred to as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyethoxyphenyl) ) Propane, 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (having an average added mole number of ethoxy groups of 2.6, commonly known as "D-2.6E"), 2,2-bis(4 -(Meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane is preferable, Bis-GMA and D-2.6E are more preferable, and Bis-GMA is further preferable.

Examples of the aliphatic bifunctional monomer include glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di( (Meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexane Diol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-bis(3-(meth)acryloyloxy-2-hydroxypropoxy)ethane, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl)di(meth)acrylate, N-methacryloyloxyethylacrylamide, N-methacryloyloxypropylacrylamide, N-methacryloyloxybutylacrylamide, N-(1-ethyl-(2-methacryloyloxy)ethyl)acrylamide , N-(2-(2-methacryloyloxyethoxy)ethyl)acrylamide and the like. Among these, glycerol di(meth)acrylate, triethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth) ) Acrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)di(meth)acrylate, N-methacryloyloxyethylacrylamide (Common name “MAEA”), N-methacryloyloxypropyl acrylamide are preferred.

Examples of trifunctional or higher monomers include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol. Tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetra(meth) Examples thereof include acrylate and 1,7-di(meth)acryloyloxy-2,2,6,6-tetra(meth)acryloyloxymethyl-4-oxyheptane. Among these, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate is preferable.

Among the above-mentioned hydrophobic monomers (D) having no acidic group, from the viewpoints of mechanical strength and handleability of the cured product, aromatic bifunctional monomers and aliphatic bifunctional monomers are used. -Based monomers are preferable, and from the viewpoint of adhesiveness, mechanical strength of a cured product, etc., Bis-GMA, D-2.6E, triethylene glycol dimethacrylate (commonly known as "3G"), 2,2,4-trimethyl. Hexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (commonly known as "UDMA") and MAEA are more preferable, Bis-GMA, 3G, UDMA and MAEA are further preferable, and Bis-GMA is particularly preferable. The hydrophobic monomer (D) having no acidic group may be used alone or in combination of two or more.

The content of the hydrophobic monomer (D) having no acidic group in the dental composition of the present invention is not particularly limited, but from the viewpoint of improving the adhesive force, the polymerization contained in the dental composition. It is preferably 9 parts by mass or more, more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, and 30 parts by mass or more with respect to 100 parts by mass of the total amount of the polymerizable monomer. It is particularly preferable that the amount is 40 parts by mass or more, and further 50 parts by mass or more. Further, from the viewpoint that the permeability to the tooth structure is improved and the adhesive strength is also improved, the content is 90 parts by mass with respect to 100 parts by mass of the total of the polymerizable monomers contained in the dental composition. It is preferably not more than 80 parts by mass, more preferably not more than 80 parts by mass, further preferably not more than 75 parts by mass, particularly preferably not more than 70 parts by mass.

[Polymerization initiator (E)]
From the viewpoint of adhesiveness, the dental composition of the present invention preferably further contains a polymerization initiator (E). As the polymerization initiator (E), a known polymerization initiator can be used, and for example, a photopolymerization initiator (E-1), a chemical polymerization initiator (E-2) and the like can be used. As the polymerization initiator (E), one type may be used alone, or two or more types may be used in combination, for example, a photopolymerization initiator (E-1) and a chemical polymerization initiator (E-2). ) And may be used together. The polymerization initiator (E) is preferably the photopolymerization initiator (E-1).

(I) Photopolymerization initiator (E-1)
Examples of the photopolymerization initiator (E-1) include (bis)acylphosphine oxides (including salts thereof), thioxanthones (including salts such as quaternary ammonium salts), ketals, α-diketones. , Coumarins, anthraquinones, benzoin alkyl ethers, and α-aminoketone compounds.

Among the (bis)acylphosphine oxides, examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 2,6-dichlorobenzoyldiphenylphosphine oxide. 2,2,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi(2,6-dimethylphenyl) ) Examples include phosphonates.

Among the (bis)acylphosphine oxides, examples of the bisacylphosphine oxides include bis(2,6-dichlorobenzoyl)phenylphosphine oxide and bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine. Oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis( 2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenyl Examples thereof include phosphine oxide and bis(2,3,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide.

The acylphosphine oxides may be water-soluble acylphosphine oxides. Examples of the water-soluble acylphosphine oxides include those having an ion such as an alkali metal ion, an alkaline earth metal ion, a pyridinium ion, or an ammonium ion in the acylphosphine oxide molecule. The water-soluble acylphosphine oxides can be synthesized by the methods disclosed in, for example, European Patent No. 0009348, JP-A-57-1972289 and the like.

