JP3449755B2 - Adhesive set - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to hard tissue of a living body,
Adhesion operation to acrylic and dentin with dentin
When doingUsed forFor the purpose of enhancing adhesion
Composition for pretreatment of living hard tissue
objectAnd a specific acrylic adhesive
Adhesive setAbout. [0002] 2. Description of the Related Art In today's dental treatment, there is a partial lack of teeth.
Restoration materials such as composite resin, dental alloy, and porcelain
Acrylic prosthesis is often used when prosthetic
If used. The adhesion of this type of adhesive to teeth
Dramatically improved by quality improvement over the past 20 years,
But it has not reached the perfect level. That is, tooth and restoration
A gap is created at the adhesive interface of the object, and bacteria
Invading and causing secondary caries and pulpitis, repair
If the restoration relies on gluing, the restoration itself may fall off
Have been reported to be possible. Such troubles
Efforts to reduce as much as possible continue before the bonding operation
Apply some kind of primer on the tooth surface
/ Adhesive strength has been enhanced recently
Was. [0003] For example, Journal of Dent
al Research Vol. 63, P1087-
1089 (1984) describes glutaraldehyde / 2-
From hydroxyethyl methacrylate (HEMA) / water
Primer composition shows adhesion enhancing effect with dentin
It is described. However, this technology does not
Triammonium ethylenediaminetetraacetate
Clear the smear layer (cutting chip layer) on the dentin surface with aqueous salt solution.
Without adhesion (demineralization removal), the adhesion enhancement effect
There was a weakness that was not. Then this cleanin
Primers have been developed that eliminate the need for tagging. For example,
62-223289 has a maleic acid,
Primers to which acids such as tribromoacetic acid and hydrochloric acid are added
Clear adhesion to enamel and dentin without cleaning
It is described that it is significantly improved. Dental materials and instruments
Vol. 9, pp. 65-73 (1990) describes HEMA aqueous solution.
Add N-methacryloylalanine or N-acryloyl
Plastic with monomer containing acidic group such as lanin
Immers have no access to enamel and dentin without cleaning
It is described that the adhesion is significantly improved. Further
In addition, JP-A-4-8368 discloses that (i) water is 0.5 to 90 weights.
%, (Ii) 5-90 weight parts of a polymerizable compound having a hydroxyl group.
%, (Iii) a polymerizable compound having an acidic group 0.1 to 90
% By weight, and (iv) an amino compound having an acidic group.
A primer composition containing from 0.01 to 30% by weight is disclosed.
Have been. The patent discloses a model having an acidic group in an aqueous HEMA solution.
Compared to the primer to which nomer was added,
By adding an appropriate amount of an amino compound having
It claims to dramatically improve adhesion to quality. [0004] These primers are each
Adhesive effect is observed in the usage claimed by Hu
But, in practice, it's still incomplete
I can't get it. For example, the ply of Japanese Patent Application Laid-Open No.
When using a combination of light-cured dental adhesives,
A remarkable adhesion enhancement effect appears, but with a chemically polymerized adhesive
The effect is slight with the combination of. In addition,
Non-polymerizable acid components contained in the primer elute
However, it has been pointed out that it causes harm to the dental pulp. Dentistry
Materials and Instruments, Vol. 9, pages 65-73 (1990)
The primer is in combination with the chemical polymerization type adhesive,
Demonstrates adhesion-enhancing effect, but to a degree relative to bovine enamel
103kg / cm^Two80 kg / cm for bovine dentin^Two
Secondary caries, restoration loss, pulpitis, etc.
Insufficient to completely solve the problem caused by lack of clothing
It is. Primer set disclosed in JP-A-4-8368
The product is excellent in combination with a photopolymerizable adhesive
Shows adhesion enhancing effect, but in combination with chemical polymerization type adhesive
Is less effective. [0005] SUMMARY OF THE INVENTION The present invention
In relation to the current situation, it is related to the polymerization method of acrylic dental adhesive
Significantly improved adhesion to both enamel and dentin
Primer for living hard tissueAnd Acri
Adhesive set made by combiningProvide
It is intended to be. [0006] Means for Solving the Problems The present inventors have solved the above problems.
