JPH0789820A - Primer composition - Google Patents

Abstract

PURPOSE:To provide a primer composition which is suitable for giving strong adhesion of a dental adhesive repairing material to the substrate such as hard tissues in living bodies, particularly natural tooth dentin or glass ionomer cement. CONSTITUTION:The primer composition comprises 5 to 70wt.% of water, (A) 5 to 90wt.% of a compound of the formula (R1 is H, methyl; R2 is 2 to 20 C alkylene), for example, 2-(meth)acryloxyethyl hydrogen maleate and (B) 5 to 70wt.% of a compound bearing an amide group and a hydroxy group, for example, N-methylolacryl-amide or N-(2-hydroxyethyl)methacrylamide. The composition may contain further radically polymerizable monomers. In addition to the dental field, the composition can be used in the fields of surgery, orthopedics, or plastic surgery, too.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to primer compositions. More specifically, the present invention relates to a case where a bonding material or a dental adhesive restorative material such as a composite resin is adhered to a base material such as enamel and dentin of natural tooth substance or dentin or glass ionomer cement, in particular, between the both. The present invention relates to a primer composition suitable for imparting strong adhesiveness to.

[0002]

2. Description of the Related Art In the field of dentistry, adhesion restoration by composite resin has become widespread with the progress of dentin adhesion technology. Adhesion to enamel 30-40
Since a strong adhesive force is obtained by the% phosphoric acid treatment agent, its clinical technique is being established. However, phosphating agents are clinically problematic with respect to dentin in terms of excessive demineralization of mineral components of the dentin and stimulation of pulp. Therefore, it is strongly desired to bond them without the acid treatment process.

Under such demand, in recent years, remarkable progress has been made on the bond strength of dentin. For example, the 1st International Congress on Dental Materials (International Congress on
Dental Materials: International
Congress on Dental Material
ls) 236-237 (1989) and Dental Engineering.
31-38 (1987), acid treatment of dentin was carried out, and then a solution A as a primer [70% 2-hydroxyethylmethacrylate (2-HEMA) + 6% o] was used.
-Methacryloxytyrosine amide (MTYA)] and B solution (2% glutaraldehyde aqueous solution) mixed with a primer, and methyl methacrylate (MMA) / partially oxidized tributylborane (TBB-O) resin provides high adhesive strength. It is reported that

For example, it is described that after the treatment with 40% phosphoric acid, the treatment with the mixed primer of the solutions A and B shows 164 kgf / cm ² . However, the bond strength of dentin without acid treatment was 48 kgf / cm ² , and the essential bond strength was not obtained. In other words, although this method has progressed in terms of adhesive strength, strictly speaking, the adhesive strength without acid treatment is still low, and in that sense, the essential adhesive strength to dentin has not yet been reached. Absent. This is acknowledged by the proponent of the above technique in the disclosure text.

Recently, a primer composition which does not require acid treatment, that is, a hard tissue primer composition containing water, a water-soluble film-forming agent and an acid salt has been proposed (Japanese Patent Laid-Open No. 1-58242). -113057).

However, when the primer composition is used for bonding the dentin of the tooth and the composite resin, the adhesive strength is greatly affected by the kind and blending amount of the acid salt. In some cases, this primer composition is used. There are drawbacks such as inferior adhesive strength when not in use.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is a bonding material for a hard tissue of a living body, in particular, a base material such as enamel and dentin of natural dentin or glass ionomer cement. An object of the present invention is to provide a primer composition suitable for imparting strong adhesiveness between dental adhesive restorative materials such as or a composite resin, when they are adhered.

[0008]

That is, the present invention provides water and the following structural formulas;

[Chemical 2] [I] (in the above formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 20 carbon atoms) and a compound having an amide group and a hydroxyl group in the molecule. A featured primer composition.

The primer composition of the present invention solves the problems of the prior art and enables bonding of a bonding material, a composite resin or the like to a base material such as enamel and dentin of living hard tissue, especially dentin or glass ionomer cement. When bonding the dental adhesive restorative material, strong adhesiveness can be imparted between the two.

Water is contained as an essential component in the composition of the present invention. Water is preferably clinically acceptable as a storage stability and medical ingredient, and is essentially free of impurities that are harmful to the components of the composition and the adhesive effect, and is preferably distilled water (or purified water) or ion-exchanged water (or Deionized water)
Is preferred.

