JP3465748B2 - Dental adhesive set - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a dental adhesive set.
I do. More specifically, mainly tooth, metal, organic
Strongly adheres to restorations made of ceramics, ceramics, etc.
The present invention relates to a dental adhesive set that can be used. [0002] 2. Description of the Related Art When restoring a tooth, the fossa of the tooth
Often, the restoration or the like is adhered to the sinus surface.
One type of dental adhesive set used for this bonding
And etchant, primer (undercoat) and curing
Some are composed of a neutral composition. From these three specific components
The general procedure for using a dental adhesive set is as follows.
It is. That is, first apply an etching agent to the tooth surface
And a smear layer that exists on the tooth surface and inhibits adhesion
Remove. Next, the primer and the curable composition are sequentially applied.
Cloth. After applying the curable composition, the restoration is mounted.
The curable composition is cured while wearing
Do. [0003] When restoring teeth, etc.,
There is a demand for a slight increase in the adhesive strength with the restoration
I have. In order to meet this demand, the above-mentioned etching agent,
What kind of primer and curable composition respectively
It is being considered whether to use them together. On the other hand, the above-mentioned etching agent, primer
Also, the search for the components themselves of the curable composition is also performed.
ing. Of these, some are used as etching agents.
Features include organic carboxylic acids and iron phosphate
A solution consisting of an aqueous solution has been proposed.
337319). [0005] SUMMARY OF THE INVENTION
Using an etching agent consisting of an aqueous solution of iron and iron phosphate
In this case, the adhesion between the tooth and the restoration as described above
There is a demand for increasing the strength even a little. Therefore,
An aqueous solution of the above organic carboxylic acid and iron phosphate
Any kind of primer and curing for etching agents
The challenge is to know whether to use a water-soluble composition
I have. [0006] Means for Solving the Problems The inventors of the present invention have the above-mentioned features.
Consisting of carboxylic acid and iron phosphate aqueous solution
What kind of primer and curable composition
As a result of intensive research on whether to combine and use,
Those containing sulfinates as primers,
And carica having a carboxyl group as a curable composition
Polymerizable monomer, radical polymer having the carboxyl group
Radical polymerizable monomer other than compatible monomer and radical weight
The combination of the initiator and the etching agent
And found that the above-mentioned problems can be solved.
The Ming has been completed. That is, the present invention relates to an etching agent, a primer,
Adhesive set made of a hardener and a curable composition.
The etchant is an organic carboxylic acid and iron phosphate water.
Solution, and the primer contains sulfinateas well as
(Meth) acrylate compoundsIs contained, and the curability is
The composition is a radical polymerizable monomer having a carboxyl group.
, A radical polymerizable monomer having the carboxyl group or less
From outside radical polymerizable monomer and radical polymerization initiator
This is a dental adhesive set. [0008] Etching agent used in the present invention
Consists of an aqueous solution of organic carboxylic acid and iron phosphate
It is. As the above-mentioned organic carboxylic acids, known organic carboxylic acids can be used.
Organic carboxylic acids can be used without limitation. This
Examples of carboxylic acids include formic acid, acetic acid, lactic acid, and lactic acid.
Acid, valeric acid, hexanoic acid, lauric acid, pyruvic acid,
Lysine, methacrylic acid, acrylic acid, crotonic acid, benzoate
Monocarboxylic acids such as perfumed acid, oxalic acid, succinic acid, tartar
Acid, glutaric acid, fumaric acid, maleic acid, malonic acid,
Dicarboxylic acids such as traconic acid and itaconic acid, citric acid,
Tolcarboxylic acids such as trimellitic acid and trimesic acid;
Tetracarboxylic acid such as tylenediaminetetraacetic acid alone
Alternatively, two or more kinds can be blended and used. Example before
Citric acid, succinic acid, pill
Vinic acid, oxalic acid, tartaric acid are preferred. [0010] In addition, as the above-mentioned iron phosphate, a known resin is used.
Iron phosphate can be used without limitation. This iron phosphate
For example, ferrous phosphate, ferric phosphate, etc. alone
Or a mixture of two or more. [0011] The organic carboxylic acid and iron phosphate of the present invention
The concentration of each is not particularly limited, but usually the two components
5 to 50% by weight of organic carboxylic acid based on solution
%, Preferably 5 to 30% by weight, and the content of iron phosphate is 0.1%.