As a result of intensive studies to achieve this,
Primer composition prepared with a limited composition ratioWhen
By combining with acrylic adhesiveReach the challenge
The inventors have found what can be achieved, and have reached the present invention. That is, the book
The invention is,(A) 5 to 30 vinyl compounds having an acidic group
%, (B) a water-soluble vinyl compound having a hydroxyl group
50% by weight,(C) 35-75% by weight of water,(D) aromatic
2 to 15% by weight of a sulfinate and (e) an aromatic second
Or / and containing 2-15% by weight of a tertiary amine
Primer compositionAnd (i) an acrylic having an acidic group
Monomer, (ii) Acrylic monomer without acid group
And an acrylic adhesive comprising (iii) a polymerization initiator
Adhesive set made by combining with adhesiveAbout. Hereinafter, the present invention will be described more specifically.
The vinyl compound having an acidic group used in the present invention
Acidic groups are monoester phosphate and diester phosphate
Group, phosphonic acid group, phosphonic acid monoester group, phosphine
Phosphoric acid derivatives such as diacid groups, carboxyl groups, sulfo
Acid group. Vinyl compounds having such acidic groups and
Is 2- (meth) acryloyloxyethyldihydride
Lodien phosphate, 6- (meth) acryloyl oxy
Sihexyl dihydrogen phosphate, 10- (meth
T) Acryloyloxydecyldihydrodienephosph
Ethyl, 2- (meth) acryloyloxyethylphenyl
Lehydrodiene phosphate, bis (2- (meth) a
(Cryloyloxyethyl) hydrogen phosphate
G, 2- (meth) acryloyloxyethyl hydrogen
Enphenylphosphonate, 6- (meth) acryloyl
Oxyhexyl phosphinate, N- (10-phosphono
(Decyl) (meth) acrylamide, 4-vinylbenzene
Phosphoric acid, phosphorus such as 4-vinylbenzyl phonic acid
Acid derivatives, (meth) acrylic acid, succinic mono (2-
(Meth) acryloyloxyethyl), isophthalic acid
(2- (meth) acryloyloxyethyl), 4- (meth)
T) acryloyloxyethyl trimellitic acid, 11,
11-dicarboxyundecyl (meth) acrylate,
N- (meth) acryloylalanine, N- (meth) acyl
Liloyl-5-aminosalicylic acid, 4-vinylbenzoic acid
Carboxylic acid compounds such as 2- (meth) acrylamide
-2-methylpropanesulfonic acid, styrenesulfonic acid
And the like. [0008] Among these compounds, adhesion is particularly increased.
A group of compounds having a strong effect are phosphoric acid derivatives,
(Meth) acryloyloxydecyl dihydrodieneho
Sulfate, 2- (meth) acryloyloxyethyl ester
Phenylhydrogen phosphate or 2- (meth)
Liloyloxyethyl hydrogendiene phenyl phosphone
Is a typical example. The vinyl compound having an acidic group is 1
Not only the kinds but also a plurality of them may be appropriately used. Those good
The preferred concentration is 5 to 30% by weight and deviates from this range.
Then, the adhesion enhancing effect is remarkably reduced. Next, the hydroxyl group used in the present invention has
The water-soluble vinyl compound will be described. Hydroxyl group
Means hydroxyl group of alcohol, carboxylic acid, phenols
Is not included. Water solubility is 10% by weight or more at room temperature
Means solubility. A specific example is 2-hydroxyethyl.
(Meth) acrylate, propylene glycol mono
(Meth) acrylate, glycerin mono (meth) acryl
Rate, erythritol mono (meth) acrylate,
N-erythritol di (meth) acrylate, N-methyl
Roll (meth) acrylamide, N-hydroxyethyl
(Meth) acrylamide, N, N-di (hydroxyethyl
(Meth) acrylamide. [0010] Among these compounds, the point of the adhesion enhancing effect is given.