Specific examples of the water-soluble acylphosphine oxides include, for example, monomethylacetylphosphonate sodium salt, monomethyl(1-oxopropyl)phosphonate sodium salt, monomethylbenzoylphosphonate sodium salt, monomethyl(1-oxobutyl)phosphonate sodium. Salt, monomethyl(2-methyl-1-oxopropyl)phosphonate sodium salt, acetylphosphonate sodium salt, methyl 4-(hydroxymethoxyphosphinyl)-4-oxobutanoate sodium salt, methyl 4-oxo- 4-phosphonobutanoate monosodium salt, acetylphenylphosphinate sodium salt, (1-oxopropyl)pentylphosphinate sodium salt, methyl 4-(hydroxypentylphosphinyl)-4-oxobutanoate. Sodium salt, acetylpentylphosphinate sodium salt, acetylethylphosphinate sodium salt, methyl 4-(hydroxymethylphosphinyl)-4-oxobutanoate lithium salt, 4-(hydroxymethylphosphinyl)- 4-oxobutanoic acid dilithium salt, acetylphosphinate sodium salt, acetylmethylphosphinate oxime sodium salt, acetylmethylphosphinate-O-benzyloxime sodium salt, acetylmethylphosphinate semicarbazone sodium salt Formylmethylphosphinate sodium salt, methyl(1-oxopropyl)phosphinate sodium salt, acetylmethylphosphinate thiosemicarbazone sodium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt, 2, Examples thereof include potassium salt of 4,6-trimethylbenzoylphenylphosphine oxide and ammonium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide.

Among these (bis)acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine Particularly preferred is the oxide, the sodium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide.

Examples of the thioxanthones include thioxanthone, 2-chlorothioxanthen-9-one, 2-hydroxy-3-(9-oxo-9H-thioxanthen-4-yloxy)-N,N,N-trimethylpropanami. 2-Hydroxy-3-(1-methyl-9-oxo-9H-thioxanthen-4-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-( 9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthene -2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(3,4-dimethyl-9H-thioxanthen-2-yloxy)-N,N,N- Trimethyl-1-propanaminium chloride, 2-hydroxy-3-(1,3,4-trimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanami Examples include aluminum chloride.

Among these thioxanthones, 2-chlorothioxanthen-9-one, 2-hydroxy-3-(3,4-dimethyl-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1- Propanaminium chloride is preferred.

Examples of the ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

Examples of the α-diketones include diacetyl, benzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′-oxybenzyl, and acenaphthenequinone. To be Among these, camphorquinone is particularly preferable from the viewpoint of having the maximum absorption wavelength in the visible light region.

Examples of the coumarins include 3,3′-carbonylbis(7-diethylaminocoumarin), 3-(4-methoxybenzoyl)coumarin, 3-thienylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3- Benzoyl-7-methoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3-(p-nitrobenzoyl)coumarin, 3-(p-nitro) Benzoyl)coumarin, 3,5-carbonylbis(7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3′-carbonylbiscoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoylbenzo[ f]coumarin, 3-carboxycoumarin, 3-carboxy-7-methoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo[f]coumarin, 3-benzoyl -6-nitrocoumarin, 3-benzoyl-7-diethylaminocoumarin, 7-dimethylamino-3-(4-methoxybenzoyl)coumarin, 7-diethylamino-3-(4-methoxybenzoyl)coumarin, 7-diethylamino-3- (4-diethylamino)coumarin, 7-methoxy-3-(4-methoxybenzoyl)coumarin, 3-(4-nitrobenzoyl)benzo[f]coumarin, 3-(4-ethoxycinnamoyl)-7-methoxycoumarin, 3-(4-dimethylaminocinnamoyl)coumarin, 3-(4-diphenylaminocinnamoyl)coumarin, 3-[(3-dimethylbenzothiazole-2-ylidene)acetyl]coumarin, 3-[(1-methylnaphtho[ 1,2-d]thiazol-2-ylidene)acetyl]coumarin, 3,3′-carbonylbis(6-methoxycoumarin), 3,3′-carbonylbis(7-acetoxycoumarin), 3,3′-carbonyl Bis(7-dimethylaminocoumarin), 3-(2-benzothiazoyl)-7-(diethylamino)coumarin, 3-(2-benzothiazoyl)-7-(dibutylamino)coumarin, 3-(2-benzo Imidazoyl)-7-(diethylamino)coumarin, 3-(2-benzothiazoyl)-7-(dioctylamino)coumarin, 3-acetyl-7-(dimethylamino)coumarin, 3,3'-carbonylbis(7 -Dibutylaminocoumarin), 3,3'- Carbonyl-7-diethylaminocoumarin-7'-bis(butoxyethyl)aminocoumarin, 10-[3-[4-(dimethylamino)phenyl]-1-oxo-2-propenyl]-2,3,6,7- Tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolidin-11-one, 10-(2-benzothiazoyl)-2, Examples include 3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolidin-11-one.

Among these coumarins, 3,3'-carbonylbis(7-diethylaminocoumarin) and 3,3'-carbonylbis(7-dibutylaminocoumarin) are preferable.

Examples of the anthraquinones include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone and 1-hydroxyanthraquinone. ..

Examples of the benzoin alkyl ethers include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.

Examples of the α-aminoketone compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one.

Among these photopolymerization initiators (E-1), at least one selected from the group consisting of (bis)acylphosphine oxides, α-diketones and coumarins is preferable. As a result, a dental composition having excellent photocurability in the visible light region and the near-ultraviolet light region and exhibiting sufficient photocurability using any light source of a halogen lamp, a light emitting diode (LED) and a xenon lamp. Become.

(Ii) Chemical polymerization initiator (E-2)
As the chemical polymerization initiator (E-2), conventionally known ones can be used, and specific examples thereof include organic peroxides and inorganic peroxides.

