JP3517882B2 - Curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a novel curable composition.
Related. For details, give a cured product with high tensile strength.
In addition, even in moist conditions, biological hard tissues such as dentin, metallic materials
Material, a hydrophilic surface such as a ceramic material,
With a curable composition that has high adhesive strength to objects including
is there. [0002] 2. Description of the Related Art Relatively small teeth formed by dental caries
In recent years, composite resin and
Las ionomer cement, amalgam, etc. are used
But composite resin and glass ionoma
-Cement has a color tone and transparency similar to teeth,
It is frequently used as an aesthetic material. However, these two types of dental filling materials
Have been pointed out various clinical problems. For example, composite resins have high mechanical strength.
Although it has a certain degree of strength, it does not have
When filling, use an adhesive called a bonding material.
Need to be used. However, the use of such bonding materials
Not only complicates clinical operations, but also
If water enters, the adhesive strength will be significantly reduced.
There is convenience. Furthermore, even if bonding materials are used,
Insufficient adhesive strength between git resin and teeth, especially dentin
There is a problem that is minutes. Therefore, it is called the cervix
At the border of the tooth with the gingiva, dentin appears on the tooth surface
Loss of composite resin is often a problem
Has become. [0005] Therefore, the contact between the composite resin and the tooth substance is considered.
In order to improve the adhesion, various types of dentin
Adhesive monomers have been developed. For example, JP-A-57-3
No. 8749 discloses 2- (3,4-dicarboxybenzo).
Yloxy) -1,3-dimethacryloyloxypropa
Are disclosed. But curing with this monomer
Composition is easy to adsorb coloring components on the surface of the cured product,
It has disadvantages such as insufficient strength. See also
No. 1-127717 discloses a polyphenol of bisphenols.
Epoxy compound poly (meth) acrylate, (meth)
Acryloyloxyl group-containing aromatic polycarboxylic acid or
Is an acid anhydride thereof, a (meth) acrylate compound,
A curable composition comprising an inorganic filler and a curing agent is disclosed.
ing. However, this composition is used as a filling material
The disadvantage is that the adhesive strength with the teeth
Have. On the other hand, glass ionomer cement is
Bonding because it is a more hydrophilic material than composite resin
It adheres to the tooth without using any material, but its adhesive strength is
At present, it is still insufficient and has low mechanical strength. [0007] SUMMARY OF THE INVENTION The prior art described above
A curable composition that can solve problems in surgery
Then, the present inventor first wrote an acidic group-containing vinyl monomer, i.
Curing containing ON-eluting filler and polymerization initiator
A composition was proposed. [0008] Then, the curable composition proposed earlier
In addition, composite resin and glass
Like nomar cement, etc.
Increases the mechanical strength of the cured product to be cured
It is desired to prevent any adsorption to the surface. Therefore, complicated operations are required for its use.
No need, it can be firmly adhered to the dentin even when wet
Less coloration and higher strength
There is a demand for the development of curable compositions. [0010] Means for Solving the Problems The present inventors have proposed the above-mentioned technology.
We worked diligently to overcome the issues. As a result, acidic groups
Containing vinyl monomer, ion eluting filler, nonionic
COMPOSITION CONTAINING POLYMER SURFACTANT AND POLYMERIZATION INITIATOR
But adheres firmly to teeth even when cured under wet conditions,
And the cured product has sufficient strength
Thus, the present invention has been completed. That is, the present invention relates to (A) a vinyl monomer having an acidic group.
Nomer, (B) ion eluting filler, (C) nonion
Curing Containing System-Based Surfactant and (D) Polymerization Initiator
It is an acidic composition. As the above-mentioned acidic group-containing vinyl monomer,
Known monomers can be used without being limited to,
Among them, those having a carboxylic acid or phosphonic acid group are preferred.
For example, those having the following structure are exemplified.
You. [0013] Embedded image[0014] Embedded image[0015] Embedded image[0016] Embedded image[0017] Embedded image [0018] Embedded image[0019] Embedded image [0020] Embedded image[0021] Embedded image Particularly preferred among these are monomers containing an acidic group.
For example, those represented by the structural formula (1)
Those represented by the structural formula (2) and those represented by the structural formula (3)
And the structure represented by the structural formula (4)
The one represented by the formula (7) and the one represented by the structural formula (8)
, The one represented by the structural formula (9), the structural formula
R11 is -CH2CH2- represented by (10),
R11 represented by the structural formula (10) is [0023] Embedded image And represented by the structural formula (11)
R14 represented by the above structural formula (12) is -CH2
A compound represented by the structural formula (13)
Wherein 6 is -CH2CH2-, the structural formula (13)
Wherein R16 is -CH2CH2CH2-,
R18 represented by the structural formula (14) is [0025] Embedded image Is a compound represented by the structural formula (14)
R18 [0027] Embedded image Which is represented by the structural formula (14)
R18 [0029] Embedded imageWhich is represented by the structural formula (15)
R20 is -CH2CH2-, R21 is OH,
R20 represented by the structural formula (15) is -CH2CH2
-, R21 [0031] Embedded image Which is represented by the structural formula (15)
R20 [0033] Embedded image Wherein R21 is OH;
R15 shown in (15) [0035] Embedded image Wherein R 21 is OH;
R15 shown in (15) [0037] Embedded image And those wherein R21 is OH. In addition to the acidic group-containing vinyl monomer,
In addition, other vinyl monomers (acid group-containing vinyl monomers or less)
It is also a preferred embodiment to use an external vinyl monomer).
