JPS63199204A - Polymerizable composition - Google Patents

Abstract

PURPOSE:To obtain a composition providing a cured material having extremely high transparency, excellent mechanical properties such as surface hardness, tensile strength, wear resistance, etc., by blending inorganic powder having a specific refractive index and particle diameters with a specific amount of polymerizable vinyl monomer. CONSTITUTION:(A) 100pts.wt. polymerizable vinyl monomer [e.g. methyl methacrylate, 2,2-bis(methacryloxyphenyl)propane, etc.] is blended with (B) 100-240pts.wt. inorganic powder (e.g. barium oxide, titanium oxide, etc.) having 0.07-0.1mum average particle diameter and a refractive index shown by formula I [Y is refractive index of polymer obtained by polymerizing vinyl monomer of the component A; d is average particle diameter (mum)] and, if necessary, (C) 10-120pts.wt. inorganic powder having 0.1-3mum average particle diameter and a refractive index (X) shown by formula II to give the aimed composition.

Description

[Detailed description of the invention] (Industrial application field) The present invention has transparency before and after polymerization.

In particular, the present invention relates to a polymerizable composition that has outstanding transparency after polymerization and can exhibit excellent mechanical properties after polymerization.

(Prior Art and Problems to be Solved by the Invention) A polymerizable composition that provides a transparent cured product after polymerization is used as a coating material whose interior can be seen through. on the other hand,
In recent years, in the field of dentistry.

Attempts have been made to use an identification tag made of a thin metal plate with information engraved on it, which is then covered with a transparent coating material and retained on the side of the tooth, for identification purposes. In such applications, the covering material has sufficient compressive strength and strength to withstand the harsh environment of the oral cavity.
It is required to provide a cured product that has mechanical properties such as abrasion resistance and has a high degree of transparency that allows the information stamped on the identification tag to be read. Moreover, the coating material is gR
When attaching the tag, it is necessary to have a certain degree of transparency even before curing to confirm the position of the identification tag and the presence or absence of air bubbles in the coating layer.

Conventionally, as a polymerizable composition that provides a cured product with transparency, ultrafine powdered silica whose particle size is much smaller than the wavelength of light in the visible region was used as a polymerizable composition using 2,2-bis[4-(3-methacryloxy)- 2-Hydroxypro? It is blended with an acrylic vinyl monomer such as [xyphenyl]glo/f, and the following paraboloids are used.

However, in the above composition, when the amount of ultrafine powdered silica is increased in order to obtain the required mechanical properties, the transparency of the cured product decreases due to the difference in refractive index with the polymer. Significantly decreased. Moreover.

Addition of the above-mentioned ultrafine powdered silica increases the viscosity of the polymerizable composition, making it easier for air bubbles to be mixed in, and the air bubbles also cause the problem that the identification tag appears distorted. Therefore, instead of the ultrafine powdered silica added to the vinyl monomer, it may be possible to use an inorganic filler having the same refractive index as the polymer of the vinyl monomer. However, polymerizable compositions using such inorganic fillers do not have sufficient transparency before curing, and therefore, in the above-mentioned applications, the problem arises that it is impossible to confirm the position of the identification tag or the presence or absence of bubbles in the coating layer.

(Means for Solving the Problems) The present inventors have conducted extensive research in order to develop a polymerizable composition that solves the above problems. As a result, we obtained the knowledge that in polymerizable compositions containing a high proportion of inorganic filler, the particle size and refractive index of the inorganic filler are organically related to each other and affect transparency before and after curing. . and,
Based on this knowledge, we conducted further research and found that when an inorganic powder with a specific particle size and refractive index is blended with vinyl monomer in a specific ratio, it becomes transparent before polymerization and can be polymerized in one step. The present invention was completed based on the discovery that a cured product having excellent transparency and mechanical properties can be obtained by using the method.

The present invention comprises (a) 100 parts by weight of a polymerizable vinyl monomer, and (b) an average particle size of 0.07 μm or more and 0.1 μm.
and the refractive index (X) is the refractive index of the polymer obtained by polymerizing the vinyl monomer of (,), and d is the average particle diameter (in μm). (hereinafter referred to as fine inorganic powder) 1
00 to 240 parts by weight of the polymerizable composition.

In the present invention, the refractive index was directly measured using an Atsube refractometer for vinyl monomers and polymers, and by the immersion method for inorganic powders.

Note that the measurement temperature was 23°C.

In the present invention, any known monopolymerizable vinyl monomer can be used without particular limitation as long as it has transparency before and after polymerization. Among these, vinyl monomers having a difference in refractive index before and after polymerization of 0.05 or less, preferably 0.04 or less are suitable. In particular, vinyl monomers having an acrylic group and/or a methacrylic group, which have excellent transparency after one polymerization, are preferably used. A specific example of such vinylmo/-r- is as follows.

b) Monofunctional vinyl monomers methyl methacrylate: ethyl methacrylate: isopropyl methacrylate; hydroxyethyl methacrylate; tetrahydrofurfuryl methacrylate; glycidyl methacrylate; and these 7 acrylates or acrylic acid, methacrylic acid, p-methacryloxybenzoic acid, N-2 -Hydroxy-3-methacryloxyprobyl-N-phenylchrycine, 4-methacryloxyethyl trimellitic acid and its anhydride, 6-methacryloxyhexamethylenemalonic acid, 10-methacryloxydecamethylenemalonic acid, 2-methacryloxy Ether dihydrogonphos 7ate, 10-methacryloxydecamethylene dihydrodanphosphate, 2-hydroxyethylhydrogenphenylphosphonate.

0) Difunctional 1 [t, vinyl monomer (1) aromatic compound type 212- His(methacryloxyphenyl)zolopane:
2,2-bis(4-(3-methacryloxy)-2-hydroxyglopoxyphenyl)pronoqune; 2,2-bis(4-methacryloxyethoxyphenyl) 20pan:
2,2-bis(4-methacryloxyjethoxyphenyl)7°eI pan: 2,2-bis(4-methacryloxytetraethoxyphenyl)pro/dan; 2,2-bis(
4-methacryloxypentaethoxyphenyl)propane: 2.2- to 'X(4-methacryloxypolyethoxyphenyl):" o zp 7;
methacryloxydigropoxyphenyl)propane: 2(
4-Methacryloxyethoxyphenyl)-2(4-methacryloxyjethoxyphenyl)ronofon:2(4
-methacryloxyjethoxyphenyl)-2(4-methacryloxytriethoxyphenyl)propane: 2(4-
Methacryloxydigropoxyphenyl)-2(4-methacryloxytriethoxyphenyl)gulo/4-2.2
-Bis(4-methacryloxypropoxyphenyl)pro/dan: 2*2-bis(4-methacryloxyisopropoxyphenyl)7°oa4 and their acrylates; 2-hydroxyethyl methacrylate, 2-hydroxyzorobyl methacrylate, 3-chloro-2-
Sheaduct obtained from the addition of a vinyl monomer having a 10H group such as hydroxyzolobyl methacrylate or these acrylates with a diisocyanate compound having an aromatic group such as diisocyanate methylbenzene or 4,4'-diphenylmethane diisocyanate. ii) Aliphatic compounds (ethylene glycol dimethacrylate; diethylene glycol dimethacrylate) : ) IJ ethylene glycol dimethacrylate; butylene glycol dimethacrylate; neopentyl glycol dimethacrylate: propylene glycol dimethacrylate: 1,3-butanediol dimethacrylate 1,4-butanol dimethacrylate: 1,6-hexanethool dimethacrylate and these acrylates: 2-hydroyaethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate or These acrylates can be obtained by addition of vinyl monomers having an -OH group with diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, and methylene bis(4-cyclohexyl isocyanate). Sheaduct: acrylic anhydride, methacrylic anhydride; 1,2-bis(3-methacryloxy-2-hydroxypropoxy)ethyl, di(2-methacryloxyethyl)phosphate, di(3-methacryloxypropyl)phox7ate ”) trifunctional vinyl monomers trimethylol pronotrimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate and their acrylates; tetrafunctional vinyl monomers pentaerythritol tetramethacrylate.