Examples of the organic peroxide include ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, peroxyester, and peroxydicarbonate. Among these, hydroperoxides and peroxyesters are particularly preferable, and peroxyesters are most preferable, from the viewpoint of safety, storage stability, and a comprehensive balance of radical generation ability.

Examples of the ketone peroxide include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methyl cyclohexanone peroxide, cyclohexanone peroxide and the like.

Examples of the hydroperoxide include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide. And so on.

Examples of the diacyl peroxide include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide and the like.

Examples of the dialkyl peroxide include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis. Examples include (t-butylperoxyisopropyl)benzene and 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne.

Examples of the peroxyketal include 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane and 2,2-bis(t- Butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 4,4-bis(t-butylperoxy)valeric acid n-butyl ester and the like can be mentioned.

Examples of the peroxy ester include α-cumyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-butyl peroxypivalate, 2,2,4-trimethylpentyl peroxy-2-ethyl hexanoate. , T-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-3 , 3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxyvaleric acid and the like.

Examples of the peroxydicarbonate include di-3-methoxybutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropylperoxydicarbonate, di-n- Examples thereof include propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, diallyl peroxydicarbonate and the like.

Examples of the inorganic peroxide include peroxodisulfate and peroxodisulfate. Among these, peroxodisulfate is preferable from the viewpoint of curability. Specific examples of the peroxodisulfate include sodium peroxodisulfate, potassium peroxodisulfate, aluminum peroxodisulfate, ammonium peroxodisulfate and the like.

The content of the polymerization initiator (E) in the dental composition of the present invention is not particularly limited, but from the viewpoint of adhesiveness and the like, the total amount of the polymerizable monomers contained in the dental composition is 100 parts by mass. It is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, further preferably 0.05 parts by mass or more, and 0.1 parts by mass or more. It is particularly preferable, it is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 7 parts by mass or less.

[Polymerization accelerator (F)]
The dental composition of the present invention may further contain a polymerization accelerator (F). The polymerization accelerator (F) is preferably used together with the above polymerization initiator (E). As the polymerization accelerator (F), known polymerization accelerators can be used, and examples thereof include amines, sulfinic acids (including salts), borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds. , Vanadium compounds, halogen compounds, aldehydes, thiol compounds, sulfites, hydrogen sulfites, thiourea compounds and the like. As the polymerization accelerator (F), one type may be used alone, or two or more types may be used in combination.

The amines are classified into aliphatic amines and aromatic amines. Examples of the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine. N-methyldiethanolamine, N-ethyldiethanolamine, N-n-butyldiethanolamine, N-lauryldiethanolamine, 2-(dimethylamino)ethylmethacrylate, N-methyldiethanolaminedimethacrylate, N-ethyldiethanolaminedimethacrylate, triethanolaminemono Examples thereof include tertiary aliphatic amines such as methacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine and tributylamine. Of these, tertiary aliphatic amines are preferable, and N-methyldiethanolamine and triethanolamine are more preferable, from the viewpoints of adhesiveness and storage stability of the dental composition.

Examples of the aromatic amine include N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis( 2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-isopropylaniline, N,N -Bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-diisopropylaniline, N,N-bis(2-hydroxyethyl)-3,5 -Di-t-butylaniline, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, N,N-dimethyl -3,5-Dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-isopropylaniline, N,N-dimethyl-4 -T-butylaniline, N,N-dimethyl-3,5-di-t-butylaniline, ethyl 4-(N,N-dimethylamino)benzoate, methyl 4-(N,N-dimethylamino)benzoate , Propyl 4-(N,N-dimethylamino)benzoate, n-butoxyethyl 4-(N,N-dimethylamino)benzoate, 2-[(meth)benzoic acid 4-(N,N-dimethylamino)benzoate Acryloyloxy]ethyl, 4-(N,N-dimethylamino)benzophenone, butyl 4-dimethylaminobenzoate, 4-(dimethylamino)benzonitrile and the like can be mentioned. Among these, N,N-bis(2-hydroxyethyl)-p-toluidine, ethyl 4-(N,N-dimethylamino)benzoate, and 4 from the viewpoint of providing excellent adhesiveness to the dental composition. N-butoxyethyl n-(N,N-dimethylamino)benzoate and 4-(N,N-dimethylamino)benzophenone are preferred.

Examples of the sulfinic acids include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, and sodium benzenesulfinate. , Potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate , Lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, 2, Potassium 4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, 2,4. Examples thereof include sodium 6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate and calcium 2,4,6-triisopropylbenzenesulfinate. To be Among these, sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate are particularly preferable.

The borate compound is preferably an aryl borate compound. Examples of the aryl borate compound include borate compounds having 1 to 4 aryl groups in one molecule.

Examples of the borate compound having one aryl group in one molecule include trialkylphenylboron, trialkyl(p-chlorophenyl)boron, trialkyl(p-fluorophenyl)boron, trialkyl[3,5-bis] (Trifluoromethyl)phenyl]boron, trialkyl[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, trialkyl(p- Nitrophenyl)boron, trialkyl(m-nitrophenyl)boron, trialkyl(p-butylphenyl)boron, trialkyl(m-butylphenyl)boron, trialkyl(p-butyloxyphenyl)boron, trialkyl(m -Butyloxyphenyl)boron, trialkyl(p-octyloxyphenyl)boron, trialkyl(m-octyloxyphenyl)boron (the alkyl group in each of the above examples is an n-butyl group, an n-octyl group, an n-dodecyl group Etc.), these salts (sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinoli Aluminum salt, ethylquinolinium salt, butylquinolinium salt, etc.) and the like.

