JP2016056145A - Non-solvent system adhesive composition for dentistry - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-solvent system adhesive composition for dentistry which exhibits excellent adhesiveness to any of dental enamel and dentin, and substantially contains neither water nor an organic solvent.SOLUTION: The invention provides a non-solvent system adhesive composition for dentistry containing neither water nor an organic solvent, wherein (A) a polymerizable monomer component,(B) aromatic amine having an electron withdrawing group, and(C) a polymerization initiator are contained; and the polymerizable monomer component (A) contains a phosphoric acid monomer (a1) having a phosphate acidic group (>P(=O)OH) and a sulfonic acid monomer (a2) having a sulfonic acid group at the following mass ratio; (a1):(a2)=98:2-67:33, and simultaneously contains the sulfonic acid monomer (a2) and the aromatic amine (B) at a ratio so that the molar ratio of an aromatic amino group and a sulfonic acid group (the aromatic amino group/sulfonic acid group) becomes 0.8 or more.SELECTED DRAWING: None

Description

  The present invention relates to a dental adhesive composition used in the field of dentistry, and more particularly to a non-solvent dental adhesive composition that does not contain water or an organic solvent.

  In the restoration of a cavity formed in a tooth structure by caries or the like, when the cavity is not so large, a restoration material called a composite resin is widely used. This restoration material called a composite resin is a curable composition containing a polymerizable monomer component, a polymerization initiator, and a filler. This is directly filled into the cavity and cured by irradiation with light to cure the cavity. That's it.

By the way, since the composite resin does not have adhesiveness to the tooth, an adhesive called a bonding material is used to adhere to the tooth.
Such a bonding material is a curable composition containing a polymerizable monomer component and a curing agent. In general, in order to improve adhesion to a tooth such as enamel or dentin, a polymerizable monomer is used. As a part of the body component, an acidic group-containing monomer having a decalcifying property (etching effect) on the tooth is used, and further, water and a hydrophilic volatile organic solvent are used to fully exhibit this decalcifying property. It is blended. In other words, when this bonding material is filled in the cavity, the acidic monomer penetrates into the enamel and dentin of the cavity due to decalcification, and the cured product is firmly adhered to the cavity by being cured in this state. By fixing and curing the above-described composite range on this, the restoration by the composite resin is effectively performed.

However, when the cavity is repaired using the bonding material as described above, it is necessary to remove water and an organic solvent contained in the bonding material by blowing air before curing the cavity. This is because when water or an organic solvent is present, curing failure or curing delay occurs.
Therefore, a non-solvent dental adhesive composition that does not contain water or an organic solvent has also been proposed for the purpose of omitting steps such as air blowing for removing water and the organic solvent (for example, patent documents). 1 and 2).

  None of the above non-solvent dental adhesive compositions use a phosphate monomer as the acidic group-containing polymer, but since they do not contain water or an organic solvent, the decalcification power is insufficient, Adhesive strength to enamel is unsatisfactory.

In order to increase the deashing power, a polymerizable monomer having a sulfonic acid group as an acidic group (sulfonic acid monomer) is used in combination with a phosphoric acid monomer or a carboxylic acid monomer having a carboxyl group as an acidic group. This is also known (see, for example, Patent Documents 3 to 5).
However, since the sulfonic acid monomer is a strong acid, the adhesion to the enamel is improved, but there is a problem that the adhesion to the dentin is reduced due to excessive decalcification. In addition, the sulfonic acid monomer is incompatible with other monomers in the absence of water or an organic solvent. For this reason, a solvent such as water is inevitably required, and a non-solvent dental adhesive composition is required. Has the fundamental problem that it cannot be applied.

  Furthermore, in order to avoid the above-mentioned compatibility problem, a non-solvent dental adhesive composition in which a zirconia filler treated with a sulfonic acid monomer is used in combination with a phosphoric acid monomer has been proposed (Patent Document 6). ). However, in such means, since the sulfonic acid monomer is adsorbed and held by the zirconia filler, it does not contribute to deashing, and eventually the adhesion to the enamel becomes insufficient.

Special table 2008-510038 JP2008-260752 JP 2005-225839 A JP-A-8-310912 Special table 2007-520465 Special table 2009-522279

  Accordingly, an object of the present invention is to provide a non-solvent dental adhesive composition that exhibits excellent adhesion to both enamel and dentin and is substantially free of water and organic solvents. There is to do.

  For the polymerizable monomer having a sulfonic acid group (sulfonic acid-based monomer), the present inventors are concerned with deashing properties and other polymerizable monomer components in the absence of water or an organic solvent. As a result of examining the behavior of the above, when an aromatic amine having an electron withdrawing group is combined with a sulfonic acid monomer, excessive decalcification is suppressed and moderate decalcification is achieved in the absence of a solvent such as water. Thus, the inventors have found that the adhesion to enamel and dentin can be improved and the compatibility of the sulfonic acid monomer with other polymerizable monomers has been found, and the present invention has been completed.

According to the present invention,
(A) a polymerizable monomer component;
(B) an aromatic amine having an electron withdrawing group;
(C) a polymerization initiator;
Including
The polymerizable monomer component (A) includes a phosphoric acid monomer (a1) having a phosphoric acid acidic group (> P (= O) OH), a sulfonic acid monomer having a sulfonic acid group (a2), and In the following mass ratio:
(A1) :( a2) = 98: 2-67: 33
As well as
The sulfonic acid monomer (a2) and the aromatic amine (B) are contained at a ratio such that the molar ratio of aromatic amino group to sulfonic acid group (aromatic amino group / sulfonic acid group) is 0.8 or more. A non-solvent dental adhesive composition is provided.
In the present invention, the electron withdrawing group means a group having a substituent constant (σ _p ) greater than 0. For the substituent constants (σ _p ) of various substituents, refer to Organic Chemistry Glossary, Second Edition, Moto Koga et al., Asakura Shoten, p. 236 (ISBN 4-254-140371).

In the non-solvent dental composition of the present invention,
(1) The phosphoric acid monomer (a1) and the sulfonic acid monomer (a2) are contained in a total amount of 5% by mass or more of the polymerizable monomer component (A).
(2) The phosphoric acid monomer (a1) contains a (meth) acryloyloxy group as a polymerizable group,
(3) The (meth) acryloyloxy group and the phosphoric acid acidic group are bonded to each other through a divalent group having a total carbon number of 4 to 12,
(4) The aromatic amine (B) has a carboxyl group or an alkoxycarbonyl group as an electron withdrawing group,
(5) The aromatic amine (B) is one in which the electron withdrawing group is bonded to dimethylaminobenzoic acid,
(6) The polymerization initiator (C) contains a photopolymerization initiator,
(7) Furthermore, the filler (D) is contained in an amount of 5 to 900 parts by mass per 100 parts by mass of the polymerizable monomer component (A),
Is preferred.

The non-solvent dental adhesive composition of the present invention does not contain water or an organic solvent. Therefore, when repairing a cavity using this, the spraying of air for removing water or the organic solvent is used. The process can be omitted.
Moreover, although it does not contain water or an organic solvent, it exhibits high adhesion to enamel and dentin. Therefore, this composition can be used not only as a bonding material that directly fills the cavity generated in the tooth, but also as a self-adhesive composite resin that does not require a bonding material. It can also be used as a dental adhesive for a prosthesis made of ceramic or the like.

  In the present invention, the adhesiveness as described above is such that the sulfonic acid monomer (a2) used in combination with the phosphoric acid monomer (a1) is compatible with other monomers and the dentin is excessively removed by the sulfonic acid monomer (a2). This is achieved because ash is improved by the aromatic amine (B) having an electron withdrawing group.