Particularly preferred is 2-hydroxyethyl (meth) a
Acrylate, glycerin mono (meth) acrylate,
PO represented by rititol mono (meth) acrylate
Riol mono (meth) acrylate. These are 1
Not only the species but also a plurality of them may be used in combination as appropriate,
The concentration is between 10 and 50% by weight. Deviate from this range
And the adhesion enhancing effect is undesirably reduced. Next, the water used in the present invention is
It must not contain microorganisms and harmful components,
Preferably purified by distillation or / and membrane filtration
Can be. Water content is 35-75% by weight, more preferable
Or 50 to 65% by weight. If you deviate from this range,
This has an adverse effect on the wear enhancement effect. In the present invention, the above three main components, ie, (a)
Vinyl compound having an acidic group, (b) water having a hydroxyl group
(D) an aromatic compound in addition to a soluble vinyl compound and (c) water
A sulfinic acid salt and (e) an aromatic secondary amine and / or
And tertiary amine as polymerization initiator or accelerator
I do. Vinylation of aromatic sulfinates with acidic groups
Aromatic sulfinic acid is formed on contact with
Acid sulfinic acid / aromatic secondary or tertiary amine pairs
Room temperature polymerization starts when combined. Furthermore, this primer set
When the product comes in contact with cold-setting dental acrylic adhesive
The organic peroxide normally contained in the adhesive is a primer
To the sulfinic acid / amine / organic peroxide
Product system is formed and the polymerization reaction proceeds more rapidly
become. The aromatic sulfinate used in the present invention
Benzenesulfinic acid, p-toluenesulfur
Acid, o-trienesulfinic acid, ethylbenzenesulfur
Finic acid, decylbenzenesulfinic acid, dodecylben
Zensulfinic acid, 2,4,6-trimethylbenzenes
Ruphinic acid, 2,4,6-triisopropylbenzenes
Rufinic acid, chlorobenzenesulfinic acid, naphthalene
Lithium salts such as sulfinic acid, sodium salts, potassium
Salt, rubidium salt, cesium salt, magnesium salt,
Lucium salt, strontium salt, iron salt, copper salt, zinc salt,
Ammonium salt, tetramethylammonium salt, tetra
Ethyl ammonium salts can be mentioned. They are
Not only one kind but also plural kinds may be used in combination. preferable
The concentration is 2 to 15% by weight,
The adhesion enhancing effect is greatly reduced. Next, the aromatic secondary and tertiary compounds used in the present invention are used.
And tertiary amines such as N-methylaniline,
Chill-p-toluidine, N-methyl-m-toluidine,
N-methyl-o-toluidine, N-ethanol-port
Luisin, N-ethanol-m-toluidine, N-eta
Nor-o-toluidine, p-methylaminobenzoic acid
Chill, ethyl m-methylaminobenzoate, o-methyla
Ethyl minobenzoate, p-methylaminoanisole, m
-Methylaminoanisole, o-methylaminoanisole
1-methylaminonaphthalene, 2-methylaminona
Phthalene, N, N-dimethylaniline, N, N-dimethyl
Lep-toluidine, N, N-dimethyl-m-toluidine
N, N-dimethyl-o-toluidine, N, N-die
Tanol-p-toluidine, N, N-diethanol-m
-Toluidine, N, N-diethanol-o-toluidine
, Ethyl p-dimethylaminobenzoate, m-dimethyl
Ethyl aminobenzoate, o-dimethylaminobenzoic acid
Chill, p-dimethylaminoanisole, m-dimethyla
Minoanisole, o-dimethylaminoanisole, 1-
Dimethylaminonaphthalene, 2-dimethylaminonaphthalene
Len and the like can be mentioned. These are just one kind of
Alternatively, a plurality of them may be appropriately used. Preferred concentrations are 2-1
Within the range of 5% by weight.
The enhancement effect is greatly reduced. The primer composition of the present invention contains
Add volatile water-soluble organic solvents as necessary in addition to
May be obtained. Specifically, ethyl alcohol, propylene
Alcohol, isopropyl alcohol, acetone, etc.
