JPH0228204A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing a specific metallic element-containing inorganic filler and (meth)acrylate and useful as dental composite resins, adhesives, denture base materials, impression materials, etc. CONSTITUTION:The objective composition consisting of (A) a metallic element- containing filler having the surface pretreated with an oxo acid (derivative) of pentavalent phosphorus expressed by formula I {A1 is organic group having radically polymerizable ethylenically unsaturated double bond and 5-60C organic group, preferably a group expressed by formula II [R1 is H or methyl; R2 is 4-40C (m+1)-valent organic group having 4-40C hydrocarbon in which atoms linked to Y1 and Y2 are all C; Y1 is -COO-,-COS-, etc.; Y2 is O, S, etc.; m is 1-4; k is 0 or 1]; A2 is OH, mercapto, halogen, 1-60C organic group or at least one of A1 and A2 is 4-60C nydrocarbon; X1 is O or S; X2 is OH, mercapto or halogen} and (B) at least one radically polymerizable monomer of (meth) acrylates.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a curable resin composition. More specifically, it is a novel curable resin composition containing an inorganic filler whose surface has been treated with an organic phosphorus compound. The curable resin composition in the present invention refers to a composition containing an inorganic filler and a polymerizable monomer as essential components, and is used for industrial materials and materials for biological hard tissue. These include molding compositions, dental composites and resins (tooth filling restoration materials, crown prosthetic materials such as inlay crowns, denture materials, abutment tooth building materials, etc.), dental adhesives,
Examples include denture base materials, impression materials, artificial bones, and bone cement.

(Prior art) In recent years, compositions containing inorganic fillers and polymerizable monomers as essential components, such as dental composite resins, have come to be used in the field of dentistry. Inorganic fillers are usually used after being subjected to surface treatment in advance.By performing surface treatment, wetting of the interface between the filler and the polymerizable monomer in the composition is improved, and the filler content is increased.
As a result of the improved dispersibility of the filler, in a composite resin formed by polymerizing and curing a polymerizable monomer, the adhesion between the filler and the resin interface is strengthened and the mechanical strength is improved. Silane coupling agents represented by γ-methacryloyloxyglobiltrimethoxysilane are known as surface treatment agents used for this purpose in the field.

Looking broadly at industry, in addition to silane coupling agents, titanate coupling agents, zircoaluminate coupling agents, higher alkyl alcohols, higher fatty acids, and organic phosphate esters are used as surface treatment agents for inorganic fillers. It is publicly known.

Among these, organic phosphoric acid esters are relevant to the present invention, so the main points thereof will be described below.

Japanese Patent Publication No. 60-3431 describes an inorganic filler surface-treated with the following organic phosphate ester.

(However, R1 in the above formula is hydrogen or a methyl group, R2 is an alkylene group having 2 to 6 carbon atoms or a rogene-substituted derivative thereof, or a polyoxyethylene group -CH2-CH2
It shows n0-CH2-CH2+ (n=1-20) and (n=1-20). ) Inorganic powder whose surface has been modified with one or more organic phosphorus compound treatment agents selected from the group shown in (representing alkyl, alkenyl, aryl, alkoxy, alkenoxy, aryloxy, or a group having a substituent on an organic group thereof) is disclosed.

In addition to these, JP-A-56-54795, JP-A-57-
Similar techniques are described in JP-A No. 128728, JP-A-57-168954, JP-A-57-198735, and the like.

These known industrial resin compositions are made by mixing a high molecular weight resin and a surface-treated inorganic filler. Since the high molecular weight resin has no or few reactive groups, there is a low possibility that the high molecular weight resin and the surface treatment agent will form a high chemical bond.
Improvements in mechanical performance also have limits. Therefore, a resin composition with excellent mechanical properties in which the resin and the surface treatment agent are highly bonded is desired.

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

In the above-mentioned known technology, there is no mention of improving the water resistance of the resin composition or the possibility of applying it to dentistry.
Known organophosphorus compounds cannot be expected to be effective for the purposes of this invention.

Most of the inorganic fillers that have been widely used in the world contain large amounts of silicon (for example, silica and silica-based glasses), but there are also inorganic fillers that contain metals, metal oxides, or salts as their main components. There are only a few practical examples in which it has been incorporated as a main component, and a major reason why it has not been actively used as a main component in paraboloids is that the surface treatment technology for these has not been established.

In other words, even if a conventionally known silane-based or titanium-based surface treatment agent is used for these inorganic fillers, the surface treatment effect as remarkable as that for silica cannot be obtained. Therefore, in resin compositions containing a large amount of these fillers that have been treated with conventionally known surface treatment agents,
Inconveniences such as a decrease in material strength (especially under humid conditions) and filler falling off due to poor bonding at the resin-inorganic filler interface have been unavoidable.

However, when the above-mentioned metals, metal oxides, salts, etc. are introduced as inorganic fillers, it is possible to obtain resin compositions having more preferable performance than conventional compositions containing silica.

For example, by replacing silica with metal oxides such as alumina or zirconia, dental composite resins with excellent aesthetics, mechanical strength, and chemical stability can be provided.
On the other hand, by incorporating a filler similar to natural tooth substance, such as hydroxyapatite, it is possible to provide a dental adhesive material that is less harmful and has excellent biocompatibility. Furthermore, by using metal fillers, it is possible to develop new types of dental composites that have ductility and toughness.

In view of these circumstances, it has been desired to develop a surface treatment technique that can effectively act on inorganic fillers containing metal elements as described above.

An object of the present invention is to provide a resin composition comprising a surface-treated metal element-containing inorganic filler and a radically polymerizable monomer, in order to greatly improve the performance of the resin composition containing the inorganic filler. It is. According to the present invention, a resin composition can be obtained that has properties that cannot be obtained with conventional resin compositions containing silica.

Further, according to the present invention, since the surface treatment agent and the radically polymerizable monomer are highly chemically bonded, a resin molded article with excellent mechanical performance can be obtained. A preferred use of the resin composition of the present invention is a dental composition.

The following description will focus on the dental composition, but it goes without saying that the resin composition of the present invention is not limited to dental use.

(Means for Solving the Problems) As a result of extensive studies to solve the above-mentioned problems, the present inventors have discovered that an organic phosphorus compound having a specific molecular structure is an inorganic filler containing a metal element. The present inventors have discovered that it can be used as an extremely effective surface treatment agent for surface treatment, and have completed the present invention.

That is, the resin composition provided by the present invention has the following general formula % formula % (1) [However, AI has at least one ethylenic double bond capable of radical polymerization and has 5 to 5 carbon atoms. 60
represents an organic group within the range of A2 is a hydroxyl group,
represents a mercapto group, ), a rogen atom, or an organic group having 1 to 60 carbon atoms, and at least one of AI and k has at least one hydrocarbon group having 4 to 60 carbon atoms.
Contains. Xl represents an oxygen atom or a sulfur atom,
X2 represents a hydroxyl group, a mercapto group, or a halogen atom] and (b) an inorganic filler containing a metal element whose surface has been previously treated with pentavalent phosphorous oxic acid or its derivative; and (b) methacrylate and acrylate. A curable resin composition comprising at least one radically polymerizable monomer selected from the group consisting of:

The inorganic filler used in the resin composition of the present invention is characterized by containing a metal element as a component. A line is drawn, and the elements located to the left of the line are hydrogen, and the elements on the line are B, Si, As, and Te.

and excluding At. Among these metals, those useful for the purpose of the present invention include, for example, At, Mg, Ca
.

Ti, Cr, Fe, Co, Ni, Cu, Z
n, Sr, Zr, Pd, Hg.

Examples include Sn, Ba, Pt, Au, La, etc.

These metal elements are in inorganic fillers.

It can take various forms. For example, the most common AtzOa, ZnO, Cab, Ti0z,
ZrO2, LazO3゜BaQ, Fe2e3.5r
Including oxides such as 02, etc., At(OH
) hydroxides such as a, halides such as CaFz, or BaSO4-? Sulfates like CaSO4, carbonates like CaCO3(7), Ca)IPO4+
Ca(H2PO4)z, Ca3(PO4)2,
Ca2Pz07, Ca(PO3)2゜Ca4P2O
9, Mg2P4012, At(PO3)3, A
It is contained in the form of various salts such as phosphate salts such as 2PO4.

In addition to the case where these metal compounds exist as a single component in the inorganic filler, they may also be present in a multi-component system such as ceramics or minerals.

In the case of a multi-component system, not only a plurality of metal elements are present, but also components other than metal elements, such as %5iOz.

P2O5, B2O3, Si3N4. SiC, B4C,
It is also permissible to contain BN or the like. Examples of these are K2O-TiO2, BaO-TiO2, Ca0-A
zzO3 and zircon (SiOz-Zro2 series),
Sian (SiOz-Atz03-83N4 series)
, La Gala, Z, Ceramic 7x (La203-Az2
0a-8iO2 series, Tatoeba ShottGM31-68
4(H)), Ba glass (BaO-A1203-B20
3-8i02 series, such as ShottGM27-884
181), 5hott8235o, Ray-8or
b T-2000o, Ray-SorbT-300
0■) Sr glass (5r02-At203-3i02 series, e.g. 5hott 0M32-0870, Ray
-8orb T-4000■), various Ca0-P2O5-containing crystallized glasses known as Saranihaioglass, and hydroxyapatite.

Furthermore, in addition to these forms, metal powder may also be used as it is as a filler. In this case, the metal may be used alone or as an alloy.

The inorganic filler used in any of the cases described above must be insoluble in water since it is used under highly humid conditions such as dental applications. Insolubility as used in the present invention is defined as solubility with a saturated solubility of 0.1% by weight or less in water at room temperature.

There are no restrictions on the shape of these inorganic fillers, and various shapes and sizes, such as spherical, crushed, needle, and Weisker plate shapes, can be selected depending on the purpose. Further, the particle size of these inorganic fillers is not particularly limited, but those in the range of 5 nm to 0.5 fl are usually preferably used. Note that the particle size here refers to the average value of the maximum diameter and minimum diameter of the filler.

The greatest feature of the present invention is that the above-mentioned inorganic filler is
It is used after surface treatment is performed in advance with pentavalent phosphorous ochonic acid represented by formula (1) or a derivative thereof (hereinafter sometimes referred to as an organic phosphorus compound). (Hereinafter, the untreated filler may be referred to as inorganic filler (A).) The chemical structure of the organic phosphorus compound (1) is
Specific examples of "ethylenic double bonds capable of radical polymerization" include the following.

H2C=C- (however, Zt is /・rogen atom), H2
C=CH-0-.

H2C: =CH-8-.

H2C=CH-NH- H2C=CH-CH=CH-, H2C=CH.

Among these ethylenic double bonds, ethylenic double bonds of acrylic acid, methacrylic acid, or styrene are preferably used in the present invention. If the surface treatment of the inorganic filler (A) is carried out using an organic phosphorus compound having a chemical structure obtained by removing the above-mentioned double bond from the organic phosphorus compound (1), the adhesion between the filler and the matrix will be poor and the object of the present invention will not be achieved at all. It is something that cannot be achieved.

Next, the organic group referred to in the present invention is (a) a hydrocarbon group [where hydrogen is 7, rogene, hydroxyl group, carboxyl group, mercapto group, cyano group, and phosphonic acid group.

or Naka) At least one of the above hydrocarbon groups is connected by at least one of the following bonding parts -〇-, -C-, -S- or a bonding part in which they are bonded to each other and combined. means a structured group.

below, With a concrete example, This will be explained in more detail.

Examples belonging to the hydrocarbon group in (a) -CH3, -CH2-F-CHz. CH31-@l
÷CH2 hits. .

-CH2CH2CHCH2CH2- -CHt-CH2CH-CHt-.

Example 10C belonging to a group consisting of a hydrocarbon group and a bonding part
HzCH20K) OCH2CHzCOO [Phase] H3 H H H CH3 H2C=C-COOCHz \ CH3 H2C2CHCOOCH2CHCH2CCH2CH2-
CH3 The hydrocarbon group contained in at least one of the organic groups A1 and A2, that is, one or both, has the same meaning as the hydrocarbon group defined in (a) above, and has 4 to 6 carbon atoms. It is something. However, structures in which one hydrocarbon group is substituted with three or more of these hydrophilic substituents are judged to be disadvantageous from the purpose of the present invention, since they reduce the hydrophobicity of hydroxyl groups, carboxyl groups, and phosphonic groups. Ru.

When the number of carbon atoms in the hydrocarbon group is less than 4, problems often arise in the water resistance of the resulting resin composition, but when the number of carbon atoms is 4 or more, and more preferably 5 or more, it is at a preferable level as a dental material. The water resistance is particularly poor when the number of carbon atoms is 8 or more.

The number of carbon atoms in A1 influences the surface treatment effect, and when the carbon number is in the range of 5 to 60, a surface treatment effect that provides desired physical properties as a dental material can be obtained. Furthermore, when A2 is an organic group, A2
The number of carbon atoms also affects the surface treatment effect, and the number is 6.
It is preferably 0 or less.

Among the organic phosphorus compounds represented by the general formula (1), from the viewpoints of reactivity with the inorganic filler surface, copolymerizability with the polymerizable monomer (b), ease of synthesis, etc., Particularly preferably used are the compounds described below.

In the compound represented by the general formula (1), (+)
At has the following general formula [where R1 is a hydrogen atom or a methyl group, R2 has at least one hydrocarbon group having 4 to 40 carbon atoms,
and represents a (m+1)-valent organic group having 4 to 40 carbon atoms in which all atoms bonded to Yl and Y2 are carbon atoms, and Y
l represents -COO+, -cos +, -CONR3-, R3 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and Y2 represents an oxygen atom, a sulfur atom or -
is a monovalent organic group represented by N-, m is an integer from 1 to 4, and k is 0 or 1], and A2 is a hydroxyl group, a mercapto group, or a halogen atom. be.

Knowing the compound explained in (1), XI is oxygen, X
A compound in which 2 and A2 are hydroxyl groups is one of the preferred compounds, and is included in group (i)-a.

(+) -a Organic phosphorus compound (i)-a is the most effective group of compounds when the inorganic filler contains a base metal element. Examples of base metal elements are At, Mg, Ca, and Ti.

Fe, Co, Cr, Ni, Cu, Zn, S
r, Zr, Sn, Ba, La.

Examples include Cr, etc., and special K Az2o3, Ti0z
, Zr0z.

Metal oxides such as FezO3, ZnO, CaCO5,
Metal salts such as Ca3 (PO2゜Azpo4), hydroxyapatite, and Ti, Fe, Co,
It is highly effective against metal powders containing Cr, Ni, Cu, Zn, etc.

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

H (CH2)7CH3 CH3 CH3 CH30 H2C=C-Coo+CHz) 4-0÷CH2)4
-0-P-OHH CH3 αX+CH2) to CH3 Suh OH OH OH Suh OH3 OH In the compound shown in (1), Xl is oxygen, A2 and is a group (i)-b and the halogen is chlorine. Preferred specific examples are shown below.

Specific examples of this compound are shown below.

α i is an integer from 4 to 40 a) H3 O Ha α In the third group of compounds shown in the margin (i) below, Xl bonded to P is S, and A2 and X2 are hydroxyl groups, mercapto groups, or It is a compound that is a halogen atom. Let this group be (i) -c.

(i) -c The organic phosphorus compound (i) -c exhibits an excellent surface treatment effect on inorganic fillers containing not only base metal elements but also noble metal elements. Examples of precious metals mentioned here are Pd,
Examples include Ag, Pt, and Au. In addition, among these compounds, etc. can be mentioned.

Furthermore, these Chi tautomer with It exists as such.

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

i is an integer from 4 to 40) Ha CH3 CH3CH3CH3S HzC=C-COOCHCH2CH2CH-0-P-O
HH Ji-1 CH3 CH3 CH3 H CH3 CH3 H CH3 CH3 Ha CH3 CH3 CH3 α i is an integer of 4 to 40] α = Other compounds used in the present invention are - In the compound shown in formula (1), ( i At has the following general formula [however, s R' + R2, Yt, Yl,
m H yo D k #i R1. described in compound 1).
Synonymous with R2, Yt, Yl, m and k] A monovalent organic group represented by the following general formula Yl and the atoms bonded to Yl are all carbon atoms, and the number of carbon atoms is 1 to 4 o represents a (j+1)-valent organic group, represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms;
represents an oxygen atom, a sulfur atom, or -N-, j represents an integer from 0 to 4, and t represents C or 1] This is a compound that is a monovalent organic group represented by the following formula.

In the compound represented by (11), Xs is oxygen,
One of the preferred compounds is the X2 hydroxyl group.
This is called (ii) -a group.

(ii) -a (It) The organic phosphorus compound of -a is also effective for fillers containing base metal elements, and the organic phosphorus compound of (i)
-a is essentially the same inorganic filler as the target of surface treatment.

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

i=an integer of 4 to 40] [Ha In the compound shown in the margin (ii) below, Xt is oxygen,
Compounds in which 2 is a 7-rogen atom such as chlorine, bromine, fluorine or iodine are classified as (ii) -b group. ... Preferred compounds in which the rogene atom is chlorine are shown by the structural formula below.

(ii) -organophosphorus compound (ii) -b is a compound (iiia) in which the hydroxyl group of also exists between the compounds (i)-st and (i)-a.

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

In the compound shown below in the margin (Hs O = mountain), Xl bonded to P is S, and Xl
is a hydroxy group, a mercapto group, or a norogen atom (ii) -c.

(ii) -c Similar to (i)-c, organic phosphorus compound -c is effective for inorganic fillers containing base metals or noble metal elements. Compound (ii) -c is easier to synthesize than (+)-c and has excellent stability, so it can be used advantageously.

Tsuba A specific example of the -P- group of the compound (!ri-c is h )h Jinno They are related to isomers.

Next, compound (ii) - A specific example of C is shown below.

i is an integer from 4 to 40) tt α (itt 10 to 100) Roughly speaking, the following organic phosphorus compounds can be used in the present invention.

0! At is the following formula [where R1, R2, Yt, Y2. m and k are compound (ii) K-described 1. R2, Yl
, Y2. is one organic group represented by the following general formula [however, R1, R2, Yl, Y2. j, and t
is in the compound), Rt+ R2, Yl, Y
2. Synonymous with j and t, Xl and Me are the compound (i
) tlC has the same meaning as Xl and Xl described] It is a compound that is a monovalent organic group represented by the following.

The structural formula of this compound is shown below.

This compound is designated as group (iii).

Organophosphorus compounds 611) are effective for fillers containing base metal elements as well as for the sulfur-free compounds mentioned above, when Xl and Xl do not contain sulfur atoms. When Xr, Xr, and/or Xl contain a sulfur atom, it is also effective against fillers containing noble metal elements, as in the above-mentioned compounds containing sulfur atoms. Izu Y2: Y2. m==j, k=
Symmetrical structures such as tc7) are preferably used for ease of synthesis.

Specific examples of compound (110) are shown below.

(i is an integer from 4 to 40) H3 H3 (JM h In all of the organic phosphorus compounds (i) to G11), is a long chain without bulky branched chains and has a certain chain length. preferable. The reason for this is presumed to be that by using a compound having a higher R2, the surface of the inorganic filler can be densely covered with molecules of the surface treatment agent.

To explain R2, R2 is particularly preferable when 1m is 1.
The structure of is as follows.

-R4-Y3 (-Rs-Y3+FIR4- [However,
When h is O or 1°h=o, R4 represents a hydrocarbon group having 4 to 20 carbon atoms, and Y3 represents an oxygen atom. h
= 1, R4 represents a hydrocarbon group having 2 to 9 carbon atoms, and 1 represents a hydrocarbon group having 4 to 20 carbon atoms,
Y3 represents an oxygen atom, -COO- or 10OC-] Specific examples of R2 are shown below.

+CH2chi0+CH2juice, +CH2) 0(
-CH2 wither.

442゜(Double O
H2CH200C (toc 0OCH2CH2--CHz
CH2CH2CHz00C+CH2q. COOCH2C
H2CH2CI(Z-Other preferred structures of R2 are as follows.

+CH2)- [However, i is an integer from 4 to 40] In the present invention, in addition to the above-mentioned organic phosphorus compounds (i) to 611), the following organic phosphorus compounds are also suitably used as a surface treatment agent.

(i is an integer from 4 to 40)
hosphorus compound (G M K
Written by osola 5-poff.

Wiley, 1950), Organopho
sphorus Monomers and Polym
ers (Ye, L. Gefter, Prega
mon Press 1962).

Modern Organic Synthesis Series 5, Organophosphorus Compounds (edited by the Organic Synthetic Chemistry Association, Gihodo, 1971) Be1lstein
(Springer = Verlag) etc. may be used as a reference.

More specifically, JP-A-58-128393 and JP-A-58-192891. JP-A-58-21687, JP-A-58-21688. Japanese Patent Publication No. 59-139392. JP-A-59-135272%, JP-A-59-142268, JP-A-60-166363. Japanese Patent Publication No. 60-166364.
A method of modifying the surface of an inorganic filler (A) using an organic phosphorus compound (1) is 1. Surface treatment of powder using a surface treatment agent. It can be carried out using generally known methods, and can be roughly divided into wet methods and dry methods.

In the wet method, an inorganic filler (5) and an organic phosphorus compound (1
) is suspended in an appropriate amount of a solvent such as water, alcohol, hexane, benzene, toluene, xylene, etc., and stirred thoroughly. However, the solvent used at this time,
The optimum values of conditions such as reaction temperature and reaction time vary depending on the combination of the inorganic filler (A) and the organic phosphorus compound (1), but can be easily found by a person skilled in the art. After stirring for a specified period of time, the solvent was distilled off under reduced pressure.
Surface treatment is completed when it is removed by a method such as A or freeze-drying.

In this case, it is desirable to include a heating step in any of the processing steps. The heating may be performed while stirring the slurry consisting of the inorganic filler (5), the organic phosphorus compound (1), and the solvent, or while the solvent is being distilled off. In some cases, the solvent may be further heated after distillation. In particular, heating in a suspended state with a solvent improves dispersibility.
The filler surface is evenly treated. The heating temperature is 5
The temperature is preferably in the range of 0°C to 150°C. If it is lower than 50°C, the heating effect will be poor, and if it exceeds 150°C, there is a risk that the radically polymerizable double bond will react.

When X2 is a hydroxyl group or a mercapto group in the organic phosphorus compound (1), it is also possible to react with the inorganic surface by desalting reaction using the alkali metal salt, ammonium salt, etc. of the compound by the above-mentioned wet treatment method. be.

In the dry method, the inorganic filler (A) is placed in a mixer such as a Henschel mixer or a pump blender, and while stirring, the organic phosphorus compound (1) is sprayed as is or diluted with a suitable solvent. At this time, it is desirable to stir while heating. This method is suitable for processing large quantities of filler.

In any of the above treatment methods, the amount of organic phosphorus compound used for the inorganic filler is preferably at least an amount that can cover most of the surface of the inorganic filler with a monomolecular film of the organic phosphorus compound. This dragon is the value of the specific surface area of the inorganic filler measured by the BET method etc.

It can be estimated from the proportion of metal elements on the surface. For example, the smaller the particle size of the inorganic filler. As the proportion of metal elements on the surface increases, the amount of organic phosphorus compound required increases; however, numerically, in the present invention, taking these conditions into account, It is used in an amount of 0.01 to 100 parts by weight.

Determined based on experiments.

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

By the way, it is also possible to prepare a resin composition by mixing a predetermined amount of an organic phosphorus compound into a radically polymerizable monomer and kneading an unsurface-treated inorganic filler into the mixture.

However, compared to the method of the present invention which uses an inorganic filler that has been surface-treated in advance, this method has a lower dispersibility of the filler.
This is undesirable because it is inferior in terms of the amount of filler packed into the polymerizable monomer and the mechanical strength of the resulting resin product.

By the way, it is often used in dental composite resins. In the case of a silica-based glass powder containing a metal element such as barium or lanthanum, a large number of silanol groups exist on its surface. When an organic phosphorus compound (1) is used for surface treatment of such an inorganic filler.

Although it has a surface treatment effect on metal elements, it has a poor effect on silanol groups, so desired results cannot be obtained. For glass fillers with a high silica content, it is desirable to use a known silane coupling agent 1, such as γ-methacryloyloxyglobiltrimethoxysilane, in combination with the organic phosphorus compound (1).

In such a case, a two-step treatment method is adopted 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 modified method, a method in which the surface treatment of the present invention is performed after treatment with a silane coupling agent, or a method in which the organic phosphorus compound (1) and the silane coupling agent are mixed to perform a one-step treatment is also possible.

The radically polymerizable monomer used in the composition of the present invention is one that can be copolymerized with the organic phosphorus compound (1) used as a surface treatment agent, and is a (meth)acrylate monomer [denoted as (meth)acrylate]. means both methacrylate and acrylate] is used.

In addition to these, there are also esters with monohydric or dihydric alcohols such as α-cyanoacrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, and itaconic acid, and (meth)acrylamides such as N-isobutylacrylamide. , vinyl esters of carboxylic acids such as vinyl acetate, vinyl ethers such as butyl vinyl ether,
Minor amounts of comonomers such as mono-N-vinyl compounds such as N-vinylpyrrolidone, styrene derivatives, etc. may also be included.

An example of a (meth)acrylate thread pick is methyl (
meth)acrylate, ethyl(meth)acrylate, lauryl(meth)acrylate, benzyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate,
Monofunctional (meth)acrylates such as dimethylaminoethyl (meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate
Acrylate, neobentyl glycol di(meth)acrylate, 1.6-hexanethiol di(meth)acrylate, 1.10-decanediol di(meth)acrylate, bisphenol A di(meth)acrylate, 2.
2-bis[(meth)acryloyloxypolyethoxyphenyl]furopane, 2,2-his(4-(3-methacryloxy-2-hydroxypropoxy)phenylpropane (sometimes referred to as Bis-GMA), 2, 2.
4-) Bifunctional monomers such as the adduct of 1 mol of dimethylhexamethylene diisocyanate and 2 mol of 2-hydroxyethyl (meth)acrylate; 3-functional monomers such as the adduct of 1 mol of dimethylhexamethylene diisocyanate and 2 mol of 2-hydroxyethyl (meth)acrylate; (meth)acrylate.

2,2.4-) Tetrafunctional monomers such as an adduct of 1 mol of dimethylhexamethylene diinocyanate and 2 mol of glycerin di(meth)acrylate can be mentioned. These monofunctional and polyfunctional (meth)acrylates may be used alone or in combination of two or more.

In addition to the above-mentioned monomers, it is desirable to use known adhesive monomers in combination, particularly when adhesive properties are expected to tooth tissue or dental metals. Such monomers have acidic groups in their molecules.

here However, zl is F.

α.

Br or ) groups, etc. Also includes acid halogen groups.

adhesive material The following compounds are specific examples of mer. shown.

H3 H3 H3 H3 CH3 COoH / 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, and is usually based on 1 part by weight of the polymerizable monomer. The surface-treated inorganic filler ranges from 0.01 parts by weight to 100 parts by weight. A more detailed explanation of the composition ratio will be given later.

In addition to the inorganic filler, other fillers may be added to the composition of the present invention, if necessary. The filler may be either inorganic or organic,
Examples of the inorganic filler include inorganic fillers containing silica as a main component, such as quartz, amorphous silica, and borosilicate glass. These fillers are used after being subjected to surface treatment in advance with a silane coupling agent. On the other hand, organic fillers include polymer powders such as polymethyl methacrylate, polyvinyl chloride, polystyrene, etc.
Organic-inorganic fillers such as those disclosed in No. 11 can be mentioned.

The composition of the present invention, which is a mixture of an inorganic filler and a polymerizable monomer, can be polymerized by heating it to 100°C or higher or applying external energy such as irradiation with an electron beam. Although it can be cured and converted into a molded article, in the main use of dental compositions, it is a common practice 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 thermally polymerizing (meth)acrylate, organic peroxides such as benzoyl peroxide (referred to as BPO), di-t-butyl peroxide, and cumene hydroperoxide are used.

Compounds such as 2.2'-azobisisobutyronitrile and 1.1'-azobis(cyclohexane-1-carbonitrile) are preferably used.

On the other hand, when performing room temperature polymerization, benzoyl peroxide/dimethylaniline type, cumene hydroperoxide/thiourea type, ascorbic acid/Cu2+ salt type, organic sulfinic acid (or its salt)/amine/persuranide type, etc. In addition to the above oxidation-reduction initiators, tributylborane, organic sulfinic acids, and the like are also suitably used.

On the other hand, when photopolymerization is performed by irradiation with visible light, α
Preferred are oxidation-reduction systems such as -diketone/tertiary amine, α-diketone/aldehyde, α-diketone/mercaptan. α-diketones include tetracamphorquinone, diacetyl, 2,3-bentanedione, benzyl, acenaphthenequinone, phenanthraquinone, etc.; tertiary amines include N;

N-dimethylamine ethyl methacrylate, ethyl N,N-dimethylaminobenzoate, Michler's ketone, etc. Aldehydes include citronellal, lauryl aldehyde, O-phthaldialdehyde & p-octyloxybenzaldehyde, mercaptans include 1-decanethiol, Examples include thiosalicylic acid, 2-mercaptobenzoxazole, 4-mercaptoacetophenone, etc. Furthermore, an α-diketone/organic peroxide/reducing agent system in which an organic peroxide is added to these oxidation-reduction systems In the case of photopolymerization by ultraviolet irradiation, 2,4.6-1-limethylbenzoyldiphenylphosphine oxide, henzine methyl ether, benzyl dimethyl ketal, benzophenone, 2-methylthioxanthone, diacetyl , benzyl, azobisisobutyronide IJ/l/.

A visible light photopolymerization initiator such as tetramethylthiuram disulfide is also preferably used.

The appropriate amount of these polymerization initiators to be added is in the range of 0.01 to 10% based on one polymerizable monomer (b).

Additionally, additives such as polymerization inhibitors, ultraviolet absorbers, fluorescent agents, pigments, etc. may be added to the resin compositions of the present invention, if necessary.

In the dental composition of the present invention, depending on its wide range of uses, the inorganic filler [Inorganic Filler (5)
There is a degree of freedom in selecting both the type of organic phosphorus compound (1) which is the surface treatment agent] and the polymerizable monomer are appropriately selected to prepare one composition.

In the case of dental compositions, the following compositions are used. Dental composite resins require high strength and aesthetics (particularly transparency). In order to meet this requirement, 1.
Using an alumina filler with a refractive index of 60 to 1.70 and a (meth)acrylate monomer with a refractive index of 1,50 to 1.60 after polymerization and curing, furthermore, a refractive index of 1.50 to 1.50.
1.60 silica-based inorganic filler is used together. By using these components, the refractive indexes can be made to be close to each other, so transparency can be excellent, and mechanical performance can also be improved by adding an alumina filler.

In this case, the particle size and addition amount of the filler can be appropriately selected depending on the purpose.

Furthermore, in dental adhesive materials intended for adhesion to teeth, particularly dentin, it is desirable to use inorganic fillers with excellent biocompatibility. Such fillers include:
Examples include hydroxyapatite, calcium phosphate, calcium hydrogen phosphate, calcium diphosphate, calcium metaphosphate, calcium birophosphate, and various bioglasses. Furthermore, for the purpose of strengthening tooth structure, it is also possible to use a fluorine-containing inorganic filler powder such as calcium fluoride. These fillers are surface-treated with an 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 blending 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 Fischer sealant, the inorganic fillers include alumina, titanium oxide,
Metal oxides such as zirconium oxide and fluorocarbons are preferably used, and the amount of these fillers is in the range of 0.01 to 5 parts by weight per 1 part by weight of the polymerizable monomer.

By the way, the resin composition of the present invention is provided to users in various processed states depending on its use. An example is shown below.

(1) 1-paste (or liquid) filler A filler in the form of a paste (or liquid) made by mixing polymerizable monomers and 1 polymerization initiator at once.The polymerization initiator is a photopolymerization initiator or/and heating For the purpose of polymerization ~
A high temperature type polymerization initiator is used.

CI+) 2 paste (or liquid) state Two pastes (or) in which the oxidizing agent and reducing agent of an oxidation-reduction type polymerization initiator that can be polymerized at room temperature are separated and mixed together with a filler and a polymerizable monomer. liquid.

(iii) Powder-liquid state Consists of a powder mixture of the above reducing agent (or oxidizing agent) and filler powder, and the above oxidizing agent (or reducing agent)'f: a solution (liquid agent) of the dissolved polymerizable monomer. 0 GV) The composition in the molded states (1) to (iii) is molded and then polymerized and cured. This is the case with dentures.

The composition of the present invention provided to dentists or dental technicians in the semi-processed state of (i) to (iii) is shaped by the hands of these users, polymerized and hardened, and functions as a dental material. You will be able to demonstrate your abilities.

(effect) The surface was previously treated using an organic phosphorus compound (1).

A composite material containing a water-insoluble metal element-containing inorganic filler and a radically polymerizable monomer is prepared using a known technique, that is, the above-mentioned inorganic material has been surface-treated in advance using a known silane coupling agent. It exhibits a level of high performance that cannot be achieved with composite materials using fillers or silica-based fillers. For example, surface modification using a silane coupling agent has little effect on metal salt powders such as calcium carbonate, calcium phosphate, and hydroxyapatite. Therefore, composite materials using these fillers have poor mechanical strength and It could not be used in appropriate dental applications where strength is required. However, if the surface of the metal salt is modified using an organic phosphorus compound (υ), the adhesion between the filler and the matrix resin will be significantly improved, and high-strength dental materials using the metal salt as a filler will also be possible.

Furthermore, the surface modification effect of the silane coupling agent on metal powder is weak, and the strength of the resulting composite material rapidly decreases under wet conditions.

It has been extremely difficult to use this material as a dental material, but by surface treatment using an organic phosphorus compound (1), it has become possible to obtain a dental composite material with significantly improved initial strength and wet strength. Now you can.

Furthermore, although the surface modification effect of the silane coupling agent is considerably recognized, organic phosphorus compounds are also used in fillers such as metal acids 11, such as aluminum oxide and titanium oxide, which have problems with the water resistance of the adhesion between the resin matrix and the filler. The surface treatment according to (1) showed remarkable effectiveness, and it became possible to introduce these fillers into dental composite resins.

One major feature of the present invention is the high density packing of inorganic filler into the resin matrix. Particle size 1μm
The following so-called submicron fillers have a viscosity-increasing effect even after surface treatment with a known silane coupling agent, so it is difficult to incorporate them into a polymerizable monomer solution at high density. This was difficult for ultrafine particles with a particle size of 0.1 μm or less. However, the viscosity increasing effect of submicron fillers surface-treated using organic phosphorus compound (1) is significantly weakened, and the viscosity increasing effect is 1.5 to 3 times higher than when the surface is treated with a known silane coupling agent. It is now possible to bottle filler. Due to this.

Q has made it possible to further improve the hardness, compressive strength, abrasion resistance, etc. of dental composite resins. Another feature is the improvement in the aesthetics and X-ray opacity of dental composite resins. A filler containing a metal element, especially a heavy metal element, has excellent X-ray opacity, and if a large amount of filler is used, it is easy to produce a dental composite resin having X-ray contrast properties superior to that of enamel. Furthermore, it is easier to make the refractive index higher than that of quartz (n==x, 55).

By using a filler that has a refractive index closer to that of natural teeth (n=1.61 to 1.63), we have created a dental composite resin with excellent esthetics that has optical properties such as light reflection and refraction that are similar to those of natural teeth. It is easy to create.

The present invention can be applied to materials for biological hard tissue. Specifically, in addition to dental composite resins (e.g., tooth filling and restorative materials, crown prosthetic materials such as inlays and KRAKUN, denture materials, and abutment tooth building materials), dental adhesives (e.g., bonding agents, composite materials, etc.) It is also applied to wearable resin cements, fushers and sealants), denture base materials, and impression materials, contributing to the high functionality of these dental materials.

In addition, applications in the field of orthopedics include bone cement containing hydroxyapatite, artificial bones made from composites of hydroxyapatite and organic polymers, etc.
Artificial bones reinforced with ceramic swisscar are expected.

For industrial purposes, it can be used as a material for artificial astronomical stones, decorative boards, and various mechanical parts.

EXAMPLES Next, the present invention will be explained 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 ni'/V
Alumina (Showa Denko, AL-1608G-4'-cho 501, 200 g of toluene and 3 g of 10-methacryloyloxydecyl dihydrodiene phosphate) were placed in a flask and heated under reflux for 2 hours with vigorous stirring.

After cooling, the alumina powder was separated from the cloudy solution, thoroughly washed with toluene, vacuum dried for 12 hours, and further heated in air at 90°C for 2 hours to obtain a filler with surface treatment. .

The phosphorus content of this powder was determined by fluorescent X-ray analysis,
Estimating the adsorption amount of 10-methacryloyloxydecyl dihydrodiene phosphate, it is found that 100% of alumina powder
Next, 2.2-bis[methacryloyloxypolyethoxyphenyl]globan (with an average of 2.6 ethoxy groups in the molecule)
35 parts by weight (hereinafter referred to as D-2,6E), an adduct of 1 mole of 2,2,41J methyl hexamethylene diinocyanate and 2 moles of glycerin dimethacrylate (hereinafter referred to as U-4TH) 40 parts by weight, 25 parts by weight of neopentyl glycol dimethacrylate (hereinafter referred to as NPC), and 1 part by weight of benzoyl peroxide were mixed to obtain a polymerizable monomer composition. and 30 parts by weight of this composition.

Seventy parts by weight of the above surface-treated filler were mixed and kneaded to obtain a monopolymerizable composite composition (paste).

The following evaluations were performed using this composition.

(1) Consistency Which filler has good wettability with polymerizable monomers?

It can be said that the kneaded composition has excellent dispersibility in the polymerizable monomer and has a soft viscosity. Therefore, by measuring the consistency as an index of viscosity, it is possible to judge whether the surface treatment is good or bad. In this experiment, the values measured by the following method were determined. That is, Q,
Weigh out 5m of paste and place it on a glass plate (5X
5 cm ) and placed in a mound at the center. Next, a glass plate (5 x 5 m
) was gently placed on the paste and after 120 seconds had elapsed, the long axis and short axis of the spread paste were measured through a glass plate, and the arithmetic mean value of both was determined as the consistency. The values are given in Table 1 and are the average of 1 shift of 3 repeated independent measurements.

(11) Bending strength One bending strength was measured as an index of the adhesive strength between the polymerized and cured resin matrix and the filler. First, put the above paste into a 2x2x30ml mold and heat it to 130°C.
After curing by heating for 1 hour, the sample was removed from the mold to obtain a prismatic test piece. This test piece was stored in air at 37°C for one day, and then subjected to a three-point bending test (distance between both end supports = 20fi, crosshead speed = 1w/m1n) using an Instron universal testing machine. The results shown in Table 1 are the average values of 10 measurements.

G11) Water resistance of bending strength A bending test piece prepared according to the procedure in Section 11 was immersed in water at 70°C.
The flexural strength was measured after immersion for 0 days to accelerate deterioration. By comparing with the initial bending strength described in Section 11, it is possible to judge whether the water resistance is good or bad. The average values of the 10 test pieces are shown in Table 1.

Examples 2 to 41 The organic phosphorus compounds shown in Table 1 were used in place of the 10-methacryloyloxydecyl dihydrodiene phosphate used in Example 1, and the results were evaluated in the same manner as in Example 1. Shown in the table.

1/, lower margin Comparative Example 1 A paste was prepared using alumina powder that was not surface-treated in place of the surface-treated alumina filler used in Example 1, and the consistency and The results of measuring the bending strength are also shown in Table 2.

Comparative Examples 2 to 5 Instead of the organic phosphorus compound used in Example 1, the same evaluation as in Example 1 was conducted using alumina powder whose surface was treated with an organic phosphorus compound as shown in Table 2. The results are shown in Table 2.

Comparative Example 6 Add 10 parts by weight to 30 parts by weight of the polymerizable monomer used in Example 1.
- 0.83 parts by weight of alumina powder (methacryloyloxydecyldinohydrodiene phosphate) was mixed, and 69.17 parts by weight of alumina powder without surface treatment was added thereto and mixed and kneaded to prepare a paste. The results of measuring consistency and bending strength using similar methods are also shown in Table 2.

Compared to the product obtained in Example 1, the flexural strength is significantly reduced.

Examples 42-50 Titanium oxide powder (rutile type, average particle size = 0.2 μm) 4
09,) 400 ru of toluene and 42 organic phosphorus compounds shown in Table 3 were mixed and heated under reflux for 2 hours. After cooling, the titanium oxide powder was washed with toluene, vacuum dried, 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 filler were mixed and kneaded to obtain a paste.

Using this paste, the consistency and bending strength were measured in the same manner as in Example 1.

The results are shown in Table 3.

Comparative Examples 7 to 11 Paster was prepared under the conditions of Example 42 using a filler surface-treated with the organic phosphorus compound shown in Table 3 and a filler without surface treatment on the titanium oxide powder. Using this base), the consistency and bending strength were measured in the same manner as in Example 1, and the results are shown in Table 3.

Examples 51-59 Hydroxyapatite powder (average particle size 75 μm) 502
was mixed with 150 ml of toluene and organic phosphorus compound 12 shown in Table 4, and surface treatment was performed 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 bending strength were tested in the same manner as in Example 1, and the results are shown in Table 4.

Comparative Examples 12 to 16 A filler in which the hydroxyapatite powder was surface-treated with an organic phosphorus compound shown in Table 4 and a filler without surface treatment were used.

A paste was prepared under the conditions of Example 51. Using this paste, the consistency and bending strength were measured in the same manner as in Example 1, and the results are shown in Table 4.0 Examples 60 to 63 50f of silver powder (particle size = 50 μm or less) was added to 100ml of toluene.
0.52 of the organic phosphorus compounds shown in Tables 1 and 5 were placed in a flask, and a surface-treated filler was obtained in the same manner as in Example 1. 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. The consistency and bending strength of this paste were measured in the same manner as in Example 1, and the results are shown in Table 5.

Comparative Examples 17 and 18 Pastes were prepared under the conditions of Example 600 using a filler in which the silver powder was surface-treated with an organic phosphorus compound shown in Table 5 and a filler without surface treatment.

Using this base If, the consistency and bending strength were measured in the same manner as in Example 1, and the results are shown in Table 5.

Example 64 La glass ceramics manufactured by Shott (GM-316
840°n=1.56) was ground in a vibrating ball mill to obtain a powder with a particle size range of 0.1 to 20 μm and an average particle size of 2.8 μm.

A surface treatment II & inorganic filler was obtained using 2 parts by weight of γ-methacryloxyglobil trimethoxysilane per 100 parts by weight of this powder according to a suitable method.

Next, the average particle size is 0.02 μm, and the BET specific surface area is 100 r.
n”/2, alumina fine powder with a refractive index n=1.65 (
Made by Nippon Aerosil, aluminum oxide C) 50
A mixture of 15 ml of 2.10-methacryloyloxydecyl dihydrodiene phosphate and 500 ml of toluene was heated under reflux for 3 hours. After cooling, the filler was collected by centrifugation, and after vacuum drying for 24 hours, it was further dried in air for 90 minutes.
The mixture was heated at ℃ for 2 hours to obtain a surface-treated alumina fine powder filler. Elemental analysis of this alumina powder revealed that the ash content was 85.
．． It was 5% by weight. The same polymerizable monomer composition (n=1.528) as in Example 1 was used as the polymerizable monomer, and 0.5 parts by weight of 2.4.6 was added instead of BPO to 100 weight of the composition. - IJ methylbenzoyldiphenylphosphine oxide was blended.

500 parts by weight of the surface treated La glass filler.

180 parts by weight of the surface-treated fine powder alumina filler and 100 parts by weight of the polymerizable monomer were mixed and kneaded, followed by vacuum defoaming to obtain a polymerizable composition (paste). Konohest nixenon lamp (Dent manufactured by Kulzer)
Acolor Ta.

Note that the definitions and measurement methods of various quantities in this example are as shown below.

(i) Bending strength: Using the same mold as in Example 1, polymerization and hardening was performed in a prescribed manner, and then immersed in water at 37°C for 24 hours, using an Instron universal testing machine at a crosshead speed of 1 tm/min.
A three-point bending test was conducted with a distance between fulcrums of 201111. Measured values are average values of 10 samples.

(ii) Put the compressive strength paste into a cylindrical mold with a diameter of 4 m and a height of 4 m,
After polymerization and curing according to the prescribed method, remove from the mold and heat at 37°C.
, immersed in water for 24 hours and tested at a crosshead speed of 2 m++1/min using an Instron universal testing machine.
It was measured with The measurement value is the average value of 10 samples.

(iii) The Brinell hardness paste was put into a mold with a diameter of 10 m and a thickness of 5 m, the upper surface was pressed against a cover glass, and then polymerized and hardened by a predetermined method.

The cured product was taken out from the mold, and the surface in contact with the glass was ground by 0.5 with 4220 sandpaper, and the surface was used as the test surface.

GV) Transparency paste 20IEIIφX0.851! Form into a disk shape.

After curing in a prescribed manner, this was used as a test piece.

The evaluation method was to measure the chromaticity using a chromaticity meter (Nippon Denshokusha Rifu Σ80 model) with a standard white board placed behind the test piece (L) and a standard black board placed behind the same test piece. Difference ΔL from brightness (L2) when measuring chromaticity by placing
was measured and used as an index of transparency. In this evaluation method, ΔL
The larger the value, the higher the transparency.

(V) Refractive index The refractive index of alumina and inorganic filler is determined using an Atsube refractometer using the D line of a sodium lamp as a light source, and using short methane in which sulfur is dissolved, bromonaphthalin, methyl salicylate, dimethylformamide, etc. as a solvent. Measured by immersion method. Refractive index after curing of polymerizable monomer (nP)
A cured product obtained by thermally polymerizing a polymerizable monomer in which 0.51 parts of benzoyl peroxide was dissolved at 110°C for 30 minutes after degassing was molded into a rectangular parallelepiped of 51111 x 101111 x 201111 as a test piece. (■1) Average particle size and particle size range for alumina fine powder measured using a transmission electron microscope particle size distribution analyzer CAP.
Measurement was performed using A500 model. The measurement principle is a light transmission centrifugal sedimentation method (combined with natural sedimentation).

Example 65 Cured product obtained after similar photopolymerization using the same paste used in Example 64 (no heating was performed)
Table 6 also shows the results of similar tests.

Comparison row 19 30 parts by weight of γ-methacryloxyglobyltrimethoxysilane was mixed with 100 parts by weight of the alumina fine powder used in Example 64 at a blending ratio of outside the surface according to a standard method, but the viscosity was high. It was impossible to practice.

Comparative Example 20 Average particle size 0.016 pm, BET specific surface 1j 130
m"/2, 30 parts by weight of γ
-Methacryloxyglobil trimethoxysila...1 The above fine powder silica filler was used instead of the polymerizable monomer and the fine powder alumina filler.

Although they were mixed at the same blending ratio, the viscosity was too high to mix.

Comparative Example 21 Average particle size 0.04 μm, BET specific surface area 50 rr? /
? 15 parts by weight of γ-methacryloxypropyltrimethoxysilane per 100 parts of fine silica powder (manufactured by Nippon Aerosil, Aerosil 0X-50 (8)), instead of the polymerizable monomer and fine powder alumina filler. Table 6 shows the results of a similar test conducted on samples using the above silica filler, mixed and kneaded at the same blending ratio, and cured by the same polymerization method.

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-4,TH, and 1 part by weight of benzoylperoxy (BPO) were mixed and dissolved to form a polymerizable monomer. Obtained a mass. 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. Table 6 also shows the results of a similar test conducted on a cured product obtained by heating and polymerizing this paste at 130° C. for 1 hour.

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, but the paste did not become suitable as a dental material and could not be kneaded. Ta.

Comparative Example 23 Using 200 parts by weight of the fine powder silica filler used in Comparative Example 21 and 1 part by weight of 100 parts by weight of the polymerizable monomer used in Example 66, the same evaluation as in Example 66 was conducted. Shown in the table.

Example 67 The cured product produced in Example 66 was pulverized in a vibrating ball mill and classified into powders having a particle size range of 0.1 μm to 100 μm and an average particle size of 15 μm. Separately, 70 parts by weight of D-2,6E, 30 parts by weight of 1.6-hexafthiol dimethacrylate, and 0.5 part by weight of 2,4.6=trimethylbenzoyldiphenylphosphine oxide were mixed and dissolved to obtain a polymerizable monomer. Body composition was obtained. 20 parts by weight of this composition, 5 parts by weight of the above powder
5 parts by weight and 25 parts by weight of the fine powder alumina filler used in Example 64 were mixed and kneaded to obtain a polymerizable composition. Regarding the cured product obtained by the same polymerization method as Example 64,
The results of a similar test are shown in Table 6.

Comparative Example 24 The cured product produced in Comparative Example 23 was pulverized in a vibrating ball mill and then classified for 1 time to obtain powder with a particle size range of 0.1 μm to 100 μm and an average of 14 μm.

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

Example 68 The hydroxyapatite powder used in 'JNill J51 was ground in a rotary ball mill to obtain a powder with an average particle size of 4.5 μm.
-Methacryloyloxydecyl dihydrodiene phosphate 1.5F was mixed and surface treated in the same manner as in the example. A powder-liquid adhesive was prepared using this filler with the composition shown below.OA agent (liquid) D-2,6E PC 2-hydroxyethyl methacrylate 50 parts by weight 25 parts by weight 1 part by weight 10 parts by weight 15 parts by weight 1 Part by weight 0.05 10-methacryloyloxydecyl dihydrodiene phosphate benzoyl peroxide hydride a quinone monomethyl ether Agent B (powder) Above surface treated hydroxyapatite filler Sodium benzenesulfinate N,N-jetanol-p-toluidine 100 parts by weight 0.3 parts by weight 0.3 parts by weight In preparing agent B, a solution in which sodium benzenesulfinate and N,N-jetanol I)-) luidine were dissolved in 10 parts by weight of methanol was sprayed onto the filler. The methanol was then evaporated.

An adhesion test was conducted on the dentin of a denture using Agents A and B. That is, the crown of an adult molar was cut off with a cutter while water was poured on it to expose the dentin. The dentin surface was acid-etched for 1 minute with a 40% orthophosphoric acid aqueous solution, washed with water, and then the moisture on the surface was blown off with an air gun. Next, double-sided adhesive tape with a hole of 5 mm diameter was attached to the mounting surface. Furthermore, fix the denture so that the cross section is horizontal, and insert an inner diameter of 6Ia over the hole in the tape.
A plastic ring with Iφ and height of 5fi was placed so that the centers of the holes coincided. Next, appropriate amounts of Part A and Part B were kneaded at a weight ratio of 1:4 (about 1 minute), and when it became a soft paste, it was press-fitted into the plastic ring, a hook for bow tension test was inserted, and it was left standing for 30 minutes. .

After that, it was immersed in water at 37°C for 24 hours, and then tested at a crosshead speed of 2 m11/m using an Instron universal tester.
The adhesive strength was measured using fn (average value of 5 test pieces).

Further, the bending strength of this cured product was measured at its initial value and after being immersed in water at 70° C. for 10 days, and the results are shown in Table 7.

Comparative Example 25 Prepared with the same composition, using γ-methacryloyloxypropyltrimethoxysilane in place of 10-methacryloyloxydecyldihydrodiene phosphate used as the surface treatment agent in Example 68, performing illegal surface treatment. Table 7 shows the results of the same tests conducted on the adhesives prepared above.

Comparative Example 26 An adhesive was prepared and the same test was conducted. The results are also shown in Table 7.

Table 1: Example 69 The hydroxyapatite powder used in Example sl was ground in a vibrating ball mill to obtain powder with an average grain size of 2.3 μm. This powder 200F was mixed with 600 ml of toluene and 102 10-methacryloyloxydecyl dihydrogen phosphate, and surface treatment was performed in the same manner as in Example 69. A polymerizable composition was obtained by mixing 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. This was poured into a mold and polymerized under heat and pressure at 140'C for 1 hour to obtain a molded product having physical properties and biocompatibility suitable for use as an artificial tooth root or artificial bone.

Example 70 Adding a coloring agent to the photopolymerizable composition prepared in Example 64,
Three types of pastes with chromaticity after curing as shown in Table 8 were prepared (each color tone is suitable for tooth and neck, dentin, and enamel).0 Gold, silver, and palladium alloy (manufactured by GC) , cast sea urchin tJ') was cast, a metal frame suitable as a resin veneer for the maxillary central incisors was created, and an operation was performed on this frame to shield the metal color.
A car (Kulzer Dentacolor Operator A-20) was applied, and a xenon lamp (Kulzer
g Light irradiation was performed for 90 seconds using Dentacolor X5 (9). Build up the prepared tooth and neck paste here 3
Light irradiation was performed for 0 seconds. After dentin paste was built up on top of it and irradiated with light for 30 seconds, enamel paste was built up on top of that and irradiated with light for 90 seconds. Subsequently, this was placed in a hot air dryer and heated at 120° C. for 20 minutes. After cooling, the shape was corrected, and a good muzzle pair was created by performing puff polishing.

Table *The chromaticity is determined by preparing a disk-shaped cured product with a thickness of 0.85 al and a diameter of about 20 mm, using a color difference meter (Nippon Denshoku Σ8) against a standard white board as a background.
0 type).

Claims (12)

[Claims] (1) (a) The following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, A_1 has at least one ethylenic double bond capable of radical polymerization, and has 5 to 6 carbon atoms.
A_2 represents a hydroxyl group, a mercapto group, a halogen atom, or an organic group having a carbon number of 1 to 60, and at least one of A_1 and A_2 has a carbon number of 4 to 60. contains at least one hydrocarbon group. X_1 represents an oxygen atom or a sulfur atom; and (b) at least one radically polymerizable monomer selected from the group of methacrylates and acrylates. (2) A_1 has the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [However, R_1 has a hydrogen atom or a methyl group, R_2 has at least one hydrocarbon group having 4 to 40 carbon atoms, and The atoms bonded to Y_1 and Y_2 are all carbon atoms, representing a (m+1)-valent organic group with 4 to 40 carbon atoms, and Y_1 is -COO-, -COS-, or -CO
NR_3-, 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 ▲There are numerical formulas, chemical formulas, tables, etc.▼, and m is 1 to 4. The curable resin according to claim 1, wherein A_2 is a hydroxyl group, a mercapto group, or a halogen atom. Composition. (3) A_1 is the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, R_1, R_2, Y_1, Y_2, m and k are described in claim 2,
Synonymous with Y_1, Y_2, m and k] A monovalent organic group represented by A_2 is the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [However, R'_1 is a hydrogen atom or a methyl group , R'_
2 represents a (j+1)-valent organic group having 1 to 40 carbon atoms in which all atoms bonded to Y'_1 and Y'_2 are carbon atoms, and Y'_1 is -COO-, -COS-, or -C
ONR'_3-, 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 ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , 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. (4) A_1 is the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, R_1, R_2, Y_1, Y_2, m and k are R_1, R_2 described in claim 2
, Y_1, Y_2, m and k] is a monovalent organic group represented by the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [However, R'_1, R'_2, Y'_1, Y'_2,
j and l are R as described in claim 3.
'_1, R'_2, Y'_1, Y'_2, synonymous with j and l, X_1 and X_2 are synonymous with X_1 and X_2 described in claim 1] The curable resin composition according to claim 1, which is a curable resin composition. (5) The curable resin composition according to claim 2, wherein X_1 is an oxygen atom, and both X_2 and A_1 are hydroxyl groups. (6) The curable resin composition according to claim 2, wherein X_1 is an oxygen atom, and both X_2 and A_1 are chlorine atoms. (7) The curable resin composition according to claim 2, wherein X_1 is a sulfur atom. (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) Claim 3 in which X_1 is a sulfur atom
The curable resin composition described in . (11) m is 1 and R_2 is the following general formula ▲ mathematical formula,
There are chemical formulas, tables, etc.▼ [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 has 2 to 9 carbon atoms
R_5 represents a hydrocarbon group having 4 to 20 carbon atoms, and Y_3 represents an oxygen atom, -COO- or -OOC-. Or the curable resin composition according to item 4. (12) m is 1 and R_2 is the following general formula ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼ [However, i is an integer from 4 to 40] The curable resin composition according to claim 2, 3, or 4.