That is, as shown by the following formula, a sulfonic acid group (strong acid) of a sulfonic acid monomer and an amino group of an aromatic amine having an electron withdrawing group form a mild salt by an equilibrium reaction. In the following formula, the sulfonic acid monomer is represented by RSO ₃ H, and the electron withdrawing group is represented by EWG.
As described above, since the sulfonic acid monomer and the aromatic amine form a gradual salt, the strong acidity of the sulfonic acid group is moderately lowered, so that the sulfonic acid can be used despite the absence of a solvent such as water. The monomer is compatible with another monomer (for example, a phosphoric acid monomer), and the characteristic improvement by the sulfonic acid monomer is stably exhibited.

  In addition, as described above, the acidity (decalcification power) of the mild salt of the sulfonic acid monomer and the aromatic amine is lower than that of the sulfonic acid monomer. Is prevented. That is, a dense enamel is formed on the tooth surface, and a porous dentin is formed on the lower side of the enamel. Therefore, when a strong acid such as sulfonic acid penetrates, decalcification occurs. Excessively progresses, and such excessive demineralization causes a decrease in adhesion. This is because the polymerized cured product of the adhesive composition cannot be stably held. However, the acidity of the above-mentioned salt is lower than that of the sulfonic acid monomer (sulfonic acid group), and as a result, it is possible to effectively prevent excessive demineralization of the dentin and to improve the adhesion to the dentin. It is.

Furthermore, the mild salt of a sulfonic acid monomer and an aromatic amine is a salt of a strong acid and a weak base, and its acidity (decalcification power) is higher than that of a phosphoric acid monomer, and it is effective in decalcifying enamel. It is sufficiently acidic. Therefore, the non-solvent dental adhesive composition of the present invention exhibits high adhesion to enamel even though no solvent such as water is present.
Moreover, according to the study by the present inventors, when a sulfonic acid monomer is used, the adhesive strength to the tooth tends to decrease with time, or the strength of the cured product tends to decrease. This is because the sulfonic acid group is a strong acid and thus promotes hydrolysis and transesterification in the cured product. However, in the present invention, since the sulfonic acid monomer forms a mild salt with the aromatic amine, hydrolysis and transesterification are suppressed, and as a result, it is possible to effectively avoid a decrease in adhesion and strength. .

By the way, the acidity and compatibility of the mild salt of sulfonic acid monomer and aromatic amine compared with sulfonic acid monomer (RSO ₃ H) and phosphoric acid monomer (RPO ₄ H ₂ ) is as follows: It has become.

The non-solvent dental adhesive composition of the present invention contains (A) a polymerizable monomer component, (B) an aromatic amine, and (C) a polymerization initiator as basic components. D) Contains fillers and other additives.
Since such a composition does not contain a solvent that causes poor curing or curing delay, that is, water or an organic solvent, there is an advantage that the step of removing the solvent by blowing air or the like can be omitted when this is cured. As long as there is no inconvenience such as poor curing or delay in curing, mixing of a trace amount of water or organic solvent (for example, 3% by mass or less per composition) is allowed. Therefore, some of the ingredients to be blended are sold in a form containing water or organic solvent (for example, colloidal silica). In such a case, water or organic solvent is removed to an allowable limit. It is used for the preparation of the composition.
Hereinafter, each component will be described.

<(A) Polymerizable monomer component>
In the present invention, the polymerizable monomer component (A) is radically polymerizable and adheres to a restoration material such as an enamel or dentin and a composite resin or a prosthesis by polymerization and curing. It is a basic component for forming a highly cured product.

Moreover, in order to express decalcification with respect to a tooth substance (especially enamel) and permeability with respect to a tooth substance (especially dentin), this polymerizable monomer component (A) is at least phosphoric acid type monomer (a1) and It is necessary to contain the sulfonic acid monomer (a2).
Further, all of the polymerizable monomer component (A) may be a phosphoric acid monomer (a1) and a sulfonic acid monomer (a2), but the phosphoric acid monomer (a1) and the sulfonic acid monomer ( It may contain other acidic monomer (a3) having an acidic group other than the above, as long as it does not adversely affect the properties such as adhesion to the tooth in the absence of a solvent in combination with a2). The non-acidic monomer (a4), that is, a polymerizable monomer having no acidic group may be contained.

Phosphoric acid monomer (a1);
The phosphoric acid monomer is a compound having a phosphoric acid acidic group (> P (= O) OH) and a group containing a polymerizable unsaturated bond, that is, a polymerizable group.

  Examples of the polymerizable group include acryloyloxy group, methacryloyloxy group, acrylamide group, methacrylamide group, vinyl group, allyl group, ethynyl group, and styryl group. In particular, acryloyloxy group, methacryloyloxy group, acrylamide group, and methacrylamide group are preferable from the viewpoint of curing speed, and (meth) acryloyloxy group (acryloyloxy group, methacryloyloxy group) is most preferable.

The phosphoric acid acidic group is a group having a structure represented by> P (═O) OH, and specifically includes a phosphinic acid group, a phosphonic acid group, a hydrogen phosphonate monoester group, and dihydrogen phosphate. Examples thereof include a monoester group and a hydrogen phosphate diester group.
Such a phosphoric acid acidic group not only has a high decalcification effect on the tooth, but also has an essential binding force to the composite resin and the tooth, which is advantageous in obtaining particularly high adhesive strength.

The following compounds can be illustrated as specific examples of the phosphoric acid monomer in which the above phosphoric acid acidic group is bonded to the polymerizable group described above.
A phosphoric acid monomer having a phosphinic acid group;
Bis (2-methacryloxyethyl) phosphinic acid bis (3-methacryloxypropyl) phosphinic acid bis (4-methacryloxybutyl) phosphinic acid-based phosphoric acid monomer
3-methacryloxypropylphosphonic acid 2-methacryloxyethoxycarbonylmethylphosphonic acid 4-methacryloxybutoxycarbonylmethylphosphonic acid 6-methacryloxyhexyloxycarbonylmethylphosphonic acid 2- (2-ethoxycarbonylallyloxy) ethylphosphonic acid hydrogen phosphonate monoester A phosphoric acid monomer having a group;
2-methacryloxyethylphosphonic acid mono (methacryloxyethyl) ester 2-methacryloxyethylphosphonic acid monophenyl ester phosphoric acid monomer having dihydrogen phosphate monoester group or hydrogen phosphate diester group;
However, in the above compounds, R ¹ represents a hydrogen atom or a methyl group.

In the present invention, the (meth) acryloyloxy group among the phosphoric acid monomers exemplified above is particularly high in deashing property in the absence of water or an organic solvent, and exhibits high adhesive strength. It is preferably bonded to a phosphoric acid acidic group (> P (= O) OH) via a divalent group having 4 to 12 total carbon atoms, and the phosphoric acid acidic group is preferably dihydrogen phosphate monoester. ester [-0-P (= O) (OH) 2] or hydrogen phosphate diester group _{[(-O-) 2 P (=} O) OH] a is what is particularly preferred.
In addition, as long as the bivalent group which couple | bonded the (meth) acryloyloxy group and the phosphoric acid acidic group exists in the range whose total carbon number is 4-12, either linear or branched It may have a form and may contain an oxygen atom or the like.

  Said phosphoric acid-type monomer can also be used individually by 1 type, and can also be used in combination of 2 or more type.

Sulfonic acid monomer (a2);
The sulfonic acid monomer is a compound having a molecular structure in which a sulfonic acid group (—SO ₃ H) is bonded to a polymerizable group containing a polymerizable unsaturated bond, and has an adhesive property to a tooth in the absence of moisture. Used to complement.
Examples of the polymerizable group include acryloyl group, methacryloyl group, acrylamide group, methacrylamide group, vinyl group, allyl group, ethynyl group, and styryl group, similar to the phosphoric acid monomer described above. .