Can be mentioned. These are primer compositions
[(A) + (b) + (c) + (d) + (e)] 100 weights
0 to 500 parts by weight with respect to parts by weight
It is. Addition exceeding 500 parts by weight weakens the adhesion enhancing effect
Will be. The primer composition of the present invention comprises
Outside if necessary, photopolymerization initiator, polymerization inhibitor, pigment,
Additives such as fragrances and fillers can be added if desired.
it can. UV or / and visible as photopolymerization initiator
Effective wavelength of lightWhenIs preferable, for example, camphor
Quinone / 4-dimethylaminobenzoic acid ester, can
Furquinone / 4-dimethylaminobenzophenone type,
MosquitoNFerquinone / aromatic sulfinate salt, mosquitoNFa
-Quinone / 2-mercaptobenzoxazole,NH
Quinone / 5-alkylbarbituric acid, benzoy
Alkyl ether, benzyl dialkyl ketal,
Lorothioxanthone, 2,4,6-trimethylbenzoy
Ludiphenylphosphine oxide is preferably used.
It is. Constituting the primer composition of the present invention
(A) a vinyl compound having an acidic group and (d) an aromatic sulfone
When finates are mixed in the same solution, storage stability is remarkable.
The time between primer preparation and use
If the length is long, both components are necessarily stored in separate containers
It is necessary to adopt a two-part packaging form. The component (a)
(D) can coexist with all components except the component, and
Component (d) can coexist with all components except component (a)
Therefore, although there are many combinations of two divisions of all components,
[(A) + (b)] / [(c) + (d) +
(E)], [(a) + (b) + (c)] / [(c) +
(D) + (e)], [(a) + (b) + (c) +
(E)] / [(c) + (d) + (e)], [(a) +
(C) + (e)] / [(b) + (d) + (e)]
Can be mentioned. The primer composition of the present invention is prepared by the following procedure.
Therefore, it is used for adhesion of a living hard tissue. (1) Primer
-The composition as an adherend, ie tooth enamel, tooth dentin,
Or apply to the surface of bone (2) Leave for 10 seconds to 10 minutes
To allow the primer composition to penetrate the adherend (3) Surplus
(4) Acrylic that removes primer by air blow
Primer based dental or orthopedic adhesive
And apply it to the other adherend (dentalNPositive
Resin, metal, ceramics, resin, biological hard tissue)
And glue it. When used in combination with the primer composition of the present invention.
Acrylic adhesive usedAgent, (I) an acid having an acidic group
(Ii) an acrylic monomer having no acidic group
And (iii) a polymerization initiator.You.More needed
(Iv) those to which fillers are added according to
Can be As an acrylic monomer having an acidic group
Is 10- (meth) acryloyloxydecyl dihydride
Lodien phosphate, 2- (meth) acryloyl oxy
Siethylphenyl hydrogen phosphate, bis
[2- (meth) acryloyloxyethyl] hydrogen
Enphosphate, 4- (meth) acryloyloxye
Tiltrimellitic acid, 11,11-carboxyundeci
(Meth) acrylate and the like. An acrylic monomer having no acidic group is used.
Methyl (meth) acrylate, butyl (meth)
Relate, 2-hydroxyethyl (meth) acrylate
G, 2- (dimethylamino) ethyl (meth) acrelay
G, γ-methacryloyloxypropyl trimethoxy
In addition to mono (meth) acrylates such as orchids, triethylene
Glycol di (meth) acrylate, neopentyl
Recall di (meth) acrylate, 1,6-hexanedi
Alldi (meth) acrylate, 1,10-decandio
Diol (meth) acrylate, 2,2′-bis [((me
TA) acryloyloxypolyethoxy) phenyl] pro
Bread, 2,2'-bis [4- (3- (meth) acryloyl
Ruoxy-2-hydroxypropoxy) phenyl] pro
Bread (referred to as Bis-GMA), trimethylol eta
Tri (meth) acrylate, di-2- (meth) acryl
Loyloxyethyl, 2,2,4-trimethylhexame
Chillend carbamate and the like. Benzoylperoxa is used as a polymerization initiator.
