JPS5829313B2 - Pyrophosphate derivatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to pyrophosphate ester derivatives, in particular polymerizable pyrophosphate derivatives that have utility as diluents for adhesives for dental treatment or fillers based on curable resin compositions. It concerns monomers.

Although various cements have been the mainstream filling materials for partially missing teeth, heat- or photo-curable resin compositions are also attracting attention.

When filling defects with these filling materials, their adhesion to the tooth structure may be a problem, and if the adhesion is insufficient, they may fall off after filling, or they may cause marginal sealing. Due to the lack of moisture, saliva etc. may invade and induce secondary caries deep within the body.

Furthermore, when attaching an orthodontic band or the like, the adhesion between the band and the tooth structure is a problem.

For this reason, various adhesives including cyanoacrylate adhesives have been developed, but they are not necessarily satisfactory in terms of affinity for teeth.

According to recent research, it is becoming clear that in order to have satisfactory adhesion to teeth, it must have both affinity for enamel and affinity for dentin. Showa 52-113089
No. etc. have been proposed.

The present invention has been made as a result of these rings, and has succeeded in developing a new compound that can be used as an adhesive with even better affinity for enamel and dentin.

That is, the new polymerizable monomer provided in the present invention has the general formula (wherein R means allyl, acryloyloxy (lower) alkyl or methacryloyloxy (lower) alkyl, respectively, and the (lower) alkyl in R is It is a pyrophosphoric acid ester derivative represented by (optionally substituted with halogen).

The compound represented by the above general formula (I) is produced according to the following reaction formula.

However, the symbol R has the same meaning as before.

Regarding the reaction mechanism in which compound (I) is produced from the compound hole, a part of compound □□□ is hydrolyzed to form compound M.
It is believed that this reacts with an unreacted compound in the presence of an amine, which is a dehydrochlorination agent, to produce compound (I).

The group represented by R in each of the above general formulas is explained below.

R means allyl, acryloyloxy (lower) alkyl or methacryloyloxy (lower) alkyl, respectively, and the vinyl group contained therein is responsible for imparting polymerizability to the compound.

The (lower) alkyl in R includes methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl,
Examples include alkyls having 1 to 6 carbon atoms such as pentyl and hexyl, and such (lower) alkyls may be further substituted with halogens such as fluorine, chlorine, bromine and iodine.

Next, the manufacturing process for manufacturing compound (I) will be explained.

Compound (9) → Compound Object Compound W is reacted with phosphorus oxychloride under anhydrous conditions.

Although phosphorus oxychloride also serves as a reaction solvent, an appropriate organic solvent may be used in combination depending on the case.

Although the reaction temperature is not particularly limited, it is usually preferable to carry out the reaction with or under heating.

Compound name→Compound ■ Under anhydrous conditions, an alcoholic compound represented by ROH is allowed to act on the compound.

The reaction is usually carried out in a solvent, and preferred solvents are those that do not adversely affect the progress of the reaction, such as methylene chloride and chloroform.

Although there are no particular restrictions on the reaction temperature, it is preferable to carry out the reaction under mild conditions, such as cooling or dropping.

Compound W→Compound (I) The reaction proceeds via Compound (7), and hydrolysis and dehydrochlorination condensation are performed over time.

For hydrolysis, simply adding water is sufficient, and it is desirable that the reaction temperature be moderate.

Organic bases or inorganic bases are used to carry out dehydrochloric acid condensation, but these are added at the same time as hydrolysis progresses, and the hydrolyzed product is dehydrochlorinated and unhydrolyzed one after another. Compound (I) is provided.

Although the type of base used in combination is not limited, organic bases are preferably tertiary amines such as trialkylamine and pyridine, and inorganic bases are preferably weak bases such as carbonates.

The target substance (I) thus obtained is a polymerizable monomer, and is polymerized by the vinyl group in R.

Polymerization is progressed by light, heat, ultraviolet rays, etc., and a polymerization initiator or a polymerization accelerator is added as necessary.

When used as an adhesive for a missing tooth, etc., it may be used alone or in combination with a general-purpose filling material.

When obtaining a polymer from the above monomers, the duration of the gel state is short, so the time required for hardening after filling is short, and there is less burden on the patient, and the viscosity during kneading is too high. Therefore, workability is good.

It is also highly useful as a diluent for fillers made of curable resins.

After curing, it exhibits extremely favorable physical properties such as adhesive strength, edge sealing properties, and thermal expansion resistance, so it not only has high utility value as the above-mentioned dental adhesive, but also has good properties as an industrial material. It can be applied to a wide range of fields.

