JPH0640837A - Adherent pretreatment composition and bonding method - Google Patents

Abstract

(57) [Summary] [Object] To provide an adhesive pretreatment composition capable of strongly adhering a resin and a resin composite material by bringing the adhesive pretreatment composition into contact with the surface of a tooth.
Further, by using a curable composition having a composition similar to the adhesive pretreatment composition, an adhesive method for further strongly adhering is provided. [Structure] (Meth) acrylate monomer having at least one hydroxyl group in one molecule, (meth) acrylate monomer having at least one carboxyl group in one molecule, and polyfunctional (meth) An adhesive pretreatment composition containing an acrylate-based monomer, an amino acid derivative and water.
Further, the above adhesive pretreatment composition for adhering a curable composition containing a (meth) acrylate-based monomer having at least one hydroxyl group in one molecule, a polymerization initiator, and a filler was used. Bonding method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive pretreatment composition and a bonding method for strongly bonding a resin or a resin composite material to a tooth. More specifically, particularly in the treatment of teeth, an adhesive pretreatment composition showing excellent adhesive performance to a resin, a resin composite material, a metal casting, etc. Regarding the bonding method that was used.

[0002]

2. Description of the Related Art In dental treatment, adhesion between a tooth and a restorative material is important. Currently, as dental restoration materials, resins,
Although resin composite materials, metal castings, ceramics, etc. are used, these materials generally do not have adhesiveness to teeth. Therefore, many curable compositions (adhesives) that fill gaps between these restorative materials and teeth and that adhere to both have been proposed. However, in many cases, the adhesive force between the tooth, particularly dentin, and the adhesive was insufficient.

Up to now, there has been known a method of treating the surface of a tooth by acid etching in order to obtain a sufficient adhesive force to the tooth (Buonocore, MG, et al., J. Den.
t. Res., 34, 849-853, 1955). Examples of typical etching agents include phosphoric acid, citric acid containing a metal salt, and an aqueous solution such as EDTA. The applicant of the present invention applies this technique to apply tri-n-butylborane (T) as a polymerization initiator.
BB), and 4-methacryloyloxyethyl trimellitic anhydride (4-M) as an adhesion promoting monomer.
An adhesive containing ETA) has been proposed (Japanese Patent Laid-Open No. 63-
162,710). Even if an adhesive containing benzoyl peroxide (BPO), which is a polymerization initiator used in a dental curable composition, and a tertiary amine, or a sulfinic acid is used without using TBB, it is high. No adhesive strength was obtained.

[0004] Munksgaad and Asmussen use such a polymerization initiator to apply an adhesive to the acid-etched tooth surface by further treating it with a primer in order to improve the adhesive strength. (Munksgaad, EC, Asmussen, J.Dent.Res., 63,1087-108)
9, 1984 and JP-A-63-279,851). In the proposal, acids such as phosphoric acid and citric acid and N-phenylglycine (NPG) are used as acid etching agents.
An aqueous solution containing an amino acid such as is used, and a resin or a resin composite material is adhered using a composition comprising glutaraldehyde, 2-hydroxyethyl methacrylate (HEMA) and water as a primer (coating agent).

On the other hand, Bowen et al., After etching the tooth surface with an aqueous solution containing iron oxalate, subsequently contacted with an acetone solution of NPG or a reaction adduct of NPG and glycidyl methacrylate (GMA) (NPG-GMA). , 1 mol of pyromellitic dianhydride and HEMA2
Molar addition product (PMDM) or 3,3 ', 4,
Addition product of 1 mol of 4'-benzophenone tetracarboxylic dianhydride and 2 mol of HEMA (BTDA-HEMA)
Alternatively, a method of adhering a resin or a resin composite material by bringing an acetone solution of 4-META into contact (Japanese Patent Publication No. 2-5
No. 8,244 and US Pat. No. 4,521,550), and after etching the tooth surface with a nitric acid aqueous solution containing NPG, PMDM or BTDA
A method (US Pat. No. 4,659,751) for adhering a resin or a resin composite material by bringing an acetone solution of -HEMA or 4-META into contact is proposed.
However, the above-mentioned proposals have problems that the number of operations for bonding is large, which is troublesome and the bonding strength is insufficient.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in the prior art. Adhesiveness showing excellent adhesiveness to dentin, particularly dentin, by a simpler operation. It is to provide a pretreatment composition.

