JPS63218703A - Photocurable composite composition - Google Patents

Abstract

PURPOSE:To obtain a composition having the same transparency before and after polymerization and useful as a composite resin for dental restoration taking advantage of its great hardening depth, by compounding a polymerizable vinyl monomer, a filler having high refractive index, a filler having low refractive index and a photo-polymerization initiation catalyst. CONSTITUTION:The objective composition is composed of (A) a polymerizable vinyl monomer (e.g. methyl methacrylate and vinyl acetate), (B) a high-refractive index filler having a refractive index (nDF) of formula I (nDM is refractive index of the polymerizable vinyl monomer; nDP is refractive index of a polymer produced by polymerizing said vinyl monomer) (nDF is preferably 1.51-1.58), (C) a filler having a refractive index (nDF) of formula (nDF is preferably 1.46-1.52) and (D) a photo-polymerization initiation catalyst capable of starting polymerization by visible light having a wavelength range of 390-700mn (e.g. a combination of photo-sensitizer such as benzyl and a photo-polymerization accelerator such as N,N-dimethylaniline).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photocurable polymerization compositions that initiate polymerization with visible light.

[Problems to be solved by conventional technology and invention]

Conventionally, composite compositions in which a vinyl monomer that can be combined with an inorganic or organic filler is mixed have been widely used in various fields in order to improve scientific and engineering properties and reduce volumetric shrinkage during storage. For example, in the dental field, 2,2-bis(4-(3-methacrylate)-2-hydroxypcepothousandiphenyl)propane (bisphenol Addition product of A and glycidyl methacrylate) is added to the thick noodles, and glass beads with a particle size of several 1 μm or crushed quartz or strontium glass are added to the thick noodles as a filler. de1
Composite compositions that are cured by combination are generally used.

At present, there are roughly two types of methods used to initiate polymerization of such polymerization compositions for dental restorations. One method utilizes the redox reaction of BPO-m tertiary amine, and in this case, polymerization is initiated by kneading two types of pastes immediately before use. The other method utilizes a photocatalyst such as chinones, and starts the process by irradiation with visible light or ultraviolet light.

In this case, there is only one type of paste and it does not need to be kneaded. Therefore, the latter photocatalytic method has been increasingly used in recent years due to its ease of clinical operation.

One of the major problems with composite compositions for dental restorations using photocatalysts is that polymerization becomes non-uniform. That is, when such a composite composition is combined in a tooth cavity, light is scattered or absorbed within the material, making it difficult for the amount of light necessary for polymerization to reach the corner bottom.

Therefore, there is a problem in that more unpolymerized 7-mer particles tend to remain, especially at the bottom of the corners. Therefore, improving the light transmittance of composite compositions has become an important research topic as one of the countermeasures for such problems.

For example, a method has been reported in which the cure depth of a composite composition is improved by using a filler having a refractive index intermediate to that of a vinyl monomer and a vinyl polymer obtained by polymerizing the vinyl monomer. However, above-1 ■■■--
--With one method, the transparency of the cured product after polymerization becomes too high, making it difficult to obtain a cured product with a translucency similar to that of natural teeth. The reason for this is that, in general, the difference in refractive index between the vinyl monomer preferably used in the adhesive composition for dental restorations and the vinyl polymer obtained by combining the vinyl polymer is approximately 0.03 or less. As a result, the difference in refractive index between the filler and the vinyl polymer becomes even smaller.However, in order to obtain a cured product with the same translucency as natural teeth, the difference in refractive index between the filler and the vinyl polymer becomes smaller. This is because the difference must be around 0.04.

Therefore, in order to obtain a cured product with a color similar to that of natural teeth, it is necessary to reduce the transparency of the cured product, and as a means of achieving this, pigments with strong hiding power such as titanium dioxide or zirconium dioxide are usually added. . However, such methods result in an interlayer that simultaneously reduces light transmittance in the composite composition, resulting in a reduction in cure depth.

Furthermore, the dental restorative composite composition is required to have the translucency of natural teeth and to have as small a change in transparency as possible before and after polymerization. This is because the color of human teeth varies from person to person.

Alternatively, it varies depending on the repair site, and the dentist needs to select the one that best matches the color around the perforation from among composite compositions with several different colors. At this time, if there is a large change in the transparency of the composite composition before and after polymerization, it is impossible to predict the change and select the color tone. In the aforementioned ■■■■■■I-■■■■■I■- composite composition, the refractive index of the filler is exactly in the middle of the refractive index of the vinyl monomer and the vinyl polymer obtained by combining the vinyl monomers. Except in some cases, the transparency changes significantly before and after polymerization. If the refractive index of the filler is exactly in the center of the vinyl monomer obtained by polymerizing the vinyl monomer, there will be no change in transparency due to a change in the refractive index around 1. However, as mentioned above, the transparency of the cured product is higher than that of natural teeth.

As mentioned above, photocuring shop's composite composition for dental restorations:
There is a need to develop a composite composition that has an appropriate translucency after polymerization, has as little change in transparency before and after polymerization as possible, and has a high cure depth, which is an important technical issue.

[Means to solve problems]

Non-researchers have conducted intensive research with the aim of solving the above technical hakama problem. As a result, they discovered that the above problems could be solved by using two types of fillers having specific refractive indexes, and completed the present invention.

That is, the present invention is directed to &) nM gold monomer filler (hereinafter referred to as high refractive index filler); however, nM
:Refractive index of polymerizable vinyl monomer! lP: the vinyl monomer 1k has the same refractive index as the obtained polymer (hereinafter referred to as a low refractive index filler) and d) polymerization can be initiated by visible light of 390 nm to 7 Q Q nm. This is a photocurable composite composition comprising a photopolymerization initiation catalyst.

One component of the photocurable polymer composition in accordance with the invention is a polymerizable vinyl septamer. The vinyl nitrate is not particularly limited, and generally known ones can be used. Typical examples that are generally preferably used include acrylic groups and/or
Or, it is a monomer capable of combining with a methacrylic group.

Specific examples are as follows.

a) Monofunctional vinyl monomers methyl methacrylate; ethyl methacrylate; isopropyl methacrylate; hydrobovine diethyl methacrylate; tetrahydrofurfuryl methacrylate; glycidyl methacrylate; and these acrylates or acrylic #, methacrylic acid.

P-Methacryloxybenzoin*. N-2-hydroxy-3
-Methacryloxypropyl-N-phenylglycine, 4
- Methacrylic bovine diethyl trimellitic acid and its anhydride.

6-methacryloxyhexamethylenemalonic acid. 10-methacrylic acid methylene malonic acid, 2-methacrylic acid ethyl dihydrogen phosphate, 10-methacrylic acid methylene dihydrogen 7-osphate.
2- and doro thousand ethyl hydrogen phenyl 7 male 7 onate.

2) Bifunctional vinyl monomer (T) Aromatic compound type 2, 2-bis(methacrylodiphenyl)propane; 2
．． 2-bis(4-(3-methacryloxy)-2-hydrobordipropoxyphenyl)propane; 2.2-bis(4
-Methacryloxyphenyl)propane: 2,2
-bis(4-methacryloxyjethoxyphenyl)propane 52t2-bis(4-methacryloxytetraethoxydiphenyl)propane; 2,2-bis(4-methacryloxypropyl) diphenyl)propane; 4-methacryloxyyl ('ll ethoxydiphenylpropane; 2.

2-bis(4-methacryloxydibutetraboxyphenyl)
Propane; 2 (4-Methacrylo 1,000 Shed 1,000 Diphenyl)
)-2(4-methacryloxyjethoxyphenyl)propaneyz(+-methacryloxyjethoxy7enyl)-
-
2(4-methacryloxytriethoxyphenyl)propane; 2.2-bis(4-methacrylocyprobodiciphenyl)propane; 2゜2-i:'X(4-methacryloyloxytriethoxyphenyl)propane and their acrylates :2-Hydro 1,000 diethylmeth? Relay 1,
A vinyl monomer having an 10H group such as 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate or these acrylates, and diisocyanate methylbenzene, 4.4'
- sheaducts obtained from addition with diisocyanate compounds having aromatic groups, such as diphenylmethane diisocyanate, based on aliphatic compounds ethylene glycol dimethacrylate; diethylene glycol dimethacrylate; triethylene glycol dimethacrylate; butylene glycol dimethacrylate ; neopentyl glycol dimethacrylate; propylene glycol dimethacrylate; 1,3-butanediol dimethacrylate); 1,4-butanediol dimethacrylate; 1,6-hexanesiol dimethacrylate and their acrylates; 2-hydrothousand diethyl methacrylate, 2-hydroxypropyl methacrylate.

3-chloro-2-hydroxypropyl methacrylate or a vinyl monomer having an -OH group, such as these acrylates, and methylene diisocyanate,
Trimethylhexamethylene diincyanate.

Diisocyanate methylcyclo to beef san.

Sheaduct obtained from addition with diisocyanate compounds, such as in7-olone diincyanate, methylene bis(4-cyclohebosilisocyanate): acrylic anhydride.

Anhydrous methacrylic R: l, 2-bis(3-methacryloxy-2- and methacryloxy-2-ethyl, di(2-methacryloxyethyl) 7-mole 7-ate, di(3-methacryloxy-dipropyl) phosphate) Royal a-functional vinyl monomers Trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol tritacrylate, trimethylolmethane trimethacrylate and these acrylates Tetrafunctional vinyl monomers Pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate and Diisocyanate methylbenzene, diisocyanate methyl cyclohexane, iso7-olone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylene bis(4-cyclohexyl isocyanate), 4,4'-diphenylmethane diisocyanate, tolylene-2,4 In addition to vinyl monomers such as sheaduct and higher obtained from the addition of diisocyanate compounds such as -diisocyanate and glycidol dimethacrylate, those generally known for industrial use can be used. Typical examples that are generally suitably used include: vinyl esters such as vinyl acetate and vinyl propion; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and imbutyl vinyl ether; styrene, vinyltoluene, and α-methylstyrene. , chloromethylstyrene, stilbene, and other alkenylbenzenes are preferably used.

In the claims of the present application and the detailed description of the invention, the term "polymerizable vinyl monomer" includes not only a single component but also a vinyl monomer mixture consisting of a number of vinyl monomers.

When using multiple types of polymerizable vinyl monomers, if the vinyl monomer has an extremely high viscosity at room temperature, or if it is a single vinyl monomer, it is preferable to use it in combination with a low-viscosity polymerizable vinyl monomer. This combination is not limited to Class 29, but may include three or more types. or,
Since a polymer made only of monofunctional vinyl monomers does not have a crosslinked structure, the mechanical strength of the polymer generally tends to be poor. For this reason, when monofunctional vinyl monomers are used, they are preferably used in conjunction with polyfunctional vinyl monomers. The most preferred combination of polymerizable vinyl monomers is a method in which a difunctional vinyl heptanomanoaromatic compound is used as a main component and an aliphatic compound of the difunctional vinyl monomer is combined. In addition, for example, combinations of trifunctional vinyl monomers and tetrafunctional vinyl monomers, aromatic compounds of difunctional vinyl monomers and aliphatic compounds of trifunctional vinyl monomers and/or tetrafunctional vinyl monomers can be used. Combinations of these, and combinations in which a monofunctional vinyl monomer is further added to these combinations can be suitably employed.

Next, although the composition ratio in the combination of the above vinyl monomers may be determined as necessary, the composition ratio that is generally suitably employed will be shown.

(1) The aromatic compound of the difunctional vinyl monomer is 30~
80% by weight, the same aliphatic compound 70-20]1[m% (27EWm vinyl monomer is 30-100% heavy duty, tetrafunctional vinyl monomer is O-70xli% (3) Aromatic of difunctional vinyl monomer The compound is 3
0-60% by weight, aliphatic compounds 5-3011L*%
The trifunctional vinyl monomer preferably has a composition ratio of 10 to 801%, and the tetrafunctional vinyl monomer preferably has a composition ratio of 0 to 50ml%.

The refractive index of the vinyl monomer preferably used in the composite composition of the present invention is in the range of 1.45 to 1.55, and the refractive index of the vinyl polymer obtained by combining the vinyl monomers is 150. The range is from 1.60 to 1.60. More preferably, the vinyl monomer has a refractive index of L48 to L5.
The refractive index of the vinyl polymer obtained by combining the vinyl monomers is in the range of 1.52 to 1.56.

Furthermore, the 1K fle used in the composite composition of the present invention
The difference in refractive index between the natonyl monomer and the vinyl polymer obtained by combining the vinyl monomers is preferably within 0.04.

Monomers with a difference in refractive index greater than the above range generally have large polymerization shrinkage and are therefore unsuitable for use in dental restorative composite compositions. This is because composite compositions for dental restorations are used by being polymerized and hardened within the tooth cavity, but if the composite composition has a large polymerization shrinkage,
Bacteria tend to invade the gap created between the composite composition and the tooth after the treatment, which is undesirable because it causes new caries (secondary caries) to occur in the cavity.

The photocurable composite composition of the present invention uses a combination of two types of fillers having different refractive indexes, ie, a high refractive index filler and a low refractive index filler. High refractive index fillers have a refractive index that is close to vinyl polymers, and low refractive index fillers have refractive indices that are relatively close to vinyl monomers. By using these high refractive index fillers and low refractive index fillers in combination, the composite composition of the present invention has a higher hardening depth compared to conventional interlocking composites containing pigments such as titanium dioxide. The thing has become clear. In addition, the transparency of the cured product obtained by polymerizing the composite composition of the present invention can be made comparable to that of natural teeth, and the change in transparency is smaller than the change in transparency between before and after 1 cup of the composite composition. It became possible to do so.

Below, such fillers will be described in more detail.

The refractive index (no) of the high refractive index filler needs to satisfy the following formula.

However, nD: refractive index of vinyl monomer that can be combined nD; obtained by polymerizing the vinyl monomer Refractive index of Rarero polymer Preferably, the following formula should be satisfied.

P The refractive index (n) of the high refractive index filler is nD+0.04
If it is higher, the transparency of the cured product becomes too low and it is not possible to obtain an -IM cured product having a translucency similar to that of natural teeth. Furthermore, if nD is less than T (nD+nP), the difference in transparency before and after polymerization becomes too large, making color matching very difficult for clinical use.

The refractive index (n o ) of the r' low refractive index filler has a value that satisfies the following formula.

M F' P n -0,04≦nD (nD-0,04) It is desirable that the following formula be satisfied.

nM-0,02≦n"<nP-0,04[)
DD F' P The refractive index (n) of the low refractive index filler is n D-o, o
In the case of 4 or more, the transparency of the cured product becomes too high,
In order to achieve the same translucency as natural teeth, a new layer of highly invisible pigment is added for peace of mind. However, if nD is lower than nD-0.04, the light transmittance in the composition becomes low, making it impossible to obtain a high curing depth.

Furthermore, rLF' has a membership fee that satisfies the following formula.8 If the refractive index of the low refractive index filler is higher than this range, the difference in transparency before and after polymerization based on the difference in refractive index becomes too large.

The refractive index of the high refractive index filler and the low refractive index filler used in the composite composition of the present invention is limited depending on the type of vinyl hexamer, but in the case of the preferred vinyl hexamer described above, Generally, the refractive index of the high refractive index filler is in the range of 148 to 1.62, and the refractive index of the low refractive index filler is preferably in the range of 1.43 to 1.56. More preferably, the refractive index of the high refractive index filler is 1.51 to 1.
．． 58, and the refractive index of the low refractive index filler is 1.58.
It ranges from 46 to 1.52.

Each filler used in the present invention may be inorganic or organic as long as it has the above refractive index, and generally known fillers are used. Commonly used inorganic materials include inorganic oxides containing silica, such as quartz, cristobalite, eucryptite, subodumene, carnegitite, orthoclase, albite, anorthite, etc. Natural minerals or silica-alumina-calcia-sodium oxide-[potassium], silica-alumina-boron oxide-potassium fermentation-barium oxide, silica-calcia
Examples include glasses whose main components are boron oxide-sodium oxide-potassium oxide-zinc oxide, silica-sodium oxide-potassium oxide-lead oxide, and the like.

Furthermore, JP-A-58-110414, JP-A-58-110414,
151321, JP 58-152804, JP 58-156524, JP 58-156526, JP 59-54616, and JP 59-101409. Substances that can be combined with silica, Groups Ⅰ and Ⅲ of the periodic table.

It is also possible to use an inorganic oxide whose main constituents are at least one metal oxide selected from the group consisting of Group Ⅰ and Group Ⅰ and silica, and whose particle size is 0.1 μm to 1.0 μm. You can do it.