Examples of the borate compound having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi(p-chlorophenyl)boron, dialkyldi(p-fluorophenyl)boron and dialkyldi[3,5-bis(trifluoromethyl). ) Phenyl]boron, dialkyldi[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, dialkyldi(p-nitrophenyl)boron, dialkyldi (M-Nitrophenyl)boron, dialkyldi(p-butylphenyl)boron, dialkyldi(m-butylphenyl)boron, dialkyldi(p-butyloxyphenyl)boron, dialkyldi(m-butyloxyphenyl)boron, dialkyldi(p- Octyloxyphenyl)boron, dialkyldi(m-octyloxyphenyl)boron (the alkyl group in each of the above examples is an n-butyl group, an n-octyl group, an n-dodecyl group, etc.), salts thereof (sodium salt, lithium) Salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium Salt etc.) and the like.

Examples of the borate compound having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri(p-chlorophenyl)boron, monoalkyltri(p-fluorophenyl)boron and monoalkyltri[3. ,5-bis(trifluoromethyl)phenyl]boron, monoalkyltri[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, Monoalkyltri(p-nitrophenyl)boron, monoalkyltri(m-nitrophenyl)boron, monoalkyltri(p-butylphenyl)boron, monoalkyltri(m-butylphenyl)boron, monoalkyltri(p- Butyloxyphenyl)boron, monoalkyltri(m-butyloxyphenyl)boron, monoalkyltri(p-octyloxyphenyl)boron, monoalkyltri(m-octyloxyphenyl)boron (the alkyl group in each of the above examples is n -Butyl group, n-octyl group, n-dodecyl group, etc.), salts thereof (sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium). Salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, etc.) and the like.

Examples of the borate compound having four aryl groups in one molecule include tetraphenylboron, tetrakis(p-chlorophenyl)boron, tetrakis(p-fluorophenyl)boron and tetrakis[3,5-bis(trifluoromethyl). ) Phenyl]boron, tetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, tetrakis(p-nitrophenyl)boron, tetrakis (M-Nitrophenyl)boron, tetrakis(p-butylphenyl)boron, tetrakis(m-butylphenyl)boron, tetrakis(p-butyloxyphenyl)boron, tetrakis(m-butyloxyphenyl)boron, tetrakis(p- Octyloxyphenyl)boron, tetrakis(m-octyloxyphenyl)boron, (p-fluorophenyl)triphenylboron, [3,5-bis(trifluoromethyl)phenyl]triphenylboron, (p-nitrophenyl)tri Phenylboron, (m-butyloxyphenyl)triphenylboron, (p-butyloxyphenyl)triphenylboron, (m-octyloxyphenyl)triphenylboron, (p-octyloxyphenyl)triphenylboron, salts thereof (Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt , Butylquinolinium salt, etc.) and the like.

Among these aryl borate compounds, borate compounds having 3 or 4 aryl groups in one molecule are preferable from the viewpoint of storage stability. The aryl borate compounds may be used alone or in combination of two or more.

Examples of the barbituric acid derivative include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, 5- Ethyl barbituric acid, 5-isopropyl barbituric acid, 5-cyclohexyl barbituric acid, 1,3,5-trimethyl barbituric acid, 1,3-dimethyl-5-ethyl barbituric acid, 1,3-dimethyl-5 -N-butyl barbituric acid, 1,3-dimethyl-5-isobutyl barbituric acid, 1,3-dimethyl-5-cyclopentyl barbituric acid, 1,3-dimethyl-5-cyclohexyl barbituric acid, 1,3 -Dimethyl-5-phenyl barbituric acid, 1-cyclohexyl-1-ethyl barbituric acid, 1-benzyl-5-phenyl barbituric acid, 5-methyl barbituric acid, 5-propyl barbituric acid, 1,5- Diethyl barbituric acid, 1-ethyl-5-methyl barbituric acid, 1-ethyl-5-isobutyl barbituric acid, 1,3-diethyl-5-butyl barbituric acid, 1-cyclohexyl-5-methyl barbituric acid , 1-cyclohexyl-5-ethyl barbituric acid, 1-cyclohexyl-5-octyl barbituric acid, 1-cyclohexyl-5-hexyl barbituric acid, 5-butyl-1-cyclohexyl barbituric acid, 1-benzyl-5 -Phenylbarbituric acid, thiobarbituric acids, salts thereof, and the like. Examples of the salts of these barbituric acid derivatives include alkali metal salts and alkaline earth metal salts (including magnesium salts), and more specifically, sodium 5-butylbarbituric acid, 1,3 , Sodium 5-trimethylbarbiturate, sodium 1-cyclohexyl-5-ethylbarbiturate, and the like.

Particularly suitable barbituric acid derivatives are 5-butylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, and the like. Is the sodium salt of.

