JPH0782279A - Polymerization curable phosphazene compound for dental use - Google Patents

Abstract

PURPOSE:To provide a new phosphazene compound exhibiting remarkable mechanical properties as a binder and a filler for dental use, having high adhesivity and resistant to dissolution. CONSTITUTION:This compound is expressed by the formula I [n is 3-18; (X) is group of the formula II (R is 1-11C alkyl or alkylene); (Y) is chlorine; the sum of the number of (X) groups and the number of (Y) groups in the molecule is 2 for one recurring unit]. It can be produced e.g. by substituting the chlorine atom of a dichlorophosphazene (NPCl2)n with a hydroxymethacrylate ester.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a dental restoration restoration material,
More specifically, the present invention relates to a dental filling material, and more particularly to a resin of a novel dental polymerization curable phosphazene compound having high mechanical properties and adhesiveness. Since it has a large size and strongly adheres to tooth substance and metal, it can be widely used as a dental resin cement and a filler.

BACKGROUND OF THE INVENTION The starting material of the dental polymerization curable phosphazene compound of the present invention is dichlorophosphazene (NPCl ₂ ) n, and when a linear compound is obtained, it is generally a cyclic trimer (NPCl 2). ₂ ) ₃ obtained by ring-opening polymerization, and n can be optionally varied according to conventional techniques (eg HR ALLCOC).
K), "Nitrogen-phosphorus compounds", (1972, Academic Press, New York City). According to the present invention, n is preferably 3 to 18 in the case of a linear compound, and when n is 19 or more, the viscosity of the compound in which chloro bound to phosphorus is replaced with a hydroxyalkyl methacrylate ester described below increases. Therefore, it is not practical. There is no prior art relating to a polymerization-curable phosphazene compound in which a part or all of the chlorine of the above linear compound is replaced with a hydroxyalkyl methacrylate ester.

[0003]

Heretofore, zinc phosphate cement and carboxylate cement have been used in the pasting of dental restorations, but the former has large mechanical strength but no adhesive strength. The latter has a relatively high adhesive strength, but has a low mechanical strength. Furthermore, not only are cements hardened as they dissolve in saliva, there is a risk of secondary erosion, but they also have a strong acidity. There are drawbacks. Resin-based cement has been proposed as one of the measures to solve these drawbacks. That is, the main component of this type of cement is a mixture of a methacrylate monomer and a filler which have been conventionally used in dentistry, or a mixture of a methacrylate phenyl and phthalic acid derivative and a filler, both of which are peroxides. Although it is cured with amide and amines and sulphonic acid, it is unsatisfactory as a permanent adhesive for dental restorations because not only the adhesive strength decreases due to large polymerization shrinkage but also the mechanical strength is small. .

On the other hand, as a dental filler, silicate cement and amalgam have been conventionally used. Silicate cement has good operability and color tone, but has a fatal drawback that its solubility is large. Although amalgam has good mechanical properties, there is a concern that mercury may cause harmful effects on the human body and there is a problem of environmental pollution. Since it has no properties, its purpose as a filler cannot be achieved. Therefore, in recent years, resin-based fillers have emerged as alternatives to these materials. That is,
Resins that are widely used as dental fillers are a mixture of polymethylmethacrylate and methylmethacrylate that have been used conventionally, a mixture of bisphenol A diglycidylmethacrylate and ethylene glycol-based methacrylate, urethane dimethacrylate and 2. Two
A mixture of di (4methacryloxyethoxyphenol) propane and triethylene glycol dimethacrylate, etc., is mixed with a filler such as silica powder,
Similar to resin cement, it is provided by polymerizing with peroxide-amines. However, in both the resin cement and the filler made of these methacrylate monomers, the main chain and the skeleton are composed of homo-bonds of carbon-carbon atoms, so that the polymer has small strength and hardness, water absorption, polymerization. It has a large shrinkage, a low thermal softening point, poor durability in the harsh environment of the oral cavity, and physical properties as a permanent adhesive and a filler cannot be obtained. That is, there is a limit in improving various physical properties of the polymer as long as these monomers are used.