[0007] Another object of the present invention is to provide a method for adhering a resin composition to a tooth using the adhesive pretreatment composition of the present invention. Further objects and advantages of the present invention will be apparent from the following description.

[0008]

According to the present invention, the above objects and advantages of the present invention are as follows: (A) a (meth) acrylate-based monomer having at least one hydroxyl group in one molecule. , (B) a (meth) acrylate-based monomer having at least one carboxyl group in one molecule, (C) the following general formula (I)

[0009]

[Chemical 3]

A polyfunctional (meth) acrylate-based monomer represented by: (D) the following general formula (II)

[0011]

[Chemical 4]

An amine compound represented by and (E)
It is achieved by an adhesive pretreatment composition having adhesiveness to tooth structure characterized by containing water.

That is, according to the present invention, a resin or a resin composite material is strongly applied to a tooth by contacting the surface of the tooth with an adhesive pretreatment composition exhibiting high penetrability and excellent curability for the tooth. The present invention provides an adhesive pretreatment composition capable of adhering to.

The adhesive pretreatment composition of the present invention is brought into contact with the ground tooth surface as it is, or is preliminarily prepared by etching with an etching agent such as an aqueous phosphoric acid solution, an aqueous citric acid solution containing a metal salt or an aqueous EDTA solution. The surface can be treated before use. At that time, an aqueous solution containing ferric chloride and citric acid is preferably used as the etching agent.

In the adhesive pretreatment composition of the present invention,
The component (A) is a (meth) acrylate-based monomer having at least one hydroxyl group in one molecule. Examples of such a monomer include mono (meth) acrylate monomers such as 2-hydroxyethyl (meth) acrylate and 3- (meth) acrylate.
Hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate and the like can be preferably used. The monomer having at least two or more (meth) acryloyloxy groups in one molecule is, for example, 2-hydroxy-1,3-dimethacryloyl as a condensate of (meth) acrylic acid and an aliphatic polyol. Mention may be made of the addition products of oxypropane and glycidyl (meth) acrylate (GMA) with aliphatic or aromatic polyols. More specifically, the addition product of 1 mol of bisphenol A and 2 mol of GMA (Bi
s-GMA), an addition product of 1 mol of glycerin and 2 mol of GMA (GL-GMA) or ethylene glycol 1
An addition product (E-GMA) of 2 mol of GMA and 2 mol of GMA can be mentioned as a preferable one. These (meta)
The acrylate-based monomer (A) can be used alone or in combination.

In the adhesive pretreatment composition of the present invention,
The component (B) is a (meth) acrylate-based monomer having at least one carboxyl group in one molecule. As such a monomer, an aromatic polycarboxylic acid having at least one (meth) acryloyloxy group in one molecule or an anhydride thereof is preferably used. As a (meth) acrylate-based monomer having at least one (meth) acryloyloxy group and a carboxyl group in one molecule, for example, 4- (meth) acryloyloxymethyltrimellitic acid and its anhydride, 4- (meth) ) Acryloyloxyethyl trimellitic acid (4MET) and its anhydride (4-META), 4- (meth) acryloyloxybutyl trimellitic acid and its anhydride, 4-
[2-hydroxy-3- (meth) acryloyloxy]
Butyl trimellitic acid and its anhydride, 2,3-bis (3,4-dicarboxybenzoyloxy) propyl (meth) acrylate, 2- (3,4-dicarboxybenzoyloxy) 1,3-di (meth) Acryloyloxypropane, N- (meth) acryloyl-5-salicylic acid (5-MASA), PMDM, BTDA-HEMA and the like are used, among which 4-MET, 4-META and 5-MASA are preferably used. These (meth) acrylate-based monomers (B) can be used alone or in combination.

In the adhesive pretreatment composition of the present invention,
The component (C) has the following general formula (I)

[0018]

[Chemical 5]

It is a polyfunctional (meth) acrylate-based monomer represented by: In formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group.