Next, examples of the present invention will be shown.

Example 1 In a methylene chloride solution containing 2-hydroxyethyl acrylate (26P) and pyridine (24P), phosphorus oxychloride (16f) was added dropwise while stirring and reacting at 0 to 10°C for 2 hours.

After the reaction was completed, hydrolysis was carried out in ice water, and 5% hydrochloric acid, 5%
After sequentially washing with % potassium hydroxide aqueous solution and water, it was dried with Glauber's salt.

The solvent was distilled off under reduced pressure to synthesize a colorless transparent oily pyrophosphate compound (24.5f).

■R Niji crrL-1 aX1 2900.1720.1630.1365.1160
97O NMR (CDC13): δ 6.35 (m13HX4, vinyl proton
s) 4.25 (m, 4H x 4, -CH2CH2-)d
, 1,219, n'4: 1.459425.

Example 2 In the same manner as in Example 1', phosphorus oxychloride (16P) was reacted in a methylene chloride solution containing 2-hydroxyethyl methacrylate (23,2f) and pyridine (24g), and Pyrophosphate compound (30, 11) was synthesized by the same treatment.

IR Niji Crrt-1 max -h 2950.1720,1630. 1160.98O NMR (CDCI 3): δ 6.10 (bs, IH x 4. 5.55 (m, IH proton) -CH2CH2-) vi11yICH3)* 1365, 1*d25: 1,213, n division: 1.4720 Example 3 In the same manner as in Example 1, 2-hydroxypropyl methacrylate (23,2P) and pyridine (24 Pyrophosphate compound (19,1f) was synthesized by reacting phosphorus oxychloride (16f) in a methylene chloride solution containing ?) and treating in the same manner as in Example 1.

IR:! / cm,' max1 2950 1720 1160.100O NMR (C100ON: δ 6.10 (bsll HX 4. 5.55 (m, IHX 4. 4.85 (m, 1H x 4. 4.15 (m, 2H x 4. 1 .90 (d, 3H x 4. 1630. 1375, vinyl proton) vinyl proton) CH2renHCH3) CH, CHCH3) vinyl CH3) 1.30 (m, 3H x 4, -CH2CHCH,) d
, 1.178, n'4: 1.4698 Example 4 In the same manner as in Example 1, 2-chloro-3-hydroxypropyl methacrylate) (30,1?) and pyridine (2
4S') in a methylene chloride solution containing phosphorus oxychloride (
11′) and treated in the same manner as in Example 1 to synthesize a pyrophosphate compound (28,8?).

Example 5 In the same manner as in Example 1, allyl alcohol (4tl')
and pyridine (24f) in a methylene chloride solution,
By reacting phosphorus oxychloride (16P) and treating in the same manner as in Example 1, a pyrophosphate compound (12
, (1) were synthesized.

Measurement of Adhesive Strength To measure the adhesive strength, the following composition was prepared.

As agent A, 1 part by weight of benzoyl peroxide was added to 100 parts by weight of the pyrophosphate obtained in Example 2 and thoroughly mixed to obtain a uniform dispersion.

Next, as agent B, pyrophosphate obtained in Example 2 (10
0 parts by weight) to 1 part by weight of N.N'-dimethyl-P
-) A homogeneous dispersion was obtained in the same manner by adding luidine.

When equal amounts of Part A and Part B were mixed and kneaded and the adhesion was examined, it was found to be 119 kg/ca.

The adhesive strength measurement method (sample preparation method) is as follows.

The crown of a fresh beef tooth is cut horizontally, the surface is polished with emery paper 610, and then the enamel surface is finished with a puff.

This beef is soaked in water for one day or more.

Immediately before the test, wipe off the moisture on the surface with dry air.
% phosphoric acid aqueous solution is applied, and after about 30 seconds, it is washed with water and dried again with dry air.

After applying a thin layer of the above-mentioned mixture to the surface, a kneaded product of the commercially available composite filler Adabtiic (manufactured by J&J, Inc., USA) was applied on top of the mixture, and further, on top of this a mixture of the above compositions was applied. I put Tomo's acrylic rod on it and let it harden.

After being immersed in water at 37° C. for 24 hours, adhesive strength was measured using an autograph.

Claims (1)

[Scope of Claims] (In the formula, R means allyl, acryloyloxy (lower) alkyl, or methacryloyloxy (lower) alkyl, respectively, and the (lower) alkyl in R may be substituted with halogen) A pyrophosphoric acid ester derivative characterized by: