JPS58170737A - Propyl methacrylate derivative and polymerizable monomer for dental adhesive composition composed of said compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula (when R<1> is H, then R<2> is H and R<3> is halogen, n-butyl or ethoxycarbonyl, or R<2> is ethoxycarbonyl and R<3> is H; when R<1> is cyclohexyl, then R<2> and R<3> are H). EXAMPLE:2-Hydroxy-3-p-fluorophenylaminopropyl methacrylate. USE:Polymerizable monomer for dental adhesive composition. The polymer derived from the compound of formula I has high adhesivity to the tooth. PROCESS:The exemplified compound can be prepared by dissolving glycidyl methacrylate, p-fluoroaniline and p-hydroquinone in methyl alcohol, and refluxing the solution for 20hr under stirring.

Description

Detailed Description of the Invention The present invention is based on the following general formula (1) (provided that when R1 is a hydrogen atom, R2 is a hydrogen atom and R is a halodane atom, n-butyl group, or ethoxycartenyl group, or R2 is an ethoxylic group, R3 is a hydrogen atom, and when R' is a cyclohexyl group, R2 and R5 are both hydrogen atoms.) A new compound zorovyl methacrylate derivative and a dental use comprising the compound The present invention relates to a polymerizable monomer for adhesive compositions.

In recent years, conduit resin 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 corrosion and decomposition, and can now be made in colors that are indistinguishable from natural teeth.

However, since conduit resin does not essentially adhere to tooth enamel and dentin, gaps may form between the cavity and the filled conduit resin over a long period of time. It is easy to develop caries and eventually the conduit
This also results in the resin falling off.

Conventionally, various adhesion improvers and adhesive liners have been developed to improve the adhesion between conduit resins and window walls, as well as adhesive caries-preventing plugging agents and dental sconces. A variety of dental adhesive compositions have been proposed that aim to firmly adhere to tooth structure.
Many of them have problems with durability in the oral cavity and operability during use, and there are few that adhere strongly to the teeth for a long period of time under a circular mound, which is humid and subject to rapid temperature changes like the inside of the oral cavity. .

In view of the above circumstances, the present inventors conducted extensive research into compounds that have strong adhesive strength to teeth and can be suitably used as polymerizable monomers in dental adhesive compositions, and as a result, the following results were found: General formula (1) (However, when R1 is a hydrogen atom, R2 is a hydrogen atom, R5
is a di-rhodan atom, an n-+ thyl group, or an ethoxycaryl group. When R2 is an ethoxycaryl group, R5 is a hydrogen atom, and R1 is a cyclohexyl group, R2 and Rs are both hydrogen atoms. be. ) and discovered a new compound, zorovyl methacrylate derivative, as shown in
These compounds are polymerized and hardened and exhibit strong adhesion to teeth even in water, resulting in the above-mentioned (1)
Polymers of the compound represented by the formula or copolymers of the same compound with other polymerizable monomers, even when used as tooth filling materials, adhere strongly to the window wall and therefore have poor adhesion. There is no formation of gaps or falling off of the filler, and even when used as a coating or adhesive for fillers such as conduits and resins, it can significantly improve the edge sealing properties and prevent secondary caries. The inventors have now discovered that the compound of formula (1) can be used as a polymerizable monomer for dental adhesive compositions by effectively suppressing the effects of oxidation, thereby leading to the present invention.

Therefore, an object of the present invention is to provide a novel compound represented by the above formula (1) and a polymerizable monomer for a dental adhesive composition comprising the compound. There is a particular thing.

The present invention will be explained in more detail below.

The novel compound lqpyr methacrylate derivative of the present invention is represented by the above formula (1), and more specifically contains the following compound.

(1) It is a white needle crystal with a melting point of 66-67.5℃ and is represented by the following formula (2).
2-Hydroxy-3-p-fluorophenylaminozorobyl methacrylate.

(b) 2, which is a white needle crystal with a melting point of 68.5-70°C represented by the following formula (3)
-Hydroxy-3-P-chlorophenyla azunozolovir methacrylate.

(c) 2-Hydroxy-3-p-l = nibutylphenylaminopropyl methacrylate (d) which is a slightly colored crystal with a stone melting point of 51-52°C and is represented by the following formula (4) % formula (4) Boiling point 185-189℃/0.5txH shown by formula (5)
2-Hydroxy-3-(N-cyclohexylanilino)propyl methacrylate of K.

(・) Ethyl N-(
2-hydroxy-3-methacryloyloxyzolovir)
p-Aminobenzoate.