A is -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _l-
A group represented by (l is 0 or a positive integer), or-
_{(CH 2 CH 2 O) n} -R 3 - (OCH 2 CH 2) m - (R 3 represents at least one has an aromatic ring and the divalent may contain an oxygen atom aromatic group , And n and m represent a positive integer).

Examples of the polyfunctional (meth) acrylate-based monomer represented by (I) above include ethylene glycol, diethylene glycol, triethylene glycol,
Di (meta) of glycols such as polyethylene glycol
Acrylates; 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane (m + n =
Preferred examples include 2,2-bis (4-methacryloxypolyethoxyphenyl) propanes such as 2.6, hereinafter referred to as 2.6E). These polyfunctional (meth) acrylate monomers can be used alone or in combination.

In the adhesive pretreatment composition of the present invention,
The component (D) has the following general formula (II)

[0023]

[Chemical 6]

It is an amine compound represented by: R4 is a hydrogen atom or a metal. R5 and R6 are each independently a hydrogen atom or an alkyl group which may contain various functional groups or substituents. As the component (B),
For example, N-phenylglycine, N-tolylglycine,
N, N- (3-methacryloyloxy-2-hydroxypropyl) phenylglycine and the like can be used, and among these, NPG is preferably used.

In the adhesive pretreatment composition of the present invention,
The component (E) is water. The water that can be used here is
For example, various ionic species such as distilled water, ion-exchanged water, or physiological saline may be contained.

In the adhesive pretreatment composition of the present invention, the components (A), (B), (C), (D) and (E) are added to the components (A), (B) and (C). ), (D) and (E) based on the total weight of components, preferably (A)
1 to 95 parts by weight of the component, 1 to 50 parts by weight of the component (B),
1 to 95 parts by weight of the component (C) and 0.01 to 100 parts of the component (D)
It is advantageous to include 50 parts by weight and component (E) in the range of 1 to 95 parts by weight. A more preferable composition is
The component (A) is 20 to 80 parts by weight, and the component (B) is 1 to 10
Parts by weight, the component (C) is 3 to 60 parts by weight, the component (D) is 0.05 to 10 parts by weight, and the component (E) is 20 to 70 parts by weight.

The composition of the present invention comprises the above (A), (B),
In addition to the components (C), (D) and (E), the above (A),
It may contain (meth) acrylates other than those shown in the components (B) and (C), and may also contain organic solvents such as ethanol, acetone, ether and tetrahydrofuran. Furthermore, benzoyl peroxide (BP
O) or sulfinic acid or a salt thereof can be used in combination.

The adhesive pretreatment composition of the present invention is applied to the tooth surface as it is as described above or after the tooth surface is previously treated with an etching agent to strongly strengthen the resin or resin composite material on the tooth. Glue it.

Therefore, according to the present invention, secondly, after contacting the adhesive pretreatment composition of the present invention with the tooth surface,
(F) 100 parts by weight of (meth) acrylate monomer containing 10 to 100 parts by weight of (meth) acrylate monomer having at least one hydroxyl group in one molecule, (G) polymerization initiator (F) 0.01 to 5 per 100 parts by weight of the component
Adhesion for bonding a resin composition containing 0 parts by weight and (H) a filler (F) component of 100 parts by weight to 10 to 200 parts by weight to a tooth surface A method is provided.

In the above curable resin composition, the component (F) has at least one hydroxyl group in one molecule (meta).
It is a (meth) acrylate-based monomer containing 10 to 100 parts by weight of the acrylate-based monomer. The (meth) acrylate-based monomer having at least one hydroxyl group in one molecule is, for example, the same (meth) acrylate-based monomer as the component (A) containing the adhesive composition already shown above. Can be used. Specifically, for example, in a mono (meth) acrylate monomer, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl. (Meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 1
0-hydroxydecyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate , Having an oxyethylene chain or an oxypropylene chain in the molecule such as tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.
Acrylate; 1,2- or 1,3- and 2,3-dihydroxypropane (meth) acrylate, N- (meth) acryloyl-2,3-dihydroxypropylamine, N- (meth) acryloyl-1,3- Examples thereof include dihydroxypropylamine.