[0005]

DISCLOSURE OF THE INVENTION In order to radically reform the above-mentioned fatal defects of resin cements and fillers, the present invention has conducted extensive research on compounds having various hetero bonds, and as a result, specific polymerization has been conducted. It is based on the finding that curable phosphazene compounds are particularly practical.
That is, as is known, a compound consisting of a unit represented by -P = N- is known as a semi-inorganic compound and a semi-inorganic polymer, and its main chain and skeleton are hetero-bonds of nitrogen-phosphorus atoms. Therefore, its binding energy is not only larger than that of a homo bond, but also inhibits the rotation of the molecule and has a high thermal decomposition point. In other words, the polymerized and cured product composed of the compound has very small flexibility, high hardness, poor flexibility, and has an inorganic compound character such as a small coefficient of thermal expansion, and is practically used as a dental resin. The present invention has been completed by finding that the compound has high properties. The present invention is a dental resin comprising a polymerization-curable phosphazene compound, characterized by comprising a polymerization-curable group and a chloro group represented by the following general formula. General formula

[0006]

[Chemical 3]

In the above formula, n is 3 to 18, and the group (X) is

[0008]

[Chemical 4]

Wherein R is selected from the group consisting of alkyl or alkylene groups containing 1 to 11 carbons, (Y) is a chloro group, the number of (X) groups and the number of (Y) groups in the molecule. Is greater than 0, the number of (X) groups and the number of (Y) groups may be the same or different, and the sum of the number of groups of (X) and the number of groups of (Y) is It is a chain phosphazene compound consisting of units represented by 2 per repeating unit).

Among the monohydroxyalkyl acrylate esters, hydroxymethacrylate esters are suitable as the polymerization-curable group used in the present invention, and the hydroxyalkyl group contains at least 2 carbon atoms. For example, 2-hydroxyethyl methacrylate,
2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 5-
Hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, 6-hydroxy-3-methylhexyl methacrylate, 5-hydroxyhexyl methacrylate, 5-hydroxyhexyl methacrylate, 3
-Hydroxy-2-t-butylpropyl methacrylate, 3-hydroxy-2-2-dimethylpropyl methacrylate, 3-hydroxy-2-methyl-ethylpropyl methacrylate, 12-hydroxydodecyl methacrylate and the like are included. A particularly preferred compound is 2-hydroxyethyl methacrylate.

The compound of the present invention can be obtained by directly converting chloro of dichlorophosphazene (NPCl ₂ ) n with a hydroxymethacrylate ester. In this case, in order to promote dechlorination, a tertiary amine is used. The target product can be obtained in a short time by adding a kind. Examples of the tertiary amines include trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine, tri-n-butylamine, pyridine, N, N, N-.
Tertiary amines are used, including diamines such as tetramethylethyldiamine, but preferably pyridine. On the other hand, any solvent may be used as long as it dissolves dichlorophosphazene, hydroxyalkyl methacrylate ester and pyridine, but it is necessary that the solvent does not contain water. Generally usable solvents are benzene, chloroform, cyclohexane, methylene chloride, toluene, xylene and tetrahydrofuran, but preferably benzene is used in an amount about 10 times the weight of dichlorophosphazene.
The temperature and time during the above reaction differ depending on whether the starting material, dichlorophosphazene, is linear or not, as well as the reactivity of the special hydroxyalkyl methacrylate ester used, and finally the desired target compound. That is, although it depends on the degree of substitution of chloro of dichlorophosphazene, generally, the range of 25 ° C to 90 ° C is good, the time is in the range of 1 to 160 hours, and naturally, the lower the temperature, the longer the reaction is required.

The amount of the hydroxyalkyl methacrylate ester to be reacted with dichlorophosphazene is generally the theoretical amount of the desired degree of chloro substitution of the desired compound, but in order to obtain the compound having the desired degree of chloro substitution in a short reaction time. Requires a small excess of hydroxyalkyl methacrylate ester, in which case the degree of chlorine substitution is determined from the reaction time. Also, a large excess of hydroxyalkyl ester is required to replace both (X) and (Y) of-[NP (X) (Y)]-n with hydroxyalkyl methacrylate ester.