As such a sulfonic acid monomer, for example, those represented by the following general formula (1) are suitable.
In the above formula, R ₁ represents a hydrogen atom or a methyl group,
R ₃ may have an ether bond and / or an ester bond and may have 1 to 3 carbon atoms.
0 to 2-6 valent organic residues,
Z represents an oxygen atom or an imino group (—NH—),
n ₁ is an integer of ₁ to 4,
n ₂ represents an integer of 1 or 2.

Preferred specific examples of the sulfonic acid monomer represented by the general formula (1) are as follows.

  In addition to the above, vinyl sulfonic acid and p-styrene sulfonic acid can also be used as the sulfonic acid monomer.

  Said sulfonic acid-type monomer can also be used individually by 1 type, and can also be used in combination of 2 or more type.

In the present invention, the phosphoric acid monomer (a1) and the sulfonic acid monomer (a2) described above are in the following mass ratio:
(A1) :( a2) = 98: 2-67: 33
In particular, 90:10 to 75:25
Is used in such an amount as to satisfy. That is, when the amount of the sulfonic acid monomer used relative to the phosphoric acid monomer is excessive, the adhesion to the tooth becomes extremely unstable due to excessive decalcification. Moreover, when there is too little usage-amount of the sulfonic acid type monomer with respect to a phosphoric acid type monomer, the fall of the adhesiveness with respect to a tooth | gear by absence of solvents, such as water, will appear large.

  In the present invention, the phosphoric acid monomer (a1) and the sulfonic acid monomer (a2) in total, in order to ensure appropriate decalcification for the tooth in the absence of a solvent such as water, It is preferable that the polymerizable monomer component (A) is present in an amount of 5% by mass or more, particularly 10% by mass or more.

Other acid monomers (a3);
In the present invention, on the condition that the total amount of the phosphoric acid monomer (a1) and the sulfonic acid monomer (a2) is within the above range, an acidic group other than a phosphoric acid acidic group or a sulfonic acid group is used. And other acid monomers having a polymerizable group having a polymerizable unsaturated bond can be appropriately blended. As such other acidic groups, a carboxyl group is representative, and examples of the polymerizable group include those exemplified for the phosphoric acid monomer (a1).

Non-acidic monomer (a4);
In the present invention, the balance of adhesion strength to both enamel and dentin is ensured, the water resistance is increased, the excellent adhesion strength of the cured product in the oral cavity is maintained, and the adhesion durability is improved. In view of the above, it is desirable to use the non-acidic monomer (a4) together with the phosphoric acid monomer (a1) and the sulfonic acid monomer (a2).
Such a non-acidic monomer is a compound that does not contain an acidic group and has a polymerizable group that has at least one polymerizable unsaturated bond in the molecule. Examples of the phosphoric acid monomer (a1) may be the same as those mentioned above, but acryloyl group, methacryloyl group, acrylamide group and methacrylamide group are particularly preferable.

  Typical examples of such non-acidic monomers include the following (meth) acrylate monomers, which can be used singly or in combination of two or more.

1. Mono (meth) acrylate monomers;
Methyl (meth) acrylate,
Ethyl (meth) acrylate,
Glycidyl (meth) acrylate,
2-cyanomethyl (meth) acrylate,
Benzyl (meth) acrylate,
Polyethylene glycol mono (meth) acrylate,
Allyl (meth) acrylate,
2-hydroxyethyl (meth) acrylate,
Glycidyl (meth) acrylate,
3-hydroxypropyl (meth) acrylate,
Glyceryl mono (meth) acrylate,
2- (meth) acryloxyethyl acetyl acetate and the like.

2. Polyfunctional (meth) acrylate monomers;
Ethylene glycol di (meth) acrylate,
Diethylene glycol di (meth) acrylate,
Triethylene glycol di (meth) acrylate,
Nonaethylene glycol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate,
Propylene glycol di (meth) acrylate,
Dipropylene glycol di (meth) acrylate,
2,2′-bis [4- (meth) acryloyloxyethoxyphenyl] propane,
2,2′-bis [4- (meth) acryloyloxyethoxyethoxyphenyl] propane,
2,2′-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane,
2,2′-bis {4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl} propane,
1,4-butanediol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
1,9-nonanediol di (meth) acrylate,
1,12-dodecanediol di (meth) acrylate,
Tricyclodecane dimethanol di (meth) acrylate,
Ethylene glycol diglycidyl ether di (meth) acrylate,
Trimethylolpropane tri (meth) acrylate,
Urethane di (meth) acrylate,
Epoxy (meth) acrylate and the like.

  Moreover, it is also possible to use polymerizable monomers other than the (meth) acrylate monomers as non-acidic monomers. Examples of such other polymerizable monomers include fumaric acid ester compounds such as monomethyl fumarate, diethyl fumarate, and diphenyl fumarate; styrenes such as styrene, divinylbenzene, α-methylstyrene, and α-methylstyrene dimer. Compounds; allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl carbonate, and allyl diglycol carbonate; These other polymerizable monomers can also be used alone or in combination of two or more.

  The non-acidic monomer as described above is contained in the polymerizable monomer component (A) on the condition that the total amount of the phosphoric acid monomer (a1) and the sulfonic acid monomer (a2) is within the range described above. It is preferable to be present in an amount of 10% by mass or more, particularly 20% by mass or more.

<(B) Aromatic amine>
In the present invention, the aromatic amine (B) is used together with the polymerizable monomer component (A) described above. This aromatic amine is an electron as a substituent on the aromatic ring to which the amino group is bonded. It is necessary to have an attractive group. That is, by having an electron withdrawing group, this aromatic amine forms a gradual salt with the sulfonic acid monomer (a2) described above, and reduces the acidity of the sulfonic acid monomer (sulfonic acid group). As a result, the compatibility of the sulfonic acid monomer with other monomers is enhanced, and further, overdemineralization is suppressed, and the adhesion to dentin is further enhanced. The decrease can be effectively avoided.

In the present invention, the electron-withdrawing group possessed by the aromatic amine means a substituent having a substituent constant (σ _P ) greater than 0, as briefly described above.
In addition, a substituent constant is a constant peculiar to the substituent calculated | required on the basis of the dissociation constant of unsubstituted benzoic acid at 25 degreeC in water, and is calculated | required by the following formula.
σ _P = log (K / K ₀ )
Where K ₀ is the dissociation constant of unsubstituted benzoic acid at 25 ° C.
K is the dissociation constant of the substituted benzoic acid at 25 ° C.

Incidentally, the following groups can be exemplified as the substituent having a substituent constant (σ _P ) larger than 0.
In the following examples, Ph represents a phenyl group, Me represents a methyl group, and R represents an alkyl group.
Ph: 0.05
COO ⁻ : 0.11
CH ₂ Cl: 0.12
C≡CH: 0.23
F: 0.15
Cl: 0.24
Br: 0.26
I: 0.28
CHO: 0.43
COOH: 0.44
COOR: 0.44
OCOMe: 0.31
COMe: 0.47
SO ₂ NH _2: 0.57
S (O) Me: 0.49
CF ₃ : 0.53
N ⁺ H ₃ : 0.60
CN: 0.70
SO ₂ Me: 0.73
NO ₂ : 0.81
N ⁺ Me ₃ : 0.82
N ⁺ ₂ : 1.93

  In the present invention, specific examples of the aromatic amine having the above electron-withdrawing group include the following compounds.