Id / aromatic sulfinate / aromatic secondary or /
And tertiary amines, partially oxidized tributylborane, bal
In addition to chemical polymerization initiators such as bituric acid / copper salts,
Erquinone / 4-dimethylaminobenzoic acid ethyl ester
Furfurquinone / 4-dimethylaminobenzophenone
System, camphorquinone / aromatic sulfinate system, can
Furquinone / 2-mercaptobenzoxazole,
2,4,6-trimethylbenzoyldiphenyl phosphite
Photopolymerization initiators such as oxides are preferably used.
You. As the filler, polymethyl methacrylate
, Polyethyl methacrylate, organic-inorganic composite filler
ー, silica, alumina, barium glass, lantern
And zirconia glass are preferably used. [0024] EXAMPLES The present invention will be described below with reference to examples.
The invention is not limited to these examples. Examples 1 to 7 6-methacryloyl as a vinyl compound having an acidic group
Oxyhexyl dihydrogen phosphate, hydroxyl group
2-hydroxyethyl as a water-soluble vinyl compound having
Methacrylate, distilled water, aromatic sulfinate
Sodium benzenesulfinate, tertiary aromatic amine
N, N-diethanol-p-toluidine
Then, their composition ratio was changed within the range of the present invention.
Various types of primers (compositions are listed in Table 1) were prepared. [0026] [Table 1]On the other hand, the human front teeth are
Embed resin in a metal ring and polish in the direction parallel to the tooth axis
An enamel flat sample was obtained. Embed human molars in the same way,
Polishing was performed in the direction parallel to the tooth axis to obtain a dentin plane sample. It
Each sample was stored in water until immediately before use. The enamel plane and the dentin plane are directly used.
No. 1000 silicon carbide abrasive paper before wet
Polish and rinse with water to remove surface moisture with a dental air syringe.
Blew off lightly. A ply immediately after preparation on these surfaces
(One of Examples 1 to 7) with a brush
Leave for 60 seconds and dry lightly with an air syringe
Was. Next, a commercially available dental adhesive “Panavia EX”
(Acrylic monomer with acid group, manufactured by Kuraray Co., Ltd.)
ー 、 Acrylic monomer without acid group 、 Polymerization initiator
And filler as a constituent component)
φ φ4mm cylindrical stainless steel tip
And dentin. 15 minutes after bonding
The adhesive sample is immersed in water at 37 ° C and sheared after 24 hours.
The wearing strength was measured (crosshead speed = 0.5 mm
/ Min). One condition measures seven samples, and averages them.
It is described in the lower part of Table 1. Smell in all of Examples 1 to 7
And the enamel adhesive strength is 201 kg / cm^TwoIs over
And dentin adhesive strength is 130kg / cm^TwoThat's all
Was. The sum of both is 359 kg / cm^TwoThat was all. By the way, without using primers, Panavia
The enamel bond strength when bonded only with EX is 137
kg / cm^Two, Dentin adhesive strength is 81kg / cm^TwoSo
Was. The sum of both is 218 kg / cm^TwoMet. Comparative Examples 1 to 11 The composition ratio of the present invention was determined while using the same components as in Examples 1 to 7.
11 types of primers prepared to deviate from the range of
Adhesion similar to Examples 1 to 7 using (Comparative Examples 1 to 11)
An experiment was performed. The results are shown in the lower part of Table 2. Comparative Example 1
In all 11 cases, the enamel bond strength was 192.
kg / cm^TwoBelow, dentin adhesive strength is 113 kg
/ Cm^TwoIt was below. The sum of both is 299 kg / c
m^TwoIt was below. [0031] [Table 2]Examples 8 to 14 As the vinyl compound (a) having an acidic group, M shown in Table 3
Dp, phenyl-p, 4-MET, 4-AET, 11-
Five kinds of DCUM, water-soluble vinyl compounds having a hydroxyl group
(B) two types of HEMA and EM, distilled water (c) aroma
BSS and PTSK as aliphatic sulfinates (d)
DE as a seed, aromatic secondary or tertiary amine (e)
Component (a), (b), using two kinds of PT and EPT
The composition ratio of (c), (d) and (e) is 10:30:50:
5: 5, and fixed to Examples 8 to 14 shown in Table 3.
