JPS5869805A - dental composite materials - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a dental composite material which provides a cured product with improved mechanical properties. The term is used to include not only a composite filling material for use, but also a material for fitting a crown, a composite filling material for orthodontics, an artificial tooth, and the like.

Conventionally used dental composite materials are composed of polymerizable monomers, fillers, and Togane initiators. As an m-combinable monomer, 2,2'-bis(P-(methacryloxy-β-hydroxypropoxy)phenyl)furopane (
In addition to various di(meth)acrylate monomers such as (commonly known as Bis-GM) and Q ethylene glycol dimethacrylate, there are Attempts have also been made to use a monomer having a urethane bond in the chain and two ethylenically unsaturated double bonds (commonly known as urethane di(meth)acrylate). Borogic acid glass is used as a filler.

Soda glass, glass containing heavy metal elements (e.g. barium, strontium, etc.) to provide X-ray contrast properties, aluminosilicate, glass ceramics, quartz,
Inorganic powders such as amorphous silica that have high hardness and a small coefficient of thermal expansion, so-called organic composite fillers and organic polymer powders in which the surface of the inorganic powder is coated with an organic polymer (for example, dimethacrylate polymer) are used. There is.

Organic peroxides, redox systems (for example, peroxide-amine), and the like are used as the main initiator. Also,
The inorganic filler is coated with a silanizing agent before mixing to improve its bonding to the organic matrix.The main properties that dental composite materials should have are excellent mechanical strength such as compressive strength and abrasion resistance. Since the coefficient of thermal expansion of the core and the crown of the tooth is as small as 11.4 ppm, it is desired that the dental material also has a small coefficient of thermal expansion. Traditionally used dental composite materials 9 have a thermal expansion coefficient of 50~
Although it has a value of 40 ppfv'c, which is relatively close to that of the crown of a tooth, its compressive strength is low at about 2000 to 2600 mm, and its wear resistance is also insufficient, so it is desired to improve its mechanical strength.

The present inventors have intensively studied the above-mentioned problems and found that a 5- to 4-functional (meth)acrylate monomer is used as the mucomerizable monomer, and a particle diameter of 0.1 μ to 100 is used as the filler.
Inorganic powder with an average particle diameter of 0.2 to 20 μ and within the range of 60 to 20 μ? part of Ofi and, accordingly, the particle size of 10 to 1
By using a filler obtained by mixing 40 to 10 parts by weight of inorganic fine powder with an average particle size of 10 to 50 mμ, the resulting dental composite material is superior to conventional composite materials. The present invention was completed based on the recognition that the compressive strength and abrasion resistance were significantly increased. That is,
The present invention provides a dental composite material comprising 10 to 50 parts of a polymerizable monomer, 90 to 50 parts of a powdered inorganic filler, and a polymerization initiator, wherein the polymerizable monomer is ( b) Formula - (aHr-C-ODo+?nY [In the formula, Y is a hydrocarbon residue having 4 to 15 carbon atoms whose main chain may be interrupted by oxygen (sometimes including a group having a hydroxyl group as a substituent) ), turtle is hydrogen or methyl group, m is 5 or 4] 20 to 100% by weight (based on total monomers) and (b) mono- or di(meth)acrylate system ml polymerizable monomer 80-0]1 LIIk% (based on total monomers), and the inorganic filler has (a) a particle size range of 0.1-100μ, and an average particle size of 0.2-100μ; Powder 60-90 weight g6(
(per inorganic filler) and (b) ξ consisting of 40 to 10% by weight (per inorganic filler) of powder having a particle size range of 10 to 100 mμ and an average particle size of 10 to Sowμ. It is a dental composite material with

In the present invention, the polymerizable monomer (a) is appropriately selected from the range of the above formula, and among them, Y is a hydrocarbon residue having 4 to 10 carbon atoms that may have a hydroxyl group as a substituent. Polymerizable monomers having the following are preferably used. Such monomers include trimethylolethane tri(meth)
Acrylate, trimethylolpropane tri(meth)acrylate.

Trimethylolbutane tri(meth)acrylate.