In the present invention, among the above aromatic amines, those having an electron withdrawing group having a substituent constant (σ _P ) of 0.2 to 0.8, particularly 0.3 to 0.7 are preferable. Furthermore, an electron withdrawing group having a substituent constant (σ _P ) in the range of 0.4 to 0.5, for example, a carboxyl group (σ _P = 0.44), an alkoxycarbonyl group (σ _P = 0. 44) is preferable, the aromatic amine having the electron-withdrawing group bonded to dimethylbenzoic acid is more preferable, and the electron-withdrawing group is bonded to the para position of the amino group. Aromatic amines are optimal.

The aromatic amine (B) having the electron withdrawing group as a substituent as described above can be used alone or in combination of two or more. The molar ratio (aromatic amino group / sulfonic acid group) between the group and the sulfonic acid group of the sulfonic acid monomer described above is 0.8 or more, preferably 0.9 to 3.0. is necessary.
That is, if the amount of the aromatic amine (B) used is too small, the adverse effects due to the use of the sulfonic acid monomer cannot be avoided. For example, the compatibility between the sulfonic acid monomer and other monomers is impaired. Moreover, due to excessive demineralization and the like, the adhesiveness to the dentin is reduced, and further, the adhesiveness decreases with time due to the promotion of hydrolysis and transesterification, and the mechanical strength of the cured product decreases. End up. Moreover, when there is too much usage-amount of an aromatic amine (B), the advantage (adhesion improvement with respect to a tooth | gear in the absence of a solvent) by using a sulfonic acid-type monomer will become diluted.

<(C) Polymerization initiator>
In the adhesive composition of the present invention, it is necessary to blend a polymerization initiator (C) in order to cure the polymerizable monomer component (A) described above.
As such a polymerization initiator (C), a photopolymerization initiator or a chemical polymerization initiator is used, but it can be polymerized and cured at any timing, and is suitable for polymerization and curing in the oral cavity. Therefore, a photopolymerization initiator is preferable. In addition, the chemical polymerization initiator is advantageous when curing is performed at a site where light is difficult to reach. In particular, by using a photopolymerization initiator and a chemical polymerization initiator in combination, by performing light irradiation, polymerization curing is performed. Time can be increased, and this is advantageous when the adhesive composition of the present invention is used for applications such as abutment construction.

As the photopolymerization initiator, a compound that itself generates radical species by light irradiation or a mixture obtained by adding a polymerization accelerator to such a compound is used. Examples of the compound that itself decomposes upon irradiation with light to generate a polymerizable radical species include the following.
α-diketones;
Camphorquinone, benzyl, α-naphthyl, acetonaphthene,
Naphthoquinone, 1,4-phenanthrenequinone,
3,4-phenanthrenequinone, 9,10-phenanthrenequinone, and the like.
Thioxanthones;
2,4-diethylthioxanthone and the like.
Acylphosphine oxide derivatives;
2,4,6-trimethylbenzoyldiphenylphosphine oxide,
Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like.

In addition, tertiary amines, barbituric acids, mercapto compounds, and the like are used as the above-described polymerization accelerator. Specific examples thereof are as follows.
Tertiary amines;
N, N-dimethylaniline,
N, N-diethylaniline,
N, N-di-n-butylaniline,
N, N-dibenzylaniline,
N, N-dimethyl-p-toluidine,
N, N-diethyl-p-toluidine,
N, N-dimethyl-m-toluidine,
p-bromo-N, N-dimethylaniline,
m-chloro-N, N-dimethylaniline,
p-dimethylaminobenzaldehyde,
p-dimethylaminoacetophenone,
p-dimethylaminobenzoic acid,
p-dimethylaminobenzoic acid ethyl ester,
p-dimethylaminobenzoic acid amyl ester,
N, N-dimethylanthranic acid methyl ester,
N, N-dihydroxyethylaniline,
N, N-dihydroxyethyl-p-toluidine,
p-dimethylaminophenethyl alcohol,
p-dimethylaminostilbene,
N, N-dimethyl-3,5-xylidine,
4-dimethylaminopyridine,
N, N-dimethyl-α-naphthylamine,
N, N-dimethyl-β-naphthylamine,
Tributylamine,
Tripropylamine,
Triethylamine,
N-methyldiethanolamine,
N-ethyldiethanolamine,
N, N-dimethylhexylamine,
N, N-dimethyldodecylamine,
N, N-dimethylstearylamine,
N, N-dimethylaminoethyl acrylate,
N, N-dimethylaminoethyl methacrylate,
2,2 ′-(n-butylimino) diethanol and the like.
Barbituric acids;
5-butyl barbituric acid,
1-benzyl-5-phenylbarbituric acid and the like.
Mercapto compounds;
Dodecyl mercaptan,
Pentaerythritol tetrakis (thioglycolate) and the like.

In the above polymerization accelerator, some tertiary amines have a function as the above-mentioned aromatic amine (B), but the amount of the tertiary amine used as the polymerization accelerator is small. Therefore, the aromatic amine (B) is not sufficient to fully exhibit the above-described functions.
In addition, among the above-mentioned tertiary amines, when the one not included in the above-mentioned aromatic amine (B) is used as a polymerization accelerator, the adhesive strength may be lowered. It is preferable that the molar ratio is 0.5 or less with respect to the sulfonic acid group of the sulfonic acid monomer (a2).

  As the chemical polymerization initiator, various organic peroxides classified into ketone peroxide, peroxyketal, hydroperoxide, diaryl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate are typical. Specific examples of these organic peroxides include the following.

Ketone peroxides:
Methyl ethyl ketone peroxide,
Cyclohexanone peroxide,
Methylcyclohexanone peroxide,
Methyl acetoacetate peroxide,
Acetylacetone peroxide and the like.

Peroxyketals:
1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane,
1,1-bis (t-hexylperoxy) cyclohexane,
1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane,
1,1-bis (t-butylperoxy) cyclohexane,
1,1-bis (t-butylperoxy) cyclododecane,
2,2-bis (t-butylperoxy) butane,
n-butyl 4,4-bis (t-butylperoxy) valerate,
2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane and the like.

Hydroperoxides:
P-menthane hydroperoxide,
Diisopropylbenzene hydroperoxide,
1,1,3,3-tetramethylbutyl hydroperoxide,
Cumene hydroperoxide,
t-hexyl hydroperoxide,
t-butyl hydroperoxide and the like.

Dialkyl peroxides:
α, α-bis (t-butylperoxy) diisopropylbenzene,
Dicumyl peroxide,
2,5-dimethyl-2,5-bis (t-butylperoxy) hexane,
t-butyl cumyl peroxide,
Di-t-butyl peroxide,
2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 and the like.

Diacyl peroxides:
Isobutyryl peroxide,
2,4-dichlorobenzoyl peroxide,
3,5,5-trimethylhexanoyl peroxide,
Octanoyl peroxide,
Lauroyl peroxide,
Stearyl peroxide,
Succinic acid peroxide,
m-toluoyl benzoyl peroxide,
Benzoyl peroxide and the like.

Peroxydicarbonates:
Di-n-propyl peroxydicarbonate,
Diisopropyl peroxydicarbonate,
Bis (4-t-butylcyclohexyl) peroxydicarbonate,
Di-2-ethoxyethyl peroxydicarbonate,
G-2-ethylhexyl peroxydicarbonate,
Di-2-methoxybutyl peroxydicarbonate,
Di (3-methyl-3-methoxybutyl) peroxydicarbonate and the like.