The content of water is the amount obtained by subtracting the total content of compounds other than water from 100% by weight, and usually 5 to 70% by weight, preferably 40 to 70% by weight. If the content of water is less than 5% by weight, the adhesiveness will be reduced, and if it is more than 70% by weight, the solubility will be poor and the adhesiveness will be reduced.

The composition of the present invention also comprises a compound [I] represented by the following structural formula:

[Chemical 3] Is contained as an essential component.

In the above formula, R ₁ represents a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group or a propyl group. Of these, a hydrogen atom and a methyl group are preferable.

R ₂ represents an alkylene group having 2 to 20 carbon atoms. R ₂ is a lower alkyl group such as a methyl group or an ethyl group,
Or the residue of (meth) acrylic acid ester (CH ₂ ═C
_{(R 3) COO-R 4} -) ( wherein R ₃ is a hydrogen atom or a lower alkyl group, for example a methyl group, an ethyl group or a propyl group, R ₄ is an alkylene group such as methylene group, ethylene group May be present as a substituent.

The compound [I] may be synthesized by a 1: 1 molar reaction of maleic anhydride and hydroxyalkyl (meth) acrylate.

In the present invention, for example, methyl (meth) acrylate means methyl methacrylate and methyl acrylate.

The compound [I] used in the present invention is
Specifically, for example,

CH ₂ = CHCOO (CH ₂ ) ₂ OOC-CH =
CH-COOH

Embedded image CH ₂ ═CHCOO (CH ₂ ) ₃ OOC—CH═
CH-COOH

[Chemical 6]

[Chemical 7]

CH ₂ = CHCOO (CH ₂ ) ₄ OOC-CH =
CH-COOH

CH ₂ = CHCOO (CH ₂ ) ₅ OOC-CH =
CH-COOH

CH ₂ ═CHCOO (CH ₂ ) ₆ OOC-CH
= CH-COOH

CH ₂ = CHCOO (CH ₂ ) ₈ OOC-CH
= CH-COOH

CH ₂ = CHCOO (CH ₂ ) ₁₀ OOC-CH
= CH-COOH

CH ₂ = CHCOO (CH ₂ ) ₁₂ OOC-CH
= CH-COOH

CH ₂ = CHCOO (CH ₂ ) ₁₆ OOC-CH
= CH-COOH

CH ₂ = CHCOO (CH ₂ ) ₂₀ OOC-CH
= CH-COOH

CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₂ OOC
-CH = CH-COOH

CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₃ OOC
-CH = CH-COOH

[Chemical 18]

[Chemical 19]

CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₄ OOC
-CH = CH-COOH

CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₅ OOC
-CH = CH-COOH

CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₆ OOC
-CH = CH-COOH

Embedded image _{CH 2 = C (CH 3)} COO (CH 2) 8 OOC
-CH = CH-COOH

CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₁₀ OO
C-CH = CH-COOH

CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₁₂ OO
C-CH = CH-COOH

CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₁₆ OO
C-CH = CH-COOH

CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₂₀ OO
Examples of such compounds include C-CH = CH-COOH. Among the above compounds, 2- (meth) acryloxyethyl hydrogen malate represented by (Chemical formula 4) and (Chemical formula 16) is particularly preferable.

The compounding amount of the compound [I] used in the present invention is an amount obtained by subtracting the total compounding amount of the compounds other than [I] from 100% by weight, and usually 5 to 90% by weight, preferably 10 to 10% by weight. It is 60% by weight. If the amount is less than 5% by weight, the adhesiveness will decrease, and if it exceeds 90% by weight, the adhesiveness will decrease.

The composition of the present invention further contains a compound having an amide group and a hydroxyl group in the molecule as an essential component. Examples of such a compound include N-methylol (meth)
Acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (3-hydroxypropyl)
(Meth) acrylamide, N- (4-hydroxybutyl) (meth) acrylamide, N- (5-hydroxypentyl) (meth) acrylamide, N- (6-hydroxyhexyl) (meth) acrylamide, N- (10-hydroxy) Decyl) (meth) acrylamide, N- (2,
Examples thereof include mono- or di-hydroxyalkyl (meth) acrylamides such as 3-dihydroxypropyl) (meth) acrylamide, and hydroxyalkyl amides such as N-methylolethylamide. Among these, N-methylol acrylamide, N- (2-hydroxyethyl) methacrylamide, and N- (2,3-dihydroxypropyl) methacrylamide are particularly preferable.

