JP2922358B2 - Adhesive pretreatment composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an adhesive pretreatment composition. More specifically, the present invention relates to an adhesive pretreatment composition which exhibits excellent adhesion performance to dentin particularly in dental treatment and has no adverse effects such as irritation to dental pulp.

[0002]

2. Description of the Related Art In the field of dental treatment, for preserving and restoring teeth, it is essential to bond tooth material with a polymer material, metal, dental porcelain, or the like. In order to achieve sufficient adhesive strength, various techniques have been proposed for pretreatment agents, adhesives, and the like. At the time of bonding to dentin, especially to dentin, surface treatment is generally performed by acid etching in order to improve adhesion, and typical dentin etching agents include phosphoric acid, citric acid and metal salts Aqueous solution, EDT
A aqueous solution or the like is used. However, since the acid treatment demineralizes healthy dentin and opens the dentin tubules, there is concern about secondary infection and dental pulp irritation. Under such circumstances, the emergence of an adhesive pretreatment agent composition that exhibits excellent adhesiveness to dentin and has no adverse effects such as irritation to dental pulp is desired.

[0003]

It is an object of the present invention to provide a novel adhesive pretreatment composition. Another object of the present invention is to solve the problems associated with the prior art as described above, and exhibits excellent adhesion to dentin, particularly to dentin, and to irritating pulp. An object of the present invention is to provide an adhesive pretreatment agent having no adverse effect. Still other objects and advantages of the present invention will be apparent from the following description.

[0004]

According to the present invention, the above objects and advantages of the present invention are as follows. First, (A) at least one hydroxyl group and (meth) acryloyl group in one molecule. A polymerizable monomer, (B) a polymerizable monomer having at least one (meth) acryloyl group and a carboxyl group in one molecule, (C) a compound represented by the following general formula (I)

[0005]

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An adhesive pre-treatment composition comprising a polyfunctional (meth) acrylate monomer represented by the formula (I), a visible light polymerization initiator (D), and water (E). Achieved by

[0007] The composition of the present invention has an affinity for dentin, shows high penetrative power to dentin, especially dentin, and can be polymerized from the inside of dentin, and furthermore, It has excellent adhesion and no adverse effects such as irritation to dental pulp.

[0008] In the composition of the present invention, the component (A) comprises 1
It is a polymerizable monomer containing at least one hydroxyl group and (meth) acryloyl group in the molecule. Such monomers include, for example, 2-hydroxyethyl (meth) acryl
3-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2-hydroxypropyl-1, 3-Di (meth) acrylate is preferably used.

The component (B) is a polymerizable monomer having at least one (meth) acryloyl group and a carboxyl group in one molecule. As such a monomer, an aromatic polycarboxylic acid having at least one (meth) acryloyl group in one molecule is preferably used. Examples of the component (B) include 4- (meth) acryloyloxymethoxycarbonylphthalic acid, 4- (meth) acryloyloxyethoxycarbonylphthalic acid, 4- (meth) acryloyloxybutoxycarbonylphthalic acid, and 4- [2-hydroxy -3- (meth) acryloyloxypropoxycarbonyl] phthalic acid, 2,3-bis (3,4-dicarboxybenzoyloxy) propyl (meth) acrylate, 2
-(3,4-Dicarboxybenzoyloxy) 1,3-dimethacryloyloxypropane, 4-methacryloylaminosalicylic acid, 5-methacryloylaminosalicylic acid, 4-methacryloxysalicylic acid, 5-methacryloxysalicylic acid and the like are preferably used.

The component (C) is a polyfunctional (meth) acrylate monomer represented by the general formula (I).

In the general formula (I), R ¹ and R ² independently represent a hydrogen atom or a methyl group.

A is -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _l-
(L is 0 or a positive integer), or — (CH ₂ CH ₂ O) _n —R ³ — (OCH ₂ CH ₂ )
_m- (R ³ represents a divalent aromatic group having at least one aromatic ring and optionally containing an oxygen atom, and n and m each represent a positive integer) is there.