Peroxyesters:
α, α-bis (neodecanoylperoxy) diisopropylbenzene,
Cumyl peroxyneodecanoate,
1,1,3,3-tetramethylbutylperoxyneodecanoate,
1-cyclohexyl-1-methylethyl peroxyneodecanoate,
t-hexyl peroxyneodecanoate,
t-butyl peroxyneodecanoate,
t-hexyl peroxypivalate,
t-butyl peroxypivalate,
1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate,
2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane,
1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate,
t-hexylperoxy 2-ethylhexanoate,
t-butyl peroxy 2-ethylhexanoate,
t-butyl peroxyisobutyrate,
t-hexylperoxyisopropyl monocarbonate,
t-butyl peroxymaleic acid,
t-butylperoxy 3,5,5-trimethylhexanoate,
t-butyl peroxylaurate,
2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane,
t-butyl peroxyisopropyl monocarbonate,
t-butyl peroxy 2-ethylhexyl monocarbonate,
t-hexyl peroxybenzoate,
2,5-dimethyl-2,5-bis (benzoylperoxy) hexane,
t-butyl peroxyacetate,
t-butyl peroxy-m-toluoyl benzoate,
t-butyl peroxybenzoate,
Bis (t-butylperoxy) isophthalate and the like.

  In addition to the organic peroxides described above, t-butyltrimethylsilyl peroxide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and the like can be suitably used.

  In the present invention, among the above-described organic peroxides, ketone peroxides, peroxyesters, and diacyl peroxides are preferable from the viewpoint of polymerization activity, and diacyl peroxides or hydroperoxides are particularly optimal. It is.

In the present invention, aryl borates can also be used as the polymerization initiator.
Any aryl borate can be used as long as it has at least one boron-aryl bond in one molecule, but it has high storage stability, ease of handling, and availability. From the viewpoint of ease of use, aryl borates having four boron-aryl bonds in one molecule are most preferable.
Specific examples of aryl borates having four boron-aryl bonds in one molecule include tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl). ) 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-octyl) Oxyphenyl) boron, tetrakis ( - it can be mentioned salts of boron compounds such as octyloxy phenyl) boron. As a cation forming a salt with a boron compound, a metal ion, a tertiary or quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion, or a quaternary phosphonium ion may be used. it can.

Among the above chemical polymerization initiators, a chemical polymerization initiator (see Patent Document 5) in which a combination of an acidic compound and an arylborate and a + IV and / or + V vanadium compound is used has high polymerization activity. Can be used particularly preferably. Furthermore, the combined use of the above organic oxides is most preferable because the polymerization activity can be further enhanced.
Specific examples of the vanadium compound include divanadium tetraoxide (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl-1,3-butanedionate) vanadium (IV), bis (Maltrate) oxo vanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), ammonium metavanadate (V) and the like can be mentioned.

  The amount of the polymerization initiator (C) described above is not particularly limited as long as it is an effective amount capable of curing the adhesive composition, and may be set as appropriate. It is good to set it as the range of 0.01-10 mass parts per 100 mass parts of body components (A), especially 0.1-5 mass parts. If it is less than 0.01 part by mass, the polymerization tends to be insufficient, and if it exceeds 10 parts by mass, the strength of the cured product tends to decrease.

<(D) Filler>
In the non-solvent dental adhesive composition of the present invention, a filler can be used as necessary in order to improve the strength of the formed cured product.
Such fillers include organic fillers (for example, cured resin particles) and inorganic fillers. In particular, inorganic fillers are preferably used in terms of increasing the strength of the cured product.

  Suitable examples of such inorganic fillers include quartz, silica, silica-alumina, silica-titania, silica-zirconia, silica-magnesia, silica-calcia, silica-barium oxide, silica-strontium oxide, silica-titania-sodium. Examples thereof include inorganic particles composed of metal oxides such as oxide, silica-titania-potassium oxide, titania, zirconia, and alumina.

  Among the inorganic fillers described above, zirconia and alumina are weakly basic, have high reactivity with sulfonic acid groups, and may cause deterioration of the characteristics of sulfonic acid monomers. On the other hand, silica is weakly acidic and can be suitably used. On the other hand, silica-based composite oxides such as silica-zirconia are known to be more acidic than silica and can be suitably used as well. The particle size and shape of these fillers are not particularly limited, and are used in the same manner as fillers for general dental compositions.

Further, among the above inorganic fillers, silica and silica-zirconia are preferably used, and particularly fumed silica and sol-gel silica-zirconia are most preferably used.
This fumed silica is an amorphous silica produced by a flame hydrolysis method, specifically, produced by high-temperature hydrolysis or combustion of silicon tetrachloride or a siloxane compound in an oxyhydrogen flame, The average primary particle size is about 5 to 200 nm, preferably about 5 to 150 nm, and usually has a moderate tertiary aggregate structure, which is particularly advantageous for increasing the strength of the cured product.

Such fumed silica, conventionally known ones can be any available without restriction, BET specific surface area of ^70m 2 / g or more, more preferably those of 100 to 300 m ² / g.

Sol-gel silica-zirconia is a hydrolyzable-condensable silicon compound (usually alkoxysilane) and a hydrolyzable-condensable zirconium compound (usually zirconium alkoxide) under aqueous acidic or basic conditions. It is produced by decomposing and condensing and, if necessary, firing at about 500 ° C. to 1200 ° C., and the average primary particle size is about 50 to 600 nm, preferably about 70 to 400 nm. It is suitable in terms of physical properties of the adhesive composition.
As such sol-gel silica-zirconia, conventionally known sol-gel silica-zirconia can be used without any limitation.
Moreover, the inorganic filler mentioned above improves the mechanical strength and water resistance by improving the compatibility with the polymerizable monomer component (A) by hydrophobizing with a surface treatment agent typified by a silane coupling agent. Can be made.

Examples of the silane coupling agent used for such hydrophobization include, but are not limited to, the following.
Silane coupling agent;
Methyltrimethoxysilane methyltriethoxysilane methyltrichlorosilane dimethyldichlorosilane trimethylchlorosilane vinyltrimethoxysilane vinyltriethoxysilane vinyltrichlorosilane vinyltriacetoxysilane vinyltris (β-methoxyethoxy) silane γ-methacryloyloxypropyltrimethoxysilane γ-methacryloyl Oxypropyltris (β-methoxyethoxy) silane γ-chloropropyltrimethoxysilane γ-chloropropylmethyldimethoxysilane γ-glycidoxypropyltrimethoxysilane γ-glycidoxypropylmethyldiethoxysilane β- (3,4 Epoxycyclohexyl) ethyltrimethoxysilane N-phenyl-γ-aminopropyltrimethoxysilane hexamethyldi Razan

The degree of the hydrophobization treatment is not particularly limited, but in general, for fumed silica, the M value indicating the lipophilicity is preferably 40 or more, more preferably 45 to 55, and this is preferably performed. Thereby, the dispersibility of inorganic fillers, such as a fumed silica, can be improved.
Moreover, you may use an organic-inorganic composite filler as needed. As the organic-inorganic composite filler, conventionally known ones can be used without any limitation. In particular, the organic-inorganic composite filler described in WO2011 / 115007 is preferable because the cured body strength of the resulting adhesive composition is excellent.

In the present invention, the filler described above is generally used in an amount of 5 to 900 parts by mass per 100 parts by mass of the polymerizable monomer component (A) described above. It varies considerably depending on the use of the composition.
For example, the non-solvent dental adhesive composition of the present invention can be used as a bonding material or a composite resin used for directly restoring a cavity formed in a tooth, and further, an orthodontic bracket, etc. However, when used as a bonding material, the amount of filler used may be relatively small. For example, polymerizable monomer component (A) 100 It is preferably used in an amount of 0.5 to 30 parts by mass, particularly 1 to 20 parts by mass per part by mass. Moreover, when using as a composite resin, it is desirable that the filler is used in a relatively large amount, for example, 30 to 2000 parts by weight, particularly 50 to 1000 parts by weight per 100 parts by weight of the polymerizable monomer component (A). It is preferable to use it in an amount. Further, when used as an adhesive for indirect repair (cement), it is preferably used in an amount of 30 to 900 parts by weight, particularly 50 to 300 parts by weight per 100 parts by weight of the polymerizable monomer component (A). .