5 to 30% by weight, preferably 0.5 to 10% by weight
You. The etching agent used in the present invention
Is used to adjust the viscosity if necessary.
Lolidone, carboxymethylcellulose, polyvinyla
Formulation of high-dispersion silica and other high molecular compounds such as
Can be In addition, the etching agent has an edible color.
A coloring agent such as an element can be blended. Next, the primer used in the present invention
Refers to coating before bonding using the curable composition described below.
It refers to an undercoating agent that treats a contact surface. The primer according to the present invention includes
FinatesAnd (meth) acrylate compoundsContains
You. This sulfinic acid salt is a known sulfinic acid.
Acid salts can be used without limitation. This sulfin
As the acid salt, for example, sodium benzenesulfinate
Benzene, calcium benzenesulfinate, benzenesulfur
Strontium diphosphate, ammonium benzenesulfinate
Salt, triethylammonium benzenesulfinate
Salt, benzenesulfinic acid N, N'-dimethyl-p-toate
Luidine salt or p-toluenesulfinic acid, β-naphtha
Lensulfinic acid, styrenesulfinic acid, 2,4,6
-Triethylbenzenesulfinic acid, 2,4,6-tri
Salts such as isopropylbenzenesulfinic acid
They can be used alone or in combination of two or more.
Among the sulfinates exemplified above, benzenesulfine
Acid and alkali metal of p-toluenesulfinic acid
Salts are preferable, and p-toluenesulfur is more preferable.
Sodium phosphate, sodium benzenesulfinate
is there. The primer used in the present invention is
Generally, the sulfinate is converted to a toxicologically acceptable organic
Dissolve in a solvent or a mixture of organic solvent and water to form a solution.
Used. At this time, the concentration of the sulfinate is particularly
Although not limited, usually, 0.1 to
10% by weight. Also, as described above, sulfinic acid
The organic solvent used for dissolving
Solvents can be used without limitation. With this organic solvent
Preferred are volatile, and as described below.
To primerDistributed to(Meth) acrylate compounds to be combined
Is an organic solvent that can also dissolve This preferred
Organic solvents such as acetone, methylene chloride,
Alcohols such as ethanol and isopropyl alcohol
Can be used alone or in combination of two or more.
You. In the present invention, a (meth) a
As described later, it is possible to mix a acrylate compound.
The curable composition used for
In order toDone. This (meth) acrylate compound
Uses known (meth) acrylate compounds without limitation
can do. This (meth) acrylate compound and
For example, methyl (meth) acrylate, ethyl
(Meth) acrylate, n-propyl (meth) acryle
, Isopropyl (meth) acrylate, n-butyl
(Meth) acrylate, isobutyl (meth) acrylate
G, n-hexyl (meth) acrylate, 2-ethyl
Xyl (meth) acrylate, tridecyl (meth) ac
Relate, stearyl (meth) acrylate, 2-hydride
Roxyethyl (meth) acrylate, 2-hydroxyp
Ropyl (meth) acrylate, glycidyl (meth) ac
Relate, methoxydiethylene glycol (meth)
Relate, 7-methacryloxy-1,1-heptanedica
Rubonic acid, 11-methacryloxy-1,1-undecane
Monofunctional (meth) acrylate compounds such as dicarboxylic acids
Products, ethylene glycol (meth) acrylate, diethyl
Lenglycol di (meth) acrylate, triethylene
Glycol di (meth) acrylate, tetraethylene glycol
Recall di (meth) acrylate, propylene glycol
Rudi (meth) acrylate, 1,4-butanedioldi
(Meth) acrylate, 1,6-hexanediol di
(Meth) acrylate, neopentyl glycol di (meth)
Acrylate), 1,10-decanediol di (meth)
TA) acrylate, bisphenol A di (meth) acryl
Rate, 2,2'-bis [[(meth) acryloyloxy
[Cipolyethoxyphenyl] propane, 2,2'-bis
[4- (3-methacryloyloxy-2-hydroxyp
Loxy) phenyl] propane, trimethylolpropa
(Meth) acrylate, trimethylolethanetri
(Meth) acrylate, tetramethylolmethanetetra
(Meth) acrylate, (2-methacryloxyethyl)
L) Multifunctional (meth) a such as maleic acid monoester
Acrylate compounds, etc., alone or in combination of two or more.