The polyfunctional (meth) represented by the above formula (I)
As the acrylate monomer, for example, ethylene glycol
, Diethylene glycol, triethylene glycol,
Preferred are di (meth) acrylates such as polyethylene glycol; 2,2-bis (4-methacryloxyethoxyphenyl) propane, and 2,2-bis (4-methacryloxypolyethoxyphenyl) propane. It can be mentioned as.

The component (D) is a visible light polymerization initiator. The visible light polymerization initiator is preferably an α-diketone, and typical examples include diacetyl, benzyl, camphor-quinone, and the like. Particularly, camphor-quinone derivatives having affinity for the tooth substance are preferably used. Can be Such compounds include, for example, 7,7-dimethyl-2,3-
Suitable compounds include dioxobicyclo [2.2.1] heptane-1-carboxylic acid, 10-hydroxycamphor-quinone and the like.

The component (E) is water.

The composition of the present invention comprises the above (A), (B),
For each component of (C), (D) and (E), based on the total weight of these components (A), (B), (C), (D) and (E), 1 ~ 90% by weight,
Component (B) is 1 to 50% by weight, component (C) is 1 to 90% by weight, component (D) is 0.01 to 10% by weight and (E)
Advantageously, the components are contained at from 10 to 90% by weight. More preferably, the component (A) is 20 to 60% by weight, the component (B) is 1 to 10% by weight, the component (C) is 5 to 20% by weight, and the component (D) is 0%. .05-0.5
% By weight, and the component (E) is 30 to 60% by weight.

In this case, an amine compound (F) can be added as a polymerization accelerator. Therefore, according to the present invention, secondly, an adhesive pretreatment composition further comprising (F) an amine compound in addition to the above five components (A) to (E) is provided.

The amine compound (F) is preferably an aromatic amine or an aliphatic amine. Suitable aromatic amines are substituted aromatic amines represented by the following formula (II).

[0019]

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Specific examples of such substituted aromatic amines include, for example, 4-dimethylaminobenzaldehyde,
Aldehydes such as diethylaminobenzaldehyde, 4- (methylphenylamino) benzaldehyde, 4- (β-hydroxyethylamino) benzaldehyde;

4-dimethylaminobenzoic acid, 4-diethylaminobenzoic acid, 4- (methylphenylamino) benzoic acid, 4- (β-hydroxyethylmethylamino) benzoic acid, methyl 4-dimethylaminobenzoate, 4-diethylamino Benzoic acid derivatives such as methyl benzoate, methyl 4- (methylphenylamino) benzoate, propyl 4- (β-hydroxyethylmethylamino) benzoate and phenyl 4-dimethylaminobenzoate;

Phthalic acid derivatives such as 4-dimethylaminophthalic acid and dimethyl 4-dimethylaminoisophthalate; N, N-dimethylaniline, N, N-dimethyl-p
-Toluidine, N, N-di (hydroxyethyl) -p-
Toluidine, N, N-dimethylcyanoaniline, N, N-
Dimethylnitroaniline, N, N-dimethylchloroaniline, N, N-dimethylbromoaniline, N, N-dimethyl-o-iodoaniline, N, N-diercyanoaniline, N, N-diethyl-p-chloroaniline, N, N-dipropyl-p-cyanoaniline, N, N-methylphenyl-p-cyanoaniline, N, N-β-hydroxyethylmethyl-p-chloroaniline, N, N-dimethyl-2,
Examples include aniline compounds such as 4-dicyanoaniline, N, N-dimethyl-2,4-dinitroaniline and N, N-dimethyl-2,4-dichloroaniline.

Also, amino acid derivatives such as N-phenylglycine and N-methylglycine; and aliphatic tertiary compounds such as (N, N-dimethylamino) ethanol, N, N-dimethylaminoethyl methacrylate and N, N-diethylamino methacrylate. Secondary amines are also preferred.