Examples of the triazine compound include 2,4,6-tris(trichloromethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, and 2-methyl-4,6-bis. (Trichloromethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p -Methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)- 4,6-bis(trichloromethyl)-s-triazine, 2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-bromophenyl)-4,6 -Bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s -Triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2- [2-(p-Methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(o-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)- s-triazine, 2-[2-(p-butoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4, 6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4,5-trimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(1- Naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N,N-bis (2-Hydroxyethyl)amino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-ethylamino}ethoxy]-4,6-bis( Trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,6-bis(trichloromethyl) )-S-triazine, 2-[2-{N,N-diallylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine and the like.

Among these triazine compounds, 2,4,6-tris(trichloromethyl)-s-triazine is preferable from the viewpoint of polymerization activity, and 2-phenyl-4,6-bis(trichloro) from the viewpoint of storage stability. Methyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine Is preferred. The triazine compounds may be used alone or in combination of two or more.

Examples of the copper compound include copper acetylacetone, copper (II) acetate, copper oleate, copper (II) chloride, and copper (II) bromide.

Examples of the tin compound include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, and di-n-butyltin dilaurate. Among these, di-n-octyltin dilaurate and di-n-butyltin dilaurate are preferable.

As the vanadium compound, IV-valent and V-valent vanadium compounds are preferable. Examples of the IV-valent and V-valent vanadium compounds include divanadium tetroxide (IV), vanadium acetylacetonate oxide (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), and oxobis(1-phenyl-1). , 3-butanedionate) vanadium (IV), bis(maltolate)oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), ammonium metavanadate (V), and the like.

Examples of the halogen compound include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride and dilauryldimethylammonium bromide.

Examples of the aldehydes include terephthalaldehyde and benzaldehyde derivatives. Examples of the benzaldehyde derivative include dimethylaminobenzaldehyde, p-methyloxybenzaldehyde, p-ethyloxybenzaldehyde, pn-octyloxybenzaldehyde and the like. Among these, pn-octyloxybenzaldehyde is preferable from the viewpoint of adhesiveness.

Examples of the thiol compound include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

Examples of the sulfite include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, and the like.

Examples of the bisulfite include sodium bisulfite, potassium bisulfite and the like.

Examples of the thiourea compound include 1-(2-pyridyl)-2-thiourea, thiourea, methylthiourea, ethylthiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N. '-Di-n-propylthiourea, N,N'-dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n- Examples include propylthiourea and tetracyclohexylthiourea.

The content of the polymerization accelerator (F) in the dental composition of the present invention is not particularly limited, but from the viewpoint of adhesiveness and the like, the total amount of the polymerizable monomers contained in the dental composition is 100 parts by mass. It is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, further preferably 0.05 parts by mass or more, and 0.1 parts by mass or more. It is particularly preferable, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, further preferably 7 parts by mass or less, and particularly preferably 5 parts by mass or less.

[Filler (G)]
The dental composition of the present invention may further contain a filler (G). Such a filler (G) can be roughly classified into an organic filler, an inorganic filler, and an organic-inorganic composite filler. The filler (G) may be used alone or in combination of two or more. Examples of the case of using two or more kinds in combination include the case of using together fillers having different materials, particle size distributions, morphologies, and the like. As the filler (G), a commercially available product can also be used.

Examples of the material of the organic filler include polymethylmethacrylate, polyethylmethacrylate, methylmethacrylate-ethylmethacrylate copolymer, crosslinked polymethylmethacrylate, crosslinked polyethylmethacrylate, polyamide, polyvinyl chloride, Examples thereof include polystyrene, chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, and acrylonitrile-styrene-butadiene copolymer. The organic filler may be used alone or in combination of two or more. The shape of the organic filler is not particularly limited.

Examples of the material of the inorganic filler include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, Glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, etc. Can be mentioned. The inorganic fillers may be used alone or in combination of two or more.

The shape of the inorganic filler is not particularly limited, and examples of the inorganic filler include amorphous filler and spherical filler. From the viewpoint of improving the mechanical strength of the cured product, it is preferable to use a spherical filler as the inorganic filler. Further, the use of the spherical filler improves the surface smoothness of the cured product obtained when the dental composition of the present invention is used as a self-adhesive dental composite resin. Here, the spherical filler is a photograph of the filler taken with an electron microscope, and the particles observed in the unit field of view are rounded, and the average diameter of the particles in the direction orthogonal to the maximum diameter is divided by the maximum diameter. A filler having a degree of 0.6 or more can be used. When a spherical filler is used as the inorganic filler, the average particle size is 0.05 μm or more because the filling rate of the spherical filler in the dental composition does not decrease and the mechanical strength of the cured product can be maintained. The surface area is preferably sufficient to maintain the mechanical strength of the cured product, and is preferably 5 μm or less.

The inorganic filler may be used after being subjected to surface treatment with a known surface treatment agent such as a silane coupling agent in advance in order to adjust the fluidity of the dental composition. Examples of the surface treatment agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and the like can be mentioned.

As the organic-inorganic composite filler, one obtained by previously adding a polymerizable monomer to the above-mentioned inorganic filler, forming a paste, polymerizing, and pulverizing can be used. As the organic-inorganic composite filler, for example, TMPT filler (mixed with trimethylolpropane trimethacrylate and silica filler, polymerized and then pulverized) and the like can be used. The shape of the organic-inorganic composite filler is not particularly limited.