Can be used. The (meta) access relay illustrated earlier
OH group or carboxyl group in the molecule
Are preferably used, and particularly preferred (meth)
The relevant compound is 2-hydroxyethyl (meth) acyl.
Related or 11-methacryloxy-1,1-undecane
Dicarboxylic acid. This (meth) acrylate compound
The amount of the primer blended in the primer is not particularly limited.
Per part by weight of sulfinate in the lymer, (meth)
It is 1 to 10 parts by weight of the acrylate compound. The curable composition used in the present invention
Is a radical polymerizable monomer having a carboxyl group,
Laminates other than radically polymerizable monomers having a carboxyl group
Consists of a dical polymerizable monomer and a radical polymerization initiator
It is. Carboxyl group used in the present invention
Examples of the radical polymerizable monomer having
General formula (1) [0020] Embedded image The radical polymerizable monomer represented by the formula
It is preferably used because its strength and durability can be improved. still,
In the above general formula (1), R¹Is an alkyl group or hydrogen atom
Child, R^TwoIs an organic residue having 2 to 20 carbon atoms, l is 1 or 2
An integer, m is an integer of 0 or 1, n is an integer of 1 to 3, x is
Ruboxyl group (when l = 2, x is an acid anhydride group: -CO-
It may exist in the form of O-CO-. ) Are shown. In the general formula (1), R¹Is an alkyl group
If shown, this R¹For example, a methyl group, an ethyl group
And the like. In addition, the R^TwoHas 2 to 20 carbon atoms
Can increase the strength of the cured product formed at the bonding interface.
Not only increases the bonding strength, but also
Increased adhesion durability and easy availability of materials
Preferably, R^TwoWhen the carbon number of the compound is 4 to 20, the adhesiveness is
It is more preferable because it is more excellent. And R^TwoIndicated by
Organic residues are aliphatic or aromatic
May also be partly halogen, amino, hydroxyl, etc.
It may be substituted by a substituent. The above radical radical having a carboxyl group
More specifically, examples of the compatible monomer include p-methacryloyl.
Xybenzoic acid, p-vinylbenzoic acid, 2-methacryloxy
Siethyl phthalic acid, 2-methacryloxyethyl succinic acid
Radical having one carboxyl group in the molecule such as
Compatible monomer, 7-methacryloxy-1,1-heptanedi
Carboxylic acid, 11-methacryloxy-1,1-undeca
Dicarboxylic acid, 13-methacryloxy-1,1-tri
Decanedicarboxylic acid, 4- (β-methacryloxyethyl
2) 2 in the molecule such as trimellitic acid ester and anhydride
Radical polymerizable monomer having two carboxyl groups
No. In the present invention, the carboxylic acid exemplified above is used.
Even when a radical polymerizable monomer having a sil group is used alone
Or two or more of them may be used in combination. Further, the curable composition of the present invention includes:
Less than the above-mentioned radical polymerizable monomer having a carboxyl group
An outer radical polymerizable monomer is blended. This radical polymerization having a carboxyl group
Radical polymerizable monomers other than the reactive monomer, for example,
Methyl (meth) acrylate, ethyl (meth) acryle
, N-propyl (meth) acrylate, isopropyl
(Meth) acrylate, n-butyl (meth) acryle
, Isobutyl (meth) acrylate, n-hexyl
(Meth) acrylate, 2-ethylhexyl (meth) a
Acrylate, tridecyl (meth) acrylate, steer
Ryl (meth) acrylate, 2-hydroxyethyl (meth)
(T) acrylate, 2-hydroxypropyl (meth) a
Acrylate, glycidyl (meth) acrylate, methoki
Single unit such as sidiethylene glycol (meth) acrylate
Functional radical polymerizable monomer: ethylene glycol
T) acrylate, diethylene glycol di (meth) a
Acrylate, triethylene glycol di (meth) acryl
Rate, tetraethylene glycol di (meth) acryle
Propylene glycol di (meth) acrylate,
1,4-butanediol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, neope
Ethylene glycol di (meth) acrylate, 1,10-
Decanediol di (meth) acrylate, bisphenol
A di (meth) acrylate, 2,2'-bis [((me
TA) acryloyloxypolyethoxyphenyl] propa
2,2'-bis [4- (3-methacryloyloxy
-2-hydroxypropoxy) phenyl] propane,
Limethylolpropane (meth) acrylate, trimethyl
Roll ethane tri (meth) acrylate, tetramethylo
Polyfunctionality such as methanemethanetetra (meth) acrylate
Radical polymerizable monomers, etc. alone or in combination of two or more
Can be used. Furthermore, the curable composition of the present invention
Is mixed with a radical polymerization initiator. This radical weight
As the initiator, a known radical polymerization initiator is used without limitation.