<Other ingredients>
In the non-solvent dental adhesive composition of the present invention, various compounding agents can be appropriately used in addition to the components described above. Examples of such other compounding agents are organic thickeners, polymerization inhibitors, polymerization regulators, ultraviolet absorbers, dyes, pigments, fragrances, antistatic agents, and the like. It can be used in such an amount that does not impair the adhesion to the material and the compatibility of the sulfonic acid monomer with other monomers.

<Non-solvent dental adhesive composition>
The non-solvent dental adhesive composition of the present invention is a liquid or paste-like composition, and is usually used by storing and storing the above-described components in a predetermined package. The package may be a single package with all components in one package. Also, in order to prevent gelation during storage, each component is stored in two packages as appropriate so that it can be stored in two packages when used. It is also possible to mix and use the contained components. For example, when using a two-component mixed type chemical polymerization initiator, it is preferable to store them separately in different packages. Moreover, the means of accommodating the polymerizable monomer component (A) and the polymerization initiator (C) in different packages can be appropriately employed.

Such a non-solvent dental adhesive composition of the present invention is excellent in adhesiveness to the tooth, and therefore is used in various dental applications such as bonding materials and composites used for direct restoration of teeth. It can be used as an adhesive (cement) for fixing a prosthesis (indirect restoration material) such as a resin and an orthodontic bracket, a dental coating material, a pit and fissure filling material, etc. In particular, it is effectively used as a bonding material, a composite resin, or a cement in that it does not contain an organic solvent and does not require an air blow for removing the solvent upon curing.
Furthermore, this non-solvent dental adhesive composition exhibits moderate decalcification properties even though it does not contain a solvent, and enamel and dentin teeth without using any special pretreatment agent. Excellent adhesion to quality. Therefore, when using as said bonding material, composite resin, and cement, a pre-processing agent can be abbreviate | omitted. Furthermore, when used as a composite resin, the composite resin has self-adhesiveness with respect to the tooth structure, so that the use of a bonding material can be omitted.

  Hereinafter, the present invention will be described in detail by way of examples and comparative examples, but the present invention is not limited to these examples. In addition, the abbreviations of various components used in Examples and Comparative Examples, types, and test evaluation methods for various physical properties are as follows.

<(A) Polymerizable monomer>
Phosphoric acid monomer (a1);
PM:
A 1: 1 (molar ratio) mixture of 2-methacryloxyethyl dihydrogen phosphate and bis (2-methacryloxyethyl) hydrogen phosphate GDMP:
MBP:
MHP:
MOP:
MDP:
MLP:
MHPA:

Sulfonic acid monomer (a2);
2-MMPS:
2-AMPS:
3-MPS:
3-Methacryloxypropylsulfonic acid (molecular weight 208.23)
VS:
Vinylsulfonic acid (molecular weight 108.12)
PSS:
p-Styrenesulfonic acid (molecular weight 184.21)
3-MAPS:
3-MAEPS:
3-MABPS:
3-MAHPS:

Non-acidic monomer (a4);
Bis-GMA:
D-2.6E:
UDMA:
1,6-bis (methacrylethyloxycarbonylamino) -2,2-4-trimethylhexane 3G:
Triethylene glycol dimethacrylate 14G:
Polyethylene glycol (degree of polymerization 14) dimethacrylate HEMA:
2-hydroxyethyl methacrylate

<(B) Electron-withdrawing group-containing aromatic amine>
4-DMBE:
4-MABE:
4-ABE:
4-ADMN:
4-FDMA:
4-BDMN:
4-AOMN:
4-DMBA:
4-DMA:
4-DMB:
4-DMBN:
4-DEBE:
4-DMBM:
4-DMBI:
2-DMBE:
3-DMBE:
4-DMNA:
4-DMBPA:

<Aromatic amine containing no electron withdrawing group> (Comparative Example)
DMAN:
4-DMPA:
TEOA:

<(C) Polymerization initiator>
Photopolymerization initiator;
CQ:
Camphorquinone

<(D) Filler>
F1:
Hydrophobized fumed spherical silica (average particle size 0.13 μm) with γ-methacryloyloxypropyltrimethoxysilane and spherical silica-zirconia (average particle size 0.07 μm) γ-methacryloyloxypropyltrimethoxysilane A mixture obtained by mixing the material hydrophobized by the above at a mass ratio of 70:30 F2:
Sol-gel spherical silica-zirconia (average particle size 0.15 μm)
F3:
Hydrophobized F2 with γ-methacryloyloxypropyltrimethoxysilane F4:
Organic-inorganic composite filler prepared by the method described in WO2011 / 115007 using F2 and UDMA (F2 content 80%, average particle size 20 μm)
F5:
40% zirconia sol (ZR-40BL, manufactured by Nissan Chemical Co., Ltd.) 67.8 g and 3.2 g
2-MMPS was mixed and the resulting mixture was stirred for 15 minutes and then dried at 80 ° C. for 15 hours

<Other ingredients>
Polymerization inhibitor;
BHT:
2,6-di-t-butyl-p-cresol HQME:
Hydroquinone monomethyl ether

<Measurement of dissolution time of sulfonic acid monomer>
The polymerizable monomer component (A) and the amine compound (B) were added according to the formulations described in Tables 1 to 4 so that the total amount of the polymerizable monomer component (A) used was 100 g. The solution was stirred in a 100 ml screw tube bottle using a magnetic stirrer, and the time until it became uniform was defined as the dissolution time.

<Adhesion test of adhesive for composite resin (bonding material)>
The bovine anterior teeth were removed within 24 hours after slaughter, and the enamel and dentin planes of the bovine anterior teeth were cut out under water injection so as to be parallel to the lip with # 600 emery paper.
Next, after compressed air was blown onto these surfaces for about 10 seconds and dried, a double-sided tape having a hole with a diameter of 3 mm was fixed to either the surface of enamel or dentin, and then a thickness of 0.5 mm, A paraffin wax having a hole with a diameter of 8 mm was fixed on the circular hole so as to be in the same center, thereby forming a simulated cavity.
In this simulated cavity, the adhesive composition (dental adhesive) prepared in the example was applied, allowed to stand for 20 seconds, and then exposed to a dental visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation). Light irradiation for 2 seconds. Further, a dental composite resin (Esterite, manufactured by Tokuyama Dental Co., Ltd.) was filled thereon, and irradiated with a visible light irradiator for 30 seconds to produce an adhesion test piece I.
After the test piece I produced by the above method was immersed in water at 37 ° C. for 24 hours, a metal jig was attached, and a tensile tester (Autograph AG5000 manufactured by Shimadzu Corp.) was used, and the crosshead speed was 2 mm / min. A tensile test was performed under the conditions. Eight adhesion test pieces were measured per test, and the average value was taken as the adhesive strength.

<Adhesion test of self-adhesive composite resin>
A simulated cavity was formed in exactly the same manner as the adhesive test for the composite resin adhesive.
The simulated cavity was filled with the self-adhesive composite resin prepared in Examples and Comparative Examples, left for 20 seconds, and then irradiated for 10 seconds with a dental visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation). Thus, an adhesion test piece II was produced.
After immersing the test piece II produced by the above method in 37 ° C. water for 24 hours, a metal jig was attached, and a tensile tester (Autograph AG5000, manufactured by Shimadzu Corporation) was used, with a crosshead speed of 2 mm / min. A tensile test was performed under the conditions. Eight adhesion test pieces were measured per test, and the average value was taken as the adhesive strength.