You. Typical suitable for use as other vinyl monomers
Have acrylic and / or methacrylic groups
The following is a specific example. A) Monofunctional vinyl monomer Methyl methacrylate, ethyl methacrylate, hydro
Xyethyl methacrylate, tetrahydrofurfurylme
Tacrylate, glycidyl methacrylate, and these
Acrylate, or acrylic acid, methacrylic acid,
p-methacryloxybenzoic acid, N-2-hydroxy-3
-Methacryloxypropyl-N-phenylglycine, 4
-Methacryloxyethyl trimellitic acid and its anhydride
Product, 6-methacryloxyhexamethylene malonic acid, 10
-Methacryloxydecamethylenemalonic acid, 2-methacrylic acid
Roxyethyl dihydrogen phosphate, 10-medium
Tacryloxydecamethylene dihydrogen phosphate
G, 2-hydroxyethyl hydrogen phenyl phosph
Fate. B) Bifunctional vinyl monomer (I) Aromatic compound 2,2-bis (methacryloxyphenyl) propane,
2,2-bis [4- (3-methacryloxy) -2-hydride
Roxypropoxyphenyl) propane, 2,2-bis
(4-methacryloxyethoxyphenyl) propane,
2,2-bis (4-methacryloxydiethoxyphenyi
Le) propane, 2,2-bis (4-methacryloxytet
Laethoxyphenyl) propane, 2,2-bis (4-meth
Tacryloxypentaethoxyphenyl) propane, 2,
2-bis (4-methacryloxydipropoxyphenyl)
Propane, 2 (4-methacryloxyethoxyphenyl)
-2 (4-methacryloxydiethoxyphenyl) propa
2- (4-methacryloxydiethoxyphenyl) -2
(4-methacryloxytriethoxyphenyl) propa
2- (4-methacryloxydipropoxyphenyl)-
2 (4-methacryloxytriethoxyphenyl) propa
2,2-bis (4-methacryloxydipropoxyfif
Enyl) propane, 2,2-bis (4-methacryloxy)
Isopropoxyphenyl) propane and their
Related (Ii) Aliphatic compounds Ethylene glycol dimethacrylate, diethylene glycol
Cole dimethacrylate, triethylene glycol dime
Tacrylate, butylene glycol dimethacrylate,
Neopentyl glycol dimethacrylate, propylene
Glycol dimethacrylate, 1,3-butanediol
Dimethacrylate, 1,4-butanediol dimethacrylate
Rate, 1,6-hexanediol dimethacrylate and
And their acrylates C) trifunctional vinyl monomer Trimethylol propane trimethacrylate, trimethyl
Roll ethane trimethacrylate, pentaerythritol
Rutrimethacrylate, trimethylol methane trimeta
Acrylates and their acrylates and the following structural formula
Monomers represented by (17) to (19) [0042] Embedded image(In the above structural formulas (17) to (19), R₁
Represents a hydrogen atom or a methyl group. ) D) Tetrafunctional vinyl monomer Pentaerythritol tetramethacrylate, pentae
Lisritol tetraacrylate and the following structural formula (2
0) to urethane-based monomers represented by (21) [0044] Embedded imageThe above-mentioned other vinyl monomer is one kind, or
It is possible to mix and use two or more types as necessary.
is there. The above-mentioned acidic group-containing vinyl monomer is replaced with another
When mixing vinyl monomers, use both vinyl monomers.
Of acidic vinyl monomer in blender
Is not particularly limited, but preferably 10% by weight or more,
More preferably 30% by weight or more, most preferably 50 weight%
% Or more. Formulation of this acidic group-containing vinyl monomer
If the ratio is high, the adhesiveness of the curable composition to the tooth is improved.
Tend to rise. The ion-eluting filler used in the present invention
Use known ion-eluting fillers without limitation
be able to. Of these, preferred ion-eluting fillers
1g of filler was added at 37 ° C and pH 2.2.
Elution when immersed in 50 ml of aqueous acrylic acid solution for 24 hours
2 mgeq / g to 60 mge
ion-eluting filler in the range of q / g.
You. The more preferable the amount of the eluted polyvalent metal ion is
The range is from 5 mgeq / g to 30 mgeq / g. Previous
The amount of the eluted polyvalent metal ion is 2 mgeq / g to 6
If it is within the range of 0 mgeq / g, the filler does not dissolve
Is present moderately, the strength of the cured product is improved, and the surface of the cured product is
Colored substances are less likely to be adsorbed on the surface. In addition, polyvalent metal ion
Is bonded to the acidic group of the acidic group-containing vinyl monomer.