Further, an addition product of glycidyl (meth) acrylate (GMA) and an aliphatic or aromatic polyol (including phenols) can be used, and more specifically, 1-phenoxy-2-hydroxypropyl (meth). ) Acrylate (HPPM), 1-naphthoxy-2-
Hydroxypropyl (meth) acrylate (HNP
M), an addition reaction product of 1 mol of bisphenol A and 2 mol of GMA (Bis-GMA), and the like. Among these, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate and the like are particularly preferably used. To be

The above-mentioned (meth) acrylate-based monomer having at least one hydroxyl group in one molecule is the other (meth)
It can be used as a mixture with an acrylate-based monomer.
Examples of (meth) acrylate-based monomers that can be used here include monofunctional or polyfunctional (meth) acrylate-based aliphatic esters such as methyl methacrylate, ethyl methacrylate, and hexamethylene glycol dimethacrylate, and ethylene glycol dimethacrylate. (Meth) acrylate,
Addition product 1 of ethylene oxide with diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroquinone or bisphenol A
(Meth) acrylate-based compound having an oxyethylene chain in the molecule such as a product obtained by reacting 2 mol of (meth) acrylic acid with 2 mol of 2,2,4-trimethylhexamethylene diisocyanate and 2-hydroxyethyl methacrylate 2 An example is a methacrylate-based monomer having a urethane bond in one molecule, which is similar to a molar adduct (UDMA). These (meth) acrylate-based monomers can be used alone or in combination.

The component (F) is 100 in total in the component (F).
The (meth) acrylate-based monomer having at least one hydroxyl group in one molecule is used in an amount of 10 to 100 parts by weight based on parts by weight. These (meth) acrylates can be used alone or in combination.

In the curable composition, the component (G) is a polymerization initiator. As such a polymerization initiator, a usual radical polymerization initiator can be used. As the radical polymerization initiator, for example, diacetyl peroxide, dipropyl peroxide, dibutyl peroxide,
Dicapryl peroxide, dilauryl peroxide, dilauryl peroxide, dibenzoyl peroxide,
p, p'-dichlorobenzoyl peroxide, p, p'-
Examples thereof include organic peroxides such as dimethoxybenzoyl peroxide, p, p'-dimethylbenzoyl peroxide and p, p'-dinitrodibenzoyl peroxide. Of these, dibenzoyl peroxide is preferred.

When this organic peroxide is used, for example, N, N-dimethylaniline, N, N-dimethyl p-toluidine, N, N-diethyl p-toluidine, N, N-dimethyl p-tert-butylaniline. , N, N-dimethylanisidine, N, N-dimethyl p-chloroaniline, and other aromatic amines are preferably used in combination to obtain a room temperature curing type. In addition, aromatic sulfinic acids such as benzenesulfinic acid, o-toluenesulfinic acid, p-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, chlorobenzenesulfinic acid, and naphthalenesulfinic acid, or salts thereof are used. It can also be used together.

As the polymerization initiator, other trialkylboron or its oxide may be used. Specifically, trialkyl boron, tripropyl boron, triisopropyl boron, tri-n-butyl boron, tri-n-amyl boron, triamyl boron, triisoamyl boron, tri-sec-amyl boron or a part thereof. It is possible to use a trialkylboron oxide which is oxidized. Among these, tri-n-butylboron or its partial oxide is preferably used.

The component (G) which is a polymerization initiator is (meth)
It is preferable to contain 0.01 to 50 parts by weight with respect to 100 parts by weight of the component (F) which is an acrylate-based monomer,
Further, it is particularly preferable that the amount is in the range of 0.05 to 40 parts by weight.

Among the curable compositions used in the present invention,
The component (H) is a filler. Examples of such fillers include inorganic fillers and organic composite fillers having an average particle size within the range of 0.01 to 100 μm.

