JPS60166603A - Adhesive composition for dental use - Google Patents

Abstract

PURPOSE:To provide the titled composition containing a polymer of a specific compound obtained by the reacting of glycidyl methacrylate and an amine compound, and capable of bonding firmly to the tooth for a long period even in a humid environment having severe temperature variation, e.g. in the oral cavity. CONSTITUTION:The objective composition contains the polymer of the compound of formula I (R1 is H, methyl or ethyl, R2 is phenyl which may be substituted with methyl, carboxyl or -CH2COOH, or group of formula II) obtained by the reaction of glycidyl methacrylate with an amine compound, or a copolymer of said compound and a polymerizable monomer selected from styrene, (meth)acrylic acid and its derivative. The compound of formula I is preferably 2-hydroxy-3- (N-methyl-N-phenylamino)propyl methacrylate, N-(2-hydroxy-3-methacryloxypropyl)-m-aminobenzoic acid, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a dental adhesive composition, and more particularly, the present invention relates to a dental adhesive composition that can be used as a dental adhesive composition itself, or as an orthodontic adhesive, or as a general component knot resin, etc. The present invention relates to a dental adhesive composition that can be used as an adhesive to enhance the adhesion between teeth and fillings and cleaning adhesives.

In recent years, Componot-Renone has been developed as an alternative to dental cements such as zinc phosphate cement and silicate cement for the treatment of teeth with caries. They are less susceptible to decay and can now be made in colors that are indistinguishable from natural teeth.

However, since composite resin does not essentially adhere to tooth enamel and dentin, over a long period of time, gaps may form between the tooth structure and the filled composite resin, causing secondary caries. It is easy to do so, and the result is that Componot-Lennon eventually falls out.

In the past, various adhesion enhancers (adhesive liners) have been developed to improve the adhesion between such component knot resins and cavity walls, and adhesive caries preventive fillers, orthodontic adhesives, etc. Various dental adhesive compositions have been proposed for the purpose of adhering to tooth structure, but many of them have problems such as durability in the oral cavity and operability during use. There are few materials that can strongly adhere to teeth over a long period of time in a humid environment with rapid temperature changes.

In view of the above circumstances, the present inventors conducted extensive research on dental adhesive compositions that have strong adhesive strength to teeth, and as a result, we found that the following general formula (1), which is a reaction product of glycitul methacrylate and an amine compound, (However, R1 represents a hydrogen atom, a methyl group, or an ethyl group, and R2 represents a phenyl group: a phenyl group substituted with a methyl group, a cal+j?xyl group, or a 10H2COOH group:
A polymer of the compound represented by formula (1) or a copolymer of this compound and other polymerizable monomers exhibits strong adhesion to teeth even in water. Even when it is used as a tooth filling material, it strongly adheres to the flesh wall, so there is no gap formation due to poor contact, and the filling material does not fall off.It can also be used as a liniment or adhesive for fillings such as Con4 Knot and Lennon. We have found that when used as an agent, it is suitable for the purpose of adhesion of tooth structure, as it can significantly improve the margin sealing properties and effectively suppress secondary caries, and has developed the present invention. This is what led to the eggplant.

That is, the present invention is based on the general formula (1) (where R4 is a hydrogen atom, a methyl group, or an ethyl group, and R2 is a phenyl group, a methyl group, a carboxyl group, or -CH2C00I). A polymer of the compound represented by () or one or more polymerizable polymers selected from this compound, tostyrene, acrylic acid and its conductor, and methacrylic acid and its derivatives.
A dental implant characterized by containing a copolymer with;
fffi products.

(5) The present invention will be explained in detail below.

The periodontal N composition according to the present invention is a polymer of the above-mentioned compound Fuseiji of the formula (1) or a copolymer of this compound and the above-mentioned other polymerizable monomer (hereinafter simply referred to as "polymer").
It is used as a filling material for teeth, an orthodontic adhesive, etc., or as a composite resin, etc. It is used for the purpose of adhesion to teeth, such as as an adhesive for adhering fillings and orthodontic adhesives to teeth.

Here, as the copolymer, a copolymer in which the compound represented by the formula (1) is copolymerized in a proportion of at least 1% by weight based on the component that can be copolymerized with the compound may be used.

In this case, as the compound of formula (1), for example, one or more compounds such as A to ■ shown specifically in the examples described below may be used, but in particular, A formula (6) is used. 2-hydroxy-3-(N-methyl-N-phenylamino)zolobyl methacrylate-118 N-(2-hydroxy-3-methacryloxyphenyl)-m-aminobenzoic acid; and 0
2-Hydroxy-3-mesitylaminonorobyl methacrylate, which does not play in the formula, has high adhesive strength and high durability in water, so it can be preferably used.