The particle size of the filler (G) is not particularly limited, and its average particle size can be appropriately selected. From the viewpoints of handleability of the resulting dental composition and mechanical strength of the cured product, the average particle diameter of the filler (G) is preferably 0.001 μm or more, and preferably 50 μm or less. It is more preferably 10 μm or less. In addition, in this specification, the average particle diameter of the filler (G) means the average particle diameter (average primary particle diameter) of the primary particles of the filler (G).

The average particle diameter of the filler (G) can be determined by a laser diffraction scattering method or by observing the particles with an electron microscope. Specifically, the laser diffraction/scattering method is easy to measure the particle size of particles of 0.1 μm or more, and the electron microscope observation is easy to measure the particle size of ultrafine particles of less than 0.1 μm. A laser diffraction/scattering method may be used to determine whether the thickness is 0.1 μm or more.

In the laser diffraction/scattering method, for example, a 0.2% sodium hexametaphosphate aqueous solution is used as a dispersion medium for measurement by a laser diffraction type particle size distribution measuring device (for example, “SALD-2300” manufactured by Shimadzu Corporation). The average particle size can be determined.

In the electron microscope observation, for example, a scanning electron microscope (for example, "S-4000 type" manufactured by Hitachi, Ltd.) photograph of a particle is taken, and the particle (200 particles or more) observed in a unit visual field of the photograph is taken. The average particle diameter can be determined by measuring the particle diameter using image analysis type particle size distribution measurement software (“Mac-View” manufactured by Mountech Co., Ltd.). At this time, the particle diameter of the particles is obtained as an arithmetic average value of the longest length and the shortest length of the particles, and the average particle diameter is calculated from the number of particles and the particle diameter.

The content of the filler (G) in the dental composition of the present invention is not particularly limited, and can be appropriately adjusted according to the application and the embodiment. The content of the filler (G) can be, for example, in the range of 0 to 900 parts by mass, relative to 100 parts by mass of the polymerizable monomers contained in the dental composition, and 1 part by mass. It is preferably at least 3 parts by mass, more preferably at least 3 parts by mass, further preferably at least 5 parts by mass, preferably at most 500 parts by mass, and at most 100 parts by mass. It is more preferably 50 parts by mass or less, further preferably 30 parts by mass or less, and further 20 parts by mass or less.

[Solvent (H)]
The dental composition of the present invention may further contain a solvent (H). By including the solvent (H), it is possible to further improve the adhesiveness, coatability, and penetration into the tooth structure, and it is possible to more effectively prevent the separation of each component in the dental composition. it can. An organic solvent can be preferably used as the solvent (H).

Examples of the organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-2-propanol, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, diisopropyl ether, hexane, toluene, chloroform, acetic acid. Examples include ethyl and butyl acetate. Among these, a water-soluble organic solvent is preferable in consideration of both safety to living bodies and ease of removal based on volatility, and specifically, ethanol, 2-propanol, 2-methyl-2- Propanol, acetone and tetrahydrofuran are preferred.

The content of the solvent (H) in the dental composition of the present invention is not particularly limited, can be appropriately adjusted according to the application and the embodiment, and the solvent (H) may not be necessary in some cases. The content of the solvent (H) can be, for example, in the range of 0 to 900 parts by mass with respect to 100 parts by mass of the polymerizable monomers contained in the dental composition, and can be 1 part by mass. It is preferably at least 3 parts by mass, more preferably at least 3 parts by mass, further preferably at least 5 parts by mass, preferably at most 500 parts by mass, and at most 100 parts by mass. It is more preferably 50 parts by mass or less, further preferably 40 parts by mass or less, and further 30 parts by mass or less.

[Fluorine ion-releasing substance (I)]
The dental composition of the present invention may further contain a fluoride ion-releasing substance (I). By including the fluoride ion-releasing substance (I), it is possible to impart acid resistance to the tooth structure. Examples of the fluoride ion-releasing substance (I) include metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride. As the fluoride ion-releasing substance (I), one type may be used alone, or two or more types may be used in combination.

[Other ingredients]
The dental composition of the present invention comprises the above-mentioned polymerizable monomers (phosphate group-containing monomer (A), acidic group-containing monomer (A′), and hydrophilic monomer having no acidic group). (C), hydrophobic monomer having no acidic group (D), etc.), water (B), polymerization initiator (E), polymerization accelerator (F), filler (G), solvent (H) and It may further contain one or two or more components other than the fluoride ion-releasing substance (I). Examples of the other components include a pH adjuster, a polymerization inhibitor, an ultraviolet absorber, a thickener, a coloring agent (dye, pigment, etc.), a fluorescent agent, and a fragrance. Further, the dental composition of the present invention, as the above-mentioned other components, for example, cetylpyridinium chloride, benzalkonium chloride, (meth)acryloyl oxide decylpyridinium bromide, (meth)acryloyloxyhexadecylpyridinium chloride, (meth)acryloyl. It may contain an antibacterial substance such as oxydecyl ammonium chloride and triclosan.

All the polymerizable monomers, water (B), polymerization initiator (E), polymerization accelerator (F), filler (G), solvent (H) and fluorine ion contained in the dental composition of the present invention. The total content of the releasable substance (I) is not particularly limited, but since the effect of the present invention is more remarkably achieved, it is 50% by mass or more based on the mass of the dental composition of the present invention. Is more preferable, 80% by mass or more is more preferable, 90% by mass or more is further preferable, 95% by mass or more is particularly preferable, 98% by mass or more, 99% by mass or more, and May be 100% by weight.

