JP2925155B2 - Curable resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a curable resin composition. Specifically, it is a novel curable resin composition containing an inorganic filler that has been surface-treated using an organic phosphorus compound. The curable resin composition in the present invention means a composition containing an inorganic filler and a polymerizable monomer as essential components, and is used for industrial materials and materials for living tissue. These include molding compositions, dental composite resins (tooth filling and restorative materials, inlays, crown prosthetic materials such as crowns, denture materials, abutment building materials, etc.), dental adhesives, denture bases Examples include materials, impression materials, artificial bones, bone cements, and the like.

(Prior Art) In recent years, in the field of dentistry, a composition containing an inorganic filler and a polymerizable monomer as essential components, for example, a dental composite resin has been used. The inorganic filler used for dental composite resin is
Usually, it is used after surface treatment is performed in advance. By performing the surface treatment, the wettability of the interface between the filler and the polymerizable monomer in the composition is improved, the content of the filler is increased, and the dispersibility of the filler is improved. In the molded composite resin, the adhesion between the filler and the resin interface is strengthened and the mechanical strength is improved. A silane coupling agent represented by γ-methacryloyloxypropyltrimethoxysilane is known in the art as a surface treatment agent used for such a purpose.

If we look at the industry widely, in addition to silane coupling agents, titanate coupling agents, zircoaluminate-based coupling agents, higher alkyl alcohols, higher fatty acids, and organic phosphate esters are known as surface treatment agents for inorganic fillers. It is. Among them, the organic phosphoric acid esters are related to the present invention, and the main points are described below.

JP-B-60-3431 describes an inorganic filler surface-treated with the following organic phosphate.

(Wherein R ₁ is a hydrogen or methyl group, R ₂ is an alkylene group having ₂ to 6 carbon atoms or a halogen-substituted derivative thereof,
Or polyoxyethylene group _{-CH 2 -CH 2 O-CH 2} -CH 2
_n (n = 1 to 20) or polyoxypropylene group (N = 1 to 20). JP-A-59-170131 discloses a general formula Inorganic powder whose surface is modified with one or two or more organic phosphorus compound treating agents selected from the group represented by the following formula (where R and R 'are the same or different from 1 to 30 carbon atoms) Alkyl, alkenyl, aryl, alkoxy, alkenoxy, aryloxy or a group having a substituent on these organic groups).

In addition to these, JP-A-56-54795 and JP-A-57-128728
Japanese Patent Application Laid-Open Nos. 57-168954 and 57-198735 describe similar techniques.

These known industrial resin compositions are obtained by mixing a high molecular weight resin with a surface-treated inorganic filler. Since the high molecular weight resin has no or few reactive groups, it is unlikely that the high molecular weight resin and the surface treating agent are chemically bonded to a high degree, and there is a limit in improving the mechanical performance. Therefore, a resin composition having excellent mechanical performance, in which a resin and a surface treating agent are highly bound, is desired.

In addition, the dental composition which is one of the objects of the present invention is a resin composition having excellent water resistance since its cured product is used in the oral cavity for a long period of time, and its water resistance is extremely important. Things are also desired.

In the above-mentioned known art, there is no description about improvement of the water resistance of the resin composition or possibility of application to dental use, and it is expected that a known organic phosphorus compound is effective for the purpose of the present invention. Can not.

(Problems to be Solved by the Invention) Conventionally used resin compositions that require high mechanical strength and high water resistance, especially inorganic fillers that have been frequently used in dental compositions, contain a large amount of silicon. Contains (eg, silica and glasses based on silica)
And practical examples in which an inorganic filler containing a metal, a metal oxide or a salt as a main component is blended as a main component are rare.

One of the major reasons why inorganic fillers containing these metal elements have been actively used as a main component in resin compositions requiring water resistance is that a surface treatment technique applied to them has not been established. That is, even if a conventionally known silane-based or titanium-based surface treatment agent is used for these inorganic fillers, a remarkable surface treatment effect as compared with silica is not exhibited. Therefore, in a resin composition containing a large amount of these fillers treated with a conventionally known surface treatment agent, a decrease in material strength due to poor bonding at the resin-inorganic filler interface (particularly under wet conditions) Inconveniences such as falling off of the filer had to be made.

However, when the above-mentioned metal or metal oxide or salt is introduced as an inorganic filler, a resin composition having more preferable performance than a conventional composition containing silica can be obtained.

For example, by substituting silica for metal oxides such as alumina and zirconia, it is possible to provide a dental composite resin having excellent aesthetics, mechanical strength, and chemical stability, while a natural tooth material such as hydroxyapatite can be provided. By blending a filler similar to the above, it is possible to provide a dental adhesive having little harm and excellent biocompatibility. The use of a metal filler also enables the development of a new type of dental composite having spreadability and toughness.

In view of the above, there has been a demand for the development of a surface treatment technique capable of effectively acting on an inorganic filler containing a metal element as described above.

An object of the present invention is to provide a resin composition containing a surface-treated inorganic element-containing inorganic filler and a radical polymerizable monomer in order to greatly improve the performance of a resin composition containing an inorganic filler. is there. ADVANTAGE OF THE INVENTION According to this invention, the resin composition which has the property which cannot be obtained by the conventional resin composition containing silica is obtained.

Further, according to the present invention, since the surface treating agent and the radical polymerizable monomer are highly chemically bonded, a resin molded product having excellent mechanical performance can be obtained. A preferred use of the resin composition of the present invention is a dental composition. Hereinafter, the description of the dental composition will be mainly described, but it goes without saying that the resin composition of the present invention is not limited to dental use.

(Means for Solving the Problems) The inventors of the present invention have conducted intensive studies to solve the above-described problems, and as a result, an organic phosphorous compound having a specific molecular structure has an inorganic filler containing a metal element. The present inventors have found that this can be a very effective surface treatment agent, and have completed the present invention.

That is, the resin composition provided by the present invention has the following general formula (a) Wherein A ₁ represents an organic group having at least one ethylenic double bond capable of undergoing radical polymerization and having 5 to 60 carbon atoms, and A ₂ represents a hydroxyl group, a mercapto group, or a halogen atom. Or an organic group having 1 to 60 carbon atoms, wherein at least _one of A ₁ and A ₂ has 4 carbon atoms.
It contains at least one from 60 to 60 hydrocarbon groups. X ₁ represents an oxygen atom or a sulfur atom, X ₂ represents a hydroxyl group, a mercapto group or a halogen atom.] A pentavalent phosphorus oxo acid represented by A curable resin composition comprising an inorganic filler and (b) at least one radical polymerizable monomer selected from the group of methacrylates and acrylates.

The inorganic filler used in the resin composition of the present invention is characterized by containing a metal element as a component, and the metal element according to the present invention is a long-period type periodic table, a line connecting boron and astatine. , And excludes hydrogen and the elements B, Si, As, Te, and At on the line. Among these metals, those useful for the purpose of the present invention include, for example, Al, Mg, Ca, T
i, Cr, Fe, Co, Ni, Cu, Zn, Sr, Zr, Pd, Hg, Sn, Ba, Pt, Au, La and the like.

These metal elements can take various forms in the inorganic filler. For example, the most common Al ₂ O
_{3, ZnO, CaO, TiO 2} , ZrO 2, La 2 O 3, BaO, Fe 2 O 3, SrO 2, including the oxides, such as equal, hydroxides such as Al (OH) _3, CaF halides, such as ₂ or BaSO ₄ and CaSO _4,
Such as sulfates, carbonates such as CaCO ₃ , CaHPO ₄ , Ca (H ₂
PO ₄ ) ₂ , Ca ₃ (PO ₄ ) ₂ , Ca ₂ P ₂ O ₇ , Ca (PO ₃ ) ₂ , Ca ₄ P ₂ O ₉ , Mg ₂ P
It can be contained in various salt forms such as phosphates such as ₄ O ₁₂ , Al (PO ₃ ) ₃ , AlPO ₄ .

 In addition, these metal compounds form a single component in the inorganic filler.
In addition to existing as a minute, multi-component ceramics
And may be of the same kind as minerals. Gold for multi-component systems
In addition to the existence of multiple
Min, for example, SiO_Two, P_TwoO_Five, B_TwoO_Three, Si_ThreeN_Four, SiC, B_FourIncluding C, BN, etc.
It is also acceptable to have. Examples of these are K_TwoO ・ T
iO_Two, BaO ・ TiO_Two, CaO ・ Al_TwoO_ThreeAnd zircon (SiO_Two−ZrO
_TwoSystem), Sialon (SiO_Two−Al_TwoO_Three−S_ThreeN_FourSystem), La glass
Ceramics (La_TwoO_Three−Al_TwoO_Three−SiO_TwoSystem, for example ShottG
M31-684 ), Ba glass (BaO-Al_TwoO_Three−B_TwoO_Three−SiO_Twosystem,
For example, ShottGM27-884 , Shott8235 , Ray−Sorb T−
2000 , Ray-SorbT-3000 ) Sr glass (SrO_Two−Al_TwoO_Three−
SiO_TwoSystem, eg Shott GM32-087 , Ray-SorbT-4000
), And also various known as biograss
CaO-P_TwoO_FiveContaining crystallized glass or hydroxyapatite
And so on. In addition to these forms, metal powder
It may be used as a filler as it is. This place
In this case, the metal is used alone or as an alloy.

The inorganic filler used in any of the above-mentioned cases is indispensable for being insoluble in water, because it includes use under highly wet conditions for dental use. The term “insoluble” as used in the present invention is defined as a solubility having a saturation solubility of 0.1% by weight or less in water at room temperature.

The form of these inorganic fillers is not limited at all, and various forms and sizes such as spherical, crushed, needle, whisker, and plate are selected according to the purpose. Also,
The particle size of these inorganic fillers is not particularly limited, but those having a particle size in the range of 5 nm to 0.5 mm are preferably used. Here, the particle size means an average value of the maximum diameter and the minimum diameter of the filler.

The biggest feature of the present invention is the inorganic filler described above,
The point is that the surface treatment is carried out in advance with the pentavalent phosphorus oxo acid represented by the general formula (1) or a derivative thereof (hereinafter sometimes referred to as an organic phosphorus compound) before use. (Hereinafter, an untreated filler may be referred to as an inorganic filler (A).) As a specific example of "a radically polymerizable ethylenic double bond" which is a feature of the chemical structure of the organic phosphorus compound (1). The following can be mentioned.

(However, Z ₁ is a halogen atom), Among these ethylenic double bonds, the ethylenic double bond of acrylic acid, methacrylic acid or styrene is particularly preferably used in the present invention. When the surface treatment of the inorganic filler (A) is performed using an organic phosphorus compound having a chemical structure obtained by removing the double bond from the organic phosphorus compound (1), the adhesion between the filler and the matrix is poor, and the object of the present invention is completely What is not achieved.

Next, the organic group referred to in the present invention includes (a) a hydrocarbon group [where hydrogen is a halogen, a hydroxyl group, a carboxyl group,
Mercapto group, cyano group, phosphonic acid group, Or (b) at least one of the above hydrocarbon groups has at least one of the following bonding portions It refers to a group composed of a single bond or a bond formed by bonding them together to form a complex.

 Hereinafter, a specific example will be described in more detail.

Examples belonging to (a) hydrocarbon groups Examples belonging to the group consisting of a hydrocarbon group and a bond in (b) At least one of the organic groups A ₁ and A _2, i.e. wherein the hydrocarbon group contained in either or both (i)
And has 4 to 60 carbon atoms. However, hydroxyl group, carboxyl group, phosphonic acid group, Since a hydrophilic substituent such as a group reduces the hydrophobicity of a hydrocarbon group, a structure substituted by three or more of these hydrophilic substituents per hydrocarbon group is considered disadvantageous for the purpose of the present invention. You.

When the number of carbon atoms of the hydrocarbon group is less than 4, a problem often occurs in the water resistance of the obtained resin composition. However, when the number of carbon atoms is 4 or more, more preferably 5 or more, a level suitable as a dental material is obtained. , And particularly excellent water resistance when the number of carbon atoms is 8 or more.

The number of carbon atoms of A ₁ affects the surface treatment effect, the surface treatment effect of the desired properties as a dental material is obtained in the range of 60 to no 5 carbon atoms. Further, when A ₂ is an organic group, the number of carbon atoms of A ₂ also affects the surface treatment effect, and the number is preferably 60 or less.

Among the organic phosphorus compounds represented by the general formula (1),
From the viewpoints of reactivity with the surface of the inorganic filler, copolymerizability with the polymerizable monomer (b), ease of synthesis, and the like, those particularly preferably used in the present invention are the compounds described below. .

In the compound represented by the general formula (1), (i) A ₁ is a compound represented by the following general formula: Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ has at least one hydrocarbon group having 4 to 40 carbon atoms, and Y ₁
And all the atoms bonded to Y ₂ are carbon atoms, and each represents a (m + 1) -valent organic group having 4 to 40 carbon atoms, and Y ₁ represents —COO—,
—COS—, —CONR ₃ —, wherein R ₃ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and Y ₂ represents a carbon atom, a sulfur atom or Wherein m is an integer from 1 to 4 and k represents 0 or 1.] and A ₂ is a compound which is a hydroxyl group, a mercapto group or a halogen atom. .

Among the compounds described in (i), compounds in which X ₁ is oxygen and X ₂ and A ₂ are hydroxyl groups are preferred.
This is referred to as (i) -a group.

(I) -a The organic phosphorus compound (i) -a is the most effective compound group when a base metal element is contained in an inorganic filler.
Examples of base metal elements are Al, Mg, Ca, Ti, Fe, Co, Cr, Ni, Cu, Z
n, Sr, Zr, Sn, Ba, La, Cr, etc., and in particular, Al ₂ O ₃ , TiO ₂ , Zr
Metal oxides such as O ₂ , Fe ₂ O ₃ , ZnO, CaCO ₃ , Ca ₃ (PO ₄ ) ₂ , A
metal salts such as LPO _4, hydroxyapatite, and Ti, F
Efficient for metal powders containing e, Co, Cr, Ni, Cu, Zn, etc.

 Specific examples of the (i) -a group compound are shown below.

In the compound shown in (i), the compound in which X ₁ is oxygen, and A ₂ and X ₂ are halogens such as chlorine, bromine, fluorine, iodine, etc. is a group of (i) -b, and the halogen is chlorine. Preferred specific examples are shown below.

(I) -b Specific examples of this compound are as follows.

A third group of compounds shown in (i) are those wherein X ₁ bonded to P is S and A ₂ and X ₂ are hydroxyl, mercapto or halogen atoms. This group is defined as (i) -c.

(I) -c The organic phosphorus compound (i) -c exhibits an excellent surface treatment effect on inorganic fillers containing noble metal elements as well as base metal elements. Examples of precious metals here are Pd, Ag,
Pt, Au and the like. In these compounds, Specific examples of groups include And the like. Of these, Exist as tautomers.

 Specific examples of (i) -c group compounds are shown.

Other compounds used in the present invention is a compound represented by the general formula (1), (ii) A 1 is the following formula _{[However, R 1, R 2, Y} 1, Y 2, m and k are compounds R ₁ as described in _{(i), R 2, Y} 1, Y 2, m and k synonymous] 1 represented by Wherein A ₂ is a group represented by the following general formula: [However, R _'1 is a hydrogen atom or a methyl group, _{R' 2} is
The carbon atoms are all the atoms bonded to Y ₁ and Y ₂
Represents an organic group having a valence of (j + 1) from 40 to 40, and Y ′ ₁ represents —CO
O—, —COS—, or —CONR ′ ₃ —, wherein R ′ ₃ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms,
Y ′ ₂ represents an oxygen atom, a sulfur atom or And j represents an integer from 0 to 4, and l represents 0 or 1.].

In the compounds shown in (ii), X ₁ is oxygen, the compound X ₂ is a hydroxyl group is one of those preferred, to do this and (ii) -a group.

(Ii) -a (Ii) The organic phosphorus compound of -a is also effective for inorganic fillers containing a base metal element, and the organic phosphorus compound (i)-
Inorganic fillers that are essentially the same as a are subject to surface treatment.

 Specific examples of the compound (ii) -a are shown below.

In the compounds shown in (ii), compounds in which X ₁ is oxygen and X ₂ is a halogen atom such as chlorine, bromine, fluorine or iodine are defined as (ii) -b group. Preferred compounds wherein the halogen atom is chlorine are shown by the structural formula below.

(Ii) -b The organic phosphorus compound (ii) -b, the hydroxyl group of X ₂ is one which is replaced by a chlorine atom, express similar surface treatment effect and the compound of (ii) -a in (ii) -a compound. The same relationship exists between the compounds of (i) -b and (i) -a.

 Specific examples of the compound (ii) -b are shown below.

In the compound of (ii), X ₁ bonded to P is S and X ₂
Is a hydroxy group, a mercapto group or a halogen atom, is defined as (ii) -c.

(Ii) -c Similar to (i) -c, the organic phosphorus compound (ii) -c is effective for inorganic fillers containing a base metal or a noble metal element. Compound (ii) -c can be advantageously used because it is easier to synthesize and has better stability than (i) -c.

Compound (ii) -c Specific examples of groups include Is raised. Note that Is in a tautomeric relationship.

 Next, specific examples of the compound (ii) -c are shown below.

Further, in the present invention, the following organic phosphorus compounds can be used.

(Iii) A ₁ is the following general formula _{[However, R 1, R 2, Y} 1, Y 2, m and k are compounds R ₁ as described in _{(ii), R 2, Y} 1, Y 2, m and k synonymous] 1 represented by A ₂ is a group represented by the following general formula [However, R ′ ₁ , R ′ ₂ , Y ′ ₁ , Y ′ ₂ , j, and 1 represent R ′ ₁ , R ′ ₂ , Y ′ ₁ , Y ′ ₂ , j described in the compound (ii). And l
Synonymous, X ₁ and X ₂ are compounds is a monovalent organic group represented by X ₁ and X ₂ synonymous] described in compound (i).

 The structural formula of this compound is shown below.

(Iii) This compound is referred to as group (iii).

When X ₁ and X ₂ do not contain a sulfur atom, the organic phosphorus compound (iii) is effective for a filler containing a base metal element as in the case of the above-mentioned compounds which do not contain sulfur. On the other hand, if it contains X ₁ and / or X ₂ are sulfur atoms, as well as compounds containing sulfur atoms in the compounds described above, it is observed remarkably effective even for filler containing a noble metal element. In any case, R ₁ = R ′ ₁ , R ₂ = R ′
₂ , Y ₁ = Y ′ ₁ , Y ₂ = Y ′ ₂ , m = j, and k = 1 are preferably used because of easiness in synthesis.

 Specific examples of the compound (iii) are shown below.

In any of the organic phosphorus compound (i) ~ (iii) also, R ₂ is preferably one having a bulky branched chain without and some chain length long chain. The reason is like this
It is presumed that the use of the compound having R ₂ allows the surface of the inorganic filler to be densely covered with molecules of the surface treating agent.

Referring to R ₂ , a particularly preferred structure of R ₂ when m is 1 is as follows.

−R ₄ −Y ₃ R ₅ −Y _{3 h} R ₄ − [where h is 0 or 1. When h = 0, R ₄ represents a hydrocarbon group having 4 to 20 carbon atoms, and Y ₃ represents an oxygen atom. When h = 1, R ₄ represents a hydrocarbon group having 2 to 9 carbon atoms, R ₅ represents a hydrocarbon group having 4 to 20 carbon atoms,
Y ₃ represents an oxygen atom, —COO— or —OOC—.] Specific examples of R ₂ are shown below.

Structures of other preferred R ₂ are the following.

CH _{2 i} [where i is an integer from 4 to 40] In the present invention, the organic phosphorus compounds (i) to (ii)
In addition to i), the following organic phosphorus compounds are also suitably used as the surface treating agent.

The synthesis method of these organophosphate compounds is Organophosph
orus Compound (GMKosola-poff, Wiley, 1950), O
rganophosphorus Monomers and Polymers (Ye.L. Gefter
Author, Pregamon Press 1962), Modern Organic Synthesis Series 5, Organic Phosphorus Compounds (Organic Synthetic Chemistry Association, edited by Gihodo, 19)
71) Beilstein (Springer-Verlag) can be referred to.

More specifically, JP-A-58-128393, JP-A-58-128393
192891, JP-A-58-21687, JP-A-58-21688, JP-A-59-21
139392, JP-A-59-135272, JP-A-59-142268, JP-A-60-166363, JP-A-60-166364, and JP-A-57-151607.

The method of modifying the surface of the inorganic filler (A) using the organic phosphorus compound (1) can be performed by a method generally known as a surface treatment method of powder using a surface treatment agent, The method can be broadly classified into a wet method and a dry method.

In the wet method, the inorganic filler (A) and the organic phosphorus compound (1) are mixed with an appropriate amount of a solvent such as water, alcohol, hexane, or the like.
Suspension in benzene, toluene, xylene, etc. in a slurry form and thoroughly agitate. However, the optimum values of the conditions such as the solvent used, the reaction temperature, and the reaction time vary variously depending on the combination of the inorganic filler (A) and the organic phosphorus compound (1). Can find out. After stirring for a predetermined time, the solvent was distilled off under reduced pressure.
The surface treatment is completed when it is removed by a method such as excess or freeze-drying.

In this case, it is desirable to go through a heating step in any of the processing steps. Heating may be performed while a slurry comprising the inorganic filler (A), the organic phosphorus compound (1) and the solvent is being stirred, or while the solvent is being distilled off. The solvent may be further heated after distilling off. In particular, when heated in a suspended state with a solvent, dispersibility is improved, and the surface of the filler is uniformly treated. The heating temperature is desirably in the range of 50 ° C. to 150 ° C. If it is lower than 50 ° C., the heating effect is poor, and if it exceeds 150 ° C., a radical polymerizable double bond may cause a reaction.

When X ₂ is a hydroxyl group or a mercapto group in the organic phosphorus compound (1), the compound is reacted with an inorganic surface by a desalting reaction using the alkali metal salt or ammonium salt of the compound according to the wet treatment method described above. There is also.

In the dry method, the inorganic phosphorus (A) is put into a mixer such as a Hensiel mixer or a ribbon blender, and the organic phosphorus compound (1) is sprayed as it is or diluted with an appropriate solvent while stirring. At this time, it is desirable to stir while heating. This method is suitable for processing a large number of fillers.

In any of the above-mentioned treatment methods, the amount of the organic phosphorus compound used for the inorganic filler is preferably equal to or more than an amount capable of covering most of the surface of the inorganic filler with a monomolecular film of the organic phosphorus compound. This amount can be estimated from the value of the specific surface area of the inorganic filler measured by the BET method or the like, the ratio of the metal element on the surface, and the like. For example, the smaller the particle size of the inorganic filler and the larger the ratio of the metal element on the surface, the larger the amount of the organic phosphorus compound required. Considering the conditions, 100 parts by weight of inorganic filler
0.01 to 100 parts by weight are used. However, the optimal amount of the organic phosphorus compound (1) is determined based on experiments so that the desired physical properties of the obtained resin composition are maximized.

The amount of the organic phosphorus compound (1) attached to the inorganic filler (A) can be estimated by elemental analysis, infrared analysis, X-ray fluorescence analysis, etc. of the surface-treated inorganic filler.

By the way, a method is also conceivable in which a predetermined amount of an organic phosphorus compound is mixed in a radical polymerizable monomer, and an inorganic filler that has not been subjected to a surface treatment is kneaded therein to obtain a resin composition.

However, compared to the method of the present invention using an inorganic filer which has been subjected to a surface treatment in advance, this method has a higher dispersibility of the filler, a filling amount of the filler in the polymerizable monomer, and a mechanical property of the obtained resin product. It is inferior in terms of target strength and is not desirable.

By the way, in the case of a silica-based glass powder containing a metal element such as barium or lanthanum which is often used for a dental composite resin, many silanol groups are present on the surface. When the organic phosphorus compound (1) is used for the surface treatment of such an inorganic filler, a surface treatment effect is exerted on a metal element, but the effect is poor on a silanol group, so that a desired result cannot be obtained. . For a glass filler having a high silica content, it is preferable to use a known silane coupling agent, for example, γ-methacryloyloxypropyltrimethoxysilane, together with the organic phosphorus compound (1).

In such a case, a two-step treatment method is employed in which the surface treatment of the present invention is first performed, and then the surface treatment is performed again using a silane coupling agent. As a modification, a method of performing a surface treatment of the present invention after treating with a silane coupling agent or a method of mixing the organic phosphorus compound (1) and the silane coupling agent and performing a one-step treatment is also possible.

The radical polymerizable monomer used in the composition of the present invention can be copolymerized with the organic phosphorus compound (1) used as the surface treating agent, and is a (meth) acrylate-based monomer [(meth) acrylate refers to methacrylate). And acrylate).

Besides these, α-cyanoacrylic acid, crotonic acid,
Esters with monohydric or dihydric alcohols such as cinnamic acid, sorbic acid, maleic acid, and itaconic acid; (meth) acrylamides such as N-isobutylacrylamide; and vinyl esters of carboxylic acids such as vinyl acetate. And small amounts of comonomers such as vinyl ethers such as butyl vinyl ether, mono-N-vinyl compounds such as N-vinylpyrrolidone, and styrene derivatives.

Examples of (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate,
Monofunctional (meth) acrylates such as lauryl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, neopentyl glycol di (meth)
Acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, bisphenol A di (meth) acrylate, 2,2-
Bis [(meth) acryloyloxypolyethoxyphenyl] propane, 2,2-bis [4- (3-methacryloxy-2-hydroxypropoxy) phenylpropane (Bis
-GMA), a bifunctional monomer such as an adduct of 1 mol of 2,2,4-trimethylhexamethylene diisocyanate and 2 mol of 2-hydroxyethyl (meth) acrylate, trimethylolpropane tri (meth) Examples include trifunctional monomers such as acrylates, tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate, and adducts of 1 mol of 2,2,4-trimethylhexamethylene diisocyanate with 2 mol of glycerin di (meth) acrylate. Can be. These monofunctional and polyfunctional (meth) acrylates are used alone or in combination of two or more.

In addition, in addition to the above-mentioned monomers, it is desirable to use a known adhesive monomer in combination when it is expected to have an adhesive property to teeth and dental metals. Such a monomer has an acidic group in the molecule. What is an acidic group here? In addition to the narrowly defined acidic groups such as Acid anhydride groups such as (However, Z ₁ represents F, Cl, Br or I).

The following compounds are exemplified as specific examples of the adhesive monomer.

The mixing ratio of the surface-treated inorganic filler and the polymerizable monomer varies greatly depending on the use of the resin composition of the present invention,
Usually, the amount of the inorganic filler surface-treated with respect to 1 part by weight of the polymerizable monomer is in the range of 0.01 to 100 parts by weight.
A more detailed description of the composition ratio will be described later.

In the composition of the present invention, in addition to the inorganic filler, other fillers can be further added as necessary. The filler may be any of an inorganic substance and an organic substance, and examples of the inorganic filler include quartz, amorphous silica,
An inorganic filler mainly containing silica such as borosilicate glass is exemplified. These fillers are used after a surface treatment with a silane coupling agent in advance. On the other hand, examples of the organic filler include polymer powders such as polymethyl methacrylate, polyvinyl chloride, and polystyrene;
Organic-inorganic composite fillers as disclosed in (1).

The composition of the present invention in which the inorganic filler and the polymerizable monomer are mixed is heated by heating it to 100 ° C. or higher, or by applying an external energy such as irradiating an electron beam. It can be cured to be converted into a molded product, but in the main use of the dental composition, it is a common method to facilitate polymerization and curing by adding a polymerization initiator.

The polymerization initiator used in the present invention is not particularly limited and may be any known one, but is usually selected in consideration of the polymerizability of the polymerizable monomer and the polymerization conditions. For example, when (meth) acrylate is polymerized by heating, organic peroxides such as benzoyl peroxide (referred to as BPO) di-t-butyl peroxide, cumene hydroperoxide, and 2,2'-azobisisobutyro are used. Nitrile, 1,1'-
Compounds such as azobis (cyclohexane-1-carbonitrile) are preferably used.

On the other hand, when performing room temperature polymerization, benzoyl peroxide / dimethylaniline system, cumene hydroperoxide / thiourea system, ascorbic acid / Cu ²⁺ salt system, organic sulfinic acid (or salt thereof) / amine / peroxide In addition to oxidation-reduction type initiators such as tributylborane, organic sulfinic acid, etc., are also preferably used.

On the other hand, when performing photopolymerization by irradiation with visible light,
Oxidation-reduction systems such as α-diketone / tertiary amine, α-diketone / aldehyde and α-diketone / mercaptan are preferred. α-diketones include camphorquinone, diacetyl, 2,3-pentanedione, benzyl, acenaphthenequinone, and phenanthraquinone; and tertiary amines include N, N-dimethylaminoethyl methacrylate, N, N
-Dimethylaminoethyl benzoate, Michler's ketone, aldehydes such as citronellal, lauryl aldehyde, o-phthaldialdehyde, p-octyloxybenzaldehyde, and mercaptans such as 1-decanethiol, thiosalicylic acid, 2-mercaptobenzoxazole, 4-mercaptoacetophenone and the like can be mentioned. Further, an α-diketone / organic peroxide / reducing agent system obtained by adding an organic peroxide to these oxidation-reduction systems is also suitably used. When performing photopolymerization by ultraviolet irradiation, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoin methyl ether, benzyldimethyl ketal, benzophenone, 2-methylthioxanthone, diacetyl, benzyl, azobisisobutyronitrile, In addition to tetramethylthiuram disulfide, the above-mentioned visible light photopolymerization initiator is also preferably used.

The addition amount of these polymerization initiators depends on the amount of the polymerizable monomer (b).
Is in the range of 0.01 to 10%.

In the resin composition of the present invention, if necessary, additives such as a polymerization inhibitor, an ultraviolet absorber, a fluorescent agent, and a pigment are added.

In the dental composition of the present invention, depending on its wide range of uses, an inorganic filler as a constituent component is selected according to the type of the inorganic filler (A) and the type of the organic phosphorus compound (1) as a surface treating agent. ), The polymerizable monomer is appropriately selected and the composition is adjusted.

In the case of a dental composition, the following composition is used. Dental composite resins are required to have high strength and aesthetics (especially transparency). To meet this requirement, 1.
An alumina filler having a refractive index of 60 to 1.70, a (meth) acrylate-based monomer having a refractive index of 1.50 to 1.60 after polymerization and curing, and a silica-based inorganic filler having a refractive index of 1.50 to 1.60 are used in combination. When these components are used, the components can have refractive indexes close to each other, so that the transparency is excellent and the mechanical performance can be improved by adding an alumina filler. In this case, the particle size and the amount of the filler can be appropriately selected depending on the purpose.

In addition, in the case of a dental adhesive material for bonding to teeth, particularly to dentin, it is desired to use an inorganic filler excellent in biocompatibility. Examples of such a filler include hydroxyapatite, calcium phosphate, calcium hydrogen phosphate, calcium diphosphate, calcium metaphosphate, calcium pyrophosphate, various bioglasses, and the like. Further, for the purpose of strengthening the tooth quality, it is possible to use a fluorine-containing inorganic filler such as calcium fluoride. These fillers are subjected to a surface treatment with the organic phosphorus compound (1).

As the polymerizable monomer, a system in which an adhesive monomer is blended with the (meth) acrylate monomer described above is used. The amount of the filler is in the range of 0.5 to 20 parts by weight per 1 part by weight of the polymerizable monomer.

When the dental adhesive is a fish sealant, a metal oxide such as alumina, titanium oxide, or zirconium oxide or calcium fluoride is preferably used as the inorganic filler. The content of these fillers is in the range of 0.01 to 5 parts by weight.

By the way, the resin composition of the present invention is provided to a user in various processing states depending on the use. An example is shown below.

(I) One paste (or liquid) state A filler (or liquid) is obtained by mixing a filler, a polymerizable monomer, and a polymerization initiator all at once, and the polymerization initiator is a photopolymerization initiator and / or A medium to high temperature type polymerization initiator for the purpose of heat polymerization is used.

(Ii) Two pastes (or liquids) state An oxidizing agent and a reducing agent of an oxidation-reduction type polymerization initiator capable of room-temperature polymerization are separated, and two pastes (or a mixture thereof together with a filler and a polymerizable monomer) are mixed. )liquid.

(Iii) Powder-liquid state The powder-liquid state is composed of a powder obtained by mixing the above reducing agent (or oxidizing agent) and filler powder and a solution (liquid) of a polymerizable monomer in which the above oxidizing agent (or reducing agent) is dissolved.

(Iv) Molded state The composition in the state of (i) to (iii) is molded and then polymerized and cured. A denture corresponds to this.

The composition of the present invention provided to the dentist or dental technician in the semi-processed state of (i) to (iii) is molded, polymerized and hardened by the hands of these users, and is used as a dental material. It will work.

(Effect) Surface-treated in advance using the organic phosphorus compound (1),
A composite material containing a metal element and containing a metal element-containing inorganic filler insoluble in water and a radical polymerizable monomer is a known technique, that is, the inorganic material previously surface-treated using a known silane coupling agent. It exhibits a high level of performance unattainable with a composite material using a filler or a silica-based filler. For example, in metal salt powders such as calcium carbonate, calcium phosphate, and hydroxyapatite, surface modification with a silane coupling agent has little effect, and therefore, a composite material using such a filler has poor mechanical strength, It cannot be used in dental applications where material strength is required. However, if the surface modification of the metal salt is performed using the organic phosphorus compound (1), the adhesion between the filler and the matrix resin is remarkably improved, and a high-strength dental material using the metal salt as a filler can be obtained. .

Also, with metal powders, the effect of the surface modification by the silane coupling agent is weak, and the strength of the obtained composite material decreases rapidly under wet conditions, making it extremely difficult to use it as a dental material. However, by performing a surface treatment using the organic phosphorus compound (1), a dental composite material having significantly improved initial strength and strength under wet conditions can be obtained.

In addition, although the surface modification effect of the silane coupling agent is remarkably observed, even in the case of a metal oxide having a problem in the water resistance of adhesion between the resin matrix and the filler, for example, a filler of aluminum oxide or titanium oxide, the organic phosphorus is also used. The surface treatment with the compound (1) showed a remarkable effect, and it became possible to introduce these fillers into a dental composite resin.

Another major feature of the present invention is the high density packing of the inorganic filler into the resin matrix. Particle size 1μ
m or less, a so-called submicron filler has a large viscosity increasing effect even when subjected to a surface treatment with a known silane coupling agent, and it has been difficult to fill the polymerizable monomer solution with a high density. Particularly, it was difficult to use ultrafine particles having a particle size of 0.1 μm or less. However, the effect of increasing the viscosity of the submicron filler treated with the organic phosphorus compound (1) is significantly weakened, and a 1.5 to 3 times that of the surface treated with a known silane coupling agent is required. It is now possible to pack. As a result, the hardness, compressive strength, wear resistance, and the like of the dental composite resin can be further improved.

Another feature resides in the improved aesthetics and radiopacity of the dental composite resin. A filler containing a metal element, particularly a heavy metal element, has a high X-ray opacity, and if used in a large amount, it is easy to produce a dental composite resin having an X-ray contrast property equal to or higher than enamel. Further, since it is easy to make the refractive index larger than that of quartz (n = 1.55), the use of a filler closer to the refractive index of natural teeth (n = 1.61 to 1.63) makes it possible to obtain optical characteristics such as light reflection and refraction. It is easy to create a dental composite resin having excellent aesthetics similar to each of natural teeth.

INDUSTRIAL APPLICABILITY The present invention is applicable to a material for a living hard tissue. Specifically, dental composite resin (for example, tooth filling restoration material, crown prosthesis material such as inlay and crown, denture material,
In addition to dental abutment materials), it is also applied to dental adhesives (eg, bonding agents, luting resin cements, bush sealers), denture base materials, and impression materials, and these dental materials are enhanced. To contribute.

In the application to the field of orthopedic surgery, for example, bone cement containing hydroxyapatite, artificial bone formed by combining hydroxyapatite with an organic polymer, and artificial bone reinforced with ceramic whiskers are expected.

For industrial use, it can be used as a material for artificial marble, decorative boards, and various mechanical parts.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Example) Example 1 Average particle size 0.9 μm, BET specific surface area 5.4 m^Threealuminum / g
NA (Showa Denko, AL-160SG-4 ) 50g, toluene 200ml
And 10-methacryloyloxydecyl dihydrodiene
Put 3g of phosphate into flask and stir vigorously.
The mixture was heated under reflux for an hour. After cooling, the alumina powder is removed from the suspension.
Separate the powder and wash thoroughly with toluene before
After drying under vacuum for a further 2 hours at 90 ° C in air,
A surface-treated filler was obtained. Phosphorus content of this powder
Was determined by X-ray fluorescence analysis, and 10-methacryloyl
Estimate the amount of adsorption of xyldecyl dihydrogen phosphate
Is 1.2 parts by weight per 100 parts by weight of alumina powder.
Was.

Next, 35 parts by weight of 2,2-bis [methacryloyloxypolyethoxyphenyl] propane (having an average of 2.6 ethoxy groups in the molecule and hereinafter referred to as D-2.6E),
40 parts by weight of an adduct of 1 mol of 2,4-trimethylhexamethylene diisocyanate and 2 mol of glycerin dimethacrylate (hereinafter referred to as U-4TH), 25 parts by weight of neopentyl glycol dimethacrylate (hereinafter referred to as NPG) and benzoyl peroxide One part by weight was mixed to obtain a polymerizable monomer composition. 30 parts by weight of this composition and 70 parts by weight of the above-mentioned surface-treated filler were mixed and kneaded to obtain a polymerizable composite composition (paste).

 The following evaluation was performed using this composition.

(I) Consistency The better the wetting of the polymerizable monomer, the better the dispersibility in the polymerizable monomer and the softer the viscosity of the kneaded composition. Therefore, the quality of the surface treatment can be determined by measuring the consistency as an index of the viscosity. In this experiment, the value measured by the following method was used as the consistency. That is, 0.5 ml of the paste was weighed, and the paste was allowed to stand at the center of a glass plate (5 × 5 cm). Next, a glass plate (5 × 5 cm) with a load of 40 g was gently placed thereon, and after 120 seconds had elapsed, the major axis and minor axis of the spread paste were measured through the glass plate, and the arithmetic average of both was measured. The value was taken as the consistency. The values are shown in Table 1 and are the average of three independent measurements.

(Ii) Flexural strength Flexural strength was measured as an index of the adhesive strength between the polymerized and cured resin matrix and the filler. First, the above paste was charged into a mold of 2 × 2 × 30 mm,
After curing by heating for a time, the sample was taken out of the mold to obtain a prismatic test piece. The specimen was stored in air at 37 ° C. for one day, and then subjected to a three-point bending test (distance between fulcrums at both ends = 20 mm, crosshead speed =
1 mm / min). The results shown in Table 1 are the average of 10 measurements.

(Iii) Water resistance of flexural strength The flexural test piece prepared in the manner described in Section ii was immersed in 70 ° C. water for 10 days to accelerate the deterioration, and then the flexural strength was measured. No.
By comparing with the initial bending strength described in the section ii, the quality of the water resistance can be determined. Table 1 shows the average value of the ten test pieces.

Examples 2 to 41 Using the organic phosphorus compounds shown in Table 1 in place of 10-methacryloyloxydecyl dihydrodiene phosphate used in Example 1, the results of evaluation by the same method as in Example 1 were used. The results are shown in Table 1.

Comparative Example 1 In place of the surface-treated alumina filler used in Example 1, a paste was produced using alumina powder that had not been subjected to surface treatment, and the consistency and flexural strength were measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Examples 2 to 5 Instead of the organic phosphorus compound used in Example 1,
Table 2 shows the results of the same evaluation as in Example 1 performed using alumina powder that was surface-treated using an organic phosphorus compound as shown in Table 2.

Comparative Example 6 To 30 parts by weight of the polymerizable monomer used in Example 1, 10-
0.83 parts by weight of methacryloyloxydecyl dihydrodiene phosphate was mixed, and 69.17 parts by weight of alumina powder without surface treatment was added thereto, followed by mixing and kneading to prepare a paste, and the consistency and bending were obtained in the same manner as in Example 1. Table 2 also shows the results of measuring the strength. Compared with the product obtained in Example 1, the bending strength is greatly reduced.

Examples 42 to 50 Titanium oxide powder (rutile type, average particle size = 0.2 μm) 40
g, toluene 400ml, and organic phosphorus compounds shown in Table 3
4 g were mixed and heated under reflux for 2 hours. After cooling, the titanium oxide powder was taken out, washed with toluene, dried in vacuum, and then subjected to dry heat treatment at 90 ° C. for 2 hours to obtain a surface-treated filler.

50 parts by weight of the polymerizable monomer composition used in Example 1 and 50 parts by weight of the above-mentioned filler were mixed and kneaded to obtain a paste. Using this paste, the consistency and flexural strength were measured in the same manner as in Example 1, and the results are shown in Table 3.

Comparative Examples 7 to 11 Pastes were prepared under the conditions of Example 42 using a filer which was subjected to a surface treatment using the organic phosphorus compounds shown in Table 3 and a filer which was not subjected to the surface treatment to the titanium oxide powder. Using this paste, the consistency and flexural strength were measured in the same manner as in Example 1, and the results are shown in Table 3.

Examples 51 to 59 50 g of hydroxyapatite powder (average particle size: 75 μm) was mixed with 150 ml of toluene and 1 g of an organic phosphorus compound shown in Table 4 and subjected to surface treatment in the same manner as in Example 1. 80 parts by weight of this filler and 20 parts by weight of the same polymerizable monomer composition as in Example 1 were mixed and kneaded to prepare a paste. Using this paste, consistency and flexural strength were performed in the same manner as in Example 1, and the results are shown in Table 4.

Comparative Examples 12 to 16 Pastes were prepared under the conditions of Example 51 by using a filler that had been subjected to surface treatment using the organic phosphorus compounds shown in Table 4 and a filler that had not been subjected to surface treatment on the hydroxyapatite powder. Using this paste, the consistency and flexural strength were measured in the same manner as in Example 1, and the results are shown in Table 4.

Examples 60 to 63 50 g of silver powder (particle size: 50 μm or less) were placed in a flask, and 100 ml of toluene and 0.5 g of the organic phosphorus compound shown in Table 5 were placed in a flask. 93 parts by weight of this filler and 7 parts by weight of the polymerizable monomer composition used in Example 1 were mixed and kneaded to obtain a paste. Using this paste, the consistency and flexural strength were measured in the same manner as in Example 1, and the results are shown in Table 5.

Comparative Examples 17 and 18 A paste was prepared under the conditions of Example 60 by using a filler that had been subjected to surface treatment using the organic phosphorus compounds shown in Table 5 and a filler that had not been subjected to surface treatment.
Using this paste, the consistency and flexural strength were measured in the same manner as in Example 1, and the results are shown in Table 5.

Example 64 Shot glass La glass ceramics (GM-31684) , n = 1.
56) is crushed with a vibrating ball mill and the particle size range is 0.1-20μ
m, a powder having an average particle size of 2.8 μm was obtained. 100 weight of this powder
Parts by weight of γ-methacryloxypropyltrime
Inorganic film surface-treated with toxicoxysilane
I got an Irah. Next, average particle size 0.02μm, BET specific surface area 100
m^Two/ g, alumina fine powder with refractive index n = 1.65 (Nippon Ae
Rosil, aluminum oxide C ) 50g, 10-me
Tacryloyloxydecyl dihydrodiene phosphate
Heated to reflux for 3 hours.
Was. After allowing to cool, collect the filler by centrifugation,
After drying in air, heat the surface at 90 ° C for 2 hours in the air for surface treatment
An alumina fine powder filler was obtained. Source of this alumina powder
Elementary analysis revealed an ash content of 85.5% by weight. Polymerizable monomer
As the monomer, the same polymerizable monomer composition as in Example 1 (n = 1.
528) instead of BPO for 100 parts by weight of the composition
0.5 parts by weight of 2,4,6-trimethylbenzoyldiphenylphosphine
Sulfin oxide was blended.

 500 parts by weight of the surface-treated La glass filler, surface treatment
180 parts by weight of fine alumina powder and polymerizable monomer 100
After mixing and kneading parts by weight, the mixture is vacuum degassed and the polymerizable composition
). Xenon lamp (curl)
Tour (Kulzer) Dentacolor XS 90 seconds using
After irradiating light and polymerizing and curing, heat at 120 ° C for 30 minutes.
Flexural strength, compressive strength, Brinell hardness
Table 6 shows the measurement results of the transparency and the transparency.

In addition, the definition of various quantities and the measuring method in this example are as showing below.

(I) Flexural strength The same mold as in the example was used, polymerized and cured by a predetermined method, and then immersed in water at 37 ° C. for 24 hours using an Instron universal testing machine with a crosshead speed of 1 mm / min and a distance between fulcrums of 2
A 3-point bending test was performed at 0 mm. The measured values are the average of 10 samples.

(Ii) Compressive strength The paste is charged into a cylindrical mold having a diameter of 4 mm and a height of 4 mm,
After polymerizing and curing by the prescribed method, remove from the mold 37 ℃,
What was immersed in water for 24 hours was measured at a crosshead speed of 2 mm / min using an Instron universal testing machine. The measured values are the average of 10 samples.

(Iii) Brinell hardness The paste was charged into a mold having a diameter of 10 mm and a thickness of 5 mm, and the upper surface was pressed with a cover glass and then polymerized and cured by a predetermined method.

The cured product was taken out of the mold, and the glass pressure contact surface was ground by 0.5 mm with # 220 sandpaper to obtain a test surface.

(Iv) Transparency The paste was formed into a disk shape of 20 mmφ × 0.85 mm, cured by a predetermined method, and used as a test piece. The lightness was measured using a chromaticity meter (Nippon Denshoku Co., Ltd., Type 80) and the chromaticity was measured with a standard white plate placed behind the test piece (L ₁ ).
And the difference ΔL = L ₁ −L ₂ from the lightness (L ₂ ) when the chromaticity was measured by placing a standard blackboard behind the same test piece was used as an index of transparency. In this evaluation method, the larger the value of ΔL, the higher the transparency.

(V) Refractive index The refractive index of the alumina and the inorganic filler was determined by using an Atsube refractometer, using the D line of a sodium lamp as a light source, and diluting methane, bromonaphthalene, methyl salicylate, dimethylformamide, etc., in which sulfur was dissolved, as a solvent. It was measured by the method. Refractive index after curing of the polymerizable monomer (n _P)
Is a test piece of a cured product obtained by depolymerizing a polymerizable monomer in which 0.5 part by weight of benzoyl peroxide was dissolved and then thermally polymerizing at 110 ° C for 30 minutes to form a 5 mm × 10 mm × 20 mm rectangular parallelepiped. Was measured using a refractometer.

(Vi) Range of average particle size and particle size For alumina fine powder, the range of the particle size was determined based on a transmission electron micrograph.

La glass ceramics were measured using an automatic particle size distribution analyzer, model CAPA500, manufactured by Horiba, Ltd. The measurement principle is the light transmission centrifugal sedimentation method (natural sedimentation is also used).

Example 65 Cured product obtained after performing similar photopolymerization using the same paste used in Example 64 (without heating)
Table 6 also shows the results of similar tests conducted for

Comparative Example 19 30 per 100 parts by weight of the alumina fine powder used in Example 64
Using parts by weight of γ-methacryloxypropyltrimethoxysilane, using the same La glass ceramics and polymerizable monomer as in Example 64, using an alumina filler surface-treated according to a conventional method, at the same compounding ratio. Although mixed, the viscosity was so high that kneading was impossible.

Comparative Example 20 Average particle size 0.016 μm, BET specific surface area 130 m^Two/ g
Fine powder (made by Nippon Aerosil, Aerosil 130 ) 100 weight
30 parts by weight of γ-methacryloxypropyl
Using Limethoxysilane, perform surface treatment according to the usual method,
A fine powder silica filler was obtained. La Gala identical to that in Example 64
Ceramics, polymerizable monomer and fine powder alumina
Use the above fine powder silica filler instead of
, But the viscosity was so high that kneading was impossible.

Comparative Example 21 Average particle size 0.04 μm, BET specific surface area 50 m^Two/ g silica
Fine powder (made by Nippon Aerosil, Aerosil OX-50) ) 100
15 parts by weight of γ-methacryloxypropyl
Surface treatment is carried out according to the usual method using
A powdered silica filler was obtained. La glass identical to that in Example 64
Ceramics, polymerizable monomer and fine alumina powder
-Use the above silica filler in place of
Sample mixed and kneaded at the same time and cured by the same polymerization method
Are shown in Table 6.

Example 66 40 parts by weight of D-2.6E, 40 parts by weight of 1,10-decanediol dimethacrylate, 20 parts by weight of U-4TH and 1 part by weight of benzoyl peroxide (BPO) were mixed and dissolved to form a polymerizable monomer. Obtained. 250 parts by weight of the fine powder alumina filler used in Example 64 was mixed and kneaded with 100 parts by weight of this polymerizable monomer to obtain a polymerizable composition. Paste this paste at 130 ° C, 1
Table 6 also shows the results of the same tests performed on the cured products that were heated and polymerized for a period of time.

Comparative Example 22 250 parts by weight of the surface-treated alumina filler used in Comparative Example 19 and 100 parts by weight of the polymerizable monomer used in Example 66 were mixed. Was.

Comparative Example 23 The same evaluation as in Example 66 was performed using 200 parts by weight of the fine powder silica filler used in Comparative Example 21 and 100 parts by weight of the polymerizable monomer used in Example 66. Table 6 shows the results. It was shown to.

Example 67 The cured product produced in Example 66 was ground by a vibration ball mill and classified to give a particle size range of 0.1 μm to 100 μm, and an average particle size of 15 μm.
m were obtained. On the other hand, D-2.6E 70 parts by weight, 1,6-hexanediol dimethacrylate 30 parts by weight, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide 0.
5 parts by weight were mixed and dissolved to obtain a polymerizable monomer composition. 20 parts by weight of this composition, 55 parts by weight of the powder and 25 parts by weight of the fine powder alumina filler used in Example 64 were mixed and kneaded to obtain a polymerizable composition. Table 6 shows the results of the same tests performed on the cured product obtained by the same polymerization method as in Example 64.

Comparative Example 24 After the cured product produced in Comparative Example 23 was pulverized with a vibration ball mill, the particles were classified and the particle size range was 0.1 μm to 100 μm, and the average was 14 μm.
m were obtained.

20 parts by weight of the polymerizable monomer used in Example 67, powder 55
Parts by weight and ultrafine silica filler 25 used in Comparative Example 21
The parts by weight were mixed and kneaded to obtain a polymerizable composition. The same evaluations as in Example 67 were performed. The results obtained are shown in Table 6.

Example 68 The hydroxyapatite powder used in Example 51 was pulverized with a rotary ball mill to obtain a powder having an average particle size of 4.5 μm. 50 g of this powder was mixed with 150 ml of toluene and 1.5 g of 10-methacryloyloxydecyl dihydrodiene phosphate, and subjected to surface treatment in the same manner as in Example 1. Using this filler, a powder-liquid adhesive was prepared with the following composition.

Agent A (liquid) D-2.6E 50 parts by weight NPG 25 parts by weight 2-hydroxyethyl methacrylate 10 parts by weight 10-methacryloyloxydecyl dihydrodiene phosphate 15 parts by weight Benzoyl peroxide 1 part by weight Hydroquinone monomethyl ether 0.05 Agent B ( Powder) The above-mentioned surface-treated hydroxyapatite filler 100 parts by weight Sodium benzenesulfinate 0.3 parts by weight N, N-diethanol-p-toluidine 0.3 parts by weight In preparing the B agent, sodium benzenesulfinate and N, N A solution prepared by dissolving diethanol p-toluidine in 10 parts by weight of methanol was sprayed on a filler and then the methanol was evaporated.

Using the A agent and the B agent, an adhesion test was performed on human dentin. That is, the crown portion of the human molar was poured with water and cut off with a cutter to expose the dentin. The dentin surface was subjected to acid etching with a 40% aqueous solution of orthophosphoric acid for 1 minute, washed with water, and then the surface water was blown off with an air gun. Next, a double-sided adhesive tape having a hole of 5 mmφ was attached to the surface. In addition, fix the human teeth so that the cross section is horizontal, and insert the inner diameter 6mm onto the tape hole.
A plastic ring having a diameter of 5 mm and a height of 5 mm was placed so that the centers of the holes coincided with each other. Next, an appropriate amount of the agent A and the agent B was kneaded at a weight ratio of 1: 4 (about 1 minute). When the paste became a soft paste, it was pressed into the plastic ring, a hook for a tensile test was inserted, and allowed to stand for 30 minutes. . Then, after being immersed in water at 37 ° C. for 24 hours, the adhesive strength was measured at a crosshead speed of 2 mm / min using an Instron universal tester (average value of five test pieces). The flexural strength of this cured product was set at the initial value and 70%.
The values after immersion in water at 10 ° C. for 10 days were measured and are shown in Table 7.

Comparative Example 25 Instead of 10-methacryloyloxydecyldihydrodiene phosphate used as the surface treatment agent in Example 68, using γ-methacryloxypropyltrimethoxysilane, surface treatment was performed according to a conventional method, and the same composition was used. Table 7 shows the results of the same tests performed on the prepared adhesives.

Comparative Example 26 An adhesive having the same composition as in Example 68 was prepared without performing the surface treatment on the hydroxyapatite powder used in Example 51, and the same test was conducted. The results are shown in Table 7.

Example 69 The hydroxyapatite powder used in Example 51 was pulverized with a vibration ball mill to obtain a powder having an average particle size of 2.3 μm. 200 g of this powder was mixed with 600 ml of toluene and 10 g of 10-methacryloyloxydecyl dihydrodiene phosphate, and subjected to a surface treatment in the same manner as in Example 69. 75 parts by weight of this surface-treated filler, 20 parts by weight of methyl methacrylate, 5 parts by weight of 1.10-decanediol dimethacrylate and 0.1 part by weight of benzoyl peroxide were mixed to obtain a polymerizable composition. This was poured into a mold and polymerized by heating under pressure at 140 ° C. for 1 hour to obtain a molded product having appropriate physical properties and biocompatibility as an artificial tooth root or an artificial bone.

Example 70A colorant was added to the photopolymerizable composition prepared in Example 64,
For three types of pastes whose chromaticity after curing is as shown in Table 8
(Each color is for cervical, dentin,
Suitable for naming. ). Gold and silver palladium
Alloy (manufactured by GC, Castwell) Casting and maxillary midsection
Create a suitable metal frame as a resin resin crown
And an opaque cover on this frame to block metallic colors
-(Kulzer Dentacolor Opacer A-20)
Xenon lamp (Kulzer Dentacolor XS ) 90 seconds light
Irradiation was performed. Fill the prepared cervical paste here
Then, light irradiation was performed for 30 seconds. Then put a paste for dentin
After building up and illuminating for 30 seconds, the energy is
The paste for the melt was built up and irradiated with light for 90 seconds. Continue
Put this in a hot air dryer and heat at 120 ° C for 20 minutes.
Was. After cooling down, correct the shape and then buff
As a result, a better forehead crown was created.

──────────────────────────────────────────────────の Continuation of front page (51) Int.Cl. ⁶ Identification code FI A61K 6/083 500 A61K 6/083 500 C08F 230/02 C08F 230/02 (56) References JP-A-62-135448 (JP, A) JP-A-59-170131 (JP, A) JP-A-57-168954 (JP, A) JP-A-57-198735 (JP, A) JP-A-1-90277 (JP, A) −3431 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 20/00-20/70 C08F 120/00-120/70 C08F 220/00-220/70 C08F 2 / 00-2/60 C08F 299/00-299/08 C08F 290/00-290/14 C09C 3/00-3/12 A61K 6/00-6/10 C08F 230/00-230/10 C08F 30/00- 30/10

Claims (12)

(57) [Claims] (1) The following general formula: Wherein A ₁ represents an organic group having at least one ethylenic double bond capable of undergoing radical polymerization and having 5 to 60 carbon atoms, and A ₂ represents a hydroxyl group, a mercapto group, or a halogen atom. Or an organic group having 1 to 60 carbon atoms, wherein at least _one of A ₁ and A ₂ has 4 carbon atoms.
It contains at least one from 60 to 60 hydrocarbon groups. X ₁ represents an oxygen atom or a sulfur atom, and X ₂ represents a hydroxyl group, a mercapto group or a halogen atom.] A metal element previously surface-treated using a pentavalent phosphorus oxo acid or a derivative thereof represented by the formula: And (b) a curable resin composition comprising at least one radical polymerizable monomer selected from the group consisting of methacrylates and acrylates. Wherein A ₁ is the following formula Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ has at least one hydrocarbon group having 4 to 40 carbon atoms, and Y ₁
And all the atoms bonded to Y ₂ are carbon atoms, and each represents a (m + 1) -valent organic group having 4 to 40 carbon atoms, and Y ₁ represents —COO—,
—COS— or —CONR ₃ —, wherein R ₃ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and Y ₂ represents an oxygen atom, a sulfur atom or And m represents an integer from 1 to 4, and k represents 0 or 1.] wherein A ₂ is a hydroxyl group, a mercapto group or a halogen atom. 2. The curable resin composition according to item 1 above. Wherein A ₁ is the following formula Table in _{[However, R 1, R 2, Y} 1, Y 2, m and k R ₁ described in paragraph 2 _{claims, R 2, Y 1, Y} 2, m and k synonymous] A ₂ is a monovalent organic group represented by the following general formula: [However, R _'1 is a hydrogen atom or a methyl group, R' ₂ is Y _'1 and Y' ₂ binding to atom a carbon number of all carbon atoms 1 to 40 of the (j + 1) -valent organic group And Y '
₁ -COO -, - COS-, or -CONR _'3 -, represent,
R ′ ₃ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and Y ′ ₂ represents an oxygen atom, a sulfur atom or And j represents an integer from 0 to 4, and l represents 0 or 1.] The curable resin composition according to claim 1, which is a monovalent organic group represented by the following formula: Wherein A ₁ is represented by the following general formula Table in _{[However, R 1, R 2, Y} 1, Y 2, m and k R ₁ described in paragraph 2 _{claims, R 2, Y 1, Y} 2, m and k synonymous] A ₂ is a monovalent organic group represented by the following general formula: [However, R ′ ₁ , R ′ ₂ , Y ′ ₁ , Y ′ ₂ , j, and l represent R ′ ₁ ,
Synonymous with R ′ ₂ , Y ′ ₁ , Y ′ ₂ , j and l, X ₁ and
X ₂ is the curable resin composition has been X ₁ and X ₂ as defined] represented monovalent range first claim of claims is an organic group described in paragraph 1 claims. 5. The curable resin composition according to claim ₂ , wherein X ₁ is an oxygen atom, and X ₂ and A ₂ are both hydroxyl groups. 6. The curable resin composition according to claim ₂ , wherein X ₁ is an oxygen atom, and X ₂ and A ₂ are both chlorine atoms. 7. The method according to claim 2, wherein X ₁ is a sulfur atom.
Item 2. The curable resin composition according to item 1. 8. The curable resin composition according to claim 3, wherein X ₁ is an oxygen atom and X ₂ is a hydroxyl group. 9. The curable resin composition according to claim 3, wherein X ₁ is an oxygen atom and X ₂ is a chlorine atom. 10. The curable resin composition according to claim 3, wherein X ₁ is a sulfur atom. 11. and m is 1, generally R ₂ is of the formula _{-R 4 -Y 3 R 5 -Y 3} h R 4 - [however, h is 0 or 1. When h = 0, R ₄ represents a hydrocarbon group having 4 to 20 carbon atoms, and Y ₃ represents an oxygen atom. When h = 1, R ₄ represents a hydrocarbon group having 2 to 9 carbon atoms, R ₅ represents a hydrocarbon group having 4 to 20 carbon atoms,
Y ₃ represents an oxygen atom, -COO- or -OOC- claims second represented by the representative], third or curable resin composition of the fourth Claims. 12. The method according to claim ₂ , wherein m is 1 and R ₂ is represented by the following general formula: CH _{2 i} , wherein i is an integer from 4 to 40. The curable resin composition according to the above.