JP2000344786A - Organic phosphoric acid compound, and polymerizable composition containing the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a nonaqueous polymerizable composition containing a phosphoric acid monomer excellent in preservation stability, and a phosphoric acid monomer, and excellent in preservation stability. SOLUTION: This organic phosphoric acid compound is the one having at least one of a radically polymerizable double bond, and at least one phosphoric acid residue having one or two hydroxyl groups, and further having at least one >=4C hydrocarbon group in the molecule, and contains <=1 wt.% water. The polymerizable composition contains the organic phosphoric acid monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to paints applied to metals and ceramics, rust inhibitors for metals, bone fillers, bone cements,
The present invention relates to a phosphoric acid monoester compound having a polymerizable group, which is particularly useful for dental adhesives and the like, and a polymerizable composition containing the phosphoric acid monoester compound (hereinafter sometimes referred to as a phosphoric acid monomer).

[0002]

2. Description of the Related Art Metal materials, ceramic materials,
Functional monomers having adhesive properties to living hard tissues such as teeth and bones have been studied. Particularly in the field of dental adhesives, since a tooth restoration made of metal or ceramic and adhesive strength to the tooth are required, a phosphate group having a reactivity or affinity with these materials and tissues is required. Attempts have been made to incorporate a polymerizable monomer having an acidic group such as a carboxylic acid group into a dental adhesive. According to the study by the present applicant, a polymerizable composition having a phosphate group and a phosphate monomer having a highly hydrophobic hydrocarbon group has high adhesiveness to these materials and tissues, It was clarified that a high degree of adhesive durability was exhibited even in a humid environment. The polymerizable monomer proposed by the applicant is -P (O) (OH) ₂ group, or> P (O) (O
H) and a polymerizable group such as a (meth) acryloyloxy group (hereinafter sometimes abbreviated as (meth) acrylic group in the present invention) are linked by a hydrocarbon group having a large number of carbon atoms. These techniques are disclosed in Japanese Patent Application Laid-Open Nos. 58-21607 and 58-21687 by the present applicant.
No. pp. 147-64. Incidentally, a phosphoric acid monomer particularly useful for a dental composition is synthesized by a method described in JP-A-59-139392 or the like, and is reacted with a monohydroxy (meth) acrylate compound and phosphorus oxychloride to form (meth) acrylic acid. A method synthesized as an acid ester monophosphate compound is used.

Hereinafter, the phosphate monomer of the present invention will be described mainly for dental applications. Examples of the application of the phosphoric acid monomer to the dental adhesive are roughly classified into those containing water and those not containing it depending on the object to be bonded. Dental cement, surface treatment agent for metal adhesion, bonding agent, surface treatment agent for ceramic adhesion, etc., which require adhesive strength to metals, ceramics and polymer materials, generally do not contain water in the composition, A polymerizable composition containing a hydrophobic monomer and an organic solvent is known. In addition, for teeth, a dental adhesive primer containing a phosphate monomer, water, and a hydrophilic monomer as main components is applied before bonding the restoration of the tooth, and the dental cement is applied thereon. By polymerizing and curing together with a bonding agent or the like, the tooth and the restoration of the tooth are firmly adhered.

As described above, the phosphoric acid monomer conventionally used has sufficient performance for practical use, but it is desired to further improve the following points to provide a higher-quality phosphoric acid monomer. Was. That is, among the above-mentioned dental adhesives, in the composition containing a phosphoric acid monomer, a hydrophobic monomer, and an organic solvent that does not contain water, the adhesion durability to metals and ceramics may be reduced. The phenomenon that we have found as a cause of this is that the phosphate monomer decomposes during storage. Phosphate monomers contained in the dental adhesive degrade during storage of the adhesive. It has been desired to further improve the storage stability of the phosphate monomer and the storage stability of the dental adhesive containing the phosphate monomer.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to a phosphate monomer having excellent storage stability, which is useful for a polymerizable composition for bonding living tissues such as metals, ceramics, polymer materials, teeth and bones. It is an object of the present invention to provide a non-aqueous polymerizable composition containing a phosphoric acid monomer and having excellent storage stability.