Examples of the inorganic filler include silica, silica-alumina, alumina, quartz, glass (including barium glass), titania, zirconia, calcium carbonate, kaolin, clay, mica, aluminum sulfate, barium sulfate, calcium sulfate, and oxidation. Examples thereof include titanium and calcium phosphate.

Examples of the organic composite filler include the composite filler obtained by polymerizing the surface of the above-mentioned inorganic filler with a (meth) acrylate monomer. Specifically, among the composite fillers, there is mentioned a composite filler (TMPT · f) obtained by coating finely powdered silica by polymerizing it with a monomer having trimethylolpropane trimethacrylate as a main component and pulverizing this. it can.

These fillers can be used alone or in combination. In the above curable composition, the amount of the component (H) is 1 per 100 parts by weight of the component (F).
It may be contained in the range of 0 to 200 parts by weight, and particularly preferably in the range of 20 to 150 parts by weight.

[0042]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition,
In the examples, the adhesive strength was evaluated as follows.

Fresh bovine lower anterior teeth were extracted, frozen and stored in water, and used as a dentin sample. The thawed bovine tooth enamel and dentin are processed by the rotary polishing machine ECOMET.
-III (manufactured by BUEHLER) for water injection, water resistant emery paper under shiatsu 6
Grinding was carried out to No. 00 to obtain a smooth surface. 3 ground cow teeth
It was immersed in 7 ° C. water for 15 minutes. The bovine tooth was removed from the water and the water was removed with an air gun. The 10% by weight citric acid aqueous solution (10-3) containing 3% by weight ferric chloride as an etching agent was sufficiently dipped in the sponge and applied to the ground surface.
After a second, it was washed with water and dried with an air gun. The adhesive pretreatment composition of the present invention was applied to the surface and left to stand for 15 seconds, and then dried with an air gun until the adhesive pretreatment composition could not be visually recognized (about 20 seconds). On top of this, a 1 mm thick cardboard with a 5.1 mm diameter circular hole was placed and fixed in order to define the adhesion area. The hole was filled with the curable composition of the present invention and covered with a slide glass through a polyester film having a thickness of 50 to 100 μm. After 10 minutes, remove the slide glass and polyester film,
With Super Bond C & B (manufactured by Sun Medical Co., Ltd.), the cured product and the stainless steel rod were adhered to each other, allowed to stand for 15 minutes, immersed in water at 37 ° C. for 24 hours, and then subjected to a tensile adhesion test (crosshead speed 2 mm / min). .

First, examples and comparative examples of the adhesive pretreatment composition are described below. Example 1 As an adhesive pretreatment composition, 40 parts by weight of water, 50 parts by weight of 2-hydroxyethyl methacrylate (HEMA), 10 parts by weight of triethylene glycol dimethacrylate (3G), 4-methacryloyloxyethyl trimellitic anhydride. A solution in which 3 parts by weight of (4-META) and 5 parts by weight of N-phenylglycine (NPG) were dissolved was used.
This solution was low in storage stability, and if it was early, it became gel-like and could not be used within 15 minutes after preparation of the solution, so it was prepared immediately before use. As a curable composition, 65 parts by weight of HEMA, 35 parts by weight of 2.6E, and 0.5 parts by weight of N, N-dimethyl p-toluidine (DMPT) in 0.095 parts by weight of a solution, and 100 parts by weight. Part TMPT / f
And 0.085 parts by weight of a powdery agent comprising 2.5 parts by weight of benzoyl peroxide (BPO) were mixed immediately before use, and used in a state within 20 to 60 seconds after mixing. As a result of the adhesion test, the adhesion strength to dentin is 96 ±
It was 25 kgf / cm ² . The fracture had interfacial delamination with dentin in only one part, but most of the fracture was cohesive failure of the cured product.

Example 2 In Example 1, as an adhesive pretreatment composition, 50 parts by weight of HEMA in 40 parts by weight of water, 10 parts by weight of 3G,
A solution prepared by mixing 3 parts by weight of 4-META and 5 parts by weight of NPG in 95 parts by weight of ethanol (EtOH) at a ratio of 2: 1 (weight ratio) immediately before use was used. Others were the same as in Example 1. As a result of the adhesion test, the adhesion strength to dentin is 114 ± 67 kgf /
It was cm ² . The fracture had interfacial delamination with dentin in only one part, but most of the fracture was cohesive failure of the cured product.

Example 3 In Example 1, as an adhesive pretreatment composition, 40 parts by weight of water, 50 parts by weight of HEMA, 10 parts by weight of nonaethylene glycol dimethacrylate (9G), and 3 parts by weight of 4 were used. -Equivalent to Example 1 except that a solution prepared by dissolving META and a solution prepared by dissolving 5 parts by weight of NPG in 95 parts by weight of ethanol were mixed at a ratio of 2: 1 (weight ratio) immediately before use. I went to. As a result of the adhesion test, the adhesion strength to dentin was 91 ± 11 kgf / cm ² . The fracture had interfacial delamination with dentin in only one part, but most of the fracture was cohesive failure of the cured product.

Example 4 In Example 1, as an adhesive pretreatment composition, 50 parts by weight of HEMA in 40 parts by weight of water, 10 parts by weight of 3G,
3 parts by weight 4-META and 1.0 parts by weight BPO
Was performed in the same manner as in Example 1 except that a solution in which 5 parts by weight of NPG was dissolved in 95 parts by weight of ethanol was mixed at a ratio of 2: 1 (weight ratio) immediately before use. It was As a result of the adhesion test, the adhesion strength to dentin is 9
It was 5 ± 22 kgf / cm ² . The fracture had interfacial delamination with dentin in only one part, but most of the fracture was cohesive failure of the cured product.

Comparative Example 1 In Example 1, adhesion was carried out without using the adhesive pretreatment composition, and the adhesion strength to dentin was 18 ± 14 kg.
It was f / cm ² .

Comparative Example 2 In Example 2, as an adhesive pretreatment composition, 90 parts by weight of HEMA and 10 parts by weight of 3 were used without using water.
A solution prepared by mixing a solution of G, 3 parts by weight of 4-META and a solution of 95 parts by weight of ethanol with 5 parts by weight of NPG at a ratio of 2: 1 (weight ratio) immediately before use was used.
As a result, the adhesive strength to dentin is 33 ± 17 kgf / cm.
^{Was 2} . The fracture was the interfacial peeling between the dentin and the cured product.

Comparative Example 3 HEM was used as the adhesive pretreatment composition in Example 2.
Without using A, 40 parts by weight of water, 10 parts by weight of 3
A solution prepared by mixing a solution of G, 3 parts by weight of 4-META and a solution of 95 parts by weight of ethanol with 5 parts by weight of NPG at a ratio of 2: 1 (weight ratio) immediately before use was used.
As a result, the bond strength to dentin is 21 ± 15 kgf / cm.
^{Was 2} . The fracture was the interfacial peeling between the dentin and the cured product.

Comparative Example 4 In Example 2, 40 parts by weight of water and 50 parts by weight of HEM were used without using 3G as the adhesive pretreatment composition.
A: A solution in which 3 parts by weight of 4-META was dissolved and a solution in which 95 parts by weight of ethanol was dissolved in 5 parts by weight of NPG at a ratio of 2: 1 (weight ratio) immediately before use was used.
As a result, the bond strength to dentin is 71 ± 16 kgf / cm.
^{Was 2} . Part of the destruction includes cohesive destruction of the cured product,
Most were interfacial peeling between the dentin and the cured product.

Comparative Example 5 In Example 2, as the adhesive pretreatment composition, 4-M was used.
A solution of 40 parts by weight of water, 50 parts by weight of HEMA, 10 parts by weight of 3G and 95 parts by weight of 5 parts by weight of NPG dissolved in ETA without using ETA is used in a ratio of 2: 1 immediately before use. The solution mixed by (weight ratio) was used.
As a result, the bond strength to dentin was 52 ± 1 kgf / cm ²
Met. The fracture was the interfacial peeling between the dentin and the cured product.

Comparative Example 6 In Example 2, as the adhesive pretreatment composition, NPG was used.
Without water, 40 parts by weight water, 50 parts by weight HEM
A, 10 parts by weight of 3G and 3 parts by weight of 4-META were dissolved in the solution. As a result, the adhesive strength to dentin was 20 ± 15 kgf / cm ² .

Examples and comparative examples of the curable composition are described below. Example 5 As an adhesive pretreatment composition, 50 parts by weight of 2-hydroxyethyl methacrylate (HEMA), 10 parts by weight of triethylene glycol dimethacrylate (3G), and 3 parts by weight of 4-META were dissolved in 40 parts by weight of water. A solution was prepared by mixing 5 parts by weight of NPG in 95 parts by weight of ethanol and 2: 1 (weight ratio) of the solution immediately before use. As a curable composition, 65 parts by weight of HEMA,
35 parts by weight of 2-hydroxy-1,3-dimethacryloyloxypropane (GDMA), 0.5 parts by weight of DMP
0.095 parts by weight of a solution of T and 100 parts by weight of T
A powder consisting of MPT · f and 2.5 parts by weight of BPO.
Mix 085 parts by weight just before use, from 20 seconds to 60
I used the one within the second. The result of the adhesion test,
The adhesive strength to dentin was 126 ± 43 kgf / cm ² . The failure was cohesive failure of the cured product.

Example 6 Example 5 was repeated except that 3G was used instead of GDMA used in the curable composition.
As a result of the adhesion test, the adhesion strength to dentin is 106 ± 5.
It was ² kgf / cm ² . The failure was cohesive failure of the cured product.

Example 7 Example 5 was repeated except that UDMA was used instead of GDMA used in the curable composition. As a result of the adhesion test, the adhesion strength to dentin was 67 ±.
It was 10 kgf / cm ² . Some of the fractures were interfacial peeling between the cured product and dentin, but the others were cohesive fractures of the cured product.

Example 8 In Example 5, as a solution used as a curable composition, 65 parts by weight of 2-hydroxypropyl methacrylate (HPMA), 35 parts by weight of 2.6E and 0.5 parts by weight of DMPT were used. The same procedure as in Example 5 was carried out except that it was used. As a result of the adhesion test, the adhesion strength to dentin is 71 ±.
It was 9 kgf / cm ² . The fracture was a mixed fracture including both interfacial peeling of the cured product and dentin and aggregation of the cured product.

Example 9 In Example 5, the solution used as the curable composition was 25 parts by weight of MMA, 45 parts by weight of HEMA, 3 parts by weight.
The procedure of Example 5 was repeated except that 0 part by weight of 2.6E and 0.5 part by weight of DMPT were used. As a result of the adhesion test, the adhesion strength to dentin was 81 ± 13 kgf / cm ² .
The fracture was a mixed fracture including both interfacial peeling of the cured product and dentin and aggregation of the cured product.

Comparative Example 7 In Example 5, the solution used as the curable composition contained 65 parts by weight of ethyl as a solution containing no (meth) acrylate having at least one hydroxyl group in one molecule. The procedure of Example 5 was repeated, except that methacrylate (EMA), 35 parts by weight of 2.6E and 0.5 parts by weight of DMPT were used. The adhesive strength was 0 because it peeled off at the interface with the dentin during one day immersion in 37 ° C. water.

Comparative Example 8 In Example 5, the solution used as the curable composition was 100 parts by weight of 2 parts by weight as a solution containing no (meth) acrylate having at least one or more hydroxyl group in one molecule. Example 6 was repeated except that 0.6E, 0.5 parts by weight of DMPT was used. As a result of the adhesion test, the adhesion strength to dentin was 11 ± 7 kgf / cm ² .

The above results are summarized in Tables 1 and 2.

