JPS61186304A - Dental restorative composite filling material - Google Patents

Abstract

PURPOSE:The titled material which is of photopolymerization type has improved hardness, compression strength, wear resistance, physical and clinical characteristics, comprising a specific polymerizable monomer and a photo-setting agent. CONSTITUTION:The titled material comprising 10-99wt%, preferably 20-95wt% polymerizable monomer shown by the formula I (R1-R4 are H, or methyl; X is 1-36C organic residue, especially group shown by the formula II, or formula III; n is 1-10 integer) and 0.01-20wt% preferably 0.05-10wt% based on the monomer of a photo-setting agent, especially a photosensitizer having sensitivity to visible light rays. The polymerizable monomer shown by the formula I is obtained by reacting equimolar amounts of a diester of glycerin and (meth) acrylic acid, a (poly)alkylene glycol mono(meth)acrylate, and an organic diisocyanate. The filling material is blended with 5-80wt% based on total amounts of monomers of a monofunctional or polyfunctional monomer as a viscosity modifier and 50-87wt% based on total amounts of a filler, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a dental restoration composite filling material, and more particularly to a dental restoration composite filling material containing a specific polymerizable monomer and a photocuring agent.

[Prior Art] In recent years, so-called dental composite resins, which are made of a mixture of polymerizable monomers, fillers, hardeners, etc., have been used as dental restoration composite filling materials instead of amalgam, inlays, cement, etc. became. There are two types of this composite resin. For example, there are two types of pastes in which one paste contains amines as a hardening agent and the other paste contains peroxide, which are mixed and hardened at the time of use (hereinafter referred to as paste-paste type). There is a type (hereinafter referred to as a photopolymerization type) in which a pack of paste containing a light-sensitive photocuring agent and a polymerizable monomer is cured by irradiating it with light.

This photopolymerized composite resin is a paste and
Compared to paste-type products, it is easier to handle and has higher utility value. However, various properties necessary for a dental restoration composite filling material (composite resin), such as hardness, compressive strength, or abrasion resistance, are insufficient. For example, bisphenol-based polymerizable monomers in U.S. Pat. Even if a urethane-based monomer is used as a photopolymerizable type, satisfactory performance cannot be obtained.

[Object of the Invention] The present invention provides a polymerizable monomer suitable for photopolymerization type that satisfies various performances required for dental restorative composite materials.

[Structure of the Invention] The present invention provides a photocuring agent and the following formula: % Formula % [In the formula, R, -R, each represent hydrogen or a methyl group,
X is an organic residue having 1 to 36 carbon atoms and n is 1 to 1
Indicates an integer of O. ] Provided is a dental restoration composite filling material containing at least one polymerizable monomer represented by:

One kind of the polymerizable monomers represented by the above formula (1) may be used alone, or a mixture of two or more kinds may be used.

The polymerizable monomer of the present invention has the following three components: (A) diester of glycerin and (meth)acrylic acid, (B) (poly)alkylene glycol mono(meth)acrylate, and (C) equimolar amount of organic diisocyanate. It may be obtained by reacting.

Examples of diesters of glycerin and (meth)acrylic acid include glycerin dimethacrylate, glycerin diacrylate, 1-acryloxy-3-methacryloxy-2
-hydroxypropane or mixtures thereof.

Examples of preferred (poly)alkylene glycol mono(meth)acrylates include 2-hydroxyethyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polyethylene glycol mono(meth)acrylate.
Acrylate, 2-hydroxypropyl (meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene-propylene glycol mono(meth)acrylate or mixtures thereof.

The organic residue (X) of the organic diisocyanate preferably has 1 to 36 carbon atoms, particularly preferably 6 to 20 carbon atoms, from the viewpoint of polymerization shrinkage and crosslink density. The organic residue (X) is an aliphatic hydrocarbon residue, a ring hydrocarbon residue,
Alternatively, it may be an aromatic hydrocarbon residue. The main chain of the alicyclic hydrocarbon residue may be interrupted by oxygen, nitrogen, or the like. The alicyclic hydrocarbon residue has the following formula: [wherein Y is -CH, -1-〇-1S Ot-1-CO
-1 or a substituted product thereof. It may be ko. In this case, the bonding end is preferably present at the meta or para position relative to Y. The aromatic hydrocarbon residue has the following formula: [wherein, Y has the same meaning as above. ], and in this case as well, the bonding end is preferably at the meta or para position relative to Y. Since aromatic organic residues (X) tend to be colored easily, aliphatic and alicyclic organic residues are preferred. Furthermore, when the organic residue (X) is linear or aromatic, crystals often precipitate in the synthesized polymerizable monomer. Therefore,
Preferably, it is aliphatic or alicyclic and has a side chain such as a methyl group.

It is most preferable that an odd number of side chains exist in X.

Examples of preferred organic diisocyanates include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane-diisocyanate, and cyclohexyl diisocyanate. silane diisocyanate, diphenyl ether diisocyanate, 2.4-) lylene diisocyanate, 2.6
-Dylylene diisocyanate, xylylene diisocyanate, 4.4-diphenyl diisocyanate), 4.4'
-diphenylamine diisocyanate, 1,5-naphthalene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 3-isocyanatomethyl-3.5.5-trimethylcyclohexyl-isocyanate and the like. More preferred are hexamethylene diisocyanate, 2,2,4-)limethylhexamethylene diisocyanate, or 3-isocyanatemethyl-3,5,5-trimethylcyclohexyl-isocyanate.

Although the reaction order in the synthesis of the polymerizable monomer is not particularly limited, the desired product may be efficiently obtained depending on the reactivity of the isocyanate groups of the organic diisocyanate. Although the reaction may be carried out without a solvent, it is usually preferable to carry out the reaction in a solvent. The solvent has no reactivity with any substance involved in the reaction, and includes, for example, methylene chloride, benzene, toluene, acetone, methyl ethyl ketone, xylene, and the like. The reaction is usually carried out in the presence of a catalyst.

Examples of preferred catalysts include dibutyltin dilaurate, dibutyltin dioctoate, stannous oleate, and stannous 2-ethylcaproate.

The above polymerizable monomer is contained in the material of the present invention in an amount of 15 to 100% by weight.
, preferably 20 to 95% by weight.

The curing agent used in the present invention is sensitive to light. In particular, sensitizers sensitive to visible light are preferred. Photosensitizers include benzyl, 2-chlorothioxanthone, Michler's ketone, benzoin ethyl ether, benzoin isopropyl ether, fluorenone diacetyl, camphorquinone, α-naphthyl, β
- Naphthyl, acenaphtase, etc., and several of the above photosensitizers may be used in combination. The amount of photosensitizer used generally ranges from 0.01 to 20% by weight, based on the polymerizable monomer. More preferably, 0.05 to 10% by weight of the photosensitizer is used. Further, it is possible to use a reducing agent capable of reducing the above photosensitizer when the photosensitizer is in an excited state. The amount of the reducing agent is in the range of 0 to 20% by weight, more preferably 0.1 to 10% by weight based on the polymerizable monomer. Examples of reducing agents include jetanolamine, triethanolamine, dimethylethanolamine, N-methylgetanolamine, propylamine, butylamine, hexylamine, dimethylamine, diethylamine, pentylamine, dipropylamine, dibutylamine, dipentylamine, Trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, triallylamine, ethylenediamine, trimethylenediamine,
Examples include tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, dimedylaminoethyl methacrylate, dietylaminoethyl methacrylate, and mixtures thereof.

