JPS58222095A - Salt of 1-methacryloxyethane-1,1-diphosphonic acid - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula [M is H, alkali(earth)metal, (substituted)ammonium, with the proviso that all M are not H]. USE:Having chelating ability, a polymerizable monomer for dental adhesive composition, chelating agent, ion exchange resin, etc. PROCESS:For example, 1-hydroxyethane-1,1-diphosphonic acid is added to triethylamine, to which methacrylic acid chloride is added gradually under cooling with ice. The solution is restored to room temperature, stirred, acidified with a hydrochloric acid solution, extracted with ethyl ether, a water layer is collected, alkalified with NaOH, and extracted with ethyl ether. The water layer is subjected to chromatography, and the prepared extracted solution is distilled under reduced pressure, to give a compound shown by the formula.

Description

Detailed Description of the Invention The present invention has a chelating ability and can be used in a wide range of applications such as dental adhesive compositions, chelating agents, and ion exchange resins.
Synthesizing monomer 1-methacryloxyethane-1, 1,
-Relating to diphosphonates.

In recent years, composite fistulae has been developed as an alternative to dental cements such as lead phosphate cement and silicate cement for the treatment of teeth with caries. They also have less disintegrability and can now be made in colors that are indistinguishable from natural teeth.

However, since composite e-resin essentially does not adhere to tooth enamel or dentin, gaps may form between the cavity and the filled composite resin over a long period of time, resulting in secondary caries. tends to occur, and eventually the composite
There would also be a result of Lennon dropping out.

Conventionally, various adhesion enhancers and adhesive liners have been developed to improve the adhesion between such composite resins and cavity walls, and adhesive anti-caries filling agents, orthodontic adhesives, etc. A wide range of FC adhesive compositions have been proposed for the purpose of adhering strongly to image quality1, but many of them have problems with 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 an environment as humid as the inside of the oral cavity, where the temperature is extremely high.

The present invention has been made in view of the above circumstances, and has been extensively researched to find a compound that has strong adhesive strength to teeth and can be suitably used as a polymerizable monomer, etc. of a dental adhesive composition. )7'c linkage, e.g. methacrylic acid chloride and 1-
By reacting with hydroxyethane-1,1-diphosphonic acid and optionally neutralizing it, a compound of the general formula (wherein M is selected from H, alkali metal, alkaline earth metal, ammonium and substituted ammonium) The new compound l-methacrypxyethane-1,1-
Diphosphonic acid or a salt thereof is obtained, which has excellent chelating ability, and these i-order monopolymer polymers exhibit strong adhesive strength with teeth even in water. The monomer, its homopolymer, and its comonomer with other monomers can be used as tooth filling materials1, and as adhesives or adhesives for fillings such as composite resins. Im chelating agent or l
The present invention has been completed by discovering all the advantages as an IA material.

Novel compound of the present invention 1-methacryloxyethane-1,1
-Diphosphonic acid and its salts are water-soluble colorless oily substances or crystalline substances represented by the above general formula.

This new monomer is described in, for example, "Jikken Kagaku 1lII, Vol. 19, pp. 471-482 (Maru If', May 20, 1957).
″.

1 New experimental chemistry! @i14%1oOo~1o62 pages (Maruzen.

methacrylic acid and "-°"'
Methods such as reacting with "-1.1"°'1' acid, or reacting methacrylic anhydride with 1-hydroxyethane-1,1-diphosphonic acid, etc.1 - Methacryloxyethane-1,1-diphosphonic acid can be produced and its salt can be produced by optionally neutralizing it. Preferably, it is mixed with methacrylic acid 1,1-diphosphonic acid such as methacrylic acid chloride and 1- It can be produced by reacting hydroxyethane-1,1-diphosphone M in the presence of a base in an anhydrous state with cooling, and optionally neutralizing it.