Possible divalent or higher-valent metal ions, typical examples
To show, calcium, strontium, barium,
Metal ions such as luminium, zinc and lanthanoids
You. The ion eluting filler is not particularly limited.
However, preferred examples are calcium hydroxide hydroxide.
Hydroxide, such as strontium hydroxide, zinc oxide,
Of silicate glass, fluoroaluminosilicate glass, etc.
There are oxides. Among them, fluorocarbons are preferred in terms of the color resistance of the cured product.
Lower aluminosilicate glass is the best,
is there. The above fluoroaluminosilicate glass is
Dental cement, for example, glass ionomer cement
Known ones used for applications can be used. Generally known
Composition of fluoroaluminosilicate glass used
Is silicon, 10-33;
Minium, 4 to 30; alkaline earth metal, 5 to 36;
Rukari metal, 0-10; phosphorus, 0.2-16; fluorine,
Those having 2 to 40 and residual oxygen are preferably used. Than
Preferred examples of the composition range include silicon, 15 to 25;
Luminium, 7-20; alkaline earth metal, 8-28;
Alkali metal, 0 to 10; phosphorus, 0.5 to 8; fluorine,
4 to 40 and residual oxygen. Of the above alkaline earth metal
Part or all of magnesium, strontium, barium
Strontium is particularly preferred.
To give radiopaque and high strength
Used appropriately. The alkali metal is sodium
The most common, but part or all of it is lithium or potassium.
It is also preferable to use one substituted with um or the like. Further as needed
Then, part of the aluminum is titanium, yttrium,
Place with zirconium, hafnium, tantalum, lanthanum, etc.
It is also possible to change. In addition, if necessary,
Replacing the components with other components is the physical property of the cured product obtained.
As long as it does not significantly harm the The ion-elutable filler used in the present invention
Although the amount of is not particularly limited, all vinyl monomers used are
-100 parts by weight, preferably 30 to 600 parts by weight
Parts, more preferably 50 to 400 parts by weight. ion
When the amount of the dissolvable filler is within the above range, the curable composition
The adhesive strength at the interface between the object and the tooth substance is sufficient, and
Equalize the vinyl monomer containing acidic group and the ion-eluting filler
Mixing becomes easy. [0051] Ion-eluting filler used in the present invention
Is not particularly limited, and may be obtained by ordinary pulverization.
Pulverized particles or spherical particles may be used.
Plate-like or fibrous particles can also be mixed. The particle size of the ion-eluting filler is as follows:
Although not particularly limited, for example, when filling teeth
In this case, it is desirable that the surface of the cured product is smooth,
50 μm or less, preferably 20 μm or less
used. On the other hand, if the particle size is too small,
The surface area of the filler increases,
-It is difficult to mix a large amount during
Tends to decrease. Therefore, the ion eluting
The lower limit of the preferred particle size of the filler is 0.01 μm. Nonionic surfactant used in the present invention
Can be used without particular limitation
However, they are exemplified below. Sorbitan monocaprylate, sorbitan
Monolaurate, Sorbitan monopalmitate, Sorbi
Tanmonostearate, sorbitan sesquisteaary
Sorbitan tristearate, sorbitan monostearate
Allate, sorbitan monooleate, sorbitanses
Chioleate, sorbitan trioleate, sorbitan
Monoisostearate, sorbitan sesquiisosteare
Sorbitan monoisostearate, sorbitan mo
Notol oil fatty acid ester, sorbitan sesquitol oil
Fatty acid ester, sorbitan tritol oil fatty acid esthetic
Sorbitan fatty acid esters such as Glyceryl monocap
Relate, glyceryl monomyristate, glycerylmo
Nostearate, glyceryl monooleate, glycerin
Lumonoisostearate, glyceryl distearate,
Glycerin fatty acid esters such as glyceryl dioleate
Le. Diglyceryl monostearate, diglyceryl mono
Oleate, diglyceryl monoisostearate, tet
Laglyceryl monostearate, tetraglyceryl mono
Oleate, tetraglyceryl tristearate, tet
Lasriceryl pentastearate, tetraglycerylmo
Nolaurate, hexaglyceryl monomyristate, f
Oxaglyceryl monooleate, hexaglyceryl tri
Stearate, hexaglyceryl pentastearate,
Hexaglyceryl pentaoleate, hexaglyceryl
Polylinoleate, decaglyceryl monolaurate, deca
Glyceryl monomyristate, decaglyceryl monoste
Allate, decaglyceryl monooleate, decaglyce
Ril monolinoleate, decaglyceryl monoisosteale
Decaglyceryl distearate, decaglyceryl
Dioleate, decaglyceryl diisostearate, de
Caglyceryl tristearate, decaglyceryl trio
Late, decaglyceryl triisostearate, deca
Glyceryl pentastearate, decaglyceryl penta
Isostearate, decaglyceryl heptastearate
G, decaglyceryl heptaoleate, decaglyceryl
Heptaisostearate, decaglyceryl decasteale
Decaglyceryl decaoleate, decaglyceryl
Polyglycerin fatty acid ester such as decaisostearate
Le. Propylene glycol monostearate, pentae
Risuritol stearate, polyoxyethylene sorby
Tanmonolaurate, polyoxyethylene sorbitanmo
Nopalmitate, polyoxyethylene sorbitan monos
Tearate, polyoxyethylene sorbitan tristea
Rate, polyoxyethylene sorbitan monostearate
, Polyoxyethylene sorbitan monooleate,
Lioxyethylene sorbitan trioleate, polyoxy
Polio such as ethylene sorbitan monoisostearate
Xyethylene sorbitan fatty acid ester. Polyoxye
Tylene sorbit hexastearate, polyoxyethylene
Rensorbit tetrastearate, polyoxyethylene
Tetraoleate, polyoxyethylene monolauray
And polyoxyethylene sorbite fatty acid esters.