(f) Ethyl N-((
2-hydroxy-3-methacryloyloxyzolovir)
O-aminobenzoate.

The above-described compound of formula (1) can be produced, for example, by reacting glycidyl methacrylate with a corresponding aniline derivative.

The compound of the present invention can be used as a polymerizable monomer in a dental adhesive composition in which the polymerizable monomer is polymerized. In this case, the compound of formula (1) can be used alone as a polymerizable monomer, but it can also be used as a component with other polymerizable monomers, and when used, it is polymerized and cured. In this way, a polymer of the compound of formula (1) or a copolymer with other polymerizable monomers or the like is formed and bonded to the tooth.

The dental adhesive composition containing at least one compound of the formula (1) can be used as a filling material for teeth, an adhesive for orthodontics, or as a filling agent or orthodontic agent such as a dental implant, orthodontic treatment. It can be used for the purpose of adhesion to teeth, such as being used as an undercoat (coating agent) as an adhesive for adhering adhesives etc. to teeth.

In addition, when the compound of formula (1) is used as a polymerizable monomer of a dental adhesive composition, other components of this dental adhesive composition will vary depending on the type of adhesive composition, purpose of use, etc. However, depending on the type, purpose, etc., known components that are commonly blended may be used.

For example, when using a dental adhesive composition as an adhesive filler, only the compound of formula (1) is used as a polymerizable monomer, and the compound is polymerized and cured in the presence of a curing agent before use. Although it can also be used as an adhesive filler, it is preferable that at least one of the compounds of formula (1)
A method is adopted in which the seeds are mixed with other polymerizable monomers and polymerized and cured in the presence of a curing agent at the time of use.

In this case, other polymerizable monomers that can be used in combination with the compound of formula (1) may be monofunctional or polyfunctional, such as methyl acrylate and methacrylate, hydroxyethyl acrylate, and methacrylate,
Ethylene glycol diacrylate and methacrylate, di- or tri- or tetraethylene glycol cyacrylate and methacrylate, glycidyl acrylate and methacrylate), 2,2'-bis(acryloxyphenyl) f C1/, 2,2'-bis (methacryloxyphenyl)gulonone, 2,2'-bis(4-(3
-acryloxy)-2-hydroxyproxylphenyl]! Lononane, 2,2'-bis(4-(3-methacryloxy)-2-hydroxyzoloboxylphenyl)gulononane, styrene, 1,3-butanediol diacrylate and methacrylate, tetrahydrofurfuryl acrylate and methacrylate, trimethacrylate Fl ToIJ / Tyrol! Ronofon, bisoxyethylated bisphenol A cyacrylate, and methacrylate may be blended. Also, if necessary, a compound of formula (1) may be included to adjust viscosity, curing speed, polymerization shrinkage, etc. Polymers and oligomers of polymerizable monomers are blended, and inorganic fillers such as silica, raspize, alumina, and quartz powder rings (preferably particles with a particle size of 100 pm or less) are added to improve the bonding with resin. These fillers are treated with silanizers such as r-methacryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, and ringing agents, as well as curing agents, polymerization inhibitors, coloring agents, and oxidation agents. Desired components such as inhibitors and ultraviolet absorbers may also be used.When using a combination of adenine and peroxide, or p-)luenesulfinic acid and peroxide as curing agents, polymerization If only the compound of formula (1) is used as a monomer, divide it into approximately two equal parts, add a curing agent such as amine or p-toluenesulfinic acid to one side, and add a curing agent such as peroxide to the other. If the compound of formula (1) is used by adding the other curing agent and mixing the other polymerizable monomer with the compound of formula (1), similarly divide the other polymerizable monomer into approximately two equal parts, Adding the one curing agent to one side and the other curing agent to the other side, (1)
It is preferable to manufacture the compound of the formula by mixing it in one or both of the two halves (these are mixed before use). In this case, other components are also mixed in one or both of the halves. Also, using a UV sensitizer,
In the case of curing with ultraviolet rays, it can be produced by mixing all the necessary components.

In addition, when using the compound of formula (1) as a polymerizable monomer for adhesive filler, the amount blended into the filler is not particularly limited, but even when using the other polymerizable monomers mentioned above, 1 to 30%, especially 2 to 1%, based on tobacco and other polymerizable monomers
Preferably, the amount is 5%. If the amount is less than 1%, the adhesive effect will be poor, and if more than 30% is added, the hardness of the cured product may decrease. It is preferable that the amount of the polymerizable monomer is 10 to 45% of the total amount of the filler, and the amount of the inorganic filler is 50 to 85% of the total amount of the filler.