In the present invention, in addition to the above-mentioned polymerizable monomer, one or more other monofunctional or polyfunctional monomers that mainly serve as a viscosity modifier may be mixed. Examples of monofunctional monomers include methyl (meth)acrylate, ethyl (
meth)acrylate, butyl(meth)acrylate, allyl(meth)acrylate, hydroxyethyl(meth)acrylate
Examples include acrylate, hydroxypropyl (meth)acrylate, methoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acryl styrene, and vinyl acetate. Examples of trifunctional monomers include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, and octane. Examples include diol di(meth)acrylate, glycerin di(meth)acrylate, octaethylene glycol di(meth)acrylate, dodecaethylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate. In addition, diacrylate and dimethacrylate of bisphenol A derivatives may be used,
For example, 2,2'-bis(meth)acryloxyphenylpropane, 2,2'-bis[4-(3-(meth)acryloxy)-2-hydroxypropoxyphenyl]propane, 2,2'-bis[4- (meth)acryloquine ethoxyphenyl]propane, 2,2'-bis[4-(meth)
Acryloxyjethoxyphenyl]propane, 2.2'
-bis[4-(meth)acryloxytriethoxyphenyl]propane, 2,2'-bis[4-(meth)acryloxypropoxyphenyl]propane, 2,2'-bis[
4-(meth)acryloxydipropoxyphenyl]propane, 2゜2'-bis[4-(meth)acryloxytripropoxyphenyl]propane, 2.2'-bis[4
-(meth)acryloxybutoxyphenyl]propane,
2-(4-(meth)acryloxyethoxyphenyl)-
Examples include 2'-(4-(meth)acryloxyjethoxyphenyl)propane. Furthermore, 1.2-bis[3
-(meth)acryloxy-2-hydroxypropoxy]
Ethane may also be used. In addition, trifunctional monomers include trimethylolproantri(meth)acrylate, trimethylolethanetri(meth)acrylate, trimethylolethanoltri(meth)acrylate, trimethylolmethanetri(meth)acrylate, and pentaerythritol(meth)acrylate. Examples include acrylate.

Examples of tetrafunctional monomers include tetramethylolmethanetetra(meth)acrylate. These viscosity modifiers are present in an amount of 0 to 85% by weight, more preferably 5 to 80% by weight of the total polymeric monomers.

The dental restorative composite filling material of the present invention usually contains a filler. The filler may be inorganic, organic, or a mixture thereof. Examples of inorganic fillers include soda glass, strontium glass, borosilicate glass, crystalline quartz, fused silica,
Examples include alumina silicate, amorphous silica, glass ceramic, and mixtures thereof. The particle size of the inorganic filler is not particularly limited, but it is usually about 150 microns or less, preferably about 100 microns or less.

Furthermore, several kinds of inorganic fillers having different particle sizes may be used in combination. It is preferable that the inorganic filler is subjected to a known surface treatment. Examples of surface treatment agents include silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxy-ethoxy)silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyl Trimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, or titanium compounds, such as isopropyltriisostearoyltitanate, isopropyltridecylbenzenesulfonyltitanate, tetraoctyldi(tridecylphosphite)titanate, dic Milferrate oxyacetate titanate, diisostearoyl ethylene titanate, etc. are used. As the organic filler, a polymerized powder of the polymerizable monomer (for example, methyl methacrylate) may be used. Further, a powder (composite filler) obtained by dispersing an inorganic filler in the polymerizable monomer and polymerizing it can also be used. The particle size of such a composite filler is preferably 100 μm or less. The blending amount of the filler is 1 to 99% by weight, preferably 50 to 87% by weight of the total components.

If necessary, known polymerization inhibitors, colorants, antioxidants, ultraviolet absorbers, etc. may be added to the material of the present invention.

Furthermore, anhydrous petrolatum, liquid palatine, squalane, microcrystalline wax, lanolin, beeswax, liquid lanolin, silicone oil, etc. can be added to improve surface hardening properties, if desired. The blending amount of these additives is 0 to 20% by weight of the total material, preferably 0.0%.
It is 5 to 10% by weight.

[Effect of the invention] The dental restoration composite filling material of the present invention is a photopolymerizable type,
Moreover, it has excellent hardness, compressive strength and abrasion resistance.
Excellent physical and clinical properties.

The present invention will be explained in more detail with reference to Examples.

Parts and percentages in the examples are by weight unless otherwise indicated.

Example 1 (Synthesis of polymerizable monomer M) Contents: A stirrer, a reflux condenser with a drying tube, a thermometer,
Attach a dropping funnel. 2.2.4-)limethylhexamethylene diisocyanate 126.29(
0.6 mol) was added and the temperature was raised to 40°C. Add 141.7 g of glycerin dimethacrylate (0.0 g) to the dropping funnel.
, 61 mol), a polymerization inhibitor BIT, and a urethanization reaction catalyst (di-n-butyltin dilaurate) were added at 5001) l) and 120 ppm, respectively, based on the final reaction product, and the mixture was heated for 3 hours. After the dropwise addition was completed, the mixture was further stirred at 40° C. for 5 hours. Subsequently, 86.59 (0.61 mol) of 2-hydroxypropyl methacrylate was placed in the dropping funnel, and this was added dropwise evenly over a period of 3 hours. After the dropwise addition was completed, stirring was continued at 40°C for 24 hours.

At this point, the absorption of the isocyanate group at 2340 cm''1 in the IR spectrum completely disappears and is replaced by 1530 cm''1.
In addition to confirming the generation of large absorption of urethane groups in the vicinity of ``cm-'', we also determined the quantitative determination of isocyanate (Sigga-
Hanna method or W, R, Sorenso
The reaction was terminated after confirming that the isocyanate group had almost completely disappeared using the method described by N et al.

After the reaction was completed, a slightly pale yellow viscous liquid was quantitatively obtained.

Reaction rate: 99.89%, viscosity (236C): 8200c
p; ax (C=C), l 530 (-NHCO-), NCO compound %: 0.0%. If necessary, after the reaction is complete,
The above viscous liquid was dissolved in methyl alcohol, and unreacted glycerin dimethacrylate, 2
- In addition to raw materials such as hydroxypropyl methacrylate, by-products (bifunctional urethane methacrylate, tetrafunctional urethane methacrylate) were separated. Yield is 93% based on 2,2.4-trimethylhexamethylene diisocyanate
Met. The product obtained by removing methyl alcohol after fractionation by liquid chromatography was a colorless and transparent (Gardner color number = 1) viscous liquid, and no crystal formation was observed even after cooling to 0°C. As a result of measuring the nuclear magnetic resonance spectrum, infrared absorption spectrum, etc. of the product purified in this way, it was found that the polymerizable monomer M represented by the following structural formula
, I checked it and was able to get it.

CC=C112 Blasphemy.

Polymerizable monomer M.

Preparation of Dental Restorative Composite: A polymerizable paste was prepared by mixing the following formulation.

Weight part Polymerizable monomer M, 14.7 Triethylene glycol di 9.8 Benzyl methacrylate silica powder 0.5N
-Methyljetanolamine 1.0 trial
Experiment: The obtained paste was irradiated with visible light for 30 seconds using a Shofu Daylight Lamp (Photopolymerizer manufactured by Shofu Co., Ltd.), and the cured specimen was tested under the following conditions.

Knoop hardness is measured using a sample of cured material (diameter 4 mm, height 2 mm).
xi) was stored in distilled water at 37°C for 24 hours, and the light irradiated surface was measured with a Knoop hardness tester at a load of 1009 and a pressurization time of 30.
Measured in seconds. Compression hardness is 3 jIx in diameter, 2 in height,
A 7 mm cylindrical sample of the cured product was stored in distilled water at 37°C for 24 hours, and then compressed at a rate of 1/min to determine its strength. Toothbrush wear was measured by applying commercially available toothpaste as an abrasive to a commercially available nylon toothbrush and applying a load of 500.
The surface of the cured product was reciprocated 30,000 times at 1F, and the wear rate of the cured product was calculated in weight %. The results are shown in Table-1.

Example 2 A similar paste was made using the following recipe.

Outside! 1. Navy blue polymerizable monomer M, 14.7 ethylene glycol dimethacrylate 9.8 benzyl powder 0.5N
-Methyljetanolamine 1.0 Using this paste, the same test as in Example 1 was conducted and the results are shown in Table 1.

Example 3 A similar paste was made using the following recipe.

Warm-standing 11 Adhesive polymerizable monomer M, 12.545 Triethylene glycol 7597 Neopentyl glycol dimethacrylate 5.018 Dimethacrylate γ-methacryloxypropyl 74.00
0 Methoxysilane treated alumina silicate camphorquinone o, ta.

Diethylaminoethyl methacrylate 0.780 The obtained paste was tested in the same manner as in Example 1. The results are shown in Table-1.

Example 4 (Synthesis of polymerizable monomer M2) 3-Isocyanate methyl-3 instead of 2.2.4-trimethylhexamethylene diisocyanate in Example 1
,5,5-trimedelcyclohexyl isocyanate l
33. The procedure was as in Example 1 except that 79.39 (0.61 mol) of 2-hydroxyethyl methacrylate was used in place of U (0.6 mol) and 2-hydroxypropyl methacrylate. As a result of the measurement, the following formula: OC113 Polymerizable monomer M! It was confirmed that the

Preparation of Dental Restorative Composite Material A polymeric paste was prepared by mixing the following formulation.

Parts by weight Polymerizable monomer M, 13.8672 Triethylene glycol 9.2448
Dimethacrylate γ-methacryloxypropyltri 76.000
0 methoxysilane treated fused silica powder camphorquinone 0.168O
N-methyljetanolamine 0.7200
A test similar to that in Example 1 was conducted using this paste. The results are shown in Table-■.

Comparative Example 1 A paste was prepared using the following recipe except that 2,2'-bis[4-(3-acryloxy)-2-hydroxypropoxyphenolcopropane was used as the polymerizable monomer.

Ingredients Parts by weight Above polymerizable monomers 14.7 Triethylene glycol dimethacrylate 9°8γ-methacryloxypropyltrimethoxy 74. Fused silica powder benzyl treated with O silane 0.5N
-Methyljetanolamine 1.0 The same test as in Example 1 was conducted using the obtained paste. The results are shown in Table-1.

Table-1 Examples 5 to 8 A paste was prepared with the formulation shown in Table-2, and this was used in Example 1.
The physical properties were measured in the same manner. The results are shown in Table-2.

Claims (1)

[Claims] 1. Photo-curing agent and the following formula: ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [1] [In the formula, R_1 to R_4 each represent hydrogen or a methyl group, and X has 1 carbon number ~36 organic residues and n is 1
Indicates an integer between ~10. ] A dental restoration composite filling material containing at least one kind of polymerizable monomer. 2. The dental restoration composite filling material according to item 1, wherein X in formula (1) is an aliphatic residue or an alicyclic residue. 3. The dental restoration composite filling material according to item 2, wherein the aliphatic residue or alicyclic residue has a side chain. 4. The dental restorative composite filling material according to item 1, wherein X in the formula (1) is ▲There is a mathematical formula, chemical formula, table, etc.▼ or ▲There is a mathematical formula, chemical formula, table, etc.▼. 5. The polymerizable monomer represented by formula (1) accounts for 10% of the total components.
2. The dental restorative composite filling material according to item 1, containing ~99% by weight. 6. The dental restoration composite filling material according to item 1, wherein the photocuring agent is a photosensitizer. 7. The dental restoration composite filling material according to item 6, which uses a reducing agent together with a photosensitizer. 8. The dental restoration composite filling material according to item 6, wherein the photosensitizer is contained in an amount of 0.01 to 20% by weight based on the polymerizable monomer. 9. The dental restorative composite filling material according to item 8, wherein the photosensitizer is contained in an amount of 0.05 to 10% by weight based on the polymerizable monomer. 10. The dental restoration composite filling material according to item 7, wherein the reducing agent is contained in an amount of 0 to 20% by weight based on the polymerizable monomer. 11. The dental restoration composite filling material according to item 1, wherein the dental restoration composite filling material contains a viscosity-adjusting monomer and a filler.