Polyoxyethylene glyceryl monooleate, polio
Xyethylene glyceryl monostearate, polyoxy
Ethylene glyceryl monostearate, polyoxyethylene
Polyoxyethylene such as fatty acid esters of lenglycerin vegetable oil
Tylene glycerin fatty acid ester. Polyoxyethylene
Monolaurate, polyoxyethylene monostearate
, Polyoxyethylene monooleate, ethylene glycol
Cole monooleate, ethylene glycol monostea
Rate, ethylene glycol distearate, diethyl
(Poly) ethylene glycos such as ethylene glycol stearate
Fatty acid esters. Polyoxyethylene laurylate
Ter, polyoxyethylene cetyl ether, polyoxy
Ethylene stearyl ether, polyoxyethylene ole
Yl ether, polyoxyethylene behenyl ether,
Polio such as polyoxyethylene hexyl decyl ether
Xylene ethylene alkyl ether. Polyoxyethylene poly
Lioxypropylene cetyl ether, polyoxyethylene
Polyoxypropylene decyl tetradecyl ether, etc.
Polyoxyethylene polyoxypropylene alkyl ester
-Tel. Polyoxyethylene nonyl phenyl ether,
Polyoxyethylene octyl phenyl ether
Oxyethylene alkyl phenyl ether. Polyoxy
Ethylene castor oil. Polyoxyethylene stearyl amide
Polyoxyethylene oleylamine, polyoxyethylene
Tylene stearyl propylene diamine, polyoxyethylene
Renstearic acid amide, polyoxyethylene olein
Polyoxyethylene alkylamine such as acid amide or
Fatty acid amides. Silicone-polyoxyalkylene copolymer
Coalescing. The addition amount of the nonionic surfactant is particularly
Although not limited, a preferable range is 10% of all vinyl monomers.
0.5 to 10 parts by weight per 0 parts by weight, more preferably
1 to 5 parts by weight. If the amount is less than this range,
If the effect of the surfactant is insufficient, if it exceeds this range
The mechanical strength of the cured product decreases. The polymerization initiator used in the present invention is not particularly limited.
No known radical generator is used without any limitation.
obtain. For example, benzoyl peroxide, parachloro
Benzoyl peroxide, 2,4-dichlorobenzoy
Luper oxide, acetyl peroxide, lauroy
Luper oxide, tertiary butyl peroxide
, Cumene hydroperoxide, 2,5-dimethyl
Hexane 2,5-dihydroperoxide, methyl ether
Tylketone peroxide, tertiary butyl peroxide
Organic peroxides such as xybenzoate
Azo compounds such as sobutyronitrile, tributylborane
Organic acid compounds such as acids are preferred. Also, the above organic
Polymerization is achieved by using peroxide and amine in combination.
Although it is possible to carry out at room temperature, such amines
Secondary or tertiary amino groups in which an amino group is bonded to an aryl group
Are preferably used in terms of curing acceleration. For example,
N, N'-dimethyl-p-toluidine, N, N'-dimethyl
Cylaniline, N'-β-hydroxyethyl-anili
, N, N'-di (β-hydroxyethyl) -anili
, N, N'-di (β-hydroxyethyl) -p-toluene
Idine, N-methyl-aniline, N-methyl-p-tolu
Idin and the like are preferred. Further, as a polymerization initiator, laminar
It is also preferable to use a photosensitizer that generates dicals.
is there. Benzoi is an example of a photosensitizer for ultraviolet light.
Benzoin methyl ether, benzoin ethyl ether
Ter, acetoin benzophenone, p-chlorobenzoph
Enone and p-methoxybenzophenone.
Photosensitizers that initiate polymerization with visible light are harmful to the human body
It is more preferably used because it does not require any extra ultraviolet light. This
Examples of these are benzyl, camphorquinone, α-na
Fthyl, acetonaphthene, p, p'-dimethoxybenzyl
, P, p'-dichlorobenzylacetyl, pentane
ON, 1,2-phenanthrenequinone, 1,4-phena
Nthrenquinone, 3,4-phenanthrenequinone, 9,
Α-Di such as 10-phenanthrenequinone and naphthoquinone
And ketones. Among them, camphor quinone is the best
Are also preferably used. Also, a photopolymerization accelerator is used as the photosensitizer.