〔form〕
The form of the dental composition of the present invention is not particularly limited, and various forms suitable for its use can be used. The dental composition of the present invention may be of one-part type or divided-pack type (for example, two-part type), but is preferably one-part type because the operation is simple. In both the single-material type and the divided-pack type, the materials can be stored and transported by accommodating them in an appropriate container.

<<Method for preparing dental composition>>
The method for preparing the dental composition of the present invention is not particularly limited and can be obtained by blending the above-mentioned respective components. The order of blending is not particularly limited, and each component may be blended at once or may be blended in two or more times. If necessary, they may be mixed or kneaded or may be subjected to defoaming treatment such as vacuum defoaming treatment. When the dental composition of the present invention has a packaged form, the desired dental composition can be obtained by appropriately blending the components to be included in each material.

<<Use>>
The use of the dental composition of the present invention is not particularly limited, and examples thereof include a dental primer, a dental bonding material, a dental composite resin, a dental cement, a pit fissure filling material, a swaying tooth fixing material, and an orthodontic adhesive. Although it can be preferably used for various dental applications (especially for dental adhesive materials), the dental composition of the present invention can be applied not only to a healthy tooth structure but also to a tooth structure having a carious portion. As it exhibits high adhesiveness (initial adhesive strength and adhesive durability), it is used as a dental primer, dental bonding material, dental composite resin (especially self-adhesive dental composite resin), dental cement (especially self-adhesive). As a dental cement, it is particularly preferable to use as a dental bonding material.

Examples of the dental bonding material include a so-called one-step type material that can perform the deashing step, the infiltration step, and the curing step in one step. Examples of the form of the dental bonding material include a one-material type which can be used as it is, and a two-material type which is used by mixing two materials divided into A solution and B solution immediately before use. From the viewpoint of simplification, one material type is preferable. Specific examples of the dental bonding material include the above-mentioned phosphoric acid group-containing monomer (A), water (B), a hydrophilic monomer (C) having no acidic group, and a hydrophobic monomer having no acidic group. And a polymerizable monomer (D), a polymerization initiator (E) (preferably a photopolymerization initiator (E-1)), a polymerization accelerator (F) and a filler (G) are included.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Details of various components used in the following Examples and Comparative Examples are shown below.

[Phosphoric acid group-containing monomer (A)]
-Phosphoric acid group-containing monomer (A-1)
MHP: 6-methacryloyloxyhexyl dihydrogen phosphate MDP:10-methacryloyloxydecyl dihydrogen phosphate M12P: 12-methacryloyl oxide decyl dihydrogen phosphate

-Phosphoric acid group-containing monomer (A-2)
M-3 EGP: 8-methacryloyloxytriethylene glycol dihydrogen phosphate M-4 EGP: 11-methacryloyloxytetraethylene glycol dihydrogen phosphate M-5 EGP: 14-methacryloyloxypentaethylene glycol dihydrogen phosphate

[Acidic group-containing monomer (A') other than phosphoric acid group-containing monomer (A)]
M2P:2-methacryloyloxyethyl dihydrogen phosphate M-6EGP:17-methacryloyloxyhexaethylene glycol dihydrogen phosphate

[Hydrophilic monomer having no acidic group (C)]
HEMA: 2-hydroxyethyl methacrylate

[Hydrophobic monomer (D) having no acidic group]
Bis-GMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane

[Polymerization initiator (E)]
CQ: DL-camphorquinone BAPO: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide

[Polymerization accelerator (F)]
DABE: 4-(N,N-dimethylamino)ethyl benzoate

[Filler (G)]
Inorganic filler 1: manufactured by Nippon Aerosil Co., Ltd., fine particle silica “AEROSIL (registered trademark) R 972”, average particle diameter: 16 nm

[Other ingredients]
-Polymerization inhibitor BHT: 2,6-di-t-butyl-4-methylphenol

[Preparation of artificial demineralized dentin]
An artificial demineralized dentin assuming a dental substance having a carious part was prepared as follows. That is, first, the labial surface of the bovine lower anterior tooth was polished with running water of #80 silicon carbide paper (manufactured by Nippon Kenshi Co., Ltd.) to obtain a sample in which the flat surface of dentin was exposed. The obtained sample was further ground with #1000 silicon carbide paper (manufactured by Nippon Kenshi Co., Ltd.) under running water. After the polishing, the surface water was dried by air blowing.
Next, referring to the description regarding the production of artificial demineralized dentin in Non-Patent Document 2, after coating the tooth surface excluding the central portion (4 mm x 4 mm) of the exposed dentin surface with a nail varnish, a 1N KOH aqueous solution Immersed in a demineralized aqueous solution containing 2.2 mmol/L of CaCl ₂ , 2.2 mmol/L of Na ₂ HPO ₄ and 50 mmol/L of CH ₃ CO ₂ H, which was adjusted to pH 5.0 with 5 days. Then, demineralized dentin was formed on the exposed surface of dentin.