In addition, when using a dental adhesive composition containing at least one compound of formula (1) as an adhesive for bonding a tooth to a conventional composite, a resin filling, etc., ethanol, It can be produced by containing the compound of formula (1) in an organic solvent such as diethyl ether or chloroform, and adjusting the concentration to preferably Fio, s to 30-. It may be produced by incorporating the compound of formula (1) in the polymerizable monomer in an amount of 1 to 15% of the total amount.In this case, this mixture can be dissolved in a suitable solvent. Furthermore,
It can also be manufactured and used in the same formulation as the filler. Note that if the content of the compound of formula (1) is too small or too large, it will be difficult to obtain an adhesive effect.

This dental adhesive composition is cured and used depending on its type, purpose, etc. For example, when used as a filler, the adhesive composition (filler) is filled into the cavity to be filled,
When the adhesive composition is hardened and used for adhesion between a dental filling and a tooth, for example, after forming a cavity, this adhesive composition is applied to the back wall, and then a predetermined filling is filled and hardened. use.

The dental adhesive composition containing the compound of formula (1) according to the present invention has good adhesiveness of the polymer of the compound of formula (1) to the tooth substance, and maintains high adhesive strength even in water or saliva. . Therefore, it has good durability in the oral cavity, and when used as a filling material, for example, it will firmly adhere to the tooth for a long period of time even in environments with severe temperature changes such as in the 110 cavity. Also, when used as a base coat (painting agent) for composite resins and orthodontic adhesives, etc., it firmly adheres to teeth, and it also works well with composite resins and orthodontic adhesives. It adheres strongly, thus reliably preventing gaps from forming between the tooth and the tooth, and improving margin sealing properties.
Prevention of secondary caries is achieved.

Next, production examples and examples of the present invention will be shown.

[Production Example 1] Glycisol methacrylate) 2.131 (0,015
sand).

1.671 (0,015 moles) of p-70 loaniline and 10 da of p-hydroquinone were dissolved in 115 da of methyl alcohol.
ajK was dissolved and refluxed for 20 hours while stirring.

Thereafter, the methyl alcohol was distilled off under reduced pressure, and the oily substance was left to stand to obtain pale yellow crude crystals. This was recrystallized with a mixed solvent of n-hexane-methyl alcohol to obtain 1.4N of white needle-shaped purified crystals (2-hydroxy-3-p-fluorophenylaminozorobyl methacrylate) (
Yield: 37 cm).

Melting point: 66-67.5℃ Elemental analysis value CHN Calculated value 61.65% 6.37%-5,53%
Actual value 61.69% 6.29chi 5.52
% Infrared absorption spectrum
o-) 1320, 1.180 (-COO-) Nuclear magnetic resonance spectrum: DM80-44H [Production Example 2] Glycidyl methacrylate 2.84 F (0.02 mol).

p-chloroaniline 2.55F (0.02 mol) and p
- Hydroquinone 1oIv methyl alcohol 150ml
/ and refluxed for 20 hours while stirring.

Thereafter, the methyl alcohol was distilled off under reduced pressure, and the oily substance was left to stand to obtain pale yellow crude crystals. This was recrystallized with a mixed solvent of n-hexane-methyl alcohol to obtain white needle-like purified crystals (2-hydroxy-3-p-chlorophenylaminozorobyl methacrylate) 0.34F (
Collection: 46.3 yen).

Melting point: 68.5-70℃ Elemental analysis value: Calculated value 57.89% 5.985G 5.191G
Actual value 57.91 5.95% 5.561l
lr Infrared absorption spectrum: ν 3-1 ax 3450.3350 (-NH-, -0H) 1690 (
-CO-) 1320, 1180 (-COO-) Nuclear magnetic resonance spectrum: oMso-δ6 [Production Example 3] Glycidyl methacrylate 1.70 N (0,012
mole).

1.791 (0,012 mol) of p-n-butylaniline and 10 mol of p-hydroquinone were dissolved in 9 mol of methyl alcohol.
9. Dissolved in 0.0jLl, dissolved and refluxed for 20 hours with stirring.

Thereafter, the methyl alcohol was distilled off under reduced pressure, and the oily substance lJN was left to obtain pale yellow crude crystals.
Recrystallization was performed using a mixed solvent of hexane-methyl alcohol to obtain 0.58N of pale yellow purified crystals (2-hydroxy-3-p-n-butylphenyl azunozolovir methacrylate) (yield 17-).