Tetramethylolmethane tri(meth)acrylate, Tetramethylolmethanetetra(meth)acrylate, 1
・2,4-butane tri(meth)acrylate), 1.2.
6-tri(meth)acryloxyhexane, 1.2.10
-) (meth)acryloxydecane, etc.

In addition, tri[2
-(meth)acryloxyethyl] trimellitate, tri[2-(meth)acryloxyethyl] trimesade, etc. can also be used. In the present invention, the polymerizable monomer (a) is used to obtain high mechanical properties. It is necessary to use at least 20% of the total monomers. In addition to compressive strength and abrasion resistance, actual dental composite materials must also have lower viscosity, lower shrinkage during polymerization, and a certain water absorption rate for ease of handling. In order to adjust these properties, heavy monomers (←) are usually mixed and used.

Examples of polymerizable monomers include monofunctional or difunctional monomers used in common dental composite materials (including urethane-(meth)acrylate monomers (meth)). ) acrylate monomers, styrene monomers, etc.) Among them, (meth)acrylate monomers are usually used. Examples of (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylate.
n-propyl acrylate, iso-propyl (meth)acrylate, i-butyl (meth)acrylate, iso-butyl (meth)acrylate, t-butyl (meth)acrylate 9
．． Monofunctional (meth)acrylates such as 2-hydroxylethyl methacrylate.

2 A difunctional (meth)acrylate represented by the formula (0H2=C-C00-)y-X (wherein, R, hydrogen, t, and t), such as ethylene glycol,
Diethylene glycol, triethylene glycol, tetraethylene glycol, dodecaethylene glycol.

Di(meth)acrylate such as tetradecaethylene glycol, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,
glycerin di(meth)acrylate), 2,2'-bis(
p-(r-methacryloxy-β-hydroxypropoxy)phenyl]furopane (Bis-0mm), bisphenolmushi methacrylate, neopentyl glycol di(
meth)acrylate, 2.2'-di(4-methacryloxypolyethoxyphenyl)propane (2 to 10 ethoxy groups in 1 molecule), 1.2-bis(5-methacryloxy-2-hydroxypropoxy)butane, 1 .2-bis(
Examples include di(meth)acrylates such as 5-methacryloxy-2-hydroxypropoxy)butane. Also, as the urethane(meth)acrylate monomer, 2 moles of a (meth)acrylate monomer having a hydroxyl group and 1 mole of diisocyanate are used. Examples include reaction products, such as reaction products of a urethane prepolymer having NCO terminals at both ends and a (meth)acrylate monomer having a hydroxyl group. As such a reaction product, a strip having the structure of the following formula is preferable.

(Here, R1 is hydrogen or a methyl group, R4 is an alkyl group, and Rs is an organic residue.) Specific examples include 2,2.4-) described in Japanese Patent Publication No. 51-56960.
Reaction product of lymethylhexamethylene diisocyanate and oxypropyl methacrylate, Japanese Patent Publication No. 55-556
Examples thereof include a reaction product of a urethane prepolymer having isocyanates at both terminals and 2-oxyethyl methacrylate described in No. 87.

When the dental composite material of the present invention is a filling material, the various di(meth)acrylates mentioned above may be used.To adjust the viscosity of fttptemop<ingu, triethylene glycol dimethacrylate, tetraethylene It is preferable to use glycol dimethacrylate, etc., and in order to suppress polymerization shrinkage of the cured product, it is preferable to use Bis-0mm, and in order to adjust the water absorption of the cured product, neopentyl glycol dimethacrylate, etc. Hydrophobic monomers such as acrylate and hydrophilic monomers such as 1.2bis[3(meth)acryloxy-2-hydroxypropoxy]ethane are added as appropriate.In addition, in the case of materials for dental crowns and dentures, the above-mentioned In addition to di(meth)acrylates, monomethacrylates such as methyl methacrylate are also used. In order to balance various required properties, Nanatsumer-0 can be used not only alone, but also in a mixture of two or more of the above-mentioned monomers.

In the present invention, the inorganic filler is crystalline or amorphous silicon dioxide or aluminum oxide.