Among the polymerization-curable phosphazene compounds obtained by the above-mentioned reaction, the chloro-substituted compounds which are practical as a dental resin are the number of groups of-[NP (X) (Y)]-n [(X). The total number of groups in (Y) is 2 per repeating unit.
And the number of groups of (X) and the number of groups of (Y) are greater than 0], (X) is a hydroxyalkyl methacrylate ester, (Y) is chloro, and (Y) is (X). On the other hand, it is 50 to 3 mol%. That is, when (Y) is 50 mol% or more with respect to (X), the curing time is significantly delayed, the mechanical properties of the cured product deteriorate, and the water absorption and wear increase. On the other hand, when (Y) is less than 3 mol% with respect to (X), the viscosity is significantly increased and the adhesiveness is further lowered. On the other hand, the above-mentioned (Y) is mixed with a polymerization-curable phosphazene compound of 50 to 3 mol% and a polymerization-curable phosphazene compound in which both (X) and (Y) are hydroxyalkyl methacrylate ester, and (Y) is 30 to 30%. 5 mol%
A polymerization-curable phosphazene compound prepared as a mixture within the range is also put to practical use.

In order to cure the polymerization-curable phosphazene compound of the present invention at room temperature, a general peroxide-tertiary amine-based polymerization initiator is used. In this case, the amount of the peroxide and amine used is preferably 0.05 to 5.0 parts by weight with respect to 100 parts by weight of the total amount of the monomers. Further, in the case of polymerizing with ultraviolet rays and visible light, as a photosensitizer, dibenzoyl, benzoyl, benzoin methyl ether, benzoin ethyl ether, P-chlorobenzophenone, P-methoxybenzophenone, benzoyl peroxide, ditertiary butyl peroxide, or By combining camphorquinone and amine, both are practically used clinically.

On the other hand, other polymerizable monomers which can be used by mixing with the polymerization-curable phosphazene compound of the present invention may be monofunctional or polyfunctional, and include, for example, methyl acrylate and methacrylate, hydroxy. Ethyl acrylate and methacrylate, ethylene glycol diacrylate and methacrylate, di- or tri- and tetraethylene glycol diacrylate and methacrylate, glycidyl acrylate and methacrylate, 2.2'-bis (acryloxyphenyl) propane, 2.2'-bis (methacrylate. Roxyphenyl) propane, 2.2′-bis [4- (3-methacryloxy) -2
-Hydroxypropoxyphenyl] propane and the like. Further, as vinyl ester of carboxylic acid, vinyl acetate, vinyl butyrate, vinyl stearate, ethylenically unsaturated dicarboxylic acid and its anhydride, fumaric acid,
It is also possible to use a mixture of maleic acid, itaconic acid, maleic anhydride and the like.

When the above-mentioned compound is mixed with the polymerization-curable phosphazene compound, the mixing amount thereof is changed depending on the viscosity, the curing rate and the desired physical properties, but usually 2 parts with respect to 100 parts by weight of the phosphazene compound of the present invention. ~ 100
Parts by weight are applicable. On the other hand, in order to improve abrasion resistance, hardness, strength, polymerization shrinkage and coefficient of thermal expansion of the polymerization-curable phosphazene compound, quartz, quartz, talc, alumina having a particle size of 20 μm or less, which is surface-treated with a silane and a titanate compound, Inorganic fillers such as apatite, glass beads, colloidal silica, barium silicate, nitriding and silicon carbide or organic fillers such as polymethylmethacrylate can be used.