Examples of the salts of 1-methacryloxyethane-1,1-diphosphonic acid include alkali gold salts such as lithium salts, atrium salts, and potassium salts, alkaline earth gold maple salts such as magnesium salts and calcium salts, ammonium salts, and cyclohexyl salts. Ammonium salts, etc. 1st and 2nd. Examples include salts of tertiary amines, including those in which at least one M in the above general formula is a salt of these salts. The neutralization reaction of 1-methacryloxy-1,1-diphosphonic acid can be carried out in a solvent such as ethanol after the esterification reaction and, if necessary, a drying process. Neutralizing agents include metals, metal oxides, metal hydroxides, ammonia, ammonium hydroxide and
- Tertiary amines are exemplified. Neutralization can also be carried out using an ion exchange resin. Furthermore, if necessary, salt exchange can be carried out by metathesis reaction, etc., and a mixed salt containing a plurality of cations can also be produced.

One of the preferred differences of the polymerizable monomer of the present invention is in the field of dental adhesives. When the monomer monomer of the present invention is used in this field, it can be used alone, or it may optionally contain other monomers, diluent, I2-1 crosslinking agent, etc. It can also be used as a dental adhesive composition. Such dental adhesives can be used as a filling agent for teeth, an adhesive for orthodontics, or as an adhesive for bonding fillings such as Compozot φ Lennon or orthodontic adhesives to teeth. It is used for the purpose of adhesion to teeth, such as for use in adhesives.

When the polymerizable monomer of the present invention is used in a dental adhesive, a method is employed in which a curing agent such as a polymerization initiator is added at the time of use, and polymerization and curing are carried out. At this time, other monomer monomers optionally used may be monofunctional or polyfunctional to act as a crosslinking agent, if necessary. Examples of such monomers include the following monomers.

Monofunctional monomers methyl acrylate and methacrylate, ethyl acrylate and methacrylate, butyl acrylate and methacrylate, hydroxyethyl acrylate and methacrylate, methoxyethyl acrylate and methacrylate, glycidyl acrylate and methacrylate,
Tetrahydroxyfurfuryl acrylate and methacrylate, nuthylene, etc.

polyethylene glycol diacrylate and dimethacrylate, polyethylene glycol diacrylate and dimethacrylate, butylene glycol diacrylate and dimethacrylate, neopentyl glycol diacrylate or dimethacrylate, globylene glycol diacrylate and dimethacrylate Methacrylate, 1.3-butanediol soacrylate and dimethacrylate, 1.4
-butanol diacrylate and diacrylate tote and dimethacrylate, etc.

2.2-bis(acryloxyphenyl)pronone, 2
．． 2-bis(methacryloxyphenyl) 7°rono-ben,
2.2-bis(4-(3-acryloxy)-2-hydroxyglopoxyphenyl)propane, 2.2-bis(4
-(3-methacryloxy)-2-hydroxyglopoxyphenyl]pronobase, 2,2-bis(4-acryloxyethoxyphenyl)propane, 2,2-bis(4-methacryloxyethoxyphenyl>propane, xylylene) Glycol noacrylate, xylylene glycol noacrylate, etc. □ Trifunctional aliphatic acrylate and methacrylate □ 111′ trimethylolpropane triacrylate and trimethacrylate, trimethylolethane triacrylate and trimethacrylate, etc.

In addition, in the dental adhesive or filling material using the polymerizable monomer of the present invention, a thickener or the like can be used in order to adjust the viscosity, curing speed, and polymerization shrinkage. For example, as mentioned above! ? ! ! Oligomers and polymers of glaze monomers may be used in an amount of 30M or less of all monomer monomers.

In addition, fillers can be used in dental adhesives and filling materials to improve compressive strength, hardness, and other physical properties, such as α-quartz, fumed silica, glass beads, aluminum oxide, aluminum, and the like. Although there is no particular restriction on the particle size, it is preferable to use a filler with a particle size of 100 μm or less, particularly 50 μm or less.