Note that compounds B and C are new compounds.

In the present invention, the compound of formula (0) is a polymer thereof (this (
1) The compound of formula 1 is contained in a dental adhesive composition as a homopolymer or a copolymer with other polymerizable monomers).

In this case, the other polymerizable monomer to be copolymerized with the compound of formula (1) is styrene, acrylic acid or its derivatives, methacrylic acid or its derivatives, examples of which include acrylic acid derivatives and methacrylic acid derivatives. Then, methyl acrylate and methacrylate, hydroxyethyl acrylate and methacrylate, ethylene glycol-diacrylate and methacrylate, zo- or tri- or tetraethylene glycol-diacrylate and methacrylate, glycizol acrylate and methacrylate, 2,2'-bis(acryloxy and methacrylate) roxyphenyl) f-ropane, 2,2'-bis(4-(3-
Acryloxy and methacryloxy)-2-hydroxyglopoxylphenyl], 1,3-butanediolnoacrylate and methacrylate, tetrahydrofurfuryl acrylate and methacrylate, triacrylic acid and trimethylolpromonomer methacrylate, bisoxyethylene Examples include bisphenol A cyacrylate and methacrylate.

Other components of the dental adhesive composition of the present invention may vary depending on the type of adhesive composition, purpose of use, etc., but known components that are commonly blended may be used depending on the type, purpose, etc. of the adhesive composition.

For example, when the composition of the present invention is used as an adhesive for bonding a tooth to a filling material such as a conventional composite or resin, K(1) in an organic solvent such as ethanol, ethyl ether, or chloroform may be used. It can be produced by containing 1 to 15 units of a polymer of the compound fi÷ of the formula or a copolymer of the compound of the formula (1) and other polymerizable monomers, and this can be coated as is (e.g. After the cavity is formed, the cavity is bonded and used by applying a method such as (9) applying the adhesive composition to a high grade material and then filling it with a predetermined filler. In addition, in this composition, if necessary, inorganic fillers such as silica, glass beads, alumina, quartz powder (preferably those with a particle size of 10,100 I or less), or γ-fillers may be added to these fillers to improve the bonding with the resin. Products treated with silane coupling agents such as methacryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, and vinyltrimethoxysilane, as well as curing agents, polymerization inhibitors, coloring agents, antioxidants, ultraviolet absorbers, etc. The desired ingredients can be blended.

Therefore, the dental adhesive composition according to the present invention has the above-mentioned (1).
The polymer of the compound of the formula has good adhesion to tooth structure and maintains high adhesion even in water or saliva. Therefore, it has good durability in the oral cavity, and when used as a filling material, it will firmly adhere to the tooth for a long period of time even in environments that are humid and subject to rapid temperature changes, such as the oral cavity. In addition, when used for the purpose of adhesion (10) as a coating (varnish) for composite resin, orthodontic adhesives, etc., it firmly adheres to the teeth, and the composite resin, orthodontic adhesive, etc. Therefore, the formation of gaps with the teeth is reliably prevented, the margin sealability is improved, and secondary caries can be prevented.

Hereinafter, the present invention will be specifically explained by showing experimental examples and examples. In addition, in the following examples, all parts indicate parts by weight.

[Experimental Example 1] A dental adhesive composition was prepared by dissolving the compound A-I shown below in ethanol at a concentration of 5%.

Next, the surface of the natural tooth filled with plaster in the holder and the acrylic rod 6 mm φ x 40 tones were polished to a constant smooth surface using a polisher, and then the smooth surface of the natural tooth was treated with 3M IJ acid for 30 seconds. 3
It was washed with water for 0 minutes and dried with compressed air.

Next, the dental adhesive composition was applied to the dried teeth, and after drying, the acrylic rod was adhered using an adhesive having the following formulation. For those stored at room temperature for one day and those stored in artificial saliva at 37°C for 7 days, the total contact strength was measured using a strograph (tensile speed 5/min). The results are shown in Table 1. Compound A: 2-hydroxy-3-(N-methyl-N-phenylamino)propyl methacrylate Compound B: N-(2-hydroxy-3-methacryloxypropyl)
-m-aminobenzoic acid OOH Compound C: 2-hydroxy-3-mesitylaminoglobil methacrylate Compound D: 2-hydroxy-3-p-)ruinono! Lobil methacrylate compound E: N-(2-hydroxy-3-methacryloxypropyl)
-α-phenylglycine R1-I (, R2-CHC0OH Compound F: N-(2-hydroxy-3-methacryloxypropyl)
-p-aminophenyl acetate Compound G: 2-hydroxy-3-(N-ethyl-N-phenylamino)propyl methacrylate (13) Compound H: N-(2-hydroxy-3-methacryloxyglobin )
-N-methylanthranilic acid compound I: 2-hydroxy-3-(N-methyl-N-o-tolylamino)-propyl methacrylate adhesive formulation (14) Weight ratio of (,) and (b) at the time of use Mix at a ratio of 1:1.

Table 1 According to the results shown in Table 1, it was found that the polymerized compound A-I provided the specified adhesive strength, and that the polymers of compounds A, B, and C were particularly effective. .

[Experimental Example 2] Based on the following formulation, 5 units each of Compound B or C (inventive compound) shown in Experimental Example 1 were used, and 2 polymerizable monomers copolymerizable with the inventive compound shown in Table 2 were used. ．．
Use 5% or 10% and dissolve them in ethanol,
Furthermore, dissolve 1 chloride of benzoyl 9-oxide in this,
A dental adhesive composition (4) was prepared by dissolving Compound B or C, the polymerizable monomer shown in Table 2, and benzoyl 9-oxide in ethanol.

Formula: Compound of the present invention: 5% Polymerizable monomer: 2.5% or 10% Benzoylno J? -Oxide 1% ioo, ochi Next, the adhesive properties of these dental adhesive compositions were evaluated in the same manner as in Experimental Example 1. In this case, when this composition comes into contact with the adhesive of Experimental Example 1, Compound B or C and the polymerizable monomer shown in Table 2 are copolymerized, resulting in copolymerization with Compound B or C as one copolymer component. A union is formed. Second result
Shown in the table. The results are 7 at 37℃ in artificial saliva.
These are the results for those stored for days.

Table 2 (17) HEPAk: Hydroxyethyl methacrylate EG
: Ethylene glycol-dimethacrylate TMP:) trimetherol pronoglyclate UTA: Urethane tetramethacrylate (bis(1)
, 3-dimethacryloyloxy-2-dironononotriyl)-N,N'-hexamethylenezocarnomate) ST: Styrene From the results in Table 2, a copolymer containing the compound of the present invention as one copolymerization component also appears. It is found that it has good adhesive properties.

[Experimental Example 3] 10 parts of methyl methacrylate, diethylene glycol
20 parts of dimethacrylate, bisphenol-A-diglycinol methacrylate? 50 parts and 35.0 parts of glass powder having a particle size of 100μ or less that had been subjected to 7-run cut-throwing treatment were mixed well and divided into two equal parts. -(18) on the side of N-(2-hydroxy-3-methacryloxyzolobyl)-m-aminobenzoic acid (the above compound B
) and 72 parts of N,N-trimethyl-p-toluiso, and after adding 2 parts of benzoyl peroxide to the other,
Both were mixed. Using this, as in Experimental Example 1, the acrylic rod was bonded to the smoothed tooth surface.
When its adhesive strength was measured using a strograph, it showed an average adhesive strength of 75 kg/(:In2) after being stored in water for one week.

In addition, when 2-hyProxy 3-mesitylaminoglobil methacrylate was used, it was 85 Kfl/cIIL.
It showed an adhesive strength of .

[Experimental Example 4] Diameter 49mm on the labial surface of an extracted human tooth. A cavity with a depth of 2-2.5 m was formed and its wetted walls were etched with 3M phosphoric acid for 30 seconds. Next, N-(2-hydroxy-3-methacryloxyzolobyl)-m-aminobenzoic acid (
10 parts of the compound B), 60 parts of methyl methacrylate,
After applying a thin layer to the above-mentioned liquid solution consisting of 30 parts of tetraethylene glycol-dimethacrylate, Adazotic (trade name, manufactured by Noyonson & Co., Ltd.) was filled. 30 minutes after filling, store in water at 37°C, and after 1 day, store at 4°C and 6°C.
The edge-sealing property was tested by performing a 9-Koleshi test, in which the sample was immersed in an aqueous Tsukusin solution at 0° C. 60 times for 1 minute alternately. The extracted tooth was cut at the center and examined to see if there was any pigment (tsukushin) intruding between the wet wall and the filling, but no pigment was found, and good results were obtained.

In addition, in an example in which Adaptik was directly filled without treatment with a liquid containing the compound B, the pigment (tsukushin) penetrated to the deep dark dentin or the high base.

Therefore, it was found from Experimental Examples 3 and 4 that the polymer of the compound of the present invention provides good adhesion.

[Example of real power]

Compounds A, B, C1 shown in Experimental Example 1? were dissolved in 6d of polymerization solvents shown in Table 2, and 6d under a nitrogen stream using 10I of azoisobutylnitrile as a polymerization initiator.
Polymerization was carried out at 0° C. for 5 hours.

The obtained polymer was purified using the reprecipitation solvent shown in Table 2, and 8 g of this was dissolved in the same solvent as the polymerization solvent shown in Table 2 to prepare a 30% solution of the polymer.

Table 2 Next, using a 30% solution of the above polymer, the adhesive strength of each was measured in the same manner as in Experimental Example 1 (after being stored at room temperature for one day). The results are shown in Table 3.

Table 3 From the above results, the adhesiveness of the composition of the present invention is excellent (21) It turned out that

Next, methods for producing compounds B and C, which are new compounds, will be shown as reference examples.

[Reference Example 1] N-(2-Hydroxy-3-methacryloxyzolobyl)-m-aminope In a TOOMZ eggplant flask equipped with a reflux device, 5011 L of methyl alcohol and 5.48 iP (0.04 mol) of m-aminobenzoic acid were added. , glycidyl methacrylate 7,10y-(,0.05 mol) and hydroquinone 0.1 are added and the mixture is refluxed for 6 hours with stirring. After the reaction mixture was returned to room temperature and the methyl alcohol was distilled off under reduced pressure, the residual liquid was dissolved in 40-mL IN aqueous sodium hydroxide solution, and then extracted three times with 30 portions of diethyl ether to remove unreacted glycerin. The methacrylate was removed to the ether phase. After separating the aqueous phase, the pH was adjusted to 4.5 using a 2N aqueous hydrochloric acid solution to separate an oily substance.

Next, this oily substance was extracted with 50 d of ethyl acetate, the ethyl acetate layer was separated and dried over nesium sulfate (22), and the ethyl acetate was distilled off under reduced pressure to give a pale yellow color. A crude crystal of was obtained. Furthermore, it was recrystallized from diethyl ether to give white crystals with a melting point of 115.0 to 118.0°C (
N-(2-hydroxy-3-methacryloxyprobyl-
m-aminobenzoic acid]2.0 was obtained. Yield: 18q6゜ [Reference Example 2) 2-Hydroxy-3-mesitylamine (dalicidyl methacrylate) in a 3Qml eggplant flask equipped with a reflux device) 1.42 iP (0.01 mol), 2.4.6-
1.35 f (0.01 mol) of dolimethylaniline and 10 kg of hydroquinone were added, and the mixture was heated to 2.0 g with stirring.
It was heated at 70-80°C for 4 hours. The reaction mixture was returned to room temperature and treated with Silica Dal (Wakodal C-200, trade name) 5
Column (3 cm in diameter x 20 cm in length) packed with
The target substance was separated using the following method. That is, benzene: methyl alcohol [mixing ratio 10:1 (volume ratio)]
Oil-like substance (boiling point 155.0~
157.0°C/0.2 wHg)2.4P was obtained. Yield 86.6%.

Further, after returning the reaction mixture to room temperature, distillation under reduced pressure is carried out,
155.0~157.0℃70.2mHg (It can also be synthesized by obtaining the D fraction. (Yield! 0.6j?,
Yield: 21.7cm) Applicant: Lion Corporation Agent Takashi Kojima

Claims (1)

[Claims] 1. General formula (1) (However, R1 represents a hydrogen atom, a methyl group, or an ethyl group, and R2 is a phenyl group: a methyl group, and Cal is substituted with a xyl group or a -CH2C0OH group. It is characterized by containing a polymer of a compound represented by FUE or a copolymer of this compound and one or more polymerizable monomers selected from styrene, acrylic acid and its derivatives, and methacrylic acid and its derivatives. Dental adhesive composition. 2. The compound of general formula (1) is 2-hydroxy-3-(N
-Methyl-N-phenylamino)propyl methacrylate, N-(2-hydroxy-3-methacryloxyzolobyl)-m-aminobenzoic acid, and 2-hydroxy-3-mesitylaminozolopyl methacrylate The dental adhesive composition according to claim 1.