The mixing amount is preferably 0.1 to 7 times the resin component. Further, a curing agent, a polymerization inhibitor, a colorant, an antioxidant, an ultraviolet absorber and the like are used in the above mixture as required. In order to be used in clinical practice,
The above-mentioned mixture is packaged in two forms. One paste or solution is mixed with a peroxide, and the other paste or powder is mixed with an amine-based polymerization accelerator to prepare a paste and a paste and a solution and a powder, respectively. It can be carried out by kneading for about 1 minute. In addition, a bonding material using the phosphazene compound according to the present invention, that is, a tooth substance is surface-treated with phosphoric acid, and then the compound is applied to form an adhesive layer to more strongly adhere to the tooth substance. When used as a solution, the present compound is dissolved in an organic solvent such as ethanol, chloroform and diethyl ether to a concentration of 5 to 40 parts by weight, and the solution is divided into two to form two packaging forms. Is mixed with a peroxide, and the other is mixed with an amine-based polymerization accelerator, and both are mixed and applied to the tooth structure. Then, the solvent is removed by evaporation to form an adhesive layer, which is practically used. Furthermore, in the case of the photopolymerization type, one packaging form is used, and the compound is mixed with a photosensitizer filler to form a paste,
It can be put into practical use by a method similar to a conventional surgical method by filling a tooth cavity with a thickness of 4 mm.

[0018]

The dental resin composition using the compound of the present invention has a main chain and a skeleton composed of nitrogen-phosphorus atoms, and contains a curable polymer and a chloro group. It shows the effects that could not be obtained with wood and filler. That is, a cured product of the compound exhibits excellent mechanical properties, and at the same time, a high adhesive strength is easily imparted by the low viscosity of the chloro group and the drastic improvement of the wettability of the adherend surface and the improved permeability. There is a possibility. Another effect is that the dental kneading material has good operability and can be carried out by the same clinical operation method as that of the conventional bonding material and filler.

[0019]

EXAMPLES Next, the present invention will be described more specifically with reference to examples. Reference Example 1 Polymerization-curable phosphazene compound A typical method for producing a dental polymerization-curable phosphazene compound is shown below, and the reaction time is 40 ° C., and the polymerization-curable group (X) and chlorine corresponding to the change in the reaction time are shown. The production mol% of (Y) is shown in Table 1. To 2 liters of frass, 34.8 g of cyclic trimer was dissolved in 150 ml of dehydrated benzene, 91.1 g of 2-hydroxyethyl methacrylate dissolved in 100 ml of benzene was added thereto, and then stirred under a nitrogen gas stream. 55.4 g of pyridine dissolved in 150 ml of benzene was added dropwise and reacted at 40 ° C. Next, after reacting for a predetermined time, the benzene solution was cooled to 5 ° C., and crystals of pyridine hydrochloride were filtered. The benzene solution was washed successively with 50 ml of 2N hydrochloric acid, 5% potassium carbonate and 5% sodium chloride, dehydrated with anhydrous magnesium sulfate, and benzene was removed under reduced pressure to obtain a liquid target product. . The amount of chlorine in the polymerization-curable phosphazene compound was determined by the amount of pyridine hydrochloride formed and the silver chloride method and expressed as mol%.

1) Adjustment of Filler and Measurement of Physical Properties (1) Filler As silica as a filler, 1.0 g of r-methacryloxypropyltrimethoxysilane was added to 100 ml of a 1% acetic acid aqueous solution and stirred, and then silica. After adding 100 g (average particle size 4 μm), naturally dry and then 1
It was used after being dehydrated at 15 ° C. (2) Measurement of compressive strength The sample mud kneaded at a predetermined ratio was made into a Teflon mold (4φ x 5 m
m), press the upper and lower surfaces against each other with glass plates, and after 15 minutes soak in 37 ° C water, release after 24 hours and use a compression tester to measure at a crosshead speed of 1 mm / min. did. (3) Measurement of adhesive strength One side of the adherend is exposed with the anterior labial surface of a fresh bovine tooth and embedded with a commercially available dental cold polymerization resin, and the surface is polished with emery paper # 800. The ivory surface was exposed, the surface was etched with a 50% phosphoric acid solution for 30 seconds, washed with water, and then air-dried with nitrogen gas. The other adherend was stainless steel, and the surface was # 400. It was used after being polished. A Teflon sheet having a film thickness of 45 μm was used as a spacer. Next, about 0.03 g of the sample mud kneaded at a predetermined ratio was taken and applied to both surfaces of the adherend, and 2 minutes after the start of kneading, a load of 2 kg was applied for 13 minutes, and the load was immediately removed. The test body was taken out of the water at 37 ° C., and after 24 hours, the test body was taken out of the water, and the adhesive strength was measured at a crosshead speed of 10 mm / min.