It is desirable that the inorganic filler be pretreated with a silane binder in order to improve its bond with the monomer. Silane binders for such pretreatment include vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris(β-methoxyethoxy).
Examples include silane, r-methacryloxypropyltrimethoxysilane, and N-(β-aminoethyl)-r-aminonoropyltrimethoxysilane. The content of the filler should be less than 85% of the total filling material. Combinations such as sulfinic acid or its fatty conductor and peroxide can be used. By using this two-component curing agent, the polymerizable monomer of the present invention or a composition containing it can be divided into two parts, and one of the parts can be treated with amine and P-)luenesulfinic acid. This is advantageous because peroxide or the like can be added to the other. Note that the amines include N, N
Examples include -trimethyl-p-toluidine, N,N-di(β-hydroxyethyl)-p-)luidine, N,N-trimethylaniline, and monoethanolamine. The content of amines is preferably in the range of 0.1 to 5% of the total polymerizable monopolymer. Furthermore, examples of the four rufin-fermented compounds include benzenesulfine M, p-toluene-nulfinic acid, and their sodium salts. The blending cap of sulfinic acid or its spinneret contains 2 to 6 polymerizable monomers.
% range is preferable. Examples of the peroxides include penzoylno and monooxide, no-p-polybenzoylno and monooxide, di-lauroyl peroxide, and methyl ketone peroxide.

The amount of peroxides to be blended is preferably in the range of 1 to 3% of O2 of the polymerizable monomer.

Moreover, without using a curing agent, ultraviolet sensitizers such as hahensoin methyl ether, 7cetophenone, benzophenone, 2.2.2-trichloro-4'-t-butylacetophenone, etc. By blending 3 to 3%, a composition that can be cured by ultraviolet rays can be obtained.

When the dental adhesive composition containing the polymerizable monomer of the present invention is used as a bonding agent for bonding a tooth and a conventional filling material such as composite lenone, ethanol,
A suitable solution such as noethyl ether or chloroform is suitable, and in this case, the amount of O#kld is 0.5 to 30Ii% and the amount of L<H1 to 15TL is suitable.

When the polymerizable monomer of the present invention is used as a dental drug,
The resulting polymer 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, for example, it adheres strongly to the teeth for a long period of time even in environments that are humid and subject to rapid temperature changes, such as in the oral cavity. In addition, when used as a single coat (coating agent) of composite resin or orthodontic adhesive, etc., it adheres firmly to teeth. Adhesive, thus reliably preventing gaps from forming between the tooth and the tooth, improving margin sealing properties.
prevention of secondary caries.

The polymerizable monomer of the present invention has a chelating ability. In addition to the above-mentioned dental adhesive field, tartar preventive agents are usually used because of the group and polymerizable double bonds.

Applications include adhesives, polymer modifiers, and more.
Chelate resin that takes advantage of chelating ability, ion exchange resin Mk
It can be used in a wide range of applications such as water treatment agents, metal trapping agents, etc. For these uses, the polymerizable monomer of the present invention is
It can be used directly as a monomer, as a homopolymer, or as a copolymer.

The monopolymer monomer of the present invention may be methacrylic ester, a monomer with relatively high polymerization activity, and in addition to the above-mentioned various copolymerization monomers. ,
P o e V y et al. Unsaturated hydrocarbon, vinegar. Non-fatty vinyl, polyvinyl chlorides such as vinyl chloride, vinyl ethers such as acrylonitrile and methyl vinyl ether, etc. are used, taking into consideration the use, performance, solubility such as water-solubility/water-insolubility, polymerization method, etc. and is selected appropriately.

Next, Examples of the present invention will be shown, but the polymerizable monomer of the present invention has a wide range of uses and is not limited to these Examples.

〔Example〕

1-Hydroxyethane-1.1-siphonufonic acid 5f
(0.024M) 'k) ethylamine 3
15.7i (0.15 M) of methacrylic acid chloride was gradually added to this under water cooling.
After returning to room temperature, stirring was performed for about 10 hours.◎Next,
Hydrochloric acid solution was added to make the mixture M, and the mixture was extracted with ethyl ether to collect the aqueous layer. Sodium hydroxide was added to this to make it alkaline, and after fc, the mixture was extracted with ethyl ether.

Amberly) 120B (o-muando)
The eluate obtained was distilled under reduced pressure to produce a colorless oily substance 1-methacrylate I xyethane-1,1-diphonufon (monomer A) 4
．． 3? (yield: 65%).

Elemental analysis: C6H, 208P2 C H P ! t1# value 2629% 4.41chi 22.60 Bun side value 26.55% 4.19% 2 2.3 5% infrared absorption spectrum
0-C-C=1 1450 CH,- 13800H3- 1200P-OH 1 6,85 ppmb, s, (4H,P(OR)2) Next, the partial salt of 1-methacryloxy-1,1-diphosphonic acid is prepared as follows. Manufactured by the method.

That is, l-methacrylxyethane-1 shown in Table 1.2
, 1-nophosphonic acid is prepared by mixing the corresponding metal carbonate bath solution and nemethacryloxyethane-1,1-diphosphonic acid at a molar ratio of 1:1, and adding ethanol to this.
The precipitate (Kinpeng salt) was collected by filtration.

Mata, cyclohexylammonium [U, 1 mol of cyclohexylamine and 1 mol of 1-methacryloxyethane-1,1-diphosphonic acid were mixed and stirred, and the product was further fractionated by liquid chromatography to obtain a salt. .

The infrared absorption spectra and nuclear magnetic resonance spectra of these salts are shown in Table 1.2. Furthermore, as an example, the chelating power of monomer C (sodium salt) is shown in Table 3 for calcium ions and iron ions.
The 1 g point of Ilr Nao cyclohexylammonium salt was 177-181°C.

l-Methacryloxyethane-1,1 thus obtained
- Diphosphonic acid and its 4S salts are both about 150
When heated to ℃, thermal polymerization occurred.

789 [Usage Example 1] A dental adhesive composition (primer) was prepared by dissolving Honfumei's stand-forming monomer in 5% concentrated ethanol.

Next, the surface of the natural tooth filled with plaster in the holder and the acrylic rod of 6mm diameter
Rinse with water and dry with compressed air.

Next, the dental adhesive composition (primer) was applied to the dried tooth surface, and after drying, the acrylic rod was adhered using an adhesive having the following formulation. For those stored in artificial saliva at 37°C for 14 days and 60 days, the 1&adhesion strength was measured using a strograph and fc (pulling speed 5 mm/min).
. The results are shown in Table 4.

Adhesive formulation: When used, (,) and (b) are mixed in a weight ratio of 1:1.

Table 4 [Usage Example 2] 10 parts of methyl methacrylate, 20 parts of diethylene glycol dimethacrylate, 50 parts of bisphenol-A-diglycidyl methacrylate, and 350 parts of quartz powder with a particle size of 50 μm or less treated with silane cutting were thoroughly mixed. ,9
It was divided into two equal parts. Monomer C6BB and 2 parts of N,N-dimethyl-p-)luidine were added to one of them, and 2 parts of benzoyl peroxide was added to the other, and then both were mixed. Using this, do the same as in usage example 1. An acrylic rod was adhered to the surface of a natural tooth finished on the I# side, and the adhesive force was measured using a strograph.

The results showed an average adhesive strength of 67 kg/cd after being stored in water for one week.

[Use Example 3] A cavity with a diameter of 4 mm and a diameter of 2 to 2.5 mm was formed on the labial surface of an extracted human tooth, and the cavity wall was etched with 3M phosphoric acid for 30 seconds. Next, a solution consisting of parts of monomer C or F2O, 60 parts of methyl methacrylate, and 30 parts of tetone ethylene glycol dimethacrylate was applied thinly to the wall of the cavity. product name)
I ignored it. After 30 minutes, store in water at 37℃,
After 6 days, the cells were placed in an aqueous solution of 7 chlorine at 4°C and 6θ°C for 1 min alternately.
Perform percolate dipping by dipping 0 times,
- Marginal sealing properties were tested. The extracted tooth was cut in the center and examined to see if there was any pigment (7 cusine) intruding between the cavity wall and the filling material, but no pigment intrusion was observed in any of the cases, and the results were good. Obtained.

On the other hand, in an example in which Adaptake was directly filled without treatment with a liquid containing the monomer of the present invention, the dye (7-Cusin)
It has been found that the monomer of the present invention is also effective in bonding both the tooth and the filling material.

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

Claims (1)

[Claims] (1) 1-methacryloxyethyl-Ll represented by the general formula (wherein M is selected from H, alkali metal, alkaline earth metal, ammonium, and substituted ammonium, and at least one is not H) -Nophosphonate.