[0062]

[Table 1]

[0063]

[Table 2]

Example 10 The adhesive pretreatment composition was applied directly to the ground surface of bovine dentin without the use of an etching agent. As an adhesive pretreatment composition, 40 parts by weight of water in 50 parts by weight of HEMA, 10 parts by weight of
A solution of 3 parts by weight of 3G and 3 parts by weight of 4-META and a solution of 10 parts by weight of 5-MASA and 85 parts by weight of 5 parts by weight of NPG dissolved in 85 parts by weight of ethanol were added at a ratio of 1: 1 ( A solution mixed by weight ratio) was used. As the curable composition, 0.095 parts by weight of a solution comprising 59 parts by weight of HEMA, 9 parts by weight of GDMA, 32 parts by weight of 2.6E and 0.5 parts by weight of DMPT, and 100 parts by weight of TMPT. Just before use, mix 0.085 parts by weight of a powder consisting of f and 2.5 parts by weight of BPO to 20
The one in the state within 60 seconds from the second was used. Others were subjected to the adhesion test according to the above-mentioned examples. As a result of the adhesion test, the adhesion strength to dentin was 88 ± 27 kgf / cm ² .

Example 11 As an adhesive pretreatment composition, 40 parts by weight of water in 50 parts by weight of HEMA, 10 parts by weight of 9G and 3 parts by weight of 4-.
Solution in which META is dissolved and 10 parts by weight of 5-MASA
The same procedure as in Example 10 was performed except that a solution prepared by dissolving 5 parts by weight of NPG in 85 parts by weight of ethanol and a solution of 1: 1 (weight ratio) immediately before use was mixed. As a result of the adhesion test, the adhesion strength to dentin is 64 ± 48 kgf /
It was cm ² .

Example 12 As an adhesive pretreatment composition, 40 parts by weight of water in 50 parts by weight of HPMA, 10 parts by weight of 3G, 3 parts by weight of 4-ME.
5 parts by weight of a solution of TA and 1 part by weight of BPO in 10 parts by weight of 5-MASA and 85 parts by weight of ethanol.
Immediately before use, a solution in which 1 part by weight of NPG is dissolved is used in a ratio of 1: 1.
Example 10 except that a mixed solution (weight ratio) was used.
I went the same way. As a result of the adhesion test, the adhesion strength to dentin was 72 ± 32 kgf / cm ² .

Example 13 As an adhesive pretreatment composition, 40 parts by weight of water in 50 parts by weight of HPMA, 10 parts by weight of 3G and 3 parts by weight of 4-.
Solution in which META is dissolved and 10 parts by weight of 5-MASA
The same procedure as in Example 10 was performed except that a solution prepared by dissolving 5 parts by weight of NPG in 85 parts by weight of ethanol and a solution of 1: 1 (weight ratio) immediately before use was mixed. As a result of the adhesion test, the adhesion strength to dentin is 68 ± 12 kgf /
It was cm ² .

The above results are summarized in Table 3.

[0069]

[Table 3]

[0070]

EFFECTS OF THE INVENTION The adhesive pretreatment composition of the present invention can exert an excellent adhesive force on an adhesive when adhering a tooth, particularly dentin, to a resin and a resin composite material. Higher adhesion is obtained with the use of curable compositions.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yoshiko Ono 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd.

Claims (3)

[Claims] 1. A (meth) acrylate monomer having at least one hydroxyl group in one molecule (A), and a (meth) acrylate monomer having at least one carboxyl group in one molecule (B). Body, (C) the following general formula (I): A polyfunctional (meth) acrylate-based monomer represented by
(D) The following general formula (II): An adhesive pretreatment composition comprising an amine compound represented by: and (E) water. 2. In the adhesive pretreatment composition,
When the total of the components (A), (B), (C), (D) and (E) is 100 parts by weight, the component (A) is 1 to 95 parts by weight and the component (B) is 1 to 50 parts by weight. Part, (C) component is 1 to
The adhesive pretreatment composition according to claim 1, wherein the amount of the component (D) is 0.01 to 50 parts by weight, and the amount of the component (E) is 1 to 95 parts by weight. 3. After contacting the adhesive pretreatment composition with the surface of the tooth structure, (F) 10 to 100 parts by weight of a (meth) acrylate-based monomer having at least one hydroxyl group in one molecule. 100 parts by weight of (meth) acrylate monomer contained, 0.01 to 50 parts by weight to 100 parts by weight of component (G) polymerization initiator (F), and 100 parts by weight of component (H) filler (F). And a resin composition containing 10 to 200 parts by weight of the resin composition.