Pentaerythritol tetraacrylate and diisocyanates methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate), methylene bis(4-cyclohexyl isocyanate)).

4. In addition to vinyl monomers of sheaduct or higher obtained by the addition reaction of diisocyanate compounds such as 4'-diphenylmethane diisocyanate and tolylene-2,4-diisocyanate with glycidol dimethacrylate, vinyl monomers generally known for industrial use can also be used. . For example, vinyl esters such as vinyl acetate and vinyl f-ropionate; vinyl ethers such as methylene vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether; styrene, vinyltoluene, α-methylstyrene,
Examples include alkenylbenzenes such as chloromethylstyrene and stilbene.

When using multiple types of polymerizable vinyl monomers, if the vinyl monomers have extremely high viscosity at room temperature or are solid, it is preferable to use them in combination with a polymerizable vinyl monomer of low viscosity. This combination is not limited to two types, but may be three or more types. Furthermore, since a polymer consisting only of a monofunctional vinyl monomer has a crosslinked structure and is dangerous, the mechanical strength of the polymer generally tends to be poor. For this purpose, it is preferable to use a monofunctional vinyl monomer, and when using a monofunctional vinyl monomer, a polyfunctional monomer. The most preferred combination of polymerizable vinyl monomers is a method in which an aromatic compound of a difunctional vinyl monomer is used as a main component and an aliphatic compound of a difunctional vinyl monomer is combined. In addition to this, for example, a combination of a trifunctional vinyl monomer and a tetrafunctional vinyl monomer, a combination of an aromatic compound of a difunctional vinyl monomer, an aliphatic compound of the same, and a trifunctional vinyl monomer and/or a tetrafunctional vinyl monomer. , and combinations thereof in which a monofunctional vinyl monomer is further added can be suitably employed.

Next, although the composition ratio in the above combination of vinyl monomers may be determined as necessary, the composition ratio of the polyfunctional vinyl monomer to the monofunctional vinyl monomer which is generally preferably employed will be shown.

(1) The aromatic compound of the difunctional vinyl monomer is 30~
(2) Trifunctional vinyl monomers are 30 to 100 weight percent, and tetrafunctional vinyl monomers are O to 70 percent by weight. (3) Aromatics of difunctional vinyl monomers. The compound weighs 30-60%,
The weight of the aliphatic compound is 5 to 30, the trifunctional vinyl monomer is 10 to 80, and the tetrafunctional vinyl monomer is 0.
A composition ratio of ~50% by weight is preferred.

In the polymerizable composition of the present invention, the fine inorganic powder is blended with the above polymerizable vinyl monomer.

The average particle size is 0.07 μm or more and less than 0.1 μm, preferably 0.08 μm or more and less than 0.1 μm, and the refractive index (X) is in the formula %. The refractive index of the polymer obtained by polymerizing vinyl monomers, d is the average particle diameter (unit: μm)
).

That is, when the average particle size of the fine inorganic powder is as small as 0.07 μm, increasing the amount of the fine inorganic powder in the monopolymerizable composition increases the viscosity of the composition. It is not possible to mix it with high content.

It becomes difficult to obtain a cured product having sufficient mechanical strength. In addition, if the average particle size of the fine inorganic powder is 0.1 μm or more, even if the refractive index satisfies the above range, the transparency of the polymerizable composition before polymerization decreases, and the object of the present invention is cannot be achieved. On the other hand, the refractive index of fine inorganic powder (
If X) is outside the above range, a cured product with sufficient transparency cannot be obtained even if the average particle size satisfies the above range.

The type of fine inorganic powder having such a refractive index is not particularly limited. Examples of fine inorganic powders that are particularly preferably used in the present invention include those selected from the groups represented by Groups 1, 2, 2, and 2 of the periodic table that can be bonded with silica. Both include one type of metal oxide and an inorganic oxide whose main constituents are silica. By using each of the above-mentioned metal oxides and silica as the main constituents, it is possible to easily obtain a fine inorganic powder having the above-mentioned specific refractive index.

Such inorganic oxides include the silicon atoms of silica and metal oxides of Groups 1, 2, 2, or 1 such as lithium oxide, sodium oxide, potassium oxide, magnesium oxide, and calcium oxide.

Strontium oxide, barium oxide, aluminum oxide, titanium oxide, zirconium oxide, hafnium oxide, tin oxide, lead oxide, etc. are combined with oxygen as an intermediary, and are as follows. And the above! , Group Ⅰ, Group M, and Group Ⅰ metal oxides (hereinafter simply represented by the general formula MiO, M2O, Mho
, , M'02 (where Ml is a metal of Group 1, y12 is a metal of Group ■, RI5 is a metal of Group ■, and M4 is a metal of Group ■)) can be obtained. It has a great influence on the refractive index and shape of inorganic oxides. Of course, the influence of the composition ratio 11K on the refractive index and shape will vary depending on the type of M÷O# M2O, 403° and M'02, the feeding method, manufacturing conditions, etc., but generally within the above refractive index range In addition, when trying to obtain a spherical inorganic oxide, it is preferable that the 111 base ratio of the sum of M÷O, M'O 403' and M2O3 is in the range of 1 to 20 molar ratio, particularly 5 to 15 molar ratio. M÷O, M2O, in the molar range
When selecting the total composition ratio of M÷03 and M'0□0, it will have an appropriate refractive index and be close to a true sphere with a uniform particle size.

In order to adjust the refractive index of the above-mentioned fine inorganic powder to a specific range, strontium oxide is generally used, especially among the metal oxides of Groups 1, 2, 2, and 2 of the periodic table. ,
It is preferable to use an oxide having a high refractive index in place of silica, such as barium oxide, zinc oxide, aluminum oxide, indium oxide, acid, titanium oxide, zirconium oxide, and tin oxide.

The shape of the fine inorganic powder used in the present invention is particularly preferably spherical in view of the abrasion resistance, surface smoothness, surface hardness, etc. of the resulting cured polymerizable composition. Furthermore, the particle size distribution of the fine inorganic powder is not particularly limited, but one that satisfies the purpose of the present invention is one in which the standard deviation value of the distribution is 1.30 or less. It is.

In order to maintain surface stability of the fine inorganic powder used in the present invention, it is preferable to reduce the number of silanol groups on the surface. Next, a method of drying the fine inorganic powder and then firing it at a temperature of 500 to 100 DEG C. is often suitably employed. In general, it is most suitable to use the fired fine inorganic powder after surface treatment using a friendly organosilicon compound that maintains its stability. The surface treatment method is not particularly limited and may be a known method, for example, using fine inorganic powder and a known organosilicon compound such as γ-methacryloxysolopyltrimethoxysilane or vinyltriethoxysilane.

After contacting for a certain period of time in a mixed solvent of alcohol/water,
A method for removing the solvent is employed.

In the present invention, the addition of fine inorganic powder to the polymerizable vinyl monomer described above
100 to 240 parts by weight of fine inorganic powder,
Preferably, it is necessary to carry out the addition in a range of 120 to 200 parts by weight. That is, if the proportion of the fine inorganic powder added in the polymerizable composition is less than 100 parts by weight, a cured product having sufficient mechanical properties cannot be obtained. If the addition ratio is more than 240 parts by weight, the viscosity will be extremely high and the heavy metal composition will be difficult to handle. Moreover, the transparency of the polymerizable composition or the cured product obtained by polymerizing the heavy metal composition is reduced.

The polymerizable composition of the present invention contains a polymerization initiation catalyst if necessary. The above-mentioned polymerization initiation catalyst is not particularly limited, and any known catalyst can be used without restriction. For example, a photopolymerization initiation catalyst,
A redox catalyst consisting of an organic peroxide and a tertiary amine, a thermal polymerization initiation catalyst, etc. are used. In particular, a photopolymerization catalyst is most preferably used when the composition is used as the dental coating material, since it can polymerize the composition with little air inclusion.

As the above-mentioned photopolymerization catalyst, known ones can be used without particular limitation, but in particular, when the polymerizable composition of the present invention is used in the oral cavity, the photopolymerization catalyst is 390 to 700 irn, preferably 400 to 700 irn.
Those that can be excited and initiate polymerization by irradiation with visible light at 600 nm are preferably used. Generally, as a photopolymerization initiation catalyst, it is preferable to use a photosensitizer in combination with a primary polymerization promoter.

Examples of photosensitizers suitably used include benzyl, kamphuchiquinone, and α-naphthyl.

Acetonaphcene, p,p'-dimethoxybenzyl, P
, y-dichloropenzyl diacetyl, pentanedione,
1.2-7 enanthrenequinone, 1,4-phenanthrenequinone, 3,4-7 enanthrenequinone.

9.10-7 α of enanthrenequinone, naphthoquinone, etc.
-It is a diketone. As the α-diketone in the present invention, at least one type of known α-diketones can be selected and used, and two or more types can also be used as a mixture. Moreover, camphorquinone can be used most preferably.

Examples of photopolymerization accelerators include N,N-dimethylaniline, N,N-diethylaniline, N,N-di-n-butylaniline, and N,N-dibenzylaniline.

N,N-dimethyl-p-toluidine, N,N-diethyl-p-toluidine, N,N-tumethyl-m-)luidine, p-tulomo-N,N-dimethylaniline, m-chloro-N,N-dimethyl Aniline, p-dimethylaminopenzaldehyde, p-dimethylaminoacetophenone,
p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid aminoester, N
, N-dimethyl anthranilic acid methyl ester.

N,N-dihydroxyetheraniline, N,N-')hydroxyethyl-p-toluidine% p-dimethylaminophenethyl alcohol, p-dimethylaminostilbene, N,N-dimethyl-3,5-xylidine, 4-dimethylamino Pyridine, N,N-dimethyl-α-naphthylamine, N,N-dimethyl-β-7teramine, tributylamine, tripropylamine, triethylamine, N-methyljetanolamine, N-etherjetanolamine.

N,N-dimethylhexylamine, N,N-dimethyldodecylamine, N,N-dimethylstearylamine,
N,N-dimethylaminoethyl methacrylate.

N,N-diethylaminoethyl methacrylate.

Tertiary amines such as L2'-(n-butylimino)jetanol; 5-butylbarbylic acid, 1-benzyl-
5-7enyl I4 Barbyric acid 11 such as rubituric acid
: 4 nzoylno arm - oxide, g-t-ffka4-
Organic peroxides such as Oxai-P and t-butyl/benzoate can be suitably used.

At least one type of these photopolymerization accelerators can be selected and used, and two or more types can also be used in combination.

Further, when tertiary amines are used as accelerators, tertiary amines in which nitrogen atoms are directly substituted on aromatic groups are particularly preferably used. Furthermore, in order to improve the ability to promote photopolymerization, in addition to tertiary amines, □citric acid, phosphoric acid, tartaric acid, glycolic acid, gluconic acid, α-oxyisobutyric acid,
Addition of oxycarboxylic acids such as 2-hydroxypropanoic acid, 3-hydroxypronodic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, and dimethylolpropionic acid is effective.

``As the primary and secondary redox catalysts, the organic peroxide and tertiary amine systems shown above can be suitably used.

As examples of typical redox catalysts, the organic peroxides and tertiary amines already mentioned in the photopolymerization initiation catalyst can be suitably used. The most preferred combination is benzoyl/
oxide and N,N-dihydroxyethyl-p-)luidine or penzoylno-oxide and N,N-dimethyl-p-toluidine.

In addition to the organic peroxides shown above, known thermal polymerization initiation catalysts such as azo compounds can be used without particular limitation. Typical examples that are particularly preferably used include: 2.2'-azobisisobutyronitrile; 4.
4'-azobis(4-cyanovaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-
Azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis-(cyclohexane-1-
nitrile), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis(2-methylpropionic acid)
, 2,2'-azobis(2-cyclobutylpropionic acid), 2,2'-azobis(2-(3-hydroxyphenyl)if[), 2,2'-azobis(4-nitrobeleric acid), 2 .2'-azobis(4-chlorovaleric acid) and the like.

The amount of the polymerization initiation catalyst used is %o, ooi to 5% by weight, more preferably 0.0% per 1 polymerizable vinyl monomer.
1 to 3 may be in a suitable range.

In the present invention, the above-mentioned polymerizable composition has an average particle size of 0.
1 to 3 μm, preferably 0.15 to 1 μm, and the refractive index (X') is the formula % (where Y is the refraction of the polymer obtained by polymerizing the vinyl monomers in (,) above). By adding inorganic powder (hereinafter referred to as coarse inorganic powder) within the range of This is preferable because the viscosity of the composition before curing can be reduced without reducing the transparency of the cured product, and the workability during use can be further improved. Also, by adding the coarse inorganic powder,! It becomes possible to adjust the transparency of the composite composition before curing. That is, as the amount of coarse inorganic powder added increases, the transparency of the polymerizable composition gradually decreases. Therefore, by adjusting the amount of the coarse inorganic powder added so as to reduce the transparency within a range that allows the polymerizable composition to maintain its transparency, it is possible to improve the transparency between before and after polymerization. Changes in the amount can be confirmed, which makes it possible to know the progress of polymerization.

Among such coarse inorganic powders, those with an average particle size larger than 3.0 μm tend to cause large diffuse reflection on the surface of the resulting cured product, resulting in a decrease in transparency.

When the average particle size is smaller than 0.1 μm, it becomes difficult to exhibit the above-mentioned effects. Moreover, when the refractive index is out of the above range, the transparency of the cured product obtained by polymerizing the polymerizable composition tends to decrease.

The coarse inorganic powder having such a specific refractive index may be selected from among the materials constituting the fine inorganic powder described above.

The ninth most suitable amount of coarse inorganic powder to be added to exhibit these effects described above is 10 to 120 parts by weight, preferably 20 to 120 parts by weight, per 100 parts by weight of the vinyl monomer (a) in the polymerizable composition. It is 100 parts by weight.

In the present invention, at least a portion of the fine inorganic powder or coarse inorganic powder described above may be used as a composite with a polymer obtained by polymerizing the vinyl monomer (&). A known method can be used to construct such a composite body. For example, the method disclosed in Japanese Unexamined Patent Publication No. 59-101409 is used.

In the present invention, UV absorbers such as 2-hydroxy-4-methylbenzophenone, hydroquinone, hydroquinone monomethyl ether.

Components such as a polymerization inhibitor such as 2,5-ditertibutyl-4-methylphenol and a pigment can be optionally added to the polymerizable composition of the present invention.

The method of curing the polymerizable composition of the present invention is not particularly limited.

For example, when using a photopolymerization catalyst that is excited by light in the range of 400 to 600 nm, as the light in the wavelength range mentioned above,
For example, curing may be performed using light such as a halo lamp, a xenon lamp, a laser, a fluorescent lamp, or the sun. I remember,
The temperature and irradiation time when the above-mentioned light is irradiated to polymerize the vinyl monomer vary depending on the intensity K of the irradiation light, but they can generally be appropriately determined according to the desired polymerization time. Preferably,
It is sufficient to perform the irradiation at a relatively low temperature of about 0° C. to 60° C. and for a relatively short time of about 10 seconds to several minutes.

When polymerizing the polymerizable composition of the present invention, the polymerizable vinyl monomer, fine inorganic powder, or fine inorganic powder, coarse inorganic powder, and polymerization initiation catalyst are mixed in advance and made into a paste. Generally, the catalyst is stored and irradiated with light when used, or only the polymerization catalyst of the above composition is stored separately, mixed immediately before use, and irradiated with light.

However, when storing the yeast and the photopolymerization initiation catalyst, it is necessary to shield them from light in order to prevent polymerization or deterioration of the catalyst during storage of the paste. Further, the effects of the present invention are best exhibited if air bubbles are removed from the paste by performing a vacuum defoaming operation before irradiation with light.

In addition, when using a redox catalyst, the polymerizable composition of the present invention, one containing an organic peroxide and the other containing a tertiary amine, are prepared separately in advance, and degassed under reduced pressure before use. while performing the operation.

Generally, a method is employed in which both are kneaded and then monopolymerized and cured.

On the other hand, a composite composition containing a heating polymerization catalyst is cured by single polymerization by heating to 50 to 200° C. under normal pressure or pressure.

Polymerization time may be from 10 minutes to several hours.Heat polymerization is performed using nitrogen gas.
It is preferable to carry out the reaction in an inert gas such as helium or alpine. Since a cured product obtained by heating polymerization in air tends to have unpolymerized portions on the surface due to the influence of oxygen, it is preferable to polish the surface after one polymerization and curing to remove unpolymerized portions. The cured product obtained by thermal polymerization is used by adhering it onto the identification tag using an adhesive.

(Effects of the Invention) As is clear from the above explanation, the polymerizable composition of the present invention consists of blending a fine inorganic powder having a specific refractive index and particle size with a polymerizable vinyl monomer KIP# in a fixed amount. It has transparency before curing, and the cured product obtained by polymerizing the polymerizable composition has extremely high transparency, and has good mechanical properties such as surface hardness, tensile strength, and abrasion resistance. It has excellent physical properties.

Further, in the present invention, by using coarse inorganic powder in a specific proportion, in addition to the above effects, it is possible to increase the blending proportion of the inorganic powder without increasing the viscosity of the polymerizable composition. Can be done. Moreover.

By adding coarse inorganic powder, it is possible to adjust the transparency of the polymerizable composition before curing to a low level, so it is possible to check whether the first polymerization is proceeding uniformly by following the change in transparency accompanying the first polymerization and curing. There is also the advantage that it can be confirmed.

In addition to adhering and covering dental G-signatures, the composite composition of the present invention can be used as a sealant for sealing pits and fissures, orthodontic brackets, fixing materials for moving teeth, dentures, and occlusal adjustment materials, etc. Can be applied.

Furthermore, it is also effective as a material in the field of molding, such as casting materials, sealing materials, and molding materials.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. In addition, measurement of the properties (particle size, standard deviation value of particle size distribution, refractive index) of the inorganic powder shown in the following sliding examples, working examples, and comparative examples 1. Polymerizable vinyl monomer and the polymerizable vinyl monomer Measurement of the refractive index of a polymer obtained by polymerizing vinyl monomers.

Further, physical properties (surface hardness, compressive strength, tensile strength, transparency) of the composite composition were measured according to the method shown below.

(1) Standard deviation values of particle size and particle size distribution of inorganic powder:
A scanning history electron micrograph of the powder is taken, and the number of particles observed within the unit field of view of the photograph (n) and the particle size (diameter The characteristic claim is calculated using the following formula.

X + σn-1 Standard deviation value = -1 = - (2) Refractive index of inorganic powder: Prepare a solvent with the same refractive index as the refractive index of the inorganic powder of the sample,
The refractive index of the solvent was taken as the refractive index of the sample.

To prepare the solvent, a sample was suspended in a solvent, and the composition of the solvent that appeared transparent (by visual observation) was determined at a constant temperature. The solvents used were pentane, hexane, cyclohexane, toluene, and styrene.

The refractive index of insulating solvents such as aniline and methylene iodide is measured using an Atsube refractometer.

(3) Refractive index of a vinyl monomer capable of monomerization and a polymer obtained by polymerizing the vinyl monomer: The refractive index of the vinyl monomer and polymer was directly measured using an Appe refractometer. Note that the measurements were performed at a constant temperature.

(4) Transparency A paste-like composite composition (hereinafter referred to as -1!-st) was placed in a stainless steel mold with a hole of 6 wam in diameter and 1 m in depth, and pressed with a polyproble/mold film.

Next, the tip of the quartz rod of the visible light irradiator White Light (trade name, Takara Pelmont Co., Ltd. M) was fixed to the pressure contact surface.
9. Light irradiation for 30 seconds. After irradiation, the cured product was removed from the mold and left in air at 37°C for 24 hours.
-1500MC.

The Y value, which is one of the tristimulus values, was measured using the method described below. Y., Myagawa et al.

Journal of Denkle Research, Volume 60, No. 5, 8
90-894 pages, according to the method shown in 1981, a standard white plate (X = 81.2, Y =
82.7, Z=93.8') is placed (hereinafter referred to as YW) and a standard black plate (X=
0.1, y=o, 1.2=0.2), the Y value (hereinafter referred to as ya) was measured, and the contrast ratio indicating the opacity of the cured product was calculated using the following formula.

Y.

Transparency was calculated using the following formula using contrast ratio.

Transparency is a value ranging from 0 to 1, and the higher the value, the more
Indicates high transparency. Note that those with a transparency smaller than 0.7 are almost opaque. Finally, in order to measure the transparency of the paste before polymerization, a paste was separately prepared in each Example and Comparative Example, which had the same filler composition and monomer composition as the demonstration paste, but did not contain a catalyst. Next, these pastes were placed in a bottle of an acrylic plate having a diameter of 10 m and having a thickness of 1 inch, and were pressed together from both sides with a film made of liglovirene. Thereafter, Yw e YB was measured in the same manner as in the case of the cured product described above, and the transparency was calculated according to the above calculation formula.

(5) Surface hardness: The paste was put into a stainless steel split mold having holes of 611 Il in diameter and 3 cm in depth, and pressed with a film made of Iliglobilene. Next, the tip of a quartz rod of a white light visible light irradiator was fixed to the pressure contact surface, and light was irradiated for 60 seconds. After irradiation, the 1-polymer cured product was removed from the mold and immersed in distilled water at 37° C. for 24 hours. After storage, the surface hardness of the irradiated surface was measured using a Micro Purinel hardness tester manufactured by Mori Shikenki.

(6) Compressive strength: The paste has a diameter of 4I+I11. The bottle was placed in a stainless steel split mold with a hole 3 m deep, and a polypropylene film was pressed against the bottle. Next, the tip of the quartz rod of Ogtilux was fixed to the pressure contact surface, and light was irradiated for 30 seconds. After irradiation, remove the 1-polymer cured product from the split mold.

Furthermore, the bottom surface of the cured product was irradiated with light for 30 seconds. Next.

After storing the cured body in distilled water at 37°C for 24 hours,
The compressive strength was measured using a Toyo Baldwin fissure tensile system, UTM-5T. Naori loss head speed is 1
0 cod/min and next.

(Tensile strength: Measurement was carried out in the same manner as the compressive strength in (6), except that the paste was pressed into a stainless steel split mold with a diameter of 6 m and a depth of 3 holes using a polypropylene cracked film in a bottle.

(8) Depth of toothbrush wear: The paste was placed in a Teflon mold having holes of 10 cm in length, 10 cm in width and 1.5 cm in depth, and was pressed with a polypropylene film. Next, the tip of a quartz rod of a white light visible light irradiator was fixed to the pressure contact surface, and light was irradiated for 60 seconds. After irradiation, the cured polymer was removed from the mold and stored immersed in distilled water at 37°C for 7 days. The cured polymer product was abraded with a toothbrush for 1500 m under a load of 400.9. The wear depth is calculated by dividing the wear weight by the density of the polymerized hardened material.

(9) Surface roughness After toothbrush abrasion, the surface roughness of the cured polymer was measured using Tokyo Seimitsu Precision Surface Roughness Meter - Fuyum A-200.

The surface roughness was expressed as a ten-point average roughness.

Viscosity of αQ Paste An appropriate amount of the paste was taken, and the viscosity of the -e-st was measured using a stone mill type high shear rheometer model IGK-120, and was expressed in poise.

In the following Examples and Comparative Examples, the following compounds will be abbreviated as follows.

Compound name (abbreviation: triethylene glycol dimethacrylate) T
EGDMA neobentyl glycol dimethacrylate)
NPCDMA Tetramethylolmethane triacrylate A-TMM-3L Tetramethylolmethane tetraacrylate A-TMMT Camphorquinone CQN
, N-dimethyl-p-)luizone DM
PTp-dimethylaminopeyl acid ethyl ester DMEE benzoyl oxide
BPO5-butylbarbic acid
5-BBA Petit Rated HyP
Roxytoluene BHTN, N-dihydroxyethyl-p-)luidine DEPT Example production 0.04 Euhydrochloric acid 5. OI and tetraethyl silicate (5
s(oc2H5)4. Nippon Colcoat Chemical Co., Ltd., trade name "Ether Silicate 28J) 176.69" was dissolved in methanol 0.447', and this solution was hydrolyzed while stirring at 30°C for about 1 hour.Thereafter, this was dissolved in tetrabutyl titanate). (TI(0-nC4H,)4. Nippon Soda a
ll) 21.4.9 and sodium methylate methanol solution (concentration 28% by weight) in Inglovir alcohol 0.
247 was added with stirring to prepare a mixed solution of tetraethyl silicate hydrolyzate and tetrabutyl titanate. Next, 1.171 g of methanol was introduced into a glass pear reaction vessel with an internal volume of 3 mm equipped with a stirrer,
Add 0.251 ammonia water bath solution (concentration: 25% by weight) to dissolve the ammoniacal alcohol solution, and add 0.8g of tetraethylsilicate to this as a ninth organosilicon compound solution to make silica seeds using 18% methanol. 10 minutes after the end of the addition, when the reaction solution became slightly milky, the above mixed solution was added over a period of about 5 hours to ensure that the reaction product precipitated.

Thereafter, 25. tetraethyl silicate was further added.
After the reaction product precipitated, a solution consisting of 0.097 g of methanol was added over about 30 minutes to the system. During the reaction, the temperature of the reaction vessel was maintained at 40°C. After the reaction was completed, stirring was continued for 30 minutes, the solvent was removed from the milky white reaction solution using an evaporator, and the mixture was further dried under reduced pressure at 80°C to obtain a milky white powder.

Next, this milky white powder was calcined at 850° C. for 1 hour and then dispersed in an agate mortar to obtain an inorganic powder containing silica and titania as freely as possible. From observation using a transmission electron microscope, this inorganic powder has a particle size in the range of 0.075 to 0.090 μm, an average particle size of 0.082 μm, a true spherical shape, and a standard particle size distribution. The deviation value is 1.04 and the refractive index is 1497. The obtained inorganic powder was further surface-treated with γ-methacryloxyglobiltrimethoxysilane.

Production Examples 2 to 7 Inorganic powder was produced in exactly the same manner as Production Example 1, except that the concentration of 1 reaction source and the amounts of tetraethyl silicate and tetrabutyl titanate in the mixed solution were changed. Manufacture ratio. The obtained inorganic powder was further surface-treated with γ-methacryloxyglobiltrimethoxysilane. reaction temperature,
Table 1 shows the amounts of tetraethersilicate and tetrabutyl titanate in the mixed solution and the properties of the obtained inorganic powder.

Production example-8 0,04'16 Hydrochloric acid 2.7f and tetraethyl silicate (ss (QC2) 1s) 4, Japan; manufactured by Lecourt Chemical Co., Ltd., product name: ethyl silicate) 28) 80°0? was dissolved in 0.41 g of isobutanol, and the solution was hydrolyzed at 35° C. with stirring for about 5 hours. Then, 35. A mixed solution of tetraethyl silicate hydrolyzate and tetrabutyl zirconate was prepared by adding Oj' and 811 Ll of sodium methylate methanol solution (concentration 28 wts) in isobutanol 0.27 K with stirring. Next, add 1.0 methanol to a glass reaction vessel with an internal volume of 3 mm and a stirrer. 0.201 ammonia aqueous solution (concentration 25
% by weight) Water o and osz were added to prepare an ammoniacal alcohol solution, and 10 minutes after the addition was completed, the reaction liquid became slightly milky white, and the above mixed solution was further added over about 5 hours to react. The product precipitated out. During the reaction, the temperature of the reaction vessel was maintained at 35°C. Thereafter, a solution consisting of 0.3 J of methanol containing 20.0 JF of tetraethyl silicate was added over about 30 minutes to the system in which the reaction product had precipitated. After the reaction was completed, stirring was continued for 30 minutes, the solvent was removed from the milky white reaction solution using an evaporator, and the mixture was further dried under reduced pressure at 80°C to obtain a milky white powder.

Next, this milky white powder was fired at 850° C. for a working time and then dispersed in an agate mortar to obtain an inorganic powder containing silica and zirconia as constituent components. From observation using a transmission electron microscope, this inorganic powder has a particle size in the range of 0.071 to 0.091 μm, an average particle size of 0.077 #c, and a true spherical shape with a particle size distribution. The standard deviation value was 1.08 and the refractive index was 1.547. The obtained inorganic powder is further
- Surface treated with methacryloxygloltrimethoxysilane.

Production Examples-9 to 11 In Production Example-8, the method was exactly the same as Production Example-8, except that the reaction temperature and the amounts of tetraethyl silicate, tetrabutyl zirconate, and sodium meth2-ate in the mixed solution were changed. An inorganic powder was produced.

The obtained inorganic powder was further surface-treated with r-methacryloxygloltrimethoxysilane. These synthesis conditions and various physical properties of the obtained inorganic powder are shown in Table 2.

Production example-12 Tetraethyl silicate) (81 (QC2H5) 4, manufactured by Nippon Colcoat Chemical Co., Ltd., trade name: Ethyl silicate 28)
42Ji' with 0.2 l of methanol! was mixed with a solution of 6.2f of barium bisisoindoxide dissolved in 0.7f of isoamyl alcohol. The mixed solution was refluxed at about 90° C. under dry nitrogen for 30 minutes, and then cooled to room temperature to prepare a mixed solution of tetraethyl silicate and barium bisisobenoxide.

Next, a glass reaction vessel with an internal volume of 10 mm and equipped with a stirrer was filled with 2.5 l of methanol, and an ammonia aqueous solution (concentration 25 vt%) of 5G Ol- was added thereto to prepare an ammoniacal methanol solution. The previously prepared mixed solution of tetraethyl silicate and barium bisisobenoxide was added over about 2 hours while maintaining the temperature of the reaction vessel at 40°C. The reaction solution became milky white within a few minutes after the addition started. After the addition was completed, stirring was continued for another hour, and then the solvent was removed from the milky white reaction solution using an evaporator, and the mixture was further dried at 80° C. under reduced pressure to obtain a milky white powder.

Next, this milky white powder was fired at 900° C. for 4 hours and then dispersed in an agate mortar to obtain an inorganic powder containing silica and barium oxide as constituent components. From observation using a scanning electron microscope, this inorganic oxide has a particle size of 0.071 to 0.094. The average particle size was 0.085 ayys, the shape was perfectly spherical, the standard deviation of the particle size distribution was 1.15, and the refractive index was 1.524. The obtained inorganic oxide was further surface-treated with γ-methacryloxyglobyltrimethoxysilane.

Production Example-13 Distilled tetraethyl silicate (5
i(QC2H5)4, manufactured by Nippon Colcoat Chemical Co., Ltd. Product name:
Ethyl silicate 28) 27 was dissolved in 0.21 g of methanol, and this solution was hydrolyzed and scaled at room temperature with stirring for about 2 hours.
-nc4H2) 4, manufactured by Nippon Soda) 3.4. P to isoprot4nol1. It was added to a solution containing OI K while stirring to prepare a mixed solution of tetraethyl silicate hydrolyzate and tetrabutyl titanate. Next,
Barium bisisobenoxide 1,5? and tetraethyl silicate 21? was dissolved in 1.0 methanol, the solution was refluxed at 90° C. under a nitrogen atmosphere for 30 minutes, and then returned to room temperature to prepare a mixed solution (B). Further, the mixed solution (1,) and the mixed solution () were mixed at room temperature to form a mixed solution (C).

Next, a glass reaction vessel with an internal volume of 10 mm and equipped with a stirrer was filled with 2.5 mm of methanol, and 500 mm of ammonia aqueous solution (concentration 25 v+t'%) was added thereto to prepare an ammoniacal methanol solution. The previously prepared mixed solution (6) was heated for about 40 minutes while keeping the temperature of the reaction vessel at 40°C.
Added over time. A few minutes after the addition started, the reaction solution became milky white. After the addition was completed, stirring was continued for another 1 hour, and then the solvent was removed from the milky white reaction solution using an evaporator, and the mixture was further stirred for 8 hours.
A milky white powder was obtained by drying under reduced pressure at 0°C.

Next, this milky white powder was baked at 800℃ for 2 hours, and then
Dispersed in an agate mortar, silica, titania and oxidation/4
An inorganic powder containing lithium as a constituent was obtained. From observation using a transmission electron microscope, this inorganic powder has a particle size of 0.065 to 0.
．． The average particle diameter was always 0.072μ, the shape was perfectly spherical, and the standard deviation of the particle size distribution was 1.080 mm.
06 and the refractive index was 1.526. The obtained inorganic powder was further surface-treated with r-methacryloxypropyltrimethoxysilane.

Production Example-14 Tetraethylsilicate (Sl(OC2H5)4, manufactured by Nippon Colcoat Chemical Co., Ltd. Product name: Ethylsilicate 28) 1
0.4y- and zirconium tetrabutoxide (Z
r (OC4H9) 4) 3. Dissolve IP in Improvil alcohol 0.21, and heat this solution at 100°C.
It was refluxed for 30 minutes under nitrogen atmosphere. Thereafter, the temperature was returned to room temperature, and this was used as a mixed solution. Next, 10.41 P of tetraethyl silicate and 1.257 P of strontium bismethoxide were added to 0.27 g of methanol, and this solution was refluxed at 80° C. for 30 minutes under a nitrogen atmosphere. After that, the temperature was returned to room temperature, and this was used as a mixed solution (). Mixed solution (A) and mixed solution (B) were mixed at room temperature, and this was used as mixed solution (C). Fill a glass reaction vessel with 2.4 J of methanol and add 500 ml of methanol. of ammonia water (concentration 25% by weight) was added to prepare an ammoniacal alcohol solution, and to this solution was added the previously prepared mixed solution (Q
was added over about 4 hours while keeping the reaction vessel at 40°C to precipitate the reaction product. Then continue,
Methanol 0.5 containing tetraethyl silicate 41P
A solution consisting of 1 was added over about 2 hours to the system in which the reaction product was precipitated. After the addition was completed, stirring was continued for an additional hour, and then the solvent was removed from the milky white reaction solution using a porator, followed by drying under reduced pressure to obtain a milky white powder.

Further, this milky white powder was calcined at 900° C. for 3 hours and then loosened using a grinder to obtain an inorganic powder whose main components were silica, zirconia, and strontium oxide.

From observation using a transmission electron microscope, this inorganic powder has a particle size of 0.
．． The average particle size is in the range of 0.070 to 0.082.
077 m), the shape was spherical, the standard deviation value of the particle size distribution was 1.20, and the refractive index was 1.532. The obtained inorganic powder was surface-treated with r-methacryloxypropyltrimethoxysilane.

Production Example-15 Tetraethyl silicate (Sl
(OC2H5) 4, manufactured by Nippon Colcoat Chemical Co., Ltd. Product name: Ethyl silica) 28) 21jl'- in methanol 0.2
After hydrolyzing this solution at room temperature for about 2 hours while stirring, tetrabutyl titanate) (Ti
(o-nc4Hg) 4, manufactured by Nippon Soda) 3.47- isopro-9-nol 1. A mixed solution of tetraethyl silicate hydrolyzate and tetrabutyl titanate was prepared by adding the mixture to a solution dissolved in Ol, while stirring. Next, aluminum tree s@a-butoxide 3. O? and tetraethyl silicate 21. P was dissolved in 1.0 mm of methanol, the solution was refluxed at 90° C. under a nitrogen atmosphere for 30 minutes, and then returned to room temperature to prepare a mixed solution.

Furthermore, the mixed solution and the mixed solution (2) were mixed at room temperature to form a mixed solution (C).

Next, a glass reaction vessel with an internal volume of 101 mm and equipped with a stirrer is filled with 2.5 mm of methanol, and 500 g of ammonia aqueous solution (concentration 25 wtl) is added to this to prepare an ammoniacal methanol solution. The mixed solution (Q) was added from a bottle over a period of about 4 hours while keeping the temperature of the reaction vessel at 40 °C.The reaction liquid became milky white within a few minutes after the addition started.After the addition was completed, stirring was continued for another 1 hour. , the solvent was removed from the milky white reaction solution using an evaporator, and further 80
A milky white powder was obtained by drying under reduced pressure at °C.

Next, this milky white powder was fired at 1000° C. for 2 hours and then dispersed in an agate mortar to obtain an inorganic powder containing silica, titania and alumina as constituent components.

This inorganic powder has a particle size of 0.00000.
The average particle size is within the range of 0.075 to 0.090.
The particle diameter was 081 μm, the shape was spherical, the standard deviation value of the particle size distribution was 1.08, and the refractive index was 1.512.

The obtained inorganic powder was further surface-treated with γ-methacryloxyglobiltrimethoxysilane.

Production Example-16 Tetraethylsilicate (Sl(OC2H5)4, manufactured by Nippon Colcoat Chemical Co., Ltd. Product name: Ethylsilicate 28) 1
280? and 0.1 dihydrochloric acid 15? was mixed and stirred at room temperature for 1 hour.

Then, tetrabutyl titanate (Ti(o-nc4
H9) 4, manufactured by Nippon Soda) 273iP and isobutanol 0
．． A mixed solution of 3 ingredients was added and thoroughly stirred and mixed. Next, this mixed solution was left at 30° C. for one week to obtain a transparent roll-shaped solid. The solid thus obtained was ground in a gall mill, calcined at 900°C for 1 hour, and then ground in a vibrating mill. The pulverized powder was classified (K) to obtain an inorganic powder containing silica and titania as constituent components.

This inorganic powder has a particle size of 0.00000.
Reeds range from 16 to 0.734L, average particle size is 0.47
sn, the standard deviation value of the particle size distribution was 1.29, and the refractive index was 1.528. The obtained inorganic powder further has γ-
The surface was treated with methacryloxyglobil trimethoxysilane.

Production Example-17 In Production Example-20, 325.
An inorganic powder containing silica and zirconia as constituent components was obtained in exactly the same manner as in Production Example 20 except that 5i' was used.

This inorganic powder has a particle size of 0.00000.
27~0.6! Within the SHL range, average particle size is 0.4
6tsn, the standard deviation value of the particle size distribution was 1.44, and the refractive index was 1.540. The obtained inorganic powder is further
- Surface treated with methacryloxyglobil trimethoxycin.

Production Example-18 Inorganic powder was produced in exactly the same manner as Production Example-14, except that the amounts of tetraethyl silicate and barium bisisobenoxide in the mixed solution, reaction temperature, and calcination temperature were changed. did. Synthesis conditions are tetraethyl silica) 208iP, 31.11-1 reaction temperature 20℃, calcination temperature 1000
℃.

As a result, the obtained inorganic powder has a particle size of 0.25 to 0.4
The cotton had an average particle diameter of 0.28, a true spherical shape, a standard deviation of particle size distribution of 1.20, and a refractive index of 1.524.

This inorganic powder was further surface-treated with r-methacryloxyglyltrimethoxycycne.

Production Example-19 In Production Example-15, the amounts of water, tetraethyl silicate, tetratutyltitanate, and barium bisiso(tonoxide) used in mixed solutions (4) and mixed solutions 0) and the reaction temperature were changed. Except for this, an inorganic powder was produced in exactly the same manner as in Production Example-15.

The synthesis conditions are: ・tetrabutyl silicate in the mixed solution)
21j', tetraptyl titanate) 3.47-1 mixed solution (B) of barium bisisobenoxide 1.5?
, tetraethyl silica) 21P, and the reaction temperature was 20°C.

As a result, the obtained inorganic powder has a particle size of 0.12 to 0.2
6. The particles had an average particle size of 0.19 μm, a true spherical shape, a standard deviation of particle size distribution of 1.06, and a refractive index of 1.526.

Production Example-20 In Production Example-16, mixed solution (4) and mixed solution CB
) An inorganic powder was produced in exactly the same manner as Production Example 23, except that the amounts of tetraethyl silicate, zirconium tetrasitoxide, and strontium bismethoxide and the reaction temperature were changed.

The synthesis conditions are as follows: mixed solution (tetraethyl silicate) 52
/-, zirconium tetracytoxide 15.6iP,
Mixed solution) Tetraethyl silicate 52iP, strontium bismethoxide 6.1? , and the reaction temperature was 40°C.

As a result, the obtained inorganic powder has a particle size of 0.10 to 0.2
5 cotton, the average particle size is 0.171 m, the shape is spherical, and the standard deviation value of the particle size distribution is 1.25.
The refractive index was 1.532.

Production Example 21 Completely the same as Production Example 17 except that the amounts of water, mixed solution, and tetraethyl silicate, tetrabutyl titanate, and aluminum-IC-toxide in mixed solution (B) were changed. Inorganic powder was produced in a similar manner.

The synthesis conditions were 0.36f of water, 1041P of tetraethyl silicate, and 1 of tetrazotyl titanate (in a mixed solution).
7.0? , aluminum tree 5e of mixed solution (B)
e-toxide 15. OJi', tetraethyl silicate) 21? and the reaction temperature was 40°C. As a result, the obtained inorganic powder had a particle size of 0.14 to 0.25 ayyc.
The average particle size is 0.20 mm, the shape is spherical, the standard deviation of the particle size distribution is 1.15, and the refractive index is 1.
．． It was 512.

Production Example-22 In Production Example-I, all methods were the same as Production Example-1, except that 1.2j of isobutanol and an ammonia aqueous solution (ammoniac alcohol consisting of 25% by weight of 1% by weight) and the temperature of the reaction vessel were 30°C. An inorganic powder was obtained.

This inorganic powder has a particle size in the range of 0.12 to 0.33 m, an average particle size of 0.25 μm, and a standard deviation value of the particle size distribution of 1.12. The refractive index was 1,523.

Production Example 23 In Production Example 8, the amounts of raw materials tetraethyl silicate and tetrabutyl zirconate and the solvent composition of the ammoniacal alcohol solution were changed to produce inorganic powder having the particle size and refractive index shown in Table 3. did.

All of the obtained inorganic powders had a standard deviation value of 1.30 or less and were spherical.

Examples 1 to 3, Comparative Examples 1 to 4 NPGD air 25 air volume 5 parts by weight TMM-3L 32.5 parts by weight and TEGDMA 32.51 parts by weight were stirred and mixed to obtain a uniform vinyl monomer mixture. The refractive index of this monomer liquid was 1.468, and the refractive index of the polymer obtained by polymerizing it was 1.503.The mouthpiece was covered with aluminum foil to shield it from light, and then CQ 0 0.5 parts by weight and 0.60 parts by weight of DMBE were added to the vinyl monomer liquid and dissolved with stirring. Next, 43 parts by weight of this vinyl monomer mixture and 57 parts by weight of the inorganic powder shown in Table 4 were sufficiently kneaded in an agate mortar to prepare a yeast-like composite composition (hereinafter referred to as paste). After preparing the yeast, defoaming was performed under reduced pressure to remove air bubbles from the paste. Using a cured product obtained by polymerizing the paste obtained in this way, surface hardness,
Compressive strength, tensile strength, toothbrush wear depth, and transparency were measured, and the results are also listed in Table 4. The yeast preparation and defoaming were performed under red light.

As a comparison, in Comparative Example-1, an inorganic powder with a particle size of 0.10 mm or more was used, and in Comparative Example-2, an inorganic powder with a particle size of 0.07 mm or smaller was used as ultrafine silica (particle size 0. .014
Shoulder, manufactured by Tokuyama Ichitatsu Co., Ltd., product name: Reolo Seal Ql 02
) was used. However, in Comparative Example 2, since it was not possible to mix a large amount of ultrafine particle silica into the vinyl monomer mixture, the mixing proportions of the vinyl monomer mixture and inorganic powder were set to 80 parts by weight and 20 m parts, respectively.

Furthermore, in Comparative Example-3, the refractive index was 0.03 from the polymer.
An example using an inorganic powder with a much higher refractive index was shown in Comparative Example 4, an example using an inorganic powder with a refractive index lower than that of a polymer by 0.03.

From the above results, the cured products of Examples 1 to 4 have a transparency of 0.
．． A value of 9 or higher means that the tsurinell surface hardness is high, and the toothbrush wear resistance and surface roughness are excellent.

On the other hand, in Comparative Example 1, the cured body using an inorganic powder with a particle size of 0.11 I'rrL or more and a refractive index difference of 0.006 from the polymer had a transparency of 0.9 or less. there were. In Comparative Example 2, the cured product using ultrafine silica had a small mixing ratio of inorganic powder and was poor in mechanical properties such as Purinelle surface hardness and tensile strength. In Comparative Examples -3 and -4, the particle size was 0.
07-1. A cured product using an inorganic powder that has a large refractive index difference from that of a polymer has a transparency of 0.
．． It was 9 or less.

Examples-5 to 8 Big-GMA 62 parts by weight, TEGDMA 38!
The mixed portion was stirred and mixed to obtain a uniform vinyl monomer mixture. The refractive index of this monomer mixture is 1.517, and the refractive index of the polymer obtained by polymerizing it is 1.547.
It was. The periphery of the container was covered with aluminum foil to shield it from light, and then 0.5 parts by weight of CQ, 0.4 parts by weight of DMP'I' and phosphorus:/j! Add 0.4 parts by weight to the vinyl monomer solution and stir and dissolve. Next, 40 parts by weight of this vinyl monomer mixture and 60 parts by weight of the inorganic powder shown in Table 4 were thoroughly kneaded in a Menowa mortar. A paste was prepared. After the paste was prepared, air bubbles were removed from the paste by defoaming under reduced pressure.

Using the paste thus obtained, surface hardness, compressive strength,
The tensile strength, toothbrush abrasion depth and transparency were measured, and the results are also listed in Table 5. The yeast preparation and defoaming were performed under red light.

Examples 9 to 12 Example 5 except that a vinyl monomer mixture consisting of 23 parts by weight of Bls-GMA, 57 parts by weight of TEGDMA, and 20 parts by weight of A-TMM-3L and the inorganic powder shown in Table 4 were used. A paste was prepared in the same manner as above, and various physical properties were measured. The results are also listed in Table 5. The refractive index of the vinyl monomer mixture and the polymer obtained by polymerizing it were 1.487 and 1.525, respectively.

Examples 13 to 18 Pastes were prepared in the same manner as in Example 5, and the physical properties shown in Table 6 were measured. The results are also listed in Table-5.

Comparative Examples 5 to 8 Yeast was produced in the same manner as in Example 5, and the physical properties shown in Table 6 were measured. The results are also listed in Table-6.

In Comparative Example 7, the blending ratio of the inorganic powder was 45 parts by weight.

Examples-19 to 25, Comparative Examples 9 to 10 B1m-10B1 or D-2,6E and TEGDMA
were stirred and mixed at the mixing ratio shown in Table 7 to obtain a uniform vinyl monomer mixture. Table 7 shows the refractive index of the vinyl monomer mixture and the polymer obtained by polymerizing the same.

Next, various physical properties were measured using a paste prepared in the same manner as in Example 5, except that the inorganic powder shown in Table 1 and the above vinyl monomer mixture were used, and the results are shown in Table 8. Also listed.

In addition, for comparison, in Comparative Example-9, vinyl monomer 10
0 parts by weight, the inorganic powder synthesized in Production Example-8 and α
-Quartz (amorphous, average grain size 5.6 brocade, refractive index 1,544
, 1.553), and in Comparative Example-10, the inorganic powder synthesized in Production Example-13 and the inorganic powder synthesized in Production Example-20 were used as the inorganic powder. are shown in Table 8.

As a result, in Examples 19 to 25, the viscosity of the paste was not high despite K having a high blending ratio of inorganic powder. Moreover, the transparency of the paste could be adjusted to be lower than the transparency after polymerization without sacrificing the transparency, mechanical properties, and surface smoothness of the cured product.

On the other hand, in Comparative Example 9, the surface roughness of the hardened body using α-quartz as the inorganic powder with a particle size larger than 3 mm was increased. In Comparative Example 10, a cured product using an inorganic powder with a particle size 0.1 larger than cotton and a large difference in refractive index from the polymer was
Transparency was lower than 0.9.

Comparative Example-11 A paste consisting of 100 parts by weight of the nine-vinyl monomer mixture (C) shown in Table 7, 100 parts by weight of the inorganic powder of Production Example-13, and 130 parts of the inorganic powder of Production Example-19 was prepared in Example 19. It was prepared in the same manner as above, and its physical properties were measured. The results are also listed in Table 8.

Example 26 29 parts by weight of Bis-GMA, 71 parts by weight of TEGDMA, and 71 parts by weight were stirred and mixed to obtain a uniform vinyl monomer mixture. The refractive index of this monomer mixture is 1.486, and the refractive index of the polymer obtained by polymerizing it is 1.486.
．． It was 525.

Next, 40 parts by weight of this vinyl monomer mixture solution, BPO0,
8 parts by weight, 0.04 parts by weight of BIT, and 60 parts by weight of the inorganic powder of Production Example-9 were sufficiently kneaded in an agate mortar to prepare a paste (this yeast is referred to as paste B).
.

On the other hand, 40 parts by weight of the above vinyl monomer mixture, DIP
Yeast was prepared using a mortar in the same manner as in B (paste with 0.6 parts by weight of T 0.6 i, 0.008 parts by weight of BHT, and 60 parts by weight of the above inorganic powder).
).

Equal amounts of Paste Man and Paste B were placed on kneaded Japanese paper, and the two were kneaded together under reduced pressure to prepare test pieces for measuring various physical properties.

The results of physical property measurements were that the Tsurinell surface hardness was 53 and the compressive strength was 4.010. The tensile strength was 525, the toothbrush abrasion depth was 5.0 stitches, and the transparency of the cured product was 0.96. still,
The transparency of the composition before polymerization was 0.84.

Example 27 After filling the yeast prepared in Example 21 into a split mold or mold for measuring various physical properties, the yeast was pressurized with nitrogen at 4 kg/mold.
Polymerization was carried out under conditions of <- and a temperature of 90°C to obtain a cured product.

The measured physical properties of the tabular body were as follows: Purinel surface hardness: 53, compressive strength: 4,500 kli/cry, A-1 tensile strength: 620 kli/cry.
? , toothbrush wear depth 3.0 shore, transparency 0.95, surface roughness 0.3. It was m. The transparency of the composition before polymerization was 0.85.

Examples-28 to 29 All examples were the same as Example-1 except that the blending ratio of the inorganic powder and vinyl monomer mixture shown in Table 9 was used in Example-15.
A paste was prepared in the same manner as in Example 3, and various physical properties were measured. The results are also listed in Table 9.

Comparative Examples-12 to 13 Pastes were prepared in the same manner as in Example-13, except that the proportions of the inorganic powder and vinyl monomer mixture shown in Table 10 in Example-13-3 were used. Physical properties were measured. The results are also listed in Table 10.

Claims (1)

[Claims] 1. (a) 100 parts by weight of a polymerizable vinyl monomer, and (b) an average particle size of 0.07 μm or more and less than 0.1 μm, and a refractive index (X) of the formula Y- 10^-^7^. ^3・d^-^5^. ＾0≦X≦
Y+10^-^7^. ^3・d^-^5^. 100 to 240 parts by weight of inorganic powder in the range of A polymerizable composition consisting of: 2, (a) 100 parts by weight of polymerizable vinyl monomer, (
b) The average particle size is 0.07 μm or more and less than 0.1 μm, and the refractive index (X) is of the formula Y-10^-^7^. ^3・d^-^5^. ＾0≦X≦
Y+10^-^7^. ^3・d^-^5^. 100 to 240 parts by weight of inorganic powder in the range of and (c) the average particle size is 0.1 to 3 μm, and the refractive index (
Inorganic powder 10 in which X') is within the range of the formula Y-0.005≦X'≦Y+0.005 (where, Y indicates the refractive index of the polymer obtained by polymerizing the vinyl monomer of (a)) -120 parts by weight of a polymerizable composition.