Fiber silicate glass, lithium aluminum silicate glass,
One or more types of X-ray opaque glass or glass ceramics containing titanium oxide and electric metals such as barium, lanthanum or strontium can be used.In particular, an inorganic filler with a particle size in the range of 0.1 to 100μ. Ball mill 1m or more coarse grains selected from quartz, fused silica, or Xll-impermeable glass ceramics.

It can be suitably obtained by pulverizing with an Oki pulverizer such as a vibrating mill, a vibrating ball mill, or a jet mill. On the other hand, particle size 10-100
Inorganic fillers with particle diameters in the mμ range can be obtained in the same manner as described above, but amorphous silica, aluminum oxide, and titanium oxide are preferred inorganic fillers because those with particle diameters in this range are easily available as commercial products. It is desirable to apply a suitable surface treatment, and such surface treatment is vinyltrichlorosilane.

This can be carried out by a known method using a silane coupling agent such as r-methacryloxypropyltrimethoxysilane. A part of the inorganic filler may be coated with an organic polymer. It is also possible to replace the part with organic powder. However, in these cases, the thermal expansion coefficient of the cured product increases due to the increase in the organic moiety, so it is desirable that the amount to be replaced be 50% or less of the total photoresist. For particles of 1 to 100μ, light transmission centrifugal sedimentation method (combined with natural sedimentation) is used.
Particles of ~100 mμ can be easily determined from electron micrographs. Note that the particle diameter was measured before silane treatment. The average particle diameter is the average coulometric value.

In the present invention, when the proportion of powder (&) in the inorganic filler is more than 90% by weight, the amount of filler in the composition can be increased and a cured product with a small coefficient of thermal expansion can be obtained. If the mechanical strength of the cured product is greatly reduced, and if the proportion of powder (a) in the filler is less than 60% by weight, the amount of filler in the composition cannot be increased. However, the cured product has a large coefficient of thermal expansion and low mechanical strength.However, the filler contains 0.
Particles in the range of 1 to 100μ (average particle size 0.2 to 20μ
) is 60 to 90 parts by weight, and accordingly 10 to 100 mμ
Particles in the range of 40 to 10 (average particle size 10 to 50)
When the irises are present, as the number of particles in the range of 10 to 100 mμ increases, the amount of filler in the composition decreases and the coefficient of thermal expansion increases, but surprisingly, the mechanical strength does not decrease uniformly. In the case of the side table with the above composition, a cured product with a preferable coefficient of thermal expansion and excellent mechanical strength was obtained.
In the present invention, since a specific 5- to 4-functional (meth)acrylate monomer is used as an essential component as a polymerizable monomer, mechanical properties such as compressive strength and abrasion resistance are further improved. In the present invention, which has been recognized to significantly improve the width, the ratio of the polymerizable monomer to the inorganic filler is 10 to sag parts of the stand-forming monomer: 90 to 50 parts by weight of the inorganic filler. It will be done. If the amount of inorganic filler is more than the amount of 903, it will be difficult to produce a good paste product, and if it is less than 50 parts by weight, the thermal expansion coefficient of the obtained cured product will be large, making it unsuitable as a composite material. The initiators used in the present invention include photosensitizers that are activated by light energy and can initiate polymerization of ethylenic double bonds, or filtrate oxides that initiate polymerization at relatively low temperatures. Although agent systems are preferred, in applications where the materials of the present invention can be cured at high temperatures (eg, dentures), substances that can decompose at high temperatures and initiate polymerization of ethylenic dibonds can also be used. Examples of photosensitizers include biacetyl, benzyl, α-su7tyl, β-su7tyl, acetonaphthacene, and camphorquinone. It is also possible to use a reducing agent that reduces the photosensitizer when it is excited by light energy.