Examples of organic fillers that can be used include:
Polymethyl methacrylate, polyethyl methacrylate, polymethyl acrylate, polyethyl acrylate,
Polymers of monofunctional methacrylates or acrylates such as poly n-butyl acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hesanodiol dimethacrylate, 2,2 -Bis[4-(3-
Polymers of difunctional methacrylates such as methacrylic group (2)-2- and doro-thousandybrobobo-diphenyl]propane, or polymers of acrylates in which the methacrylic group is substituted with an acrylic group, trimethylolpropane trimethacrylate, tetramethylolmethane trimethacrylate Examples include trifunctional or tetrafunctional methacrylate polymers such as , tetramethylolmethanetetramethacrylate, and acrylate polymers in which the methacrylic group is substituted with an acrylic group. It is also possible to use a comonomer of the above polymers. In addition to this,
Mention may also be made of polycarbonate, polystyrene, polydiallyl phthalate, polydiethylene glycol bisallyl carbonate, and the like.

It is also possible to fill the polymer with an inorganic filler to strengthen the polymer to form an organic composite filler. As the organic composite filler, one having a structure in which the inorganic filler used in the present invention is uniformly dispersed in the above polymer is suitable. Since this organic composite filler must have optical transparency, it is desirable that the difference in refractive index between the inorganic filler and the polymer be within 0.02.

The particle size and shape of the high refractive index filler and low refractive index filler used in the present invention are not particularly limited. however,
If the particles are too small, when the filler and the vinyl monomer are mixed, IIIaiI at the interface becomes large, making it difficult to fill the filler into the vinyl monomer in a multi-dimensional manner. As a result, the strength of the cured product obtained by combining the composite compositions decreases. Therefore, the particle size of the filler used in the present invention is 0.
．． It is preferable that the thickness is 0.05 μm or more. Conversely, when a filler with a large particle size is used, the surface of the cured product obtained by combining the composite composition will generally be rough, so the particle size of the filler is in the range of 0.05 μm to 100 pm. Things are good. Especially when the filler is an inorganic substance, if the particle size is large, the surface of the cured product will not only be rough, but will also have a smooth surface even after polishing. : Since it becomes difficult to obtain, the particle size is preferably in the range of 0.05 μm to 10 μm, and more preferably in the range of 0.1 μrrL to 3 μm.

The filler used in the present invention is preferably inorganic rather than organic from the viewpoint of reinforcing effect, and inorganic oxides are particularly preferred. As these fillers, it is also possible to use three or more types of fillers each having a different refractive index.

In this case, it is sufficient that the refractive index of each filler satisfies the above-mentioned conditions for a high refractive index filler or a low refractive index filler, and then both fillers with both refractive indexes are included. In addition, if the refractive index of the polymerizable vinyl monomer and the refractive index of the vinyl polymer obtained by polymerizing the vinyl monomer have the relationship shown in the following formula, in addition to the high refractive index filler and the low refractive index filler. There is a refractive index of the following formula. The proportion of the filler in the total filler is 80% or more, preferably 60% or more.

When using an inorganic oxide containing silica as the filler of the present invention, it is preferable to reduce the number of silanol groups on the surface in order to maintain its surface stability. For this purpose, a method of drying the inorganic oxide and then firing it at a temperature of 500 to 1000° C. is preferably employed. Generally, in order to maintain stability, the fired inorganic oxide is most preferably used after surface treatment using an organic silicon compound. The surface treatment method described above is not particularly limited and may be carried out by any known method, such as using an inorganic oxide and a known organosilicon compound such as r-methacrylothousandipropyltrimethoxysilane or vinyltriethoxysilane in a solvent such as alcohol. A method is adopted in which the solvent is removed after contacting for a certain period of time.

Next, in the present invention, (OJ photo-1 initiation catalyst is 390 ~
Excited by 700 thru visible light irradiation, 1
Any known material that can initiate the reaction can be used without any restriction. Preferably, a catalyst is used that initiates polymerization with visible light of 400 to 600 nm. Furthermore, it is generally preferable to use a photosensitizer in combination with a photopolymerization accelerator as the photopolymerization initiation catalyst. Examples of those suitably used as photosensitizers include benzyl, camphorone, α-naphthyl, acetonaphcene, P,P'-dimethoxybenzyl, p,p'-dichloroqbenzyl diacetyl, pentanedione, lI2- phenanthrenequinone sl
*4-7 Enanthrene Beef Non.

3.4-y enanthrene, 9.10-7 enanthrene, naphthogyno, etc.) α-sinatones.

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, camphor chinon can be used most preferably.

Examples of photopolymerization accelerators include N,N-dimethylaniline and N,N-diethylaniline.

N,N-di-n-butylaniline, N,N-dibenzylaniline, N,N-dimethyl-P-toluidine, N,N
-diethyl-p-toluidine, N,N-dimethyl-m-
) Ruijin.

P-promo N, N-dimethylaniline, m-? Lower N. N-dimethylaniline, P-dimethylaminobenzaldehyde, P-dimethylaminoacetophenone,
P-dimethylaminobenzoic acid, P-dimethylaminobenzoic acid ethyl ester.

P-dimethylaminobenzoic acid amino ester, N,N-dimethyl anthranilic acid methyl ester, N,N-dihydrobovine diethylaniline, N,
N-dihydroxyethyl-P-)luidine, P-dimethylaminophenethyl alcohol, P-1 methylaminostilbene, N,N-dimethyl-3°5-thousand silydine,
4-dimethylaminopyridine, N,N-dimethyl-α-
7-tylamine.

N,N-dimethyl-β-naphthylamine, tributylamine, tripropylamine, triethylamine, N-methylgetanolamine, N-ethylgetanolamine, N,N-dimethyl-β-naphthylamine, N,N-dimethyldodecylamine, N,N-dimethylsterylamine, N,N-dimethylaminoethyl methacrylate),
N,N-diethylaminoethyl methacrylate), 2.2
Tertiary amines such as '-(n-butylimino)jetanol; 5-butylbarbylic acid, 1-benzyl-5-
Barbylic acids such as phenylbarbic acid; benzoyl peroxide, di-t-butyl peroxide,
Organic peroxides such as t-butyl perbenzoate 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.

In addition, when used as a tertiary amine accelerator, 1Ik tertiary amines in which an aromatic group is directly substituted with a nitrogen atom are particularly preferably used. In addition to the tertiary amine, citric acid, apple powder, tartaric acid, glycol m, gluconic acid, α-oxydiisobutyric acid, 2-hydroxypropanoic acid, 3-hydroxypropanoic acid, and 3-hydroxypropanoic acid were added in order to improve the ability to promote the compound synthesis. Shiprivan I! ! ! It is effective to add oxycarboxylic acids such as 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, and dimethylolpropionic acid.

The preferred mixing ratio of the composite composition for photocuring of the present invention is as follows: &) a polymerizable vinyl monomer, b) a high refractive index filler, and C) a total filler including a low refractive index filler; The mixing ratio of vinyl monomer is 10 to 70mh.
A range of t% is appropriate, more preferably 15 to 407
This is jL Denden. Furthermore, the mixing λ amount ratio of b) and C) is 9:
A range of 1 to 3 near is appropriate, and 8:2 is more preferable.
~5:5 range. When this ratio is out of the range of 9:1 to 3, there is a drawback that the change in transparency before and after polymerization becomes large. Also, this ratio is a when one set is combined.
)* It is necessary to appropriately determine the refractive index of the vinyl polymer obtained by combining b)-a) and &). Furthermore, the photopolymerization initiation catalyst of a) is Q
, 001-51 wrinkle%, more preferably 0.01-331
A range of 1% is acceptable.

Furthermore, ultraviolet light such as 2-Hydose C4-Methylbenzophenone! The photocurable composite composition of the present invention includes ingredients such as 1[& astringent, hydroquinone, hydroquinone, hydroquinone monomethyl ether, 1-inhibitor such as 2,5-ditertiarybutyl-4-methylphenol, and * ingredient. Can be optionally added to.

The wavelength of light that combines the photocurable composite composition of the present invention is 3
90-7QQnm, preferably 400-600 nm
A range of light is used.

When using the composite composition for light irradiation of the present invention in a dental restoration resin related to the human body, it is important that the wavelength of the irradiated light is harmless to the human body. Examples of light in the wavelength range mentioned above include halogen lamps, xenon lamps, and lasers.

Light such as a fluorescent light or the sun can be used.

Further, the temperature and irradiation time when the vinyl monomer is mixed with the above-mentioned light vary depending on the intensity of the irradiated light, but can generally be appropriately determined according to the desired mixing time. Preferably, it is sufficient to perform the irradiation at a relatively low temperature of about θ°C to 60°C and for a relatively short time of about 10 seconds to several minutes.

When polymerizing a failed photocurable composite composition, a
A mixture of the polymerizable vinyl monomer (tl), the filler (O), and the photopolymerization initiation catalyst (d) may be stored in a paste form, and the source may be irradiated at the time of use. ), b), c) and d) may be stored separately and mixed immediately before use and irradiated with light. However, a) *
When storing the paste containing b) and O) and the photo-initiating catalyst, it is essential to protect the paste from light in order to prevent deterioration of the initiator or the catalyst during storage. Moreover, if a vacuum defoaming operation is performed to remove air bubbles from the paste before irradiating it with light, the effects of the present invention can be effectively exhibited on carp as well.

〔Effect of the invention〕

As is clear from the above explanation, when the photocurable composite composition of the present invention is used as a composite resin for dental restorations, it has the advantage of a large curing depth and sufficient hardness to the bottom of the cavity, and a good effect on the transparency of the tooth. It has the advantage that a suitable cured product can be obtained.

Furthermore, this composite composition is characterized in that its transparency does not change significantly after 1 cup. This has the advantage that when delicate color matching is important, such as in tooth restoration, the change in color tone before and after filling is small and color matching is easy.

As described above, the photocurable composite composition of the present invention has a number of advantages, and can be applied to dental crown resins, sealants, etc. in addition to restorative composite resins in the dental field.

〔Example〕

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, #I characteristics (
Particle size 2 Measurement of standard deviation value of particle size distribution, refractive index) 9 Measurement of refractive index of a polymerizable vinyl monomer and a polymer obtained by polymerizing the polymerizable vinyl monomer, and composite composition for light 1 Physical property values (curing depth, transparency) were measured using the following method.

(1) Standard deviation value of particle size and particle size distribution of rootless oxide; Take a scanning Yasaki wA microscopic photograph of the powder, and calculate the number of particles (nJ, and particle size) observed within the unit field of view of the photograph. The diameter (diameter X1: However, when the shape is not spherical, the horizontal direction Feret diameter is set as Xl) is calculated by the following formula.

(b) Refractive index of inorganic oxide; A solvent having the same refractive index as the inorganic oxide of the sample was prepared, and the refractive index of the solvent was taken as the refractive index of the sample. The solvent was prepared by suspending the sample in a solvent and preparing the composition of the solvent at a constant temperature so that it appeared transparent when observed with the naked eye. The solvents used were pentane, hexasan, cyclohesan, toluene, styrene, aniline, methylene iodide, etc., and the refractive index of the solvent was measured with an Atsube refractometer.

(The refractive index of the vinyl monomer of the 3331 alloy and the polymer obtained by polymerizing the vinyl monomer; The refractive index of the vinyl monomer and polymer was directly measured using an Atsube refractometer. The measurement was carried out at a constant temperature. I did it.

(4) Curing depth: The paste, which is a composite composition before polymerization, was put into a stainless steel mold with a diameter of 4 square meters and was pressed with a polypropylene film.

Next, the tip of a quartz rod of a visible light irradiator Optirax (trade name, Demetron Co., Ltd., USA) was fixed to the pressure contact surface.
Light irradiation was performed for a second. After irradiation, the sample was removed from the side plate and immersed in methanol to remove unpolymerized parts.

Next, the length of the cylindrical single-cured product was measured using a micrometer to determine the curing depth.

(5) Transparency: The paste was put into a stainless steel split mold having holes of 6 mm in diameter and 1 mm deep, and pressed with a polypropylene film. Next, the tip of the quartz rod of the visible light irradiator White Light (trade name, manufactured by Takara Belmont Co., Ltd.) was placed on the pressure contact surface. was fixed and irradiated with light for 30 seconds.

After irradiation, the cured product was removed from the split and placed in air at 37℃ for 2 hours.
After standing still for 4 hours, the Y value, which is one of the tristimulus values, was measured using a color difference meter (TC-1500MC, manufactured by Tokyo Kamishiro Co., Ltd.). At this time, a standard white plate (X=
81.2°Y=817. Z=93.8)fa:fM
If the knee is Y1m (hereinafter referred to as Yw), a standard black plate (X=0.1, Y=0.1.
The Y value (hereinafter referred to as Yb) when Z=0.2) was measured, and the contrast ratio indicating the opacity of the cured product was calculated using the following formula.

b Contrast ratio = □ w The brightness was calculated using the contrast ratio according to the following formula.

Transparency changes from 0 to 1 (11111v5), and the larger the value, the higher the distance brightness.

In addition, in order to measure the hBA concentration of the paste before 1 cup,
The paste and filler composition shown in each example and comparative example,
A paste having the same seven-mer composition and containing no catalyst was separately prepared. And these paces) Y diameter 1
The bottle was placed in an acrylic plate with a thickness of 1111 mm and has a hole of °II+, and was pressed against both sides with a polypropylene film. Thereafter, Y w e
Y b was measured, and transparency was calculated according to the above ti formula.

In addition, compounds in the following Examples and Comparative Examples are abbreviated as follows.

Compound name Abbreviation Ropantriethylene glycol dimethacrylate TEGD
MA neopentylglymethyl dimethacrylate) N
PGDIvlA Camphor Beef Non
CQP-dimethylaminobenzoic acid
DMBE thyl ester production g11 0.04% salt 1i1 with 5.0.9 and tetraethyl silicate) (Sl(QC2H,)4, manufactured by Nihon Colcoat Chemical Co., Ltd., product name: Ethyl silicate 28) 176.61 with methanol o, 441 This solution was heated to about 1
Hydrolysis was carried out with stirring for hours. Then, to this was added 25.0 g of tetrabutyl titanate (Ti (0-nc4H,) 4 m manufactured by Nippon Soda) and 0.24 g of isobutyl alcohol.
A mixed solution of tetraethyl silicate hydrolyzate and tetrabutyl titanate was prepared. Next, contents 1II31 with a stirrer
Meth, p-No., 39tx and imbutyl alcohol 0.781 were introduced into a glass reaction vessel, and 0.25
An ammonia alcohol solution was prepared by adding the ammonia aqueous solution (concentration 25 wt %) in step 7, and to this was added a solution of tetraethylsilicate α8I dissolved in methanol]8- as an organosilicon compound solution for making silica seeds. 10 minutes after the end of the addition, when the reaction solution became slightly milky, the above mixed solution was added to about 50% of the mixture.
It was added over time to precipitate the reaction raw material. During the reaction, the temperature of the reaction vessel was maintained at 30°C. After the reaction is completed, 3 more
After stirring for 0 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 900° C. for 1 hour and then dispersed in an agate mortar to obtain an inorganic oxide containing silica and titania as constituent components. From observation using a scanning electron microscope, this inorganic oxide has a particle size in the range of 0.22 to 0.42 μm, an average particle size of 0.29 μm, and a true spherical shape. The difference value was 1.11 and the refractive index was 1.503. The obtained inorganic oxide was further surface-treated with γ-methacrylic dipropyltrimethoxysilane.

(This surface-treated powder is hereinafter referred to as powder ■) Production example 2~
5 In Production Example 1, an inorganic oxide was produced in exactly the same manner as Production Example 1, except that the material of tetrabutyl titanate was changed. The obtained inorganic oxide was further surface-treated with γ-methacryloxypropyl and trimethoxysilane. (These surface-treated powders are hereinafter referred to as powders ① to ① to V.) Table 1 shows the properties of the tetrabutyl titanate and the obtained inorganic oxide.

[Example 1] 1 part of Bis-GMA 60ml and TEGDMA
401 was stirred and mixed to obtain a uniform monomer liquid. The refractive index of this seven-layer liquid is 1.516, and the refractive index of the polymer obtained by multiplying this by x is 1.546.
Met. The area around the container was covered with care aluminum foil to shield it from light, and then CQo, 4 parts by weight, and DMBE 0.47i1 (1
100% of the solution was added to the monomer solution and stirred to dissolve.

Mata, quartz powder (11 Morisha, VXS, 1.5
44 and 1.553) using a jet mill (manufactured by Seishin Enterprises, model FS-4) to obtain finely ground quartz having an average particle size of 27 μm. This powder was then surface-treated with γ-methacrylothousandipropyltrimethythodisilane. (Hereinafter, this surface-treated powder will be referred to as powder Ⅰ.) Next, 30 m of the above-mentioned and nyl monomer mixture solution and powder I2
1 part of 1'1/Li and 1 part of powder VI49] were sufficiently kneaded in an agate mortar to prepare a paste. base +
After +i+im, defoaming was performed under reduced pressure to remove air bubbles from the paste. The hardening depth of this paste was 8.1t1. Also, the transparency before and after the first part is 0.44.0 respectively.
．． 38, close to the transparency of teeth (around 0.4),
Moreover, the change before and after the first go was as small as 0.06. The results of Examples 1 to 9 are summarized in Table 2 below.

[Example 2] The same monomer mixture 3 as that used in Example 1
0]1[iit part and powder I21! j1 part.

7x parts of Powder II and 42 parts by weight of Powder VI were thoroughly kneaded in an agate mortar to prepare a paste, which was then defoamed. The same measurements as in Example 1 were carried out using this paste.

[Example 3] Example 141: The same vinyl monomer mixture as that used for toilet use was prepared using fi 30 summer parts and powder IV 15 parts.

Powder VI44.5xkk part and polymethyl methacrylate powder (manufactured by Shin Nakamura Chemical Co., Ltd., D-250-M, average particle size 3
0μrrL, refractive index 1.49) A 10.5Xt portion was sufficiently kneaded in an agate mortar to form a paste, which was then defoamed. The same measurements as in Example 1 were performed using this paste.

[Example 4] 30 parts by weight of the same vinyl monomer mixture as that used in Example 1, powder 525 Jushabu and polydiethylene glycol bisallyl carbonate (Japanese Patent Application Laid-Open No. 56-10
Disclosed in No. 4914, average particle size 40 μm, refractive index 1.496
) 17.5 The polymerized portion was thoroughly kneaded in an agate mortar.

After preparing the paste, it was defoamed. The same measurements as in Example 1 were performed using this paste.

[Example 5] 75 parts by weight of Big-GMl and 25 parts by weight of TEGDMA
Weight section! A uniform monomer solution was obtained by stirring at a mixing station.

The refractive index of this seven-layer solution is 1,530, and the refractive index of the polymer obtained by polymerizing it is 1.556.
Met. The periphery of the container was covered with aluminum foil to shield it from light, and then C'Q0.4mshabu and DMBE 0147 parts by weight were added to the vinyl monomer liquid and dissolved with stirring.

Above vinyl monomer mixture 35:i! [11 parts, 422 parts of powder, and glass beads (manufactured by Toshiba Baroteini, GB731M, average particle size 20 μm, refractive index 1.51)
2SL839: Okibe was sufficiently kneaded in an agate mortar to prepare a paste, which was then defoamed. The same measurements as in Example 1 were performed using this paste.

[Example 6] Powder [75 parts by weight was added with a vinyl heptamer mixture of Bis-MP EP P and NPGDMA (Bis-MP
IPP 19 Jyusha whisper, NPGDMA 81 Jyuyashi) 2
A paste was obtained by blending 5 parts by weight, 0.125 parts by weight of azobisisobutyronitrile, and 5 parts by weight of ethanol and thoroughly kneading the mixture.

The paste was placed under vacuum to remove air bubbles and ethanol. Thereafter, this base was polymerized under a nitrogen pressure of t-5% at a polymerization temperature of 120 DEG C. for a polymerization time of 1 hour to obtain a highly transparent polymer.

This polymer was crushed in a mortar to a size of 5 mm or less in diameter, and then further crushed in a crusher for 1 hour. After pulverization, a powder (hereinafter referred to as powder V■) that passed through a 250-mesh sieve was obtained. Powder■
Its refractive index was 1.506.

Big-GMA 63 mli! Ri and TEGDM
37 parts by weight of A were stirred and mixed to form a uniform vinyl 7mer solution. The refractive index of this monomer liquid is 1.519,
The refractive index of the polymer obtained by polymerizing this is 1.5
It was 48. Cover the area around the container with aluminum foil to shield it from light, then apply CQO, 04 double radiation and DMBE 014.
7 parts by weight were added to the vinyl monomer liquid and dissolved with stirring.

Next, 30 parts of the above vinyl 7mer mixture and powder V2
1 part by weight of the powder and 491 parts by weight of the powder were sufficiently kneaded in an agate mortar to prepare a paste, which was then defoamed. This paste
The same measurements as in Example 1 were carried out using the same.

[Example 7] Big-GMA 42N parts, TEGDMA 28
The heavy part and the A-TMM-3L30''ijL wrinkle part were stirred and mixed to form a uniform vinyl 7mer solution.The refractive index of this 7mer solution was 1.507, and the polymer obtained by combining the tlL The refractive index was 1.5°9.The container was covered with aluminum foil to shield it from light, and then CQo, 4]
! [1 part and 0.47 mltt part of DMBE were added to the monomer solution and stirred to dissolve. 30 parts by weight of this monomer mixture, 11 Lg parts of powder tvszs, and cristobalite (manufactured by vM Morisha, 43-63C.

17.5X parts (having an average particle size of 84 μm and a birefringence of 1.484 and 1.487) were sufficiently kneaded in an agate mortar to prepare a paste, which was then defoamed.

Using this paste, measurements similar to those in Example were carried out.

[Example 8] The refractive index of the monomer solution of B15-MPEPP is 1.54
0, and the refractive index of the polymer obtained by polymerizing this was 1.565. The area around this seven-piece container was covered with aluminum foil to block light, and then Bta-MPEPP 1
00! For the arm part, CQ α4mff1 part and DMB
47 parts by weight of EO was added and dissolved with stirring. next,
In this monomer mixture 303, add a part and powder [14″mii
and powder V56 parts by weight were sufficiently kneaded in an agate mortar,
After preparing the paste, it was defoamed. The same measurements as in Example 1 were performed using this paste.

[Execution @ 9] The same vinyl monomer ffi mixed liquid 30 type lid as in Example 7 and the powder IV35. ! The part and polymethyl methacrylate powder (manufactured by Shin-Nakamura Chemical Co., Ltd., D-250-M, average particle size 3 op 1nl, refractive index 1.49) 24.51 lid part were thoroughly kneaded in an agate mortar, and the paste was made into a mesh mold. It was then defoamed.

The same measurements as in Example 1 were performed using this paste.

[Comparative Example 1] Same monomer mixture 3 as that used in Example 1
01 Washibe and powder [703m Titania (5 Hara Sangyo, CR-50) for imparting opacity to the fluorescent part and the cured product 0,
o7z gills were sufficiently kneaded in an agate mortar to prepare a paste, which was then defoamed. The cure depth of this paste was 6.6 fins and was reduced by the addition of titania.

Also, the transparency before and after 1 cup is 0.54.

0.38, and the change before and after polymerization was as large as 0.16. The results of Comparative Examples 1 to 8 are summarized in Table 3 below.

[Comparative Example 2] The same vinylmo/v-mixture*30XjiIk parts as used in Example 1, 70fi parts of powder, and zirconia (first rare element) to impart opacity to the cured product were added. Manufactured by Kagaku Kogyo Co., Ltd., gp: 0.5 parts, 11 parts were sufficiently kneaded in an agate mortar to prepare a paste, which was defoamed.The hardening depth of this paste was 6.4 絽, and Zircoef 0 m
It decreased due to addition. In addition, the 6 brightness values before and after 1M are 0.57 and 0.40, respectively, and the changes before and after 1M are 0 and 1.
It was a big 7.

[Comparative Example 3] Vinyl monomer mixture 3 same as that used in Example 1
0 parts by weight, and titania (manufactured by Gohara Sangyo Co., Ltd., CR-50) for imparting obscurity to the powder ■70 parts and the cured product.
1 part of 0.15 weight fi was thoroughly kneaded in an agate mortar to prepare a paste, which was then defoamed. The hardening depth of this paste is 5
．． It was 1u. In addition, the transparency after 1 cup φJ was 0.19 and 0.41, respectively, and the change before and after polymerization was 0.2
It was large at 2.

[Comparative Example 4] Vinyl monomer mixture 3 same as that used in Example 1
Thoroughly knead 1 part of 01 and 70 parts by weight of powder in an agate mortar to prepare a paste. After 1 liter, defoaming was performed. The curing depth of this paste was &3. Furthermore, the transparency before and after polymerization was 0.77 and 0.39, respectively, and the change before and after polymerization was as large as 0.38.

[Comparative Example 5] Vinyl monomer mixture 3 same as that used in Example 1
0) 1 part and powder I 35 parts 1 part and alumina powder (
Manufactured by Sumitomo Electric Co., Ltd., AKP-20゜Average particle size 0.3 μm
+Refractive index 1.73) 35][111M was sufficiently kneaded in an agate mortar to prepare a paste, and then defoamed. The cure depth of this paste was 3.1 degrees. Further, the transparency before and after polymerization was α14 and 0.10, respectively, and the transparency after 1 polymerization was significantly lower than that of teeth. The change in transparency before and after polymerization was 0.04 - [Comparison f11J6] Vinyl monomer mixture 3, the same as that used in Example 1
0 parts by weight of powder and 135 parts by weight of powder and 111,351 parts of powder!
[Knead 1 part thoroughly in an agate mortar and make a paste of s1
g@i! The postscript was foamy. The hardening depth of this paste is 9.1
It was relevant. Moreover, the transparency before and after polymerization is 0.
68.0.52, and the change in transparency before and after polymerization was 0.
It was large, 16.

[Comparison-7] Same vinyl monomer mixture ft as used in the experiment
1some part and powder 1 [[35 superposition part and powder IV3
Five parts were thoroughly kneaded in an agate mortar to prepare a paste, which was then defoamed. The curing depth of this paste was 96R1, and the transparency after polymerization was 0.51.
It was 0.74, and the rM brightness after 1 cup was significantly higher than that of teeth. The change in transparency before and after 1 cup was as large as 0.23.

[Comparative Example 8] Vinyl monomer mixture 3 same as that used in Example I
0 parts by weight, powder IV35 heavy parts, and silica powder (manufactured by Micron, M-shaped silica S-〇, average particle size Z 3 pm)
*Refractive index: 1.463) 35 stacked parts were sufficiently kneaded in an agate mortar to prepare a paste, which was then defoamed. The hardening depth of this paste was 17 m. In addition, the transparency after polymerization lσ is 0.13 and 0.23, respectively, and the transparency after polymerization u
Agt was lower than that of teeth. The change in a8A& before and after polymerization was 0.10.

Claims (1)

[Claims] 1. a) a polymerizable vinyl monomer b) a filler having a refractive index (n^F_D) that satisfies the following formula (hereinafter referred to as a high refractive index filler) (n^M_D) + (n^ P_D)/2<n^F_D≦n
^P_D+0.04 (however, n^M_D: refractive index of a polymerizable vinyl monomer n^P_D: refractive index of a polymer obtained by polymerizing the vinyl monomer) c) A refractive index that satisfies the following formula (n^F' _D) (hereinafter referred to as low refractive index filler) n^M_D-0.04≦n^F'_D<n^P_D-0
．． 04, and n^F'_D<(n^M_D)+n^P_
D/2 (however, the definitions of n^M_D and n^P_D are the same as in item b)) and d) a photocurable composite composition consisting of a photopolymerization initiation catalyst that can initiate polymerization with visible light in the wavelength range of 390 nm to 700 nm. thing.