Of these, amine compounds having a carboxyl group and / or a hydroxyl group are preferably used. Examples of such amine compounds include N-phenylglycine, N, N-dimethylaminobenzoic acid, N, N-diethylaminobenzoic acid, N, N-di (hydroxyethyl) -p-toluidine, N-methylglycine,
(N, N-dimethylamino) ethanol and the like can be mentioned. Of these, N, N-diethylaminobenzoic acid is particularly preferred.

Further, the amine compound (F) is composed of
It is preferably used at a rate of 0.01 to 10% by weight, particularly preferably 0.05 to 0.5% by weight, based on the total weight of the component (E) and the amine compound (F).

[0026]

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.

The bovine anterior dentin or enamel was water-injected with a rotary grinder (ECOMAT III, manufactured by BUEHLER) and ground to a water-resistant emery paper No. 600 under finger pressure to obtain a smooth surface. Soak the ground bovine teeth in water at 37 ° C for 15 minutes,
An adhesive sample was used. Adhesive pre-treatment agent composition with 3 tooth surfaces
It was treated for 0 seconds and air blown for 5 seconds. Then, a photopolymerizable adhesive was applied with a sponge, and irradiated with light for 20 seconds using a visible light irradiator (TransluxCL, manufactured by Kulzer). Subsequently, cardboard having a thickness of 1 mm and a circular hole having a diameter of 5.1 mm was adhered thereto, and a composite resin (Silux, manufactured by 3M) was packed therein and irradiated with light for 1 minute. An acrylic rod was attached to the cured composite resin with an immediate heavy-duty resin (manufactured by Sun Medical Co., Ltd., Metafast), immersed in water at 37 ° C. for 24 hours, and then 2 mm / min using a universal testing machine manufactured by Instron.
A tensile test was performed at a tensile speed of.

Example 1 In 60 parts by weight of water, 30 parts by weight of 2-hydroxyethyl methacrylate (HEMA) and polyethylene glycol (n) were used.
= 9) 10 parts by weight of dimethacrylate (9G), 4-methacryloyloxyethoxycarbonylphthalic acid (4-M
ET) 3 parts by weight, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxylic acid (CAC
Q) 0.1 part by weight, N, N-diethylaminobenzoic acid 0.1 part by weight.
One part by weight (DEABA) was dissolved to obtain an adhesive pretreatment composition. Also, 2,2-bis (4-methacryloxypolyethoxy (n + m = 10) phenyl) propane (10
E) 0.5 parts by weight of 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxylic acid and 0.5 parts by weight of N, N-diethylaminobenzoic acid per 75 parts by weight And 25 parts by weight of methyl methacrylate were dissolved to obtain an adhesive. An adhesion experiment was performed using the adhesive pretreatment composition and the adhesive. After bonding to dentin, 143
An adhesive strength of kg / cm ² was obtained.

Example 2 The procedure of Example 1 was repeated, except that the amount of 4-MET in the pretreatment composition was changed to 5 parts by weight, and the adhesion was 108 kg / cm ^2. Was.

Example 3 The procedure of Example 1 was repeated, except that the amount of 4-MET in the pretreatment composition was changed to 7 parts by weight. The result was that the adhesive strength was 133 kg / cm ^2. Was.

Example 4 In Example 1, the N, N-
When the same procedure as in Example 1 was carried out except for removing diethylaminobenzoic acid, the adhesive strength was 124 kg / cm ² .

Example 5 50 parts by weight of water, 40 parts by weight of HEMA, 10 parts by weight of triethylene glycol dimethacrylate (3G), 4-M
5 parts by weight of ET, 0.1 parts by weight of camphorquinone, DEA
When the same procedure as in Example 1 was carried out except that the adhesive pretreatment composition in which 0.1 part by weight of BA was dissolved was used, the adhesive strength was 121 kg / cm ² .