<Synthesis of (B) Sulfonic Acid-Based Monomer and Electron-Attracting Group-Containing Aromatic Amine>
Among the sulfonic acid monomer (a2) and the electron-withdrawing group-containing aromatic amine (B) described above, 3-MAPS, 3-MAEPS, 3-MABPS, 3-MAHPS, 4-AOMN and 4-DMNA are: The synthesis was performed as follows.

(Synthesis of 3-MAPS)
In 100 ml of tetrahydrofuran, 5.3 g (0.22 mol) of sodium hydride was dispersed, and 17.0 g (0.2 mol) of methacrylamide was added dropwise to the dispersion under ice cooling. Stirring was continued at room temperature.
After stirring, a solution prepared by dissolving 25.6 g (0.21 mol) of 1,3-propane sultone in 50 ml of tetrahydrofuran was added dropwise under ice cooling, and the mixture was further stirred at room temperature for 2 days.
Thereafter, 150 ml of water was added, the aqueous phase was washed with toluene three times, the obtained aqueous phase was concentrated by an evaporator, and water was distilled off.
The solid on the white powder obtained was washed with acetone and then dissolved again in 50 ml of distilled water. This solution was passed through a strong acid cation exchange resin column, then concentrated again with an evaporator, and water was removed with a vacuum pump to obtain 3-MAPS (21.6 g, yield 52%).
In addition, the data of ¹ H NMR spectrum of the obtained 3-MAPS were as follows.
δ (ppm) = 1.96 (s, 3H)
2.13 (m, 2H)
2.96 (m, 2H)
3.41 (m, 2H)
5.47 (m, 1H)
5.83 (m, 1H)
8.08 (s, 1H)

(Synthesis of 3-MAEPS)
In 100 ml of tetrahydrofuran, 5.3 g (0.22 mol) of sodium hydride was dispersed, and 25.8 g (0.2 mol) of N- (2-hydroxyethyl) methacrylamide was added to the dispersion under ice cooling. The mixture was added dropwise, and after the addition, stirring was continued for another hour at room temperature.
After stirring, a solution prepared by dissolving 25.6 g (0.21 mol) of 1,3-propane sultone in 50 ml of tetrahydrofuran was added dropwise under ice cooling, and the mixture was further stirred at room temperature for 2 days.
Thereafter, 150 ml of water was added, the aqueous phase was washed with toluene three times, the obtained aqueous phase was concentrated by an evaporator, and water was distilled off.
The solid on the white powder obtained was washed with acetone and then dissolved again in 50 ml of distilled water. This solution was passed through a strong acid cation exchange resin column, then concentrated again with an evaporator, and further water was removed with a vacuum pump to obtain 3-MAEPS (30.7 g, yield 61%). The data of ¹ H NMR spectrum of the obtained 3-MAEPS was as follows.
δ (ppm) = 1.95 (s, 3H)
2.05 (m, 2H)
3.21 (m, 2H)
3.34-3.65 (m, 6H)
5.46 (m, 1H)
5.82 (m, 1H)
8.05 (s, 1H)

(Synthesis of 3-MABPS)
In 150 ml of methylene chloride, 46.0 g (0.4 mol) of N-hydroxysuccinimide and 40.5 g (0.4 mol) of triethylamine were dissolved, and 41.8 g (0.4 mol) of this solution was dissolved under ice cooling. ) Methacryloyl chloride was added dropwise.
After dropping, the mixture was stirred at room temperature for 2 hours, and 35.7 g (0.4 mol) of 4-hydroxybutylamine was added dropwise to the solution under ice cooling.
Then, after stirring at room temperature for 12 hours, methylene chloride was removed under reduced pressure. Thereafter, 100 ml of tetrahydrofuran was added to the residue, and the precipitated solid was removed by filtration. The obtained filtrate was again concentrated under reduced pressure, and the concentrated solution was purified by silica gel column chromatography to obtain N- (4-hydroxybutyl) methacrylamide (51 g, yield 81%).

In 100 ml of tetrahydrofuran, 5.3 g (0.22 mol) of sodium hydride was dispersed. Under ice-cooling,
31.4 g (0.2 mol) of N- (4-hydroxybutyl) methacrylamide obtained above
Was added dropwise, and after the addition, stirring was continued at room temperature for another hour. After stirring, a solution prepared by dissolving 25.6 g (0.21 mol) of 1,3-propane sultone in 50 ml of tetrahydrofuran was added dropwise under ice cooling, and the mixture was further stirred at room temperature for 2 days. Next, 150 ml of water was added, the aqueous phase was washed three times with toluene, and the resulting aqueous phase was concentrated with an evaporator to distill off the water.
The solid on the white powder obtained was washed with acetone and then dissolved again in 50 ml of distilled water. This solution was passed through a strong acid cation exchange resin column, then concentrated again with an evaporator, and further water was removed with a vacuum pump to obtain 3-MABPS (30.7 g, yield 61%). The data of ¹ H NMR spectrum of the obtained 3-MAEPS was as follows.
δ (ppm) = 1.44 to 1.56 (m, 4H)
1.93 (s, 3H)
2.03 (m, 2H)
2.98 (m, 2H)
3.34-3.55 (m, 6H)
5.46 (m, 1H)
5.82 (m, 1H)
8.05 (s, 1H)

(Synthesis of 3-MAHPS)
In 150 ml of methylene chloride, 46.0 g (0.4 mol) of N-hydroxysuccinimide and 40.5 g (0.4 mol) of triethylamine were dissolved, and 41.8 g (0.4 mol) of this solution was dissolved under ice cooling. ) Methacryloyl chloride was added dropwise. After dropping, the mixture was stirred at room temperature for 2 hours, and then 46.9 g (0.4 mol) of 6-hydroxyhexylamine was added dropwise to the solution under ice cooling.
Then, after stirring at room temperature for 12 hours, methylene chloride was removed under reduced pressure. Thereafter, 100 ml of tetrahydrofuran was added to the residue, and the precipitated solid was removed by filtration. The back solution was concentrated again under reduced pressure, and the concentrated solution was purified by silica gel column chromatography to obtain N- (6-hydroxyhexyl) methacrylamide (62 g, yield 83%).

In 100 ml of tetrahydrofuran, 5.3 g (0.22 mol) of sodium hydride was dispersed. Under ice-cooling,
N- (6-hydroxyhexyl) methacrylamide obtained above
37.0 g (0.2 mol)
Was added dropwise, and after the addition, stirring was continued at room temperature for another hour. After stirring, a solution prepared by dissolving 25.6 g (0.21 mol) of 1,3-propane sultone in 50 ml of tetrahydrofuran was added dropwise under ice cooling, and the mixture was further stirred at room temperature for 2 days after completion of the addition.
Next, 150 ml of water was added, the aqueous phase was washed three times with toluene, and the resulting aqueous phase was concentrated with an evaporator to distill off the water. The solid on the white powder obtained was washed with acetone and then dissolved again in 50 ml of distilled water. This solution was passed through a strong acid cation exchange resin column, then concentrated again with an evaporator, and further water was removed with a vacuum pump to obtain 3-MAHPS (38.7 g, yield 63%). The data of ¹ H NMR spectrum of the obtained 3-MAEPS was as follows.
δ (ppm) = 1.27-1.58 (m, 8H)
1.92 (s, 3H)
2.03 (m, 2H)
2.96 (m, 2H)
3.31-3.56 (m, 6H)
5.46 (m, 1H)
5.82 (m, 1H)
8.05 (s, 1H)