[Examples 1 to 11 and Comparative Examples 1 to 5]
The one-component dental bonding materials according to Examples 1 to 11 and Comparative Examples 1 to 5 were prepared by mixing the components shown in Table 1 at room temperature. Using these dental bonding materials, the adhesiveness to the artificial demineralized dentin (initial adhesive strength and adhesive durability) was evaluated according to the following method. The results are shown in Table 1.
For the one-component dental bonding material according to Example 2, a healthy dentin was used instead of the artificial demineralized dentin, and the same evaluation as the adhesiveness to the artificial demineralized dentin described below was performed. went. As a result, the initial adhesive strength was 23 MPa and the adhesive durability was 22 MPa.

-Adhesiveness to artificial demineralized dentin The artificial demineralized dentin prepared as described above was washed under running water and dried by air-blowing the surface water. An adhesive area having a thickness of about 150 μm having a circular hole with a diameter of 3 mm was attached to the dried smooth surface (portion where demineralized dentin was formed) to define the adhesion area.
The one-pack type dental bonding material produced in each of the above Examples or Comparative Examples was applied to the inside of the round hole using an applicator brush (Kurarenori Takedental Co., Ltd., product number “241-024”) and rubbed for 10 seconds. Then, the surface was air blown to dry the applied dental bonding material until the fluidity disappeared. Subsequently, the applied dental bonding material was cured by irradiating with a dental LED light irradiator (manufactured by Morita Co., Ltd., trade name "Pencure 2000") for 3 seconds.
The surface of the cured product of the obtained dental bonding material was filled with a dental filling composite resin (trade name "Clearfill (registered trademark) AP-X", manufactured by Kuraray Noritake Dental Co., Ltd.), and a release film (polyester) was filled. ). Then, a slide glass was placed on the release film and pressed to smooth the coated surface of the dental filling composite resin. Subsequently, through the release film, the dental filling composite resin is irradiated with light for 20 seconds using a dental LED light irradiator (Morita Co., Ltd., trade name "Pencure 2000"), The dental filling composite resin was cured.
A cylindrical stainless steel rod (commercial name “Panavia (registered trademark) 21” manufactured by Kurarenori Takedental Co., Ltd.) was used for the surface of the obtained cured product of the dental filling composite resin using a commercially available dental resin cement (Kurarenori Takedental Co., Ltd.). One end surface (circular cross section) having a diameter of 7 mm and a length of 2.5 cm was adhered. After adhering, the sample was allowed to stand at room temperature for 30 minutes and then immersed in distilled water to obtain an adhesion test sample. Twenty test samples for the adhesion test were prepared for each of the Examples or Comparative Examples, and immersed in distilled water and allowed to stand in a thermostat kept at 37° C. for 24 hours.
In order to evaluate the initial adhesive strength of 10 of the 20 samples, the tensile adhesive strength thereof was immediately measured after leaving still for 24 hours as described above. The tensile bond strength was measured using a universal testing machine (manufactured by Shimadzu Corporation) with the crosshead speed set to 2 mm/min. The average value of the obtained tensile adhesive strength values was taken as the initial adhesive strength.
Further, for the remaining 10 samples, in order to evaluate the adhesion durability, after further conducting 4000 thermal cycles of 1 cycle of alternately immersing in cold water at 4° C. and hot water at 60° C. for 1 minute, The tensile adhesive strength was measured in the same manner as above. The average value of the obtained tensile adhesive strength values was taken as the adhesion durability.

As is clear from the above results, the dental bonding materials (Examples 1 to 11) according to the present invention have an initial adhesive force of 13 MPa or more with respect to artificial demineralized dentin assuming a tooth substance having a carious portion. The tensile adhesive strength of 10 and the tensile durability of 10 MPa or more as the adhesive durability are developed, and not only the healthy tooth structure but also the tooth structure having a carious part (high initial adhesive strength and Adhesion durability) was shown.
On the other hand, in the dental bonding materials of Comparative Examples 1 to 5 which did not satisfy the constitution of the present invention, the initial adhesive force to the artificial demineralized dentin was 7 MPa even when high, and the adhesive durability was 3 MPa or less. ..

Claims (6)

A phosphoric acid group-containing monomer (A-1) represented by the following general formula (1), a phosphoric acid group-containing monomer (A-2) represented by the following general formula (2), water (B), and , A hydrophilic monomer (C) having no acidic group as an optional component, and a mass ratio of the monomer (C) and water (B) ([content of monomer (C)]/ [Content of water (B)]) is less than 1;

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 6 to 12.)

(In the general formula (2), R ² represents a hydrogen atom or a methyl group, and n represents an integer of 3 to 5.) Mass ratio of the phosphoric acid group-containing monomer (A-1) and the phosphoric acid group-containing monomer (A-2) ([content of phosphoric acid group-containing monomer (A-1)]/ The dental composition according to claim 1, wherein the [content of the phosphate group-containing monomer (A-2)] is 20/80 to 90/10. The dental composition according to claim 1 or 2, wherein the content of the water (B) is 1 to 900 parts by mass based on 100 parts by mass of the total amount of polymerizable monomers contained in the dental composition. Stuff. The dental composition according to claim 1, further comprising a hydrophobic monomer (D) having no acidic group. The dental composition according to claim 1, further comprising a polymerization initiator (E). The dental composition according to any one of claims 1 to 5, which is a dental bonding material.