2) Composition consisting of two packages and physical properties Example 1 Package A (liquid) Linear polymerization curable phosphazene compound, average degree of polymerization n
In _{= 16, -O- (CH 2 CH} 2) O 2 CC (CH 3)
= CH ₂ (X) is 80.4 mol% and chloro (Y) is 1
98 parts by weight of 9.6 mol% compound, 2 parts by weight of triethylene glycol dimethacrylate, 0.5 part by weight of benzoyl peroxide, 0.02 part by weight of hydroquinone monomethyl ether. Package B (powder) 100 parts by weight of silanized filler, 0.4 parts by weight of N, N-diethanol-P-toluidine. The cured product obtained by kneading the packages A and B at 70:30 (parts by weight) has a compressive strength of 2460 (170) Kg / cm ² and an adhesive strength of 3
The value was 2.0 (8.2) Kg / cm ² . Standard deviation is in parentheses.

Reference Examples 2 to 6 Package A (Liquid) The phosphazene compound of the cyclic trimer has the reaction time of 9, 12, 24, 80 and 140 hours obtained in Reference Example 1, and is 95% by weight. Parts, triethylene glycol is 5 parts by weight of rudimethacrylate, 0.5 parts by weight of benzoyl peroxide, 0.0 of hydronone monomethyl ether.
2 parts by weight. Package B (powder) Table 2 shows the compressive strength and the adhesive strength when both the packages A and B employing the same composition as used in Example 1 were kneaded at 70:30 (parts by weight). It was A comparative example is shown below the table.

Reference Example 7 Package A (Paste) A phosphazene compound of cyclic tetramer, -O (CH ₂ CH _2
2 ) O ₂ CC (CH ₃ = CH ₂ (X) 76.4 mol%, chloro (Y) 23.6 mol% 35 parts by weight of the compound, triethylene glycol dimethacrylate 2.5 parts by weight, filler 12 0.5 parts by weight, benzoyl peroxide 0.5 parts by weight, hydrononone monomethyl ether 0.02 parts by weight Package B (basto) 35 parts by weight of the same phosphazene compound used in the above package A, trimethylolpropane trimethacrylate 2. 5 parts by weight, 12.5 parts by weight of filler, 0.04 parts by weight of dimethylparatoluidine 50: 5 of packaging A and B
The compression strength of the cured product mixed with 0 (parts by weight) is 2102.
(310) Kg / cm ² , showing an adhesive strength of 0.4
It showed (6.2) Kg / cm ² . Standard deviation is in parentheses.

[0024]

Industrial Applicability The composition using the polymerization-curable phosphazene compound of the present invention exhibits excellent mechanical properties as a dental bonding material and a filler, has a large adhesive force, and is resistant to dissolution. The suitable properties of the above are completely unattainable by conventional techniques of polymer compounds consisting of cement, amalgam and homo-bond, and these remarkable effects are immovable as a permanent binder and a permanent filler. is there.

[0025]

[Table 1]

[0026]

[Table 2]

Claims (3)

[Claims] 1. A general formula: (In the above formula, n is 3 to 18, and the group (X) is And R is selected from the group consisting of alkyl or alkylene groups containing 1 to 11 carbons, (Y) is a chloro group,
The number of (X) groups and the number of (Y) groups in the molecule is greater than 0, and the number of (X) groups and the number of (Y) groups may be the same or different, The sum of the number of groups and the number of groups of (Y) is 2 per the repeating unit) A chain phosphazene compound comprising the units shown. 2. The compound according to claim 1, wherein n obtained by ring-opening polymerization of a cyclic trimer is selected from linear compounds having 3 to 18. 3. (X) is —OCH ₂ (R) O ₂ CC (C
H ₃ ) = CH ₂ , R is selected from the group consisting of alkyl groups having 1 to 11 carbon atoms, (Y) is a chloro group, and (Y) is 50 to 3 mol% based on (X) The second claim,
The compound according to item 3 or 4.