Melting point: 51-52℃ Elemental analysis value: CHN ttj[70,07$ 8.6511 4.81
11 actual 111 value 70.36Is8.7111! 4
．． 881G infrared absorption spectrum -8・1"'--1ma
! 3400.3280 (-■-, -0H) 1710 (-
CO-) 1320, 1160 (-COO-) nuclear magnetic resonance (
Vector: DM80-d6δ0.90 (1, 3H)
CH, -CI'12-CH2-CH, -δ1.40
(m = 6 H) CH5-CCH2)5-δ1-
90 (m, 3H) CH2IC unit [Production Example 4] Glycidyl methacrylate 1.421 (0.01 mol).

N-phenylcyclohexylamine 1.80 IC0,
01 mol) and zinc chloride 0.05 N (0,0003
Add 5 mol) to a 20 d volumetric flask and reduce to 80 to 80 mol while stirring.
It was heated at 90°C for 1 hour. After the reaction mixture was returned to room temperature, 5 wLt of benzene was added and adsorbed onto 200 d of silica glue, and the raw material was recovered from the benzene eluate. The liquid obtained from the chloroform eluate was distilled under reduced pressure and heated to 185-189°C.
0.5 1 (g fraction (2-hydroxy-3-(N-cyclohexylanilino)propyl methacrylate)) 1.
08Ii was obtained (yield: 434 cm).

Elemental analysis value: CHN calculation fi 71.891 8.571 4.4
11 Actual value 71.79chi 8,52chi 4.2
5th infrared absorption spectrum Niji”::: m-'345
0 (-OK') 1710 (-CO-) 1320.1160 (-〇〇〇-) Nuclear Magnetic Resonance (Cuttle: CDC1H! [Production Example 5] Glycisol methacrylate 1.42 N (0.01 mol).

1.65 N (0.01 mol) of ethyl p-aminobenzoate and 0.1 J (0.0007 mol) of zinc chloride were added to a 2017 volumetric flask and heated at 80-90°C for 1 hour while stirring. After the reaction mixture was returned to room temperature, benzene 5d was added and adsorbed onto silica fA2ooal, and the raw material was recovered from the benzene eluate. Crystals (ether N-(2-hydroxy-3-methacryloyloxyzolobyl) p-aminobenzene-)) 2.2N having a melting point of 76-79°C were obtained from the tetraroform eluate (yield 72%).

Elemental analysis value: CHN Calculated value 62.53% 6.89% 4.5
6Ls actual measurement value 6z, t3* 6.84%
4.3613450.3360(-■-,-om)17
10.1700 (-Co-) 1320 , 1180 (-COO-) nuclear magnetic resonance spectrum: coct.

δ1.30 (t = 3 H) 9-CH2-0-υ
Ni! ! [Production Example 6] Glycisol methacrylate) 1.42 II (0,01
mole).

1.6511 (0.01 mox) of ethyl 0-aminobenzoate and 0.1 N (0.0007 mol) of zinc chloride were added to a 20a/volume flask and heated at 80-90°C for 1 hour while stirring. The reaction mixture was returned to room temperature, and penzene 5W11 was added thereto and adsorbed onto silica del 200R1, and the raw material was recovered from the benzene eluate. 0.6 jl of crystals (ethyl N-(2-hydroxy-3-methacrylμyloxyzolobyl) 0-aminobenzoate) having a melting point of 67-69°C was obtained from the eluted portion of crystalline roform (yield: 20%).

Elemental analysis value: CHN Calculated value 62.53chi 6.89chi 4.56%
Actual value 62.19cm 6.78'jG 4.
46chi 3450.3350 (-Nu-, -0H) 170
0 (-Co-) 1320, 1160 (-COO-) nuclear magnetic resonance spectrum: DM80-d6...! ! ! Next, Examples will be shown to explain the adhesive effect of the compound of the present invention on tooth structure. In addition, in the following examples, parts and - are all parts by weight and -.

[Example 1] The compounds of the present invention represented by formulas (2) to (7) above were each dissolved in ethanol at a concentration of 5 to prepare a coating agent (dental adhesive composition).

Next, the surface of the natural tooth filled with plaster in the holder, the surface of the acrylic rod 6mm x 40B polished to a certain level of smoothness with a polisher, and the smooth surface of the natural tooth were treated with 3M phosphoric acid for 30 seconds.
It was washed with water and dried with compressed air.

Next, the coating agent was applied to the dried tooth surface, and after drying, the acrylic rod was adhered using an adhesive having the following formulation. The samples were stored in artificial saliva at 37°C for 14 and 60 days, and the adhesive strength was measured using a strograph (pulling speed: 5/min).