[0006]

That is, the present invention provides at least one radically polymerizable double bond and at least one phosphate residue having one or two hydroxyl groups, and has in its molecule An organic phosphoric acid compound having at least one hydrocarbon group having 4 or more carbon atoms and having a water content of 1% by weight or less. The present invention is also a polymerizable composition having excellent storage stability, comprising the above-mentioned organic phosphoric acid compound, organic solvent and / or polymerizable monomer. The water content in the phosphoric acid monomer described in the present invention is measured by the Karl Fischer method which is a general water measurement method.

Hereinafter, the present invention will be described in detail. Means for Solving the Problems The present inventors diligently studied the improvement of storage stability of a phosphoric acid monomer and the improvement of storage stability of a polymerizable composition containing a phosphoric acid monomer, an organic solvent and / or a polymerizable monomer. First, the present inventors relate to a dental adhesive which does not contain water and which is obtained by diluting a phosphoric acid monomer with an organic solvent and / or a polymerizable monomer. The cause of the decrease in durability was examined. As a direct cause, it has been found that the phosphoric acid monomer is decomposed due to long-term storage of the adhesive, and the adhesive durability is reduced.
This is considered to be the result of a decrease in the chemical bonding force and affinity of the adhesive to the adherend due to the decomposition of the phosphoric acid monomer. It was also found that the decomposition of the phosphoric acid monomer in the adhesive was promoted by moisture contained in the phosphoric acid monomer as a component of the adhesive.

[0008] Furthermore, since the decomposition of the phosphoric acid monomer is promoted by the water contained therein, the phosphoric acid monomer decomposes when stored for a long period of time or at a high temperature. The agent was found to have reduced adhesive durability.

That is, the present inventors reduce the water content of the phosphoric acid monomer in order to suppress the decomposition of the phosphoric acid monomer itself during storage. In order to ensure the storage stability of the dental composition, the water content of the phosphoric acid monomer is reduced. Admitted that it was important. The practical storage stability of the above and above is that the phosphate monomer can ensure the adhesive durability when used for a dental adhesive for more than 2 years in refrigerated storage, and that the dental adhesive can be stored at room temperature for more than 2 years.
In order to secure the adhesive durability for more than one year, the water content in the phosphoric acid monomer is desirably 1% by weight or less, more preferably 0.5% by weight or less. In the polymerizable composition comprising the phosphoric acid monomer, the organic solvent, and / or the polymerizable monomer according to the present invention, the phosphoric acid monomer is contained in the composition in an amount of 0.1 to 50% by weight, and more preferably. 1-30
% Range. Therefore, it is desirable that the amount of water contained in the entire composition containing the phosphoric acid monomer of the present invention is at most 0.5% by weight or less.

[0010] On the other hand, in the above-mentioned primer composition used for bonding teeth containing a phosphoric acid monomer, water, and a hydrophilic monomer as main components, which is a dental adhesive of the type containing water, the contained phosphoric acid monomer is used. It is effective to add a basic compound in order to greatly improve the storage stability. By adding a basic substance, the pH of the primer can be increased, and hydrolysis of the phosphoric acid monomer can be suppressed.

The phosphoric acid monomer of the present invention will be further described in detail. Organic having at least one radical polymerizable double bond and at least one phosphoric acid residue having one or two hydroxyl groups and having at least one hydrocarbon group having 4 or more carbon atoms in the molecule. Phosphoric acid compounds are particularly useful as adhesive monomers. According to the research of the present applicant, it is clear that the presence of a highly hydrophobic hydrocarbon group having 4 or more carbon atoms in the molecule contributes to high adhesiveness and durability to the aforementioned materials and living tissues. Was.

One of the phosphoric acid monomers of the present invention
A phosphoric acid residue having a hydroxyl group refers to a structural unit of> P (O) (OH) 2. Also, two hydroxyl groups
A phosphoric acid residue having the formula: -P (O) (OH)₂  The structural unit of
A phonic acid group is applicable. In addition, radical polymerization referred to in the present invention
Examples of possible double bonds include styrene groups, cyanoac
There are a ril group and a vinyl ether group.
It is a (meth) acryloyloxy group.

The phosphoric acid monomer of the present invention has at least one hydrocarbon group having 4 or more carbon atoms in the molecule. In the hydrocarbon group, a hydrogen atom may be substituted with a halogen, a hydroxyl group, a carboxyl group, a mercapto group, a cyano group, a phosphonic acid group, a phosphoric acid group, or the like. Also, the number of carbon atoms of the hydrocarbon group does not exceed 20, and the number of carbon atoms of all hydrocarbon groups in the molecule is 40 or less. It is preferable from the viewpoint of easiness. One of the preferable structures of the phosphoric acid monomer from the viewpoint of obtaining a high adhesive strength includes a hydrocarbon group having 4 or more carbon atoms,
Phosphoric acid monomers having a structure in which an organic group having a (meth) acrylate group is bonded to a phosphoric acid residue are exemplified. Examples of such phosphate monomers include:

[0014]

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Among the phosphoric acid monomers of this type, those in which the hydrocarbon group bonded to the phosphoric acid residue is an aromatic group are particularly preferred.

[0016] Further, another tag that also expresses a high adhesive force.
As monomers for ip, (meth) acrylate groups and phosphorus
Hydrophobic hydrocarbon group with 4 or more carbon atoms between the acid residue
In which an organic group containing is present as a linking group (spacer).
Monomers having a structure are preferred. That is, expressed by the following equation
Such monomers are exemplified. [H₂C = C (R¹) COO-]_p-X- (Z)_q−P
(O) (OH)₂  And [H₂C = C (R¹) COO-]_p-X- (Z)_q−P
(O) (OH)-(Z)_r-A where R¹Is a hydrogen atom or a methyl group, and p is not 1
And the integers q and r represent 0 or 1. X is
A p + 1-valent organic group containing a hydrocarbon group having 4 or more carbon atoms,
Z is an oxygen or sulfur atom, A is a monovalent organic residue]
The phosphoric acid monomer shown. Organic group represented by X
An example of the (spacer) is as follows.

[0017]

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Examples of the organic residue A are as follows.

[0019]

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Among these, particularly preferred phosphoric acid monomers are those in which the linking group (spacer) is an aliphatic group having 4 or more carbon atoms or a group containing an aromatic group having 8 or more carbon atoms. The acid monomer exhibits high affinity or reactivity with the adherend surface, and exhibits particularly high adhesive strength.

Further, it is relatively difficult to remove water from a compound having a hydrophilic group (phosphate group) such as a phosphate monomer. In the production of the phosphoric acid monomer, the following production method may be mentioned as a method for suppressing the water content.

Here, a method for synthesizing a (meth) acrylic acid ester monoester of phosphoric acid, which is particularly useful as a dental adhesive among phosphoric acid monomers, will be exemplified. A monohydroxy (meth) acrylate compound is reacted with phosphorus oxychloride in diethyl ether to obtain a (meth) acrylate monophosphate chloride, and water is added to the reaction mixture containing the phosphate chloride. In addition, it hydrolyzes the P-Cl bond. Diethyl ether and water are distilled off from the reaction mixture after the hydrolysis under reduced pressure to obtain a target (meth) acrylate monophosphate. The above-described vacuum distillation is suitable as a method for efficiently removing water in the phosphoric acid monomer. More desirably, the phosphoric acid monomer is diluted with an organic solvent capable of azeotroping with water, for example, benzene before performing the vacuum distillation, and then the distillation is performed under reduced pressure.
In addition, the addition of a salt anhydride such as anhydrous sodium sulfate, which is usually used for drying in a liquid organic compound, causes metal ions to remain in the phosphoric acid monomer and to be interposed between the phosphoric acid group of the phosphoric acid monomer and the metal ion. This is avoided because the viscosity of the phosphoric acid monomer increases due to the formation of the formed network and the distillation efficiency decreases. Further, in order to prevent polymerization at the time of distillation under reduced pressure, a small amount of a polymerization inhibitor such as dibutylhydroxytoluene is added to the reaction mixture, and dried air, more preferably, dried oxygen is introduced into the reaction mixture. Distillation is performed at 30 ° C. and 10 to 15 Torr in order to remove low boiling organic solvents.
Start with the degree and gradually increase the degree of decompression and temperature to 50
The water is distilled off under a reduced pressure of 5 to 10 Torr at ５〜60 ° C. to obtain a phosphate monomer having a low water content.

The phosphoric acid monomer of the present invention may be used alone as an adhesive to the above-mentioned various materials and living tissues. However, the phosphoric acid monomer assists the solubility of each component, adjusts the viscosity of the composition, In order to improve the mechanical strength of the cured product or to adjust other physical properties, it can be used as a polymerizable composition mixed with an organic solvent or a polymerizable monomer copolymerizable with the phosphoric acid monomer. As such an organic solvent, usually, a volatile organic solvent having a boiling point at normal pressure of 150 ° C. or lower, more preferably 100 ° C. or lower is used. For example, methanol, ethanol, isopropyl alcohol,
Acetone, methyl ethyl ketone, tetrahydrofuran,
Examples include diethyl ether, methyl acetate, ethyl acetate, butyl acetate and the like. Among them, ethanol, ethyl acetate and the like are preferably used. In addition, as the polymerizable monomer, known ones are used without any particular limitation.
(Meth) acrylate-based monomers are preferably used.
Examples of suitable (meth) acrylate monomers include:
Monofunctional (meth) acrylates such as methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid, 4- (meth) acryloyloxyethoxycarbonylphthalic anhydride, and triethylene glycol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A glycidyl di (meth) acrylate (commonly called Bis-GM
A), bifunctional (meth) such as an adduct (commonly called UDMA) of 2 mol of 2-hydroxyethyl (meth) acrylate and 2,2,4-trimethylhexamethylene diisocyanate
Trifunctional (meth) acrylates such as acrylate and trimethylolmethane tri (meth) acrylate, and tetrafunctional (meth) such as adducts of 2 mol of glycerin di (meth) acrylate and 2,2,4-trimethylhexamethylene diisocyanate Acrylates are mentioned.

The composition of the present invention may further contain a known polymerization initiator depending on the purpose. For example, in the case of carrying out a heating polymerization catalyst such as benzoyl peroxide and room temperature polymerization (chemical polymerization), the benzoyl peroxide /
Redox systems such as amines, organic sulfinic acids (or salts thereof) / amines / peroxides, and the like are preferably used. Examples of the photopolymerization catalyst include an α-diketone / reducing agent system and an ultraviolet polymerization catalyst such as benzyldimethyl ketal and acylphosphine oxide. on the other hand,
It may be provided as a polymerizable composition containing no polymerization initiator. For example, when used as a dental metal adhesive, a composition comprising a phosphoric acid monomer and an organic solvent and / or a polymerizable monomer and not containing a polymerization initiator is applied to a dental restoration made of dental metal. There is a method in which the organic solvent is volatilized, and the polymerizable composition of the present invention is further applied thereon as a bonding agent or a dental cement, and the restoration is adhered to the tooth to perform treatment. In this case, even if the polymerization initiator is not contained in the composition of the present invention, the polymerization initiator contained in the bonding agent or the dental cement migrates to the adhesive layer, or the bonding agent or the dental cement is used. Radicals generated during the polymerization are transferred to the adhesive layer, and the adhesive composition is polymerized and cured, thereby exhibiting an adhesive function.

The polymerizable composition containing the phosphoric acid monomer of the present invention is used for coating materials such as metals, ceramics, and polymer materials, paints, surface modifying (treatment) agents, bone filling compositions, and dental fillings. And the like. In particular, the use of the phosphate monomer of the present invention as a dental composition in which the phosphoric acid monomer is useful includes dental adhesives, dental cement, pit and fissure filling materials, dental composite resins, denture base resins, and the like. Examples of the dental adhesive in the composition of the present invention include a liquid monomer comprising the phosphoric acid monomer of the present invention, a solvent other than water, and / or a (meth) acrylate monomer, and a known polymerization initiator. It is a polymerizable composition. The composition exhibits excellent adhesion to metals, ceramics and polymer materials.

When used as a dental composite resin or cement, the composition containing the phosphoric acid monomer of the present invention, a solvent other than water, and / or a (meth) acrylate monomer, and a known polymerization initiator may be used. Further, a composition further containing a filler is preferable. Examples of such fillers include silica, glass containing silica as a main component (barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, etc.), inorganic fillers such as alumina, and organic powders such as polymethyl methacrylate. And an organic-inorganic composite filler. In these compositions, a monomer composition (liquid) and a filler (powder) are prepared in advance.
Or a paste-like composition mixed, or an oxidizing agent and a reducing agent in each of the filler and the monomer composition,
Immediately before use, the two can be mixed and kneaded to activate the catalyst and form a chemical polymerization. The dental composition using the phosphoric acid monomer of the present invention may further include a solvent, a polymerization inhibitor, an ultraviolet absorber, a coloring agent, an antibacterial agent, and the like, if necessary.

[0027]

EXAMPLES The present invention will be described in detail below, but the present invention is not limited to these examples.

First, a method of measuring various quantities in the embodiment will be described. (1) Measurement of water content of phosphoric acid monomer Karl Fischer reagent (Mitsubishi Chemical Corporation: titer 2.5 to 3.5 mgH ₂ ) using Karl Fischer moisture meter “MK-A2” (manufactured by Kyoto Electronics Industry Co., Ltd.). O / ml), and the water content was determined by the following formula according to the known Karl Fischer method. The average of three measurements of one phosphoric acid monomer sample was taken as the water content of the sample. Water content (% by weight) = Drip amount of Karl Fischer reagent (ml) × Title of Karl Fischer reagent (mgH ₂₎
O / ml) / sample (g)

(2) Measurement of Residual Rate of Phosphate Monomer The phosphate monomer was subjected to reverse phase chromatography column "Micro Bonder Pack _C18 " (Waters) by LC-10A type high performance liquid chromatography (manufactured by Shimadzu Corporation). Using a mixed solvent of water / methanol as a mobile phase and an ultraviolet light detector (wavelength setting: 254 nm) to determine the content of pure phosphoric acid monomer in the phosphoric acid monomer before storage by heating at 100% The content of the pure phosphoric acid monomer after storage at 45 ° C. for 14 days was defined as the residual ratio (%). The content of the phosphoric acid monomer pure product in the phosphoric acid monomer was defined as a ratio of the peak area of the phosphoric acid monomer to the entire peak area detected.

(3) Measurement of Bonding Strength of Dental Adhesive For the compositions 1 and 2 which are the dental adhesives shown in Table 1 below, the bonding strength to a dental metal was determined according to the following procedure. Was evaluated. (i) Preparation of adhesion test piece 1 (in the case of composition 1) A flat surface was formed on a cast of dental gold-silver palladium alloy "Castwell MC" (GC Corporation), and the flat surface was changed to # 1.
000 silicon carbide abrasive paper. In order to define the area to be adhered to this surface, the adhesive was thinly applied to a metal adherend prepared by sticking a tape having a hole with a diameter of 5 mm, and a dental visible light irradiator “Lightel II” (Kuraray) The adhesive is cured by irradiating the adhesive for 20 seconds with a small amount of a paste of a composite resin for dental filling “CLEARFIL AP-X” (manufactured by Kuraray Co., Ltd.) and a glass plate is placed on the paste. Then, the composite resin was cured by irradiating it with light for 40 seconds using the irradiator. Next, a dental adhesive resin cement “Panavia 21” was applied to a sandblasted flat surface of one end of a stainless steel rod having a diameter of 7 mm, and the stainless steel rod was bonded to the composite resin.