It is also preferable to use them in combination. As such a photopolymerization accelerator, N, N-di
Methylaniline, N, N-diethylaniline, N, N-
Di-n-butylaniline, N, N-dibenzylanily
N, N-dimethyl-p-toluidine, N, N-die
Cyl-p-toluidine, N, N-dimethyl-m-toluene
Gin, p-bromo-N, N-dimethylaniline, m-
Rollo-N, N-dimethylaniline, p-dimethylamino
Benzaldehyde, p-dimethylaminoacetopheno
, P-dimethylaminobenzoic acid, p-di
Methylaminobenzoic acid ethyl ester, p
-Dimethylaminobenzoic acid aminoester
, N, N-dimethylanthranilic acid methyl
Ester, N, N-dihydroxyethylaniline, N, N
-Dihydroxyethyl-p-toluidine, p-dimethyl
Aminophenethyl alcohol, p-dimethylaminosty
Lupen, N, N-dimethyl-3,5-xylysine, 4-
Dimethylaminopyridine, N, N-dimethyl-α-naph
Tylamine, N, N-dimethyl-β-naphthylamine,
Tributylamine, tripropylamine, triethylamine
Min, N-methyldiethanolamine, N-ethyldie
Tanolamine, N, N-dimethylhexylamine,
N, N-dimethyldodecylamine, N, N-dimethyls
Tearylamine, N, N-dimethylaminoethylmethac
Relate, N, N-diethylaminoethyl methacrylate
G, 2,2 '-(n-butylimino) diethanol, etc.
Tertiary amines; 5-butylvalpituric acid, 1-ben
Valpituric acid such as jyl-5-phenylvalpituric acid
And the like can be suitably used. Of these photopolymerization accelerators
At least one can be selected and used, and two more
The above may be used in combination. The amount of the polymerization initiator to be added is not particularly limited.
Instead, it may be determined appropriately. Generally, all vinyl monomers
May be selected from the range of 0.1 to 3 parts by weight. The packaging form of the curable composition of the present invention is particularly limited.
Not specified, acid group-containing vinyl monomer, ion eluting
Fillers, nonionic surfactants and polymerization initiators (photosensitized
In the form of packaging in the form of a package)
Monomer and ion eluting filler in two packs
Nonionic surfactant and polymerization initiator
In any form added to either or both
Can be selected as appropriate according to the application. [0061] The curable composition of the present invention can be used in the presence of water.
To provide high adhesive strength even for dental restorations.
It is expected that the floor will surely exhibit adhesive strength. Use of the curable composition as a dental filler
Indispensable bond for composite resin
Simplifies the clinical procedure because it does not require
This also has the advantage. Furthermore, coloring due to food and drink in the mouth
Less is. Due to these features, the curable composition of the present invention
The material is not only a dental filling material but also a composite material.
Gin bonding material, lining material, and dental sealant
To use as a filling material, other filling materials and adhesive materials
Can be done. [0064] EXAMPLES The present invention will now be described specifically with reference to examples.
However, the present invention is not limited to these examples.
Absent. The properties of the materials shown in the text and in the examples,
The measuring method of the physical properties is as follows. (1) Particle size distribution of filler A filler is dispersed in water, and a particle size distribution analyzer (MALVER) is used.
N Company). The measurement principle is scattering by laser light.
This is based on measurement of a diffraction image. (2) Filler crystal structure X-ray diffractometer (manufactured by JEOL Ltd.)
The crystal structure (morphology) was examined. (3) Amount of polyvalent metal ion eluted from filler 50 ml of a 10% by weight aqueous solution of acrylic acid (pH = 2.2)
1 g of filler is added to the mixture, and the mixture is stirred at 37 ° C. for 24 hours.
The amount of eluted ions is measured with a child absorptiometer (manufactured by Shimadzu Corporation).
It was measured. (4) Compressive strength of cured product The curable composition is placed in a mold having a hole of 3mm x 4mmφ.
After curing, it was kept at 37 ° C. for 1 hour. Required for curing
According to the visible light irradiator, white light (Taka label
(Mont, Inc.) for 30 seconds. Next, the cured product is removed from the mold and
After immersion in water at 70 ° C for 71 hours, Tensilon (Toyo Bo
Cross head speed 1mm /
The compressive strength of the cured product was measured in min. (5) Adhesive strength to tooth material While pouring the bovine teeth, polish it with # 800 emery paper,
The enamel or dentin plane was carved out. On this plane
Stick a double-sided tape with a hole of 4mm in diameter,
3mm thick paraffin wax with 6mm holes
It was pasted so that the center was aligned with the surface tape. Hard in the circular hole
After filling the curable composition, it is cured and placed in water at 37 ° C. for 24 hours.
After immersion, a stainless steel sheet with a diameter of 8 mm and a length of 18 mm
The rod was fixed with an instant adhesive. And Tensilon
Between the bovine teeth and the stainless steel rod using a tensile load
By adding a tooth speed of 10 mm / min)
The adhesive strength with the cured product was measured. Also adhesion under wet
In the above method, the strength is measured before filling the curable composition.
After applying a thin layer of water to the dentin plane using a ponge,
The measurement was performed in the same manner as described above. (6) Coloring test The curable composition is placed in a mold having a hole of 3mm x 6mmφ.
After curing, it was kept at 37 ° C. for 1 hour. Required for curing
According to the visible light irradiator, white light (Taka label
(Mont, Inc.) for 30 seconds. Cured body
Coffee (Nescafé Ek)
Sera) in a 7.4% aqueous solution at 37 ° C for 24 hours.
A color difference meter (manufactured by Nippon Denshoku Co., Ltd.)
Was measured. The smaller the ΔE * value, the smaller the color tone change.
That is, the coloring is small. The composite resin and the glass ion
Adhesive strength of Nomer cement should be
After the conversion, the measurement was performed by the same method. Production Example 1 Β-methacryloyloxy in a 300 ml eggplant-shaped flask
Ciethylhydrosuccinate (trade name: HOMS, Kyoei)
55g, glycidyl methacrylate
G (manufactured by Wako Pure Chemical Industries) 28 g, p-toluenesulfonic acid 1
1.4 g and chloroform (100 ml) were added.
Stirred for hours. 200 ml of chloroform was added to the reaction solution.
After that, 300 ml of water, 300 aqueous 1N sodium carbonate solution
and then again 300 ml of water. Anhydrous for organic layer
After adding 10 g of sodium sulfate and drying, the solvent was reduced after filtration.
The pressure was removed to obtain 73 g of a colorless liquid. In a 500 ml eggplant-shaped flask, dry trim
Lit acid chloride 32 g, pyridine 13 g, benzene
Add 200 ml, and stir under ice-cooling.
A solution prepared by dissolving 57 g in 100 ml of benzene
After the reaction, the reaction solution is returned to room temperature and stirred for 1 hour.
Stirred. Filter this solution to remove pyridine hydrochloride
Then, the solvent was removed from the filtrate under reduced pressure. The resulting product
Add 250 ml of trahydrofuran and 250 ml of water and add 1
Stirred overnight. 300 ml of chloroform was added to this solution.
The product was extracted and washed twice with 400 ml of water. Yes
After separating the organic layer, add 10 g of anhydrous sodium sulfate and dry.
After filtration, column chromatography using activated alumina
The solvent is removed under reduced pressure after the product is
49 g of a thick liquid was obtained. Infrared spectroscopy of this product, nuclear magnetic
The results of gas resonance analysis and elemental analysis are shown in Tables 1-3.
According to the measurement results, it is represented by the following structural formula (22).
It was confirmed that the compound was used. [0075] [Table 1] [0076] [Table 2][0077] [Table 3] [0078] Embedded imageEmbodiment 1 120 g of silica, 42 g of aluminum hydroxide, artificial ice crystals
28 g of stone, 78 g of aluminum phosphate, aluminum fluoride
Powder consisting of 24 g of calcium and 76 g of calcium fluoride.
Mixed powder for 3 hours in a platinum mill
And heated and melted at 1400 ° C. for 30 minutes. Followed by melting
The product is quenched in a water bath, and the obtained glass is
And crushed. The powder obtained by grinding is 400 mesh
Nylon sieve, powder 150 which passed through the sieve
g in 1 liter of methanol and within 1 hour
Those that did not settle out (hereinafter referred to as filler A) were collected.
Filler A has a particle size of 0.2 to 2.7 μm, average particle size
1.0 μm, polyvalent metal ion elution amount 16 mgeq / g,
It was crystalline. The structure synthesized according to Production Example 1
80 parts by weight of the acidic group-containing vinyl monomer of the formula (22)
20 parts by weight of droxyethyl methacrylate (HEMA)
3 parts by weight of tetraglyceryl monooleate in a mixture of
Camphorquinone (CQ), p-dimethylaminobenzo
Ic Acid Ethyl Ester (DMBE) was added to each.
10 g of 5 parts by weight dissolved and 15 g of filler A are blocked.
After mixing under light, the mixture was vacuum defoamed to prepare a curable composition. Adhesion Strength of the Curable Composition to Bovine Dentin
The degree is 10.2MPa, 10.3MPa under wet condition, compressive strength 26.
At 3 MPa, the coffee coloring amount was ΔE * = 8.7. Embodiment 2 120 g of silica, 37 g of aluminum hydroxide, artificial ice crystals
28 g of stone, 86 g of aluminum phosphate, aluminum fluoride
Powder consisting of 24 g of calcium and 68 g of calcium fluoride.