Seven types of primers were prepared. Using these primers, Examples 1 to
Enamel and dentin adhesive strength according to the method up to 7
And the results are shown in the lower part of Table 3. Enamel contact
The wearing strength is 228kg / cm^TwoAs described above, the dentin adhesive strength is 1
31kg / cm^TwoAnd the sum of both is 361k
g / cm^TwoThat was all. Vinyl compound having acidic group
(A) is a derivative of phosphoric acid, that is, MDP and phenyl-P
In some cases, a vinyl compound having another acidic group, ie, 4-M
Significantly better than ET, 4-AET, and 11-DCUM
It is clear from Table 3 that the obtained adhesive strength was obtained.
You. [0034] [Table 3]Embodiment 15 A two-component primer composition comprising the following solution A and solution B
"Primer (I)" was prepared. On the other hand, two paces consisting of the following A paste and B paste
(Chemical polymerization type) acrylic adhesive "Adhesive DP"
Was prepared.     A paste: MDP 5% by weight                   Bis-GMA 15                   1,6-hexanediol dimethacrylate 4.5                   Silane-treated silica powder 75                   Benzoyl peroxide 0.5     B paste: Bis-GMA 15% by weight                   1,6-hexanediol dimethacrylate 9.4                   Silane-treated silica powder 75                   DEPT 0.3                   2,4,6-triisopropylbenzenesulfur 0.3                   Sodium finate However, Bis-GMA is 2,2'-bis [4- (3-
Methacryloyloxy-2-hydroxypropoxy)
Enyl] propane. The primer (I) and the adhesive DP
To evaluate the adhesive strength of the adhesive set to the teeth
The following experiment was performed. First, with the solution A of the primer (I)
The solution obtained by mixing 0.1 g of Solution B was used in Examples 1 to 7.
And apply it to the prepared enamel flat sample.
Leave it for 60 seconds before dentalDDry lightly with an syringe
did. Then, paste A and paste B of adhesive DP
After kneading 0.2g each, this is 4mmφ × 4mm
Apply to a cylindrical stainless steel tip
We pressed. Similarly, primers can be applied to human dentin planes.
-Adhesion of stainless steel chip using (I) and adhesive DP
did. Adhesion into water at 37 ° C 15 minutes after adhesion
The sample was immersed and the shear bond strength was measured after 24 hours.
(Crosshead speed = 0.5 mm / min). The average of the measured values of seven samples under one condition is
Melt adhesive strength = 295 kg / cm^Two, Dentin adhesive strength
= 216kg / cm^TwoMet. The sum of both is 511kg
/ Cm^TwoIt is. By the way, use primer (I)
Adhesive strength when bonding only with adhesive DP without using
Is 145kg / cm^Two, Dentin adhesive strength is 92kg / c
m^TwoMet. Embodiment 16 Photopolymerizable acrylic adhesive consisting of the following 1 paste
"Adhesive MP" was prepared.   Adhesive MP: 2.5 parts by weight of MDP                 Bis-GMA 15                 1,6-hexanediol dimethacrylate 6.9                 Silane-treated silica powder 75                 Camphorquinone 0.3                 Ethyl 4-dimethylaminobenzoate 0.3 The primer (I) of Example 15 was adhered
(Human enamel plane, dentin plane)
4mmφ × 4mm cylindrical dental coping using adhesive MP
Composite resin "Clear fill photo core" (Kuraray
Manufactured) was pressed on it. Sliding side of the cured body,
Dental light irradiator "Lightel-II" from 4 directions (Gunma Ushio
(Made by Denki) four times for 20 seconds. 15 from bonding
After a lapse of minutes, the adhesive sample was immersed in water at 37 ° C. for 24 hours.
After a time, the shear bond strength was measured. The enamel adhesive strength is 273 kg / cm^Two
(Η = 7), dentin adhesive strength is 231 kg / cm^TwoIn
Was. The sum of both is 504 kg / cm^TwoIt is. By the way
Glue only with adhesive MP without using primer (I)
Is 132 kg / cm^Two,ivory
Quality adhesive strength is 101kg / cm^TwoMet. From Examples 15 and 16, the primer of the present invention
Regardless of the polymerization method of the acrylic adhesive to be combined,
Significantly enhances adhesion to both enamel and dentin
It is clear that it has an effect. Comparative Examples 12 and 13 Camphorquinone / 4-dimethyla which is a photopolymerization initiator
The following one-pack primer set containing ethyl minobenzoate
The product "Primer (II)" was prepared.   Primer (II): MDP 15% by weight                       HEMA 25                       Water 59                       Camphor quinone 0.5                       Ethyl 4-dimethylaminobenzoate 0.5 Combination of primer (II) and adhesive DP
In Comparative Example 12, an adhesion test was performed according to Example 15.
However, the enamel adhesive strength is 165 kg / cm^Two,elephant
Dentin bond strength is 83kg / cm^TwoMet. Both sums are
248kg / cm^TwoIt is. On the other hand, a combination of the primer (II) and the adhesive MP
An adhesion test was performed in accordance with Example 16 by combining (Comparative Example 13).
As a result, the enamel adhesive strength was 240 kg / c.
m^Two, Dentin adhesive strength is 156kg / cm^TwoMet. Both
396 kg / cm^TwoIt is. From Comparative Examples 12 and 13 using primer (II)
Is effective in enhancing adhesion due to the difference in the polymerization method of the adhesive to be combined
It is clear that there is a big difference in the fruits. Embodiment 17 One-part photopolymerizable acrylic adhesive shown below
ML "was prepared.   Adhesive ML: MDP 15                 HEMA 30                 Bis-GMA 51                 Camphor quinone 2                 Ethyl 4-dimethylaminobenzoate 2 The primer (I) of Example 15 was adhered
(Human enamel plane, dentin plane) for 60 seconds
After leaving it, air blow it lightly with a dental air syringe.
Excess primer was blown off. Add the adhesive ML on it
2mm thick with 4mmφ hole drilled on it
Place the Teflon split mold and face the adhesive ML inside the hole
And irradiated with a dental light irradiator for 20 seconds. Then in this hole
Dental composite resin "Photo Clear Fill
A "(made by Kuraray), and then re-irradiate with light from above.
Performed for 0 seconds. 15 minutes after the last light irradiation
Immerse the adhesive sample in water at 37 ° C and shear it after 24 hours
The strength was measured. The enamel adhesive strength is 312 kg / c
m^Two, Dentin adhesive strength is 226kg / cm^TwoMet. Both
Is 538kg / cm^TwoIt is. [0049] According to the present invention,Make up the adhesive setply
The mer composition is prepared in advance from living hard tissue, especially tooth enamel.
And dentinThe adhesive set of the present invention
ConfigureBy bonding with acrylic adhesive
Thus, the adhesive strength of the adhesive is significantly enhanced.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) A61K 6/00 C09J 4/02

Claims (1)

(57) [Claims 1] (a) Vinyl compound 5 having an acidic group
30% by weight, (b) 10 to 50% by weight of a water-soluble vinyl compound having a hydroxyl group, (c) 35 to 75% by weight of water, (d)
2 to 15% by weight of an aromatic sulfinate, and (e) 2 to 15% by weight of an aromatic secondary and / or tertiary amine
Yes and Help primer composition containing, the (i) an acidic group and
Acrylic monomer, (ii)
An acryl-based monomer, and (iii) an initiator comprising a polymerization initiator.
Adhesive set combining krill adhesive.