The amount of the compound having an amide group and a hydroxyl group in the molecule is 10 based on the total amount of the compounds other than the compound.
It is the amount subtracted from 0% by weight and is usually 5 to 70% by weight,
It is preferably 10 to 50% by weight. If the amount is less than 5% by weight, the adhesiveness will be lowered, and if it is more than 70% by weight, the solubility will be poor and the adhesiveness will be lowered.

The composition of the present invention may further contain a radically polymerizable monomer. Examples of the polymerizable monomer include methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate. , Bisphenol A diglycidyl (meth) acrylate and urethane di (meth) acrylates may be mentioned, and they may be appropriately blended within a range in which they can be dissolved.

The composition of the present invention may further contain other additives. For example, so-called polymerization initiators such as camphorquinone and amines or peroxides and barbituric acid derivatives; organic solvents such as alcohol and acetone; antioxidants such as hydroquinone, methoxyhydroquinone and butylated hydroxytoluene, or viscosity such as colloidal silica. You may mix | blend a regulator. Viscosity modifiers are useful when used in gel form.

The primer composition according to the present invention is a composition suitable as an undercoat when adhering an adhesive restorative material, for example, hard tissues of living bodies, particularly enamel and dentin of natural dentin or glass ionomer cement. When bonding a bonding material or a dental adhesive restorative material such as a composite resin to the substrate, a strong adhesive property is given between the two. When using the primer composition of the present invention, it is also possible to divide it into two or more solutions.

The primer composition of the present invention is intended mainly for the field of dentistry, but is also highly versatile and can be used in other fields such as surgery, orthopedics and plastic surgery. Is.

[0025]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these.

Examples 1-5 and Comparative Examples 1-3 Distilled water, 2-acryloxyethyl hydrogen malate (2-AEM), N-methylol acrylamide (M
EAA), 2-hydroxyethyl methacrylate (2-
HEMA), 4-acryloxyethyl trimellitic acid (4-AET) and sodium chloride were blended as shown in Table 1 to prepare a primer composition.

The bond strength was determined by a shear bond test between bovine dentin and a composite resin. As the method, first, freshly extracted bovine front teeth were frozen and stored immediately after extraction, and thawed and used immediately before use. The enamel was removed by grinding under running water.

The dentin embedded in an acrylic resin tube having an inner diameter of 14 mm with an instant polymerization resin was polished under running water to a water-resistant abrasive paper No. 600, and dried with compressed air to obtain a dentine adherend.

A masking tape having a hole with an inner diameter of 6 mm was attached to the surface of the adherend thus prepared, a primer was applied to the tooth surface and left for 60 seconds. Then, after drying with compressed air, a bonding agent (Clearfill Photobond; manufactured by Kuraray Co., Ltd.) was applied and dried with compressed air.

Then, a Teflon tube having an inner diameter of 5 mm was inserted into the masking tape, a composite resin (Photoclear Fill A; made by Kuraray Co., Ltd.) was filled, and visible light was irradiated for 40 seconds by Grip Light II (made by Matsukaze Co., Ltd.).
After curing, the masking tape and the Teflon tube were removed to obtain a test body.

The prepared test piece was immersed in 37 ° C. water for 24 hours and then autographed (Minepia; TCM200 type)
Using a crosshead speed of 1 mm / min. The compressive shear bond strength was measured under the conditions of.

As a control, the case where the primer was not applied (Comparative Example 3) was also carried out.

[0033]

[Table 1]

Example 6 As a primer of the present invention, 70% by weight of distilled water, 2-acryloxyethyl hydrogen malate (2-AE)
20% by weight of M) and 10% by weight of N-methylol acrylamide (MEAA) were mixed and prepared.

Specimens were prepared according to Example 1 and the shear bond strength was measured. As a result, adhesive strength: 312 kgf /
It showed cm ² .

Example 7 As the primer of the present invention, 70% by weight of distilled water, 2-acryloxyethyl hydrogen malate (2-AE)
M) 10 wt% and N-methylol acrylamide (MEAA) 20 wt% were mixed and prepared.

Specimens were prepared according to Example 1 and the shear bond strength was measured. As a result, adhesive strength: 311 kgf /
It showed cm ² .

Comparative Example 4 70% by weight of distilled water and 30% by weight of N-methylol acrylamide (MEAA) were mixed and prepared as a primer.

Specimens were prepared according to Example 1 and the shear bond strength was measured. As a result, adhesive strength: 68 kgf / c
m ² was shown.

Example 8 As the primer A of the present invention, 30% by weight of distilled water, 2-
Acryloxyethyl hydrogen malate (2-AE
50% by weight of M) and 20% by weight of N- (2-hydroxyethyl) methacrylamide (EMA) were mixed and prepared.
Using this primer, a marginal leakage test was performed using freshly extracted bovine teeth as follows.

The enamel was removed to form a circular cavity with a diameter of 2.5 mm and a depth of 1.3 mm in the crown dentin, and a marginal leakage test body was prepared according to the procedure of Example 1.

The test sample was immersed in a 0.5% basic fuchsin aqueous solution at 37 ° C. for 24 hours and then cleaved from the central part of the cavity to evaluate the degree of leakage, and almost no dye penetration was observed.

Similarly, N- in the primer component concerned is
(2-hydroxyethyl) methacrylamide (EMA)
When the primer B prepared by substituting 20% by weight of N- (2,3-dihydroxypropyl) methacrylamide (DMA) for 20% by weight was subjected to the marginal leakage test and the leakage was evaluated, the dye was obtained. Almost no intrusion was seen.

On the other hand, from primer A to 2-AEM
If only the EMA is removed, or if only the EMA is removed, or if only the 2-AEM is removed from the primer B,
In all cases where only DMA was removed, serious dye penetration to the deep part was observed.

Examples 9 to 13 As the primer of the present invention, distilled water, 2-acryloxyethyl hydrogen malate (2-AEM) and N-
Methylol acrylamide (MEAA) was mixed and prepared according to the formulation shown in Table 2, and the shear adhesive strength was measured according to the method of Example 1. The results are shown in Table 2.

[Table 2]

Examples 14 to 16 and Comparative Example 5 In evaluating the enamel adhesion of the primer of the present invention, it was determined by a shear adhesion test of the enamel and the composite resin. The method was carried out in accordance with the method of Example 1 except that the dentin of Example 1 was replaced with enamel. Distilled water, 2-acryloxyethyl hydrogen malate (2-AEM) and N-methylol acrylamide (MEAA) were prepared as the primers in the formulations shown in Table 3 and the shear adhesive strength was measured. At the same time, the case where the primer of the present invention was not used was also performed. The results are shown in Table 3.

[0047]

[Table 3]

[0048]

INDUSTRIAL APPLICABILITY The primer composition according to the present invention is a composition suitable as an undercoat for adhering an adhesive restorative material, for example, hard tissues of living bodies, especially enamel and dentin of natural dentin or glass ionomer cement. When a bonding material or a dental adhesive restorative material such as a composite resin is adhered to a substrate such as, a strong adhesive property is given between the two.

Claims (7)

[Claims] 1. Water and the following structural formula; [I] (in the above formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 20 carbon atoms) and a compound having an amide group and a hydroxyl group in the molecule. A characteristic primer composition. 2. The primer composition according to claim 1, wherein the compound [I] is 2- (meth) acryloxyethyl hydrogen malate. 3. The compound having an amide group and a hydroxyl group in the molecule is selected from N-methylolacrylamide, N- (2-hydroxyethyl) methacrylamide, N- (2,3-dihydroxypropyl) methacrylamide or a mixture thereof. The primer composition according to claim 1, wherein 4. The primer composition according to claim 1, which contains water in an amount of 5 to 70% by weight. 5. The compound [I] according to claim 1 is added in an amount of 5 to 9
The primer composition according to claim 1, wherein the primer composition is contained in an amount of 0% by weight. 6. The primer composition according to claim 1, which contains at least one compound having an amide group and a hydroxyl group in the molecule in a proportion of 5 to 70% by weight. 7. The primer composition according to claim 1, which further contains a radically polymerizable monomer.