Example 6 50 parts by weight of water, 40 parts by weight of HEMA, 10 parts by weight of triethylene glycol dimethacrylate (3G), 4-M
When the same procedure as in Example 1 was carried out except that the adhesive pretreatment composition in which 5 parts by weight of ET and 0.1 part by weight of camphorquinone were dissolved was used, the adhesive strength was 105 kg / cm ² .

Comparative Example 1 In Example 1, when the dentin was not treated with the pretreatment agent and the adhesive was directly applied to the dentin, the adhesive strength was 17 kg / cm ² .

Comparative Example 2 In Example 1, the pretreatment composition was changed to 60 parts by weight of water and HE
When the same procedure as in Example 1 was carried out except that 30 parts by weight of MA, 10 parts by weight of 9G, 0.1 part by weight of CACQ, and 0.1 part by weight of DEABA were used, the adhesive strength was 61 kg / cm ² .

Comparative Example 3 In Example 1, the pretreatment composition was changed to 70 parts by weight of water, HE
MA 30 parts by weight, 4-MET 3 parts by weight, CACQ 0.2
When the same procedure as in Example 1 was carried out except that 1 part by weight and 0.1 part by weight of DEABA were used, the adhesive strength was 71 kg / cm ² .

COMPARATIVE EXAMPLE 4 In Example 1, 70 parts by weight of water, 9 G
When the same procedure as in Example 1 was carried out except that 30 parts by weight, 3 parts by weight of 4-MET, 0.1 parts by weight of CACQ and 0.1 parts by weight of DEABA were carried out, the adhesive strength was 48 kg / cm ² . .

Comparative Example 5 In Example 1, the pretreatment composition was changed to 60 parts by weight of water, HE
Except that 30 parts by weight of MA, 10 parts by weight of 9G, and 3 parts by weight of 4-MET were carried out in the same manner as in Example 1,
The adhesive strength was 77 kg / cm ² .

[0039]

EFFECT OF THE INVENTION The adhesive pretreatment composition of the present invention does not damage healthy dentin when bonding dentin, especially dentin, to other substances, and has an adhesive force due to shrinkage at the bonding interface. Can be suppressed, the adverse effects such as irritation to the dental pulp can be eliminated, and excellent adhesive strength can be exhibited.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-63-221181 (JP, A) JP-A-62-231652 (JP, A) JP-A-3-240712 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) A61K 6/00

Claims (4)

(57) [Claims] (A) a polymerizable monomer having at least one hydroxyl group and a (meth) acryloyl group in one molecule; and (B) at least one (meth) acryloyl group in one molecule. And a polymerizable monomer having a carboxyl group, and (C) the following general formula (I): An adhesive pretreatment agent composition comprising a polyfunctional (meth) acrylate monomer represented by the formula: (D) a visible light polymerization initiator, and (E) water. 2. Component (A) is 1 based on the total weight of components (A), (B), (C), (D) and (E).
-90% by weight, component (B) 1-50% by weight, component (C) 1-90% by weight, component (D) 0.01-10% by weight and component (E) 10-90% by weight The adhesive pretreatment composition according to claim 1, wherein the composition comprises: (A) a polymerizable monomer having at least one hydroxyl group and (meth) acryloyl group in one molecule; (B) at least one (meth) acryloyl group in one molecule. And (C) a polymerizable monomer having a carboxyl group, and (C) the following general formula (I): An adhesive pretreatment agent comprising a polyfunctional (meth) acrylate monomer represented by the formula: (D) a visible light polymerization initiator, (E) water and (F) an amine compound. Composition. 4. The method according to claim 1, wherein (A), (B), (C), (D),
Based on the total weight of components (E) and (F), (A)
1 to 90% by weight of the component, 1 to 50% by weight of the component (B),
The component (C) is 1 to 90% by weight, and the component (D) is 0.01 to 90% by weight.
10% by weight, 10 to 90% by weight of component (E), and 0.1% by weight of component (F).
2. The adhesive pretreatment composition according to claim 1, wherein the composition comprises from 0.01 to 10% by weight.