(Ii) Preparation of an adhesion test piece (in the case of composition 2) A mixture of material A and material B of composition 2 is applied to a sandblasted flat surface of one end of a stainless steel rod having a diameter of 7 mm. Then, it was bonded to the metal adherend prepared in the same manner as in (i) above. (iii) Tensile test The adhesion test specimens of (i) and (ii) were stored in water at 37 ° C for 24 hours, and stored in water at 37 ° C for 24 hours as an adhesion durability test, and then placed in water at 70 ° C. The test pieces immersed for 10 days were subjected to a tensile test of an adhesive test piece at a crosshead speed of 2 mm / min using a universal testing machine (manufactured by Instron) to measure the tensile adhesive strength. The adhesive strength of the adhesive test piece under the former storage condition was defined as the initial value of the adhesive, and the adhesive strength under the storage condition of the latter was defined as the adhesive durability value. In addition, a tensile test was performed on five adhesion test pieces in one experimental system, and the average value of the five specimens was defined as the tensile adhesive strength of each experimental system.

Example 1, Example 2, Comparative Example 1, Comparative Example 2 The phosphoric acid monomer used in this example and this comparative example is 10-methacryloyloxydecyl dihydro which is widely used as a dental adhesive. Gen phosphate (hereinafter MDP) was used.

(1) MDP Storage Stability Test The water content and purity of MDP were measured according to the above-mentioned methods, and then sealed in a glass sample tube and placed in a thermostat at 45 ° C.
After storing for 4 days, the purity was measured again. Further, the dental adhesive composition shown in Table 1 was prepared using the MDP after storage under heating, and the metal adhesive strength was measured according to the method described above. The results are summarized in Table 2.

(2) Storage stability test of dental adhesive The dental adhesive composition of Table 1 prepared using MDP having various water contents was stored in a polyethylene container at 50 ° C for 21 days. Thereafter, the adhesive strength was measured, and the results are summarized in Table 2. Example 1 and Example 2 with small water content
Has a good storage stability at 45 ° C. for 14 days, and a higher value of the initial adhesive strength to metal and the adhesive water resistance of the dental adhesive manufactured using the MDP after storage. Was done. In addition, 5 of the dental adhesive composition prepared using the MDP of Examples 1 and 2 having a low moisture content
The decrease in metal bond strength after storage at 0 ° C. for 21 days is shown in Comparative Example 1,
It was small compared to 2.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

According to the present invention, by providing a phosphoric acid monomer having a low water content, a phosphoric acid monomer having excellent storage stability and a polymerizable composition having excellent storage stability can be obtained.

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Claims (6)

[Claims] 1. A hydrocarbon group having at least one radical polymerizable double bond and at least one phosphoric acid residue having one or two hydroxyl groups, and having a hydrocarbon group having 4 or more carbon atoms in the molecule. An organic phosphate compound having at least one organic phosphate compound, wherein the water content is 1% by weight or less. 2. The organic compound according to claim 1, which is an organic phosphate compound in which a hydrocarbon group having 4 or more carbon atoms, an organic group having a (meth) acrylate group, and one hydroxyl group are bonded to a phosphate residue. Phosphate compounds. 3. A (meth) acrylate group and one or two
The organic phosphoric acid compound according to claim 1, wherein the phosphoric acid residue having two hydroxyl groups is an organic phosphoric acid compound bonded by a linking group having at least one hydrocarbon group having 4 or more carbon atoms. 4. The organic phosphate compound according to claim 3, wherein the linking group is an aliphatic group having 4 or more carbon atoms. 5. The organophosphate compound according to claim 3, wherein the linking group is an organic group having at least 8 carbon atoms and containing at least one aromatic group. 6. A compound having at least one radical polymerizable double bond and at least one phosphoric acid residue having one or two hydroxyl groups, and having a hydrocarbon group having 4 or more carbon atoms in the molecule. What is claimed is: 1. A polymerizable composition comprising at least one organic phosphoric acid compound, the organic phosphoric acid compound having a water content of 1% by weight or less, an organic solvent and / or a polymerizable monomer.