Powder obtained by mixing with a mill for 3 hours is a platinum crucible
And heated and melted at 1400 ° C. for 30 minutes. Followed by melting
The product is quenched in a water bath, and the obtained glass is
And crushed. The powder obtained by grinding is 400 mesh
Powdered through a nylon sieve and passed through a sieve 150
g in 1 liter of methanol and within 1 hour
Those that did not settle out (hereinafter referred to as filler B) were collected.
Filler B has a particle size of 0.2 to 2.9 μm and an average particle size
1.1 μm, polyvalent metal ion elution amount 14 mgeq / g,
It was crystalline. The acid group-containing monomer 2- (3,4-dica)
(Ruboxybenzoyloxy) -1,3-dimethacryloy
90 parts by weight of luoxypropane and hydroxyethylmethac
Silicone-polyoxylated to 10 parts by weight of the mixture
Ethylene copolymer (trade name: TSF4445, Toshiba Silicon)
2 parts by weight, camphorquinone, p-dimethyla
Minobenzoic acid ethyl ester 1.0 each
Under light-shielding, 10 g of a dissolved amount and 15 g of filler B
And then degassed in vacuo to prepare a curable composition. Adhesion Strength of the Curable Composition to Bovine Dentin
The degree is 9.5MPa, 9.2MPa under wet, compressive strength 225MPa.
a, The coffee coloring amount was ΔE * = 8.4. Embodiment 3 120 g of silica, 27 g of aluminum hydroxide, artificial ice crystals
Stone 28g, Aluminum phosphate 101g, Aluminum fluoride
Powder consisting of 24g of calcium and 53g of calcium fluoride
The mixed powder obtained by mixing for 3 hours in a ball mill is
The mixture was placed in a pot and heated and melted at 1400 ° C. for 30 minutes. Followed by melting
The melt is quenched in a water bath, and the resulting glass is
And crushed. 400 mesh of powder obtained by grinding
Nylon sieve, powder 15 passed through the sieve
Disperse 0 g in 1 liter of methanol and within 1 hour
The material that does not settle out (hereinafter referred to as filler C) is collected
Was. Filler C has a particle size of 0.2-3.0 μm, average particle size
With a diameter of 1.1 μm and a polyvalent metal ion elution amount of 11 mgeq / g,
It was amorphous. Acid-Containing Monomer 4-Methacryloyl
50 parts by weight of oxyethoxycarbonylphthalic acid, 2, 2
-Bis [4- (methacryloxyethoxy) phenyl] p
30 parts by weight of lopan and triethylene glycol dimethacrylate
Decaglyceryl heptaole is added to a mixture of 20 parts by weight of
Eat 1 part by weight, camphorquinone, p-dimethylami
0.5% each of nobenzoic acid ethyl ester
10 g of the melted part and 15 g of Filler C
After mixing, the mixture was degassed under vacuum to prepare a curable composition. Curing above
Adhesive strength of bovine dentin to bovine dentin is 8.1 MPa, wet
Below 7.5MPa, Compressive strength 233MPa, coffee coloring amount
ΔE * = 7.9. Embodiment 4 Of the structural formula (22) synthesized according to the Production Example 1
50 parts by weight of an acidic group-containing vinyl monomer and triarylene
Polio in a mixture of 50 parts by weight of recall dimethacrylate
3 parts by weight of xyethylene nonylphenyl ether and camphor
Erquinone (CQ), p-dimethylaminobenzoic
Acid ethyl ester (DMBE) 0.5 weight each
10 g of the melted part and 15 g of filler A
After mixing, the mixture was degassed under vacuum to prepare a curable composition. The above curable composition is used as a bonding material.
Used, commercially available dental composite resin, trade name: Pal
Fakelight (manufactured by Tokuyama Soda Co., Ltd .: does not have acidic groups)
Polyfunctional vinyl monomer, silica filler, α-dike
When the main component is ton-based polymerization initiator)
Has a bond strength of 8.9 MPa with bovine dentin and 8.5 in wet conditions
MPa. The compressive strength of the curable composition alone is 2
The coffee coloring amount was 71 MPa and ΔE * = 6.1. Embodiment 5 11-methacryloxy-1,1-
50 parts by weight of undecanedicarboxylic acid, 2,2-bis [4
-(Methacryloxyethoxy) phenyl] propane 30
Parts by weight and triethylene glycol dimethacrylate 20
Polyoxyethylene nonylphenyl ether
-Tel 3 parts by weight, camphorquinone (CQ), p-dimension
Cylaminobenzoic acid ethyl ester (DM
10 g each of 0.5 parts by weight of
After mixing 15 g of color A under light shielding, vacuum defoaming and curable composition
Was prepared. Contact of the curable composition with bovine tooth enamel
The wearing strength is 8.1 MPa, the wet strength is 8.0 MPa, and the compressive strength is 32.
The coffee coloring amount was 2 MPa, and ΔE * = 6.5. Embodiment 6 2-methacryloyloxyacid of an acidic group-containing monomer
60 parts by weight of phosphate and 2,2-bis (p-2 '
-Hydroxy-3'-methacryloxypropoxyphenyi
G) Decaglyceryl mono to a mixture of 40 parts by weight of propane
Linoleate 3 parts by weight and camphorquinone (CQ), p-
Dimethylaminobenzoic acid ethyl ester
10 g of (DMBE) each having 0.5 parts by weight dissolved
And 15g of filler A are mixed under light shielding, then degassed in vacuum and cured
A composition was prepared. Contact of the above curable composition with bovine tooth enamel
The wearing strength is 7.8MPa, the wet strength is 7.4MPa, the compressive strength is 22
At 9 MPa, the coffee coloring amount was ΔE * = 7.0. Embodiment 7 Of the structural formula (22) synthesized according to the Production Example 1
80 parts by weight of an acidic group-containing vinyl monomer and hydroxyethyl
Of the monomer solution.
Prepared. Tetraglyceryl monooxide is added to this monomer solution.
3 parts by weight of N, N'-di (β-hydroxyethyl
10) A solution obtained by dissolving 1.0 part by weight of -p-toluidine
g and 15 g of Filler A (paste I)
You. ). Next, decaglyceryl hept is added to the above monomer solution.
Taoleate 3 parts by weight, benzoyl peroxide
Mix 10 g of 2 parts by weight and 15 g of filler A
(Paste II). Paste I and pace
As a result of mixing and testing at a ratio of 1: 1 by weight,
Adhesive strength to bovine dentin is 10.1MPa, 9.7 under wet conditions
MPa, compressive strength 246MPa, coffee coloring amount ΔE * =
It was 8.9. Embodiment 8 4-methacryloyloxyethoxy, an acidic group-containing monomer
50 parts by weight of cyclocarbonylphthalic acid, 2,2-bis [4-
(Methacryloxyethoxy) phenyl] propane 30 layers
20 parts by weight of triethylene glycol dimethacrylate
1 part of decaglyceryl heptaoleate is added to 1 part of the mixture.
Parts by weight, camphorquinone, p-dimethylaminobenzoy
Dissolve 0.5 parts by weight of each
After mixing 10 g of the mixture and 15 g of Filler C under light shielding,
Emptying was performed to prepare a curable composition. Adhesion strength of the curable composition to bovine dentin
The degree is 5.9MPa, 5.5MPa under wet, compressive strength 236MP.
a, The coffee coloring amount was ΔE * = 7.5. Embodiment 9 Of the structural formula (22) synthesized according to the Production Example 1
80 parts by weight of an acidic group-containing vinyl monomer and hydroxyethyl
Tetramethacrylate (HEMA) 20 parts by weight mixture
0.2 parts by weight of traglyceryl monooleate, camphor
-Quinone (CQ), p-dimethylaminobenzoic acid
0.5 parts by weight of each ethyl ethyl ester (DMBE)
10 g of a solution of
After the combination, the mixture was vacuum defoamed to prepare a curable composition. Bond strength of the above curable composition to bovine dentin
The degree is 8.5MPa, 8.4MPa under wet, compressive strength 266MP.
a, The coffee coloring amount was ΔE * = 8.2. Embodiment 10 Of the structural formula (22) synthesized according to the Production Example 1
80 parts by weight of an acidic group-containing vinyl monomer and hydroxyethyl
Tetramethacrylate (HEMA) 20 parts by weight mixture
12 parts by weight of traglyceryl monooleate, camphor
Quinone (CQ), p-dimethylaminobenzoic acid
0.5 parts by weight of ethyl ethyl ester (DMBE)
Mix 10 g of dissolved material and 15 g of filler A under light shielding
Thereafter, the mixture was vacuum defoamed to prepare a curable composition. Adhesion Strength of the Curable Composition to Bovine Dentin
The degree is 6.8MPa, 5.9MPa under wet, compressive strength 225MPa
a, The coffee coloring amount was ΔE * = 11.2. Comparative Example 1 4-methacryloyloxyethoxy of an acidic group-containing monomer
50 parts by weight of cyclocarbonylphthalic acid, 2,2-bis [4-
(Methacryloxyethoxy) phenyl] propane 30 layers
20 parts by weight of triethylene glycol dimethacrylate
Add sodium dioctyl sulfosuccinate to 3 parts by weight of the mixture.
Parts by weight, camphorquinone, p-dimethylaminobenzo
Dissolve 0.5 parts by weight of Ic acid ethyl ester
After mixing 10 g of the mixture and 15 g of the filler C under light shielding,
Vacuum defoaming was performed to prepare a curable composition. Adhesion Strength of the Curable Composition to Bovine Dentin
The degree is 2.5MPa, 2.1MPa under wet, compressive strength 238MPa.
a, The coffee coloring amount was ΔE * = 7.2.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-164807 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K 6/00 C08F 2/00 C08F 20 / 00

Claims (1)

(57) [Claims] (A) a vinyl monomer having an acidic group, (B) an ion-eluting filler, (C) Nonionic surfactant as well as (D) polymerization initiator A curable composition comprising: