JP3268673B2 - Pretreatment material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel pretreatment material which can be suitably used for bonding human hard tissues.

[0002]

2. Description of the Related Art In recent years, adhesives have been widely used in various fields such as automobiles, electronics industry, construction, and medical care, and their respective properties are required. Above all, dental adhesives used for restoring teeth for medical use are required to have strong adhesiveness and durability that can withstand a special environment in the oral cavity.

[0003] Tooth is mainly composed of enamel and dentin. For enamel which is mostly composed of inorganic material, the surface to be adhered is treated in advance with a strong acid such as phosphoric acid and then acrylic. A method of applying an adhesive composed of a system monomer solution is generally adopted, and a sufficient effect has been recognized clinically. However, when dentin, which contains a lot of organic matter and is entangled with the pulp through countless tubules, is treated with phosphoric acid or the like, the calcium component is eluted more than necessary, and the adhesive strength is rather reduced. And risk of pulp damage.

[0004] Therefore, a study on pretreatment of such dentin with a relatively mild acid such as citric acid or EDTA instead of a strong acid such as phosphoric acid was conducted, and a certain effect was obtained. When the treated material was used for enamel, sufficient adhesion could not be obtained, and it was necessary to perform another pretreatment for dentin and enamel.

[0005]

As described above, the operation of separately pretreating dentin and enamel is not only complicated, but also causes phosphoric acid to flow into the dentin during the processing of enamel. At risk of pulp damage.

An object of the present invention is to find a pretreatment material which has a sufficient adhesive force even when dentin and enamel are simultaneously treated, and which does not etch dentin more than necessary.

[0007]

Means for Solving the Problems As a result of repeated studies to solve the above problems, the present inventors have found that a combination of an organic sulfonic acid metal salt and an organic carboxylic acid having a hydrophobic group allows only dentin to be used. The present inventors have found that a sufficient adhesive force can be obtained even for enamel, and have completed the present invention.

That is, the present invention provides (A) a metal salt of an organic sulfonic acid, (B) an organic carboxylic acid having a hydrophobic group, (C)
A pretreatment material comprising water and (D) an alcohol.

The organic sulfonic acid metal salt used in the present invention can be used without any particular limitation as long as it is soluble in water.

Usually, the organic sulfonic acid metal salt is synthesized from organic sulfonic acid and an alkaline compound as raw materials.

Specific examples of the organic sulfonic acid used as a raw material include alkyl sulfonic acids such as methanesulfonic acid, ethanesulfonic acid and n-hexanesulfonic acid; benzenesulfonic acid, p-toluenesulfonic acid,
Aryl sulfonic acids such as -aminobenzenesulfonic acid, 2-amino-5-methylbenzene-1-sulfonic acid, p-phenolsulfonic acid and n-dodecylbenzenesulfonic acid; methallylsulfonic acid, p-methacryloxy-sulfonic acid And vinyl-type sulfonic acids.

Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, calcium hydroxide and primary hydroxide.
Metal hydroxides such as iron; metal carbonates such as sodium carbonate, potassium carbonate, calcium carbonate, strontium carbonate, and barium carbonate; metals such as sodium acetate, potassium benzoate, calcium lactate, ferric oxalate, and cobalt citrate Specific examples include carboxylate salts.

Examples of the metal sulfonic acid salt synthesized from the above-mentioned raw materials include salts of the above sulfonic acid with alkali metals such as sodium and potassium, salts with alkaline earth metals such as calcium, strontium and barium, iron and cobalt. And a salt with a transition metal. Of these, an alkali metal salt of an organic sulfonic acid is particularly preferred.

The amount of the organic metal sulfonate is from 1 to 30 parts by weight based on 100 parts by weight of the total of the solvent comprising water and alcohol.
Parts by weight are preferably used. When the amount is less than 1 part by weight, sufficient adhesive force cannot be obtained because the etching effect on enamel is particularly small, and when the amount is more than 30 parts by weight, the etching force on dentin is too strong to lower the adhesive force. It is not appropriate because of the tendency to do so.

The method for adding the metal organic sulfonic acid salt to the pretreatment material is as follows: (1) An organic sulfonic acid metal salt obtained by neutralizing an organic sulfonic acid and the above-mentioned alkaline compound in advance and isolating the same is used. (2) A method of adding a metal salt of an organic sulfonic acid by previously dissolving an organic sulfonic acid as a pretreatment material component in a mixed solvent of water and alcohol, and partially neutralizing the organic sulfonic acid with an alkaline compound. (3) A metal salt of an organic carboxylic acid having a hydrophobic group according to the present invention is added to a pretreatment material in advance and salt exchange occurs by adding an organic sulfonic acid, resulting in a metal salt of an organic sulfonic acid. Any method, such as a method for generating, is suitably used.

Since the neutralization reaction between the alkaline compound and the organic sulfonic acid is almost complete, when the organic sulfonic acid metal salt is formed from both raw materials in the system in the above (2), the stoichiometric calculation is required. Then, each component may be added.

The organic carboxylic acid having a hydrophobic group (hereinafter referred to as "hydrophobic carboxylic acid") used in the present invention is a carboxylic acid having an alkyl or alkenyl group having 3 or more carbon atoms in the molecule or having an aryl group. It can be used without any restrictions.

Specific examples of hydrophobic carboxylic acids that are generally preferably used include:

[0019]

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An alkyl group or a substituted alkyl carboxylic acid;

[0021]

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An alkenyl group-type carboxylic acid;

[0023]

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And a substituted aryl carboxylic acid.

Among them, particularly preferred are hydrophobic carboxylic acids represented by the following general formula.

[0026]

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(Wherein R ₁ is a hydrogen atom or a lower alkyl group, and n is an integer of 3 to 20)

[0028]

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(Wherein R ₂ is a hydrogen atom or a lower alkyl group, and R ₃ is an organic residue having 2 to 20 carbon atoms).

[0030]

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Specific compounds of (b) include:

[0032]

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And the like.

The amount of the hydrophobic carboxylic acid is preferably 1 to 20 parts by weight based on 100 parts by weight of the total of water and alcohol. When the amount is less than 1 part by weight, the adhesive strength to dentin becomes insufficient, and when the amount is more than 20 parts by weight, the adhesive force to enamel tends to decrease, which is not suitable.

As a method of adding the hydrophobic carboxylic acid to the pretreatment material, not only the method of adding the hydrophobic carboxylic acid but also a method of adding the hydrophobic carboxylic acid to the pretreatment material in advance as a metal salt of the hydrophobic carboxylic acid, A method in which a salt exchange reaction is caused by adding an acid to generate the hydrophobic carboxylic acid is also suitably used. Therefore, the pretreatment material of the present invention may contain a part of the hydrophobic carboxylic acid salt.

The water used in the present invention is not particularly limited as long as it is generally available.

The alcohol used in the present invention is not particularly limited as long as it is compatible with water. Specific examples of commonly used alcohols include lower alcohols such as methanol, ethanol, and i-propanol. However, ethanol is preferred in consideration of use in the oral cavity.

The amount of the alcohol is preferably 50 to 300 parts by weight based on 100 parts by weight of water. The 50
If the amount is less than 10 parts by weight, the solubility of the hydrophobic carboxylic acid will be insufficient. If the amount is more than 300 parts by weight, the solubility of the metal salt of vinyl sulfonic acid will be low.

In the present invention, the pretreatment material is an undercoating agent for treating the surface of an adherend before bonding using an adhesive.

As a pretreatment method, a method is generally employed in which a sponge or a small brush is used so that the surface to be adhered is completely wetted. After the pre-treatment, it is conceivable that the process proceeds to the next bonding step after blowing by drying with air, or the case where the pre-treatment is followed by once washing with water and drying to wash away excess pre-treatment material and then to the bonding step. However, the latter method is preferred for improving the adhesive strength.

After the surface to be adhered is processed using the pretreatment material of the present invention, bonding is usually performed using an adhesive.
As the adhesive composition, any commonly available adhesive composition can be used without limitation, but the following compositions are preferably used.

An adhesive composition comprising (i) a vinyl monomer having a specific acidic group, (ii) a (meth) acrylate compound, and (iii) a radical polymerization catalyst.

The vinyl compound having a specific acidic group is represented by the general formula

[0044]

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[Wherein R ₁ is an alkyl group or a hydrogen atom,
R ₂ is an organic residue having 2 to 20 carbon atoms, X is a carboxyl group (when l = 2, X may be present in the form of an acid anhydride group)
Or —OPO (OH) R ₃ group (R ₃ is a hydroxyl group, an alkoxyl group or an aryloxyl group), l is an integer of 1 or 2,
m is an integer of 0 or 1, and n is an integer of 1 to 3].

In the above formula, the group represented by R ₁ is a hydrogen atom or an alkyl group, and specific examples of the alkyl group include a methyl group and an ethyl group.

R ₂ is a divalent organic acid group having 2 to 20 carbon atoms whose main chain may be interrupted by oxygen. Carbon number 1
In the following cases, the adhesion durability under wet conditions is low. Carbon number 2
If the ratio is 1 or more, it is difficult to obtain a material, and the strength of the cured product cannot be obtained, so that the adhesive strength is low. The organic residue may be an aliphatic or aromatic organic residue as long as the number of carbon atoms is satisfied, and may be partially substituted with a substituent such as a halogen, an amino group, a hydroxyl group, or the like.

In the general formula, X is a carboxyl group or -OP
O (OH) R ₃ group, one or two of which are bonded to the organic residue. Here, the group represented by R ₃ is any one of a hydroxyl group; an alkoxyl group such as a methoxy group, an ethoxy group and a butoxy group; and an aryloxyl group such as a phenoxy group and a benzyloxy group.

As the vinyl monomer, any one having the above structure can be used without any limitation. Specific examples of vinyl monomers having an acidic group that are generally preferably used include:

[0050]

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A vinyl monomer having one carboxyl group in the molecule;

[0052]

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A vinyl monomer having two carboxyl groups in the molecule;

[0054]

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A vinyl monomer having one phosphate group in the molecule;

[0056]

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And vinyl monomers having two phosphate groups in the molecule.

In order to exhibit excellent adhesiveness, the vinyl monomer having an acidic group represented by the above-mentioned general formula is required to have R
₂ is preferably an alkylene group having 4 to 20 carbon atoms, and more preferably X is a carboxyl group.

Specific examples of these preferred vinyl monomers include 7-methacryloxy-1,1-heptanedicarboxylic acid, 11-methacryloxy-1,1-undecanedicarboxylic acid, and 13-methacryloxy-1,1-tridecanedicarboxylic acid. And dicarboxylic acids having two carboxyl groups in the molecule.

The vinyl monomer having such an acidic group is
Usually, 1 to 50 parts by weight is contained per 100 parts by weight of the total vinyl monomer in the adhesive composition.

One of the components of the adhesive composition is a (meth) acrylate compound. As the (meth) acrylate compound, a known compound which is polymerized by a radical polymerization catalyst can be used without particular limitation. Specific examples of the (meth) acrylate compounds generally preferably used include methyl (meth) acrylate and ethyl (meth).
Acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth)
Acrylate, isobutyl (meth) acrylate, n-
Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, Monofunctional vinyl monomers such as methoxydiethylene glycol (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate
Acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) Acrylate,
1,10-decanediol di (meth) acrylate, bisphenol A di (meth) acrylate, 2,2'-bis [(meth) acryloyloxypolyethoxyphenyl] propane, 2,2'-bis [4- (3- Methacryloyloxy-2-hydroxypropoxy) phenyl] propane, trimethylolpropane (meth) acrylate, trimethylolethanetri (meth) acrylate,
A polyfunctional vinyl monomer such as tetramethylolmethanetetra (meth) acrylate is used.

Another component of the adhesive composition is a radical polymerization catalyst. As the radical polymerization catalyst, a known photopolymerization initiator or chemical polymerization initiator is used. In order to exhibit high adhesive strength, a photopolymerization initiator is preferable, and diacetyl, acetylbenzoyl, benzyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, α-naphthyl β-naphthyl, Α-diketones such as 4,4′-oxybenzyl, camphorquinone, 9,10-phenanthrenequinone and acenaphthenequinone; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin propyl ether; Thioxanthone derivatives such as ethoxythioxanthone, 2-chlorothioxanthone and methylthioxanthone; benzophenone derivatives such as benzophenone, P, P'-dimethylaminobenzophenone and P, P'-methoxybenzophenone are preferably used.

As the chemical polymerization initiator, peroxides, azo compounds and the like are preferably used. Known peroxides are used without any limitation. Specifically, diacyl peroxides such as dibenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, dilauroyl peroxide, dioctanoyl peroxide, decanoyl peroxide; cumene hydroperoxide;
hydroperoxides such as t-butyl hydroperoxide; and ketone peroxides such as cyclohexanone peroxide and methyl ethyl ketone peroxide. As the azo compound, 2,2'-
Azobisisobutyronitrile, 4,4'-azobis (4
-Cyanovaleric acid), 2,2'-azobis (2,4-dimethylvaleronitrile) and the like.

The photopolymerization initiator and the chemical polymerization initiator can be used not only alone but also in combination as needed.

These radical polymerization catalysts are used in an amount of 0.05 parts by weight based on 100 parts by weight of all vinyl monomers in the adhesive composition.
It is desirable to add 10 to 10 parts by weight, preferably 0.1 to 5 parts by weight.

Further, other additives may be added at the same time as the above radical polymerization catalyst, if necessary. For example, a curing accelerator can be added.

Examples of such curing accelerators include N, N-dimethyl-P-toluidine, N, N'-dimethylbenzylamine, N-methyldibutylamine, dimethylaminoethyl methacrylate, N, N-dimethyl-m-anisidine, Amine compounds such as ethyl P-dimethylaminobenzoate; thiourea compounds such as allyl thiourea and o-tolyl thiourea; phosphite compounds such as dimethyl phosphite and dioctyl phosphite; cobalt compounds such as cobalt naphthenate; barbituric acid , 5-ethylbarbituric acid, 2-thiobarbituric acid and the like; and barium sulfonic acids such as sodium p-toluenesulfinate and sodium benzenesulfinate.

The addition amount of the curing accelerator is 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of all the vinyl monomers in the adhesive composition.

It is preferable to add a small amount of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether and butylhydroxytoluene to the adhesive composition as required.

It is preferable to add a filler depending on the object to be bonded. By adding a filler, mechanical strength and water resistance are improved, and furthermore, fluidity and coating properties can be controlled. As the filler, for example, quartz, amorphous silica, silica zirconia, clay,
Aluminum oxide, talc, mica, kaolin, glass,
Inorganic substances such as barium sulfate, zirconium oxide, titanium oxide, silicon nitride, aluminum nitride, titanium nitride, silicon carbide, boron carbide, calcium carbonate, hydroxyapatite, and calcium phosphate; polymethyl methacrylate, polyethyl methacrylate, polyvinyl chloride,
Organic substances such as polymers or oligomers such as polystyrene, polyester and nylon; and organic-inorganic composite fillers. Usually, it is preferable to use the inorganic filler that has been treated with a silane coupling agent such as γ-methacryloyloxypropyltrimethoxysilane, vinyltriethoxysilane, or the like.

The amount of the filler to be added can be appropriately selected as needed.
What is necessary is just to select from the range which becomes 1-300 weight part with respect to 00 weight part.

The adhesive composition can be divided into two stable packages and packaged as necessary in order to prevent curing during storage. For example, a package (A) comprising a vinyl monomer having an acidic group and a part of a radical polymerization catalyst and a radical polymerizable vinyl monomer and a package (B) comprising a curing accelerator and a part of a radical polymerizable vinyl monomer are used. Combinations and the like are common.

Next, the bonding method will be specifically described, but the present invention is not limited to these specific methods. When one of the adherends is a solid and the other is a paste-like material such as a light-curable composite resin, after applying the material on the solid side, it is preferably visible to the adhesive composition to increase the adhesive strength. Light is irradiated for 10 to 60 seconds. Next, the paste-like material is put thereon, and further press-contacted, irradiated with light, polymerized and cured, and both adherends are adhered. When both adherends are solid, one side is coated with an adhesive composition containing a primer and a photopolymerization initiator, the other side is coated with an adhesive composition, and then the two bodies are pressed and then bonded. Light irradiation is performed from the boundary or on the solid surface to cure and bond.

[0074]

The pretreated material of the present invention can significantly improve the adhesiveness to both dentin and enamel. In addition, it is not necessary to separately pretreat dentin and enamel, and they can be treated simultaneously, thereby simplifying the operation. The pretreatment material of the present invention is also effective for human hard tissues such as bones in addition to the adhesion of teeth as described above.

[0075]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Abbreviations of compounds

[0077]

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Examples 1 to 10 and Comparative Examples 1 to 2 A mixture of 5 parts by weight of sodium p-toluenesulfonate, 50 parts by weight of ion-exchanged water and 50 parts by weight of ethanol was mixed with a hydrophobic carboxylic acid as shown in Table 1. An acid was added to obtain a pretreatment material. The pH of the solution was confirmed using pH test paper. Next, after the dentin and the enamel were treated with the above pretreatment material, the adhesive strength was measured using the following adhesive composition.

[Measurement Method] The cow's front teeth within 24 hours after slaughter were removed, and under water injection, dentin or enamel was shaved using # 800 emery paper so as to be horizontal to the lips. Next, after blowing compressed air on the surface for about 10 seconds and drying, a paraffin wax with a hole of 4 mm in diameter is fixed to the dentin surface with a double-sided tape to form a simulated cavity having the surface as the bottom surface. did.

A pretreatment material having the composition shown in Table 1 was applied to the surface, left for 30 seconds, washed with water for 10 seconds, and then dried by blowing compressed air. Subsequently, an adhesive composition having the following composition was applied, and then a commercially available visible light irradiator “White Light” (manufactured by Takara Labelmont Co., Ltd.) was used.
Irradiated for 2 seconds. Further, a commercially available light-curable composite resin "PARFIQUE ESTELLITE" (manufactured by Tokuyama Soda Co., Ltd.) was filled thereon, pressed, and then irradiated with light again for 30 seconds to cure.

After the composite resin was cured, the paraffin wax was removed and the composite resin was left in water at 37 ° C. for 24 hours. Metal attachments were respectively attached to the cow front teeth and the cured composite resin, and the adhesion strength between the dentin and the adhesive composition was measured using a tensile tester (crosshead speed: 10 mm / min).

The composition of the adhesive composition is as follows.

Compound B 20 parts by weight 2-hydroxyethyl methacrylate 30 parts by weight Bisphenol A diglycidyl methacrylate 30 parts by weight Triethylene glycol dimethacrylate 20 parts by weight Camphorquinone 0.4 parts by weight Ethyl p-dimethylaminobenzoate 0.6 parts by weight Parts Hydroquinone monomethyl ether 0.05 parts by weight

[0084]

[Table 1]

Examples 11 to 18 The metal salts of organic sulfonic acids shown in Table 2 were replaced with 50 parts of ion-exchanged water.
A pretreatment material was prepared by dissolving in a mixture of 50 parts by weight of alcohol and 50 parts by weight of alcohol shown in Table 2, and finally, 5 parts by weight of Compound B. The pH of each solution is 2.5 to 3.
Between five. The adhesion test method and the adhesive composition were performed in the same manner as in Examples 1 to 10, and the results are shown in Table 2.

As comparative examples, the adhesive force was measured in the same manner as in the case where the organic sulfonic acid metal salt was removed (Comparative Example 3) and the case where another organic solvent was used instead of the alcohol (Comparative Example 4). 3 is shown.

[0087]

[Table 2]

Examples 19 to 26 The same procedures as in Example 4 were carried out except that the pretreatment material of Example 4 was used and the composition shown below was used as the adhesive composition (the vinyl monomers having specific acidic groups are listed in Table 3). The adhesive strength was measured in the same manner as in Nos. 1 to 10.

Vinyl monomer having acidic group x parts by weight Bisphenol A diglycidyl methacrylate 40 parts by weight Triethylene glycol dimethacrylate 60-x parts by weight Camphequinone 0.4 parts by weight Ethyl p-dimethylaminobenzoate 0.6 parts by weight Hydroquinone monomethyl ether 0.05 parts by weight Table 3 shows the adhesive strength obtained by the above method.

[0090]

[Table 3]

Examples 27 to 29 As the pretreatment materials, those shown in Example 4 were used, and as the adhesive composition, 2 of the compositions used in Examples 1 to 10 were used.
-Hydroxyethyl methacrylate, bisphenol A
The adhesive strength was measured in the same manner except that the (meth) acrylate compounds shown in Table 4 were used instead of diglycidyl methacrylate and triethylene glycol dimethacrylate. The results are shown in Table 4.

[0092]

[Table 4]

Examples 30 to 33 As the pretreatment materials, those shown in Example 4 were used, and as the adhesive composition, camphorquinone and p-dimethylaminobenzo in the compositions used in Examples 1 to 10 were used. The adhesive strength was measured in the same manner except that the photopolymerization initiator and the curing accelerator shown in Table 5 were used in place of ethyl acid. Table 5 also shows the results.

[0094]

[Table 5]

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-60-123515 (JP, A) JP-A-4-217904 (JP, A) JP-A-3-118308 (JP, A) (58) Field (Int. Cl. ⁷ , DB name) A61K 6/00 A61L 24/00

Claims (1)

(57) [Claims] 1. A metal salt of an organic sulfonic acid (A), an organic carboxylic acid having a hydrophobic group (B), water (C) and (D)
A pretreatment material comprising alcohol.