The results are shown in Table 1.

Adhesive formulation: At the time of use, (a) and C) are mixed in a weight ratio of 1:1.

Table 1 [Example 2] A cavity with a diameter of 4 mm and a depth of 2 to 2.5 mm was formed on the labial surface of an extracted human tooth, and the shoulder wall of the cavity was etched with 3M phosphoric acid for 30 seconds. After applying a solution of 10 parts of methyl methacrylate, 60 parts of methyl methacrylate, and 30 parts of tetraethylene glycol-dimethacrylate to the shoulder wall,
It was filled with Adaptik (trade name, manufactured by Jinson & Sonnen Co., Ltd.).

Thirty minutes after filling, it was stored in water at 37°C, and one day later, it was tested for margin sealing properties by performing the Nof-Colesin test, in which it was immersed 60 times for 1 minute alternately in an aqueous solution of Tsukusin at 4°C and 60°C. . Both tubes were removed at the center and cut to see if there was any penetration of the dye (Tsukusin) between the shoulder wall and the filling, but in both cases using compounds of the present invention (2) and (3) No intrusion was observed and good results were obtained.

On the other hand, in cases where Adazotik was directly filled without treatment with a liquid containing the compound of the present invention, the pigment (tsuksin) penetrated into the dentin of the window wall or the floor of the cavity. It was found that it is also effective for adhesion of both.

Applicant Lion Corporation Agent: Patent Attorney Takashi Kojima l Patent attorney Hanyo Takahata

Claims (1)

[Claims] 1. The following general formula (1) (provided that when R1 is a hydrogen atom, R2 is a hydrogen atom and R3
is a halodane atom, an n-butyl group, or an ethoxycarcanyl group. When n2 is an ethoxycar-nyl group and R5 is a hydrogen atom, and R' is a cyclohexyl group, R and R are both hydrogen atoms. . ) Propyl methacrylate derivatives. 2. The compound represented by the formula (2-hydroxy-3-p
The propyl methacrylate derivative according to claim 1, which is -:yfluorophenylaminoglobil methacrylate. 3. The compound represented by formula (1) is 2-hydroxy-3-
The propyl methacrylate derivative according to claim 1, which is p-chlorophenyladenoderovir methacrylate. 4. The compound represented by formula (1) is 2-hydroxy-3-
The propyl methacrylate derivative according to claim 1, which is p-n-butylphenyl aonoglobil methacrylate. 5. The compound represented by formula (1) is 2-hydroxy-3-
The propyl methacrylate derivative according to claim 1, which is (N-cyclohexylanilino)zorobyl methacrylate. 6. The compound represented by formula (1) is ethyl N-(2-hydroxy-3-methacryloyloxypropyl) p-
The propyl methacrylate derivative according to claim 1, which is an aminobenzoate. 7. The compound represented by formula (1) is ethyl N-(2-
Hydroxy-3-methacryloyloxypropyl) 0
-Aminobenzoate. 86 The following general formula (1) (However, when R1 is a hydrogen atom, R2 is a hydrogen atom and R3
is a halodane atom, an n-butyl group or an ethoxycartenyl group, or when R is an ethoxylic group and R is a hydrogen atom, and R is a cyclohexyl group, both R and R are hydrogen atoms. ) A polymerizable monomer for a dental adhesive composition, comprising a zorobyl methacrylate derivative represented by: 9. The compound represented by formula (1) is 2-hydroxy-3-
The polymerizable monomer according to claim 8, which is p-fluorophyl annozorobyl methacrylate. 10, the compound represented by formula (1) is 2-hydroxy-3
9. The polymerizable monomer according to claim 8, which is -p-chlorophenyla constant nozorobyl methacrylate. 11. The compound represented by formula (1) is 2-hydroxy-3
The polymerizable monomer according to claim 8, wherein =pn-butylphenylaminozorobyl methacrylate. 12 The compound represented by formula (1) is 2-hydroxy-
9. The polymerizable monomer according to claim 8, which is 3-(N-cyclohexylanilino) f-lobyl methacrylate. 13, the compound represented by formula (1) is ethyl N-(2-
Hydroxy-3-methacryloyloxyzolovir) p
9. The polymerizable monomer according to claim 8, which is -aminobenzoate. 14, the compound represented by formula (1) is ethyl N-(2-
Hydroxy-3-methacryloyloxyzolobyl) O
9. The polymerizable monomer according to claim 8, which is -aminobenzoate. 1□.