(Synthesis of 4-AOMN)
4-Dimethylaminophenol (1.4 g, 0.01 mol) and triethylamine (1.2 g, 0.012 mol) were dissolved in 10 ml of methylene chloride, and 1.0 g (0.013 mol) of acetyl chloride was added dropwise under ice cooling. . After dropping, the mixture was stirred for 1 hour, 5% aqueous potassium carbonate solution was added, and the methylene chloride layer was separated and recovered with a separatory funnel.
The recovered methylene chloride layer was concentrated by a rotary evaporator and then purified by basic alumina gel column chromatography to obtain 4-AOMN (16 g, yield 89%). In addition, the data of ¹ H NMR spectrum of the obtained 4-AOMN were as follows.
δ (ppm) = 2.10 (s, 3H)
2.90 (s, 6H)
6.56 (d, 2H)
6.91 (d, 2H)

(Synthesis of 4-DMNA)
4-dimethylaminonaphthoic acid 2.2 g (0.01 mol), isoamyl alcohol 1.8 g (0.02 mol), and p-toluenesulfonic acid monohydrate 0.19 g (0.001 mol) at 100 ° C. for 2 hours Stir. The mixture was further stirred under reduced pressure to remove excess isoamyl alcohol and water. After cooling to room temperature, the residue was purified by alumina gel column chromatography to obtain 4-DMNA (2.3 g, 81%). The data of ¹ H NMR spectrum of the obtained 4-DMNA was as follows.
δ (ppm) = 1.05 (d, 6H)
1.69-1.85 (m, 3H)
2.85 (d, 6H)
6.74 (d, 1H)
7.41 (t, 1H)
7.50 (t, 1H)
7.74 (d, 1H)
8.01 (d, 1H)
8.92 (d, 1H)

<Evaluation as bonding material>
(Example 1)
The following ingredients:
PM (phosphate monomer (a1)) 17 g
2-MMPS (sulfonic acid monomer (a2)) 3 g
4-DMBE (electron-withdrawing group-containing aromatic amine (B)) 2.9 g
3G (non-acidic monomer (a4)) 30 g
Was stirred and mixed at room temperature in a 100 ml brown screw tube bottle until uniform.
In this homogeneous solution,
BHT (polymerization inhibitor) 0.1g
HQME (polymerization inhibitor) 0.05g
D-2.6E (non-acidic monomer (a4)) 30 g
Bis-GMA (non-acidic monomer (a4)) 20 g
Cg (photopolymerization initiator) 0.6g
The mixture was stirred and mixed at room temperature until uniform, and an adhesive for composite resin (bonding material) containing no water was obtained.
About this adhesive material, the adhesion test piece I was created and the adhesive strength with respect to enamel and dentin was measured. The composition of the adhesive and the evaluation results are shown in Table 1 together with the amounts of the polymerizable monomer component (A) and the electron withdrawing group-containing amine (B).

(Examples 2 to 52)
Except for changing the type or amount of the phosphoric acid monomer (a1), the sulfonic acid monomer (a2) or the electron-withdrawing group-containing amine (B) as shown in Tables 1 to 3, the same as in Example 1 Then, an adhesive for composite resin was prepared, and the adhesive strength was similarly evaluated. The results are shown in Tables 1 to 3.
In Example 51, 16 g of filler F1 was blended together with 0.6 g of the photopolymerization initiator (CQ).

(Comparative Examples 1-10)
Except for changing the type or amount of the phosphoric acid monomer (a1), the sulfonic acid monomer (a2), or the electron withdrawing group-containing amine (B) as shown in Table 4, the same manner as in Example 1 was performed. An adhesive for composite resin was prepared, and adhesive strength was evaluated in the same manner. The results are shown in Table 4.
In Comparative Examples 6 to 8, an amine (DMAN, 4-DMPA, or TEOA) that does not contain an electron withdrawing group is used instead of the electron withdrawing group-containing amine (B).

(Comparative Example 11)
3 g of 2-MMPS (sulfonic acid monomer (a2)) was dissolved in 20 ml of acetone,
MDP (phosphate monomer (a1)) 17 g
D-2.6E (non-acidic monomer (a4)) 30 g
Bis-GMA (non-acidic monomer (a4)) 20 g
3G (non-acidic monomer (a4)) 30 g
BHT (polymerization inhibitor) 0.1g
HQME (polymerization inhibitor) 0.05g
And stirred until uniform. After stirring, the acetone is removed under reduced pressure and then
CQ (photopolymerization initiator (C)) 0.6 g
4-DMBE (electron-withdrawing group-containing aromatic amine (B)) 1.3 g
Was added until the mixture became uniform again to obtain an adhesive for composite resin.
About each obtained adhesive for composite resins, adhesive strength was evaluated similarly to Example 1, and the evaluation result was shown in Table 4 with the kind and quantity of the main component.

(Example 53)
The following prescription:
33 g of adhesive prepared in Example 5
Filler (F1) 3.4g
Filler (F3) 23.5g
Filler (F4) 40.1g
Accordingly, these components were mixed in an agate mortar and defoamed under vacuum to obtain a self-adhesive composite resin.
With respect to this self-adhesive composite resin, an adhesion test piece II was prepared and the adhesion strength to enamel and dentin was measured. The evaluation results are shown in Table 5 together with the composition of the self-adhesive composite resin.

(Examples 54 to 56, Comparative Examples 12 to 17)
As shown in Table 5, a self-adhesive composite resin was prepared in the same manner as in Example 52 except that the type and amount of the adhesive mixed with the filler or the type and amount of the filler were changed. Evaluation was made and the evaluation results are shown in Table 5.

Claims (8)

(A) a polymerizable monomer component;
(B) an aromatic amine having an electron withdrawing group;
(C) a polymerization initiator;
Including
The polymerizable monomer component (A) includes a phosphoric acid monomer (a1) having a phosphoric acid acidic group (> P (= O) OH), a sulfonic acid monomer having a sulfonic acid group (a2), and In the following mass ratio:
(A1) :( a2) = 98: 2-67: 33
As well as
The sulfonic acid monomer (a2) and the aromatic amine (B) are contained at a ratio such that the molar ratio of aromatic amino group to sulfonic acid group (aromatic amino group / sulfonic acid group) is 0.8 or more. A non-solvent dental adhesive composition characterized by that.   The non-acid according to claim 1, wherein the phosphoric acid monomer (a1) and the sulfonic acid monomer (a2) are contained in a total amount of 5% by mass or more of the polymerizable monomer component (A). Solvent-based dental adhesive composition.   The non-solvent dental adhesive composition according to claim 1 or 2, wherein the phosphoric acid monomer (a1) contains a (meth) acryloyloxy group as a polymerizable group.   The non-solvent dental adhesive composition according to claim 3, wherein the (meth) acryloyloxy group and the phosphoric acid acidic group are bonded to each other through a divalent group having 4 to 12 carbon atoms.   The non-solvent dental adhesive composition according to any one of claims 1 to 4, wherein the aromatic amine (B) has a carboxyl group or an alkoxycarbonyl group as an electron withdrawing group.   The non-solvent dental adhesive composition according to claim 5, wherein the aromatic amine (B) is a compound in which the electron-withdrawing group is bonded to dimethylaminobenzoic acid.   The non-solvent dental adhesive composition according to any one of claims 1 to 6, wherein the polymerization initiator (C) contains a photopolymerization initiator.   Furthermore, the non-solvent type dentistry in any one of Claims 1-7 which contain the filler (D) in the quantity of 5-900 mass parts per 100 mass parts of said polymerizable monomer component (A). Adhesive composition.