can do. This radical polymerization initiator is cured
If the composition is to be blended with a chemical polymerization type,
Peroxide and tertiary amine with the radical polymerization initiator
It is preferable to use them together for polymerization at room temperature.
As the organic peroxide, for example, dibenzoyl
Oxide (benzoyl peroxide), 2,4-dichlorobe
Nzoyl peroxide, dilauroyl peroxide
, Dioctanoyl peroxide, decanoyl peroxide
Diacyl peroxides such as oxides, cumene hydro
Peroxide, t-butyl hydroperoxide, etc.
Hydroperoxide, cyclohexanone peroxy
Ketones such as side, methyl ethyl ketone peroxide
Use peroxides alone or in combination of two or more
can do. Among the organic peroxides exemplified here,
Acyl peroxides such as dibenzoyl peroxide
Is preferred. The tertiary amines include, for example,
N, N-dimethyl-p-toluidine, N, N-dialdehyde
Toluidine derivatives such as roxyethyl-p-toluidine,
4- (N, N-diethylamino) benzoic acid, 4- (N,
Ethyl N-dimethylamino) benzoate, 4- (N, N-
Amines such as dimethylamino) isoamyl benzoate
Benzoic acid derivatives, 4- (N, N-dimethylamino)
Nsaldehyde, 4- (N, N-diethylamino) ben
Zaldehyde, 4- (methylhexylamino) benzure
Aminobenzaldehyde derivatives such as aldehyde, N, N-
Dimethyl-m-anisidine, N, N-dimethyl-p-a
Aniline such as nisidine, N, N-diethyl-p-anisidine
Cisidine derivative, N, N-dimethyl-m-aminophenol
Amides such as N, N-diethyl-m-aminophenol
Nophenol derivative, p-propoxy-N, N-dimethyl
Luaniline, p-butoxy-N, N-dimethylanili
, P-hexyloxy-N, N-dimethylaniline and the like
Use aniline derivatives alone or in combination of two or more
can do. Of the tertiary amines exemplified here,
When the tertiary amine is used in combination with an organic peroxide,
Toluidine induction such as N, N-dimethyl-p-toluidine
The body is preferred. In the present invention, the curable composition of the chemical polymerization type is used.
When using the product, the mixing ratio of the radical polymerization initiator,
Usually, based on the total amount of the two types of radically polymerizable monomers.
From 0.01 to 10% by weight. And the compound polymerization type
When using a curable composition of, the radical polymerization initiator and
When using an organic peroxide and a tertiary amine together,
Of organic peroxide and tertiary amine
Is usually relative to the total amount of the two types of radically polymerizable monomers.
0.01 to 5% by weight, preferably 0.05
~ 5% by weight. On the other hand, a radical polymerization initiator is
When blended in a curable composition, α-diketone is added to the latices.
It is preferably used as a dical polymerization initiator. This α
As the diketone, a known α-diketone is used without limitation.
be able to. As the α-diketone, for example, dia
Cetyl, 2,3-pentadione, 2,3-hexadio
Benzyl, 4,4'-dimethoxybenzyl, 4,
4'-diethoxybenzyl, α-naphthyl, β-naphthyl
Or camphorquinone alone or in combination of two or more
Can be used. The above α-diketone is used as a radical polymerization initiator
When used as a tertiary amine,
Can shorten the curing time.
Preferred for In the present invention, a photopolymerizable curable composition
When using a radical polymerization initiator, the
Usually, based on the total amount of the two types of radically polymerizable monomers,
0.01 to 10% by weight, preferably 0.05 to 5% by weight
It is. And, in the above case, α-diketone and
When used in combination with a tertiary amine, the α-diketone and
The mixing ratio of each of the tertiary amines is usually the same as the above two types
0.0 to the total amount of dical polymerizable monomers
It can be determined appropriately within the range of 1 to 10% by weight. Formulated in the above-mentioned photopolymerizable curable composition
The radical polymerization initiator further includes the above-mentioned organic peroxide.
Compounding is preferred because the adhesive strength can be improved.
New At this time, the mixing ratio of the organic peroxide is usually
0.0 to the total amount of the two radical polymerizable monomers
1 to 5% by weight. The curable composition of the present invention has an adhesive
Depending on the material of the elephant, it is preferable to add a filler
No. Filler improves mechanical strength and water resistance
And control fluidity and coatability
You. [0034] The curable composition of the present invention contains
Depending on hydroquinone, hydroquinone monomethyl A
Use a small amount of a polymerization inhibitor such as ter or butylhydroxytoluene.
Can be added. This filler is not limited to known fillers.
Can be used well. As this filler, for example
Quartz, amorphous silica, silica zirconia, fluoroa
Luminosilicate, clay, aluminum oxide, tal
, Mica, kaolin, glass, barium sulfate, zirconium oxide
Conium, titanium oxide, silicon nitride, aluminum nitride
, Titanium nitride, silicon carbide, boron carbide, potassium carbonate
Lucium, hydroxyapatite, calcium phosphate, etc.
Filler, polymethyl methacrylate, made of inorganic material
, Polyethyl methacrylate, polyvinyl chloride, poly
Polymers such as styrene, polyester, nylon, etc.
Filler made of organic matter such as sesame, organic-inorganic composite
Use fillers alone or in combination of two or more.
Can be. For the filler consisting of the inorganic substance
Is usually γ-methacryloyloxypropyl trimethoxy.
Silane cups such as silane and vinyltriethoxysilane
The treatment with a ring agent is preferred. The mixing ratio of the filler is not particularly limited.
However, the two types of radicals in the curable composition
1 to 300% by weight based on the total amount of polymerizable monomers
Is preferred. The curable composition of the present invention contains an organic solvent.
Preferably, no medium is included. This organic solvent, especially
Contains alcohol such as ethanol
The strength tends to decrease. This is due to the adhesive
The solidification of the coating does not reduce the thickness of the coating,
Defects are likely to occur, and alcohol plays a role as a polymerization inhibitor.
It is thought that it is fulfilling a share. Adhesion using the dental adhesive set of the present invention
The method is not particularly limited, but the bonding method usually adopted is
It is as follows. That is, the tooth surface and the like are treated with an organic carboxylic acid and
After treatment with an etching agent consisting of an aqueous solution of iron acid,
RuffinateAnd (meth) acrylate compoundsContains
Treated with primers
Radical polymerizable monomer having the carboxyl group
A radical polymerizable monomer other than the radical polymerizable monomer; and
Surface treatment with a curable composition comprising a radical polymerization initiator
Bonding method. In the above bonding method, the etching agent
After such treatment, washing and drying are usually performed. Also, the primer
The method of treatment is to attach with a sponge or a small brush.
Normally, a method is used in which the surface is completely wetted.
You. After treatment with this primer, air
Spray drying to improve adhesion.
New Furthermore, when performing surface treatment with a curable composition
Is usually pressed against the surface of the tooth
Good. When the curable composition is of a photopolymerizable type, the light
The curing is performed to cure the curable composition and bond. this
When light is irradiated, the area where the light
If the material is made of organic polymer and is transparent,
Light can be irradiated near the bonding boundary through the adherend
You. [0041] The dental adhesive set of the present invention has an adhesive strength.
Can be very high. In particular, high levels of organic components
Teeth that were previously considered difficult to adhere to
Of the present invention as an adhesive set used for bonding
Dental adhesive sets are preferred. In addition, the dental
Adhesive sets are especially suitable for teeth and metals, ceramics, organic high
Significantly improve the adhesive strength to members made of molecules, etc.
Can be done. [0042] DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail with reference to the drawings.
Examples are given, but the present invention is not limited by these examples.
It is not something to be done. Used in the following Examples and Comparative Examples
(Meth) acrylate compounds are abbreviated as follows:
I do. [0044] Embedded image [0045] Embedded imageExample 15, Reference Examples 1 to 3,Comparative Examples 1 to
4 Shown in Tables A-1 to 3 as an etchant and primer
A composition was prepared. In addition, as the curable composition,
Paste I and paste II shown in B were prepared. [0047] [Table 1][0048] [Table 2][0049] [Table 3][0050] [Table 4]The above-mentioned etching agent, primer and curing
The adhesion test was performed as follows using the conductive composition. First, remove the front teeth of the cow within 24 hours after slaughter.
Take it, pour water, and use # 800 emery paper before the cow
The dentin plane or enamel plane of the tooth was cut out. this
The dentin plane or enamel plane is shown in Tables A-1 to A-3
After treating with an etching agent for 10 seconds, the substrate was washed with water and dried.
Next, the primers shown in Tables A-1 to A-3 were coated with the dentin
After applying to the surface or enamel plane and leaving for 30 seconds,
Air was blown to dry. In addition, primer
In the case of consisting of two liquids of (i) liquid and (ii) liquid, the two liquids
Was mixed by weight immediately before use. Next prepared in advance
Mix Paste I and Paste II at equal weights.
Using a mixture of strikes I and II, the dentin plane or
A stainless steel rod (diameter 8mm) is adhered to the namel surface.
Was. After 1 hour, remove the cow front teeth with the stainless steel rod
It was immersed in water at 37 ° C. for 24 hours. Next, the cow's front teeth
After being taken out of the water, the tensile tester (Crossheads
(Peed: 10mm / min) with cow front teeth and stainless steel rod
Was measured for adhesive strength. The measurement results are shown in Tables A-1 to A-3.
Show. [0053]Reference Examples 4 to 9Comparative Examples 5 to 7reference In Example 1, paste I constituting the curable composition
11-methacryloxy-1,1-undecandical in
Lac having a carboxyl group shown in Table C in place of boric acid.
Except that dical polymerizable monomer was usedreferenceOperate as in Example 1.
And the adhesive strength was measured. Table C shows the measurement results.
You. [0054] [Table 5]Example6,7 Example3The paste I constituting the curable composition
Bisphenol A diglycidyl methacrylate in the
Instead of triethylene glycol dimethacrylate,
Example except that the radical polymerizable monomer shown in D was used3
The operation was performed in the same manner as described above to measure the adhesive strength. The measurement results
It is shown in Table D. [0056] [Table 6] [0057]Reference Examples 10 to 12 reference In Example 1, radical polymerization initiation in the curable composition
Benzoyl peroxide and N, N-dimethyl-p-
Instead of toluidine, a radical polymerization initiator shown in Table E was used.
Except usedreferenceOperate in the same manner as in Example 1 to measure the adhesive strength.
Specified. Table E shows the measurement results. In addition, radical polymerization
If the initiator is photopolymerizable, a commercially available
Sight Light Irradiator "White Light" (Takara Labelmont, Inc.)
Light irradiation from two directions for 30 seconds.
I let you. [0058] [Table 7]

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-62-231652 (JP, A) JP-A-1-144487 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K 6/00 083

Claims (1)

(57) [Claim 1] A dental adhesive set comprising an etching agent, a primer and a curable composition, wherein the etching agent comprises an aqueous solution of an organic carboxylic acid and iron phosphate. Sulfinate and (meth) acrylate for primer
The curable composition comprises a radical polymerizable monomer having a carboxyl group, a radical polymerizable monomer other than the radical polymerizable monomer having a carboxyl group, and a radical polymerization initiator. Dental adhesive set.