Peroxide and promoter systems include mixtures of peroxides and amines (e.g. benzoyl peroxide and N,N-jetanol-p-toluidine), mixtures of tocobalt peroxide promoters (e.g. methyl peroxide), Substances that can decompose at high temperatures and initiate polymerization include benzoyl peroxide and acetyl peroxide.

lauroyl peroxide, cumene hydroperoxide.

peroxides such as t-butyl hydroperoxide and 2
, 2I-azobisisobutyronitrile and the like. Generally the amount of catalyst used is 0.01 to monomer
~20J [% range. When a mixture of peroxide and accelerator is used as the polymerization initiator, the material of the present invention is divided into two parts, one containing the peroxide and the other containing the accelerator, thereby increasing the concentration of the material during storage. It is necessary to prevent hardening - therefore, in such cases the material of the invention is supplied to the user (e.g. physician, technician) in at least two or more packaging forms, and the composition is prepared by the user. In other cases, the dental composite material can be supplied as a single packaged material.In the present invention, the dental composite material refers not only to the composition consisting of the above-mentioned polymerizable reaction product and polymerization initiator, but also to the composition. It also refers to the packaged material before conditioning. If desired, an ultraviolet absorber, a coloring agent, a coagulation inhibitor, etc. can be added to the material of the present invention.

The dental material of the present invention can be used for various purposes as described above, such as tooth filling material, tooth crown material, etc., according to conventional methods. Therefore, by filling teeth,
This material hardens in a few minutes and becomes a cured product. By using the material of the present invention, it has excellent compressive strength and abrasion resistance,
A cured product with high mechanical properties not available with conventional dental materials can be obtained. Therefore, the material of the present invention can be used as a filling material for molar teeth, which cannot be satisfied with conventional filling materials.

Next, the present invention will be explained in more detail with reference to Examples.

Examples 1 to 4 Trimethylolpropane trimethacrylate (TMPT), tetramethylolmethane triacrylate (MU-TMM-5L), tetramethylolmethanetetraacrylate (MU-TMMT), ) lyethylene glycol dimethacrylate (TICGDM) as monomers ) and 2,2'-bis[p-(r-methacryloxy-β-hydroxypropoxy)phenyl]propane (Bis-G
M), benzoyl peroxide (BPO) as a curing agent,
N,N-jetanol-P-)luidine (PT-214
E), hydroquinone 7-methyl ether (M'EHQ) and 2,6-di-t-butyl-
The monomer mixture shown in Table 1 was prepared using p-cresol (BHT).The monomer mixture shown in Table 1 was used as a binder to create a dental composite filling material as shown in Table 2. The filler used was quartz powder (silanized quartz powder) with a particle size of α1 to 25# (average particle size 5 μ) whose surface was coated with r-methacryloxypropyltrimethoxysilane, and silanized quartz powder with an average particle size of 0.04β. The second method using amorphous silica (Aerosil OX-SO4 manufactured by Nippon Aerosil Co., Ltd.) (silanized amorphous silica-4z)
For each case shown in the table, equal amounts of Uniparsa, Lu paste (U paste), and catalyst paste (C paste) were taken, kneaded, and cured at room temperature. Compressive strength of cured product after storage at 57°C for 24 hours.

Brinell hardness and brush wear were measured and the results were compared to the second
Shown in the table. Note that brush wear was measured as follows. Using commercially available toothpaste diluted 1.5 times with water as an abrasive, apply this to a nylon brush and move it back and forth over the surface of the cured product 40,000 times to measure the amount of abrasion on the surface of the cured product. did.

A load of 250 t was applied to the brush.

Comparative Examples 1 to 3 Bis-GM and '! as monomers. Monomer mixtures shown in Table 5 were prepared in the same manner as in Examples using EGDM.

Table 3 (Parts by weight) Dental composite filling materials were produced using the monomer mixtures shown in Tables 1 and 5 as binders as shown in Table 4. Particle size 0.5 to 100μ (average particle size 1
0 μ) quartz powder (silanized quartz powder B) and the filler of the example were used. For each case shown in Table 4, equal amounts of C paste and C paste were taken, kneaded, and cured at room temperature. Compressive strength, Brinell hardness, and brush wear were measured in the same manner as in Example 2.

As is clear from Tables 2 and 4 of the ts4 table, the material of the present invention is compatible with conventionally used Bis-GM and TEG.
Dental composite material containing DM as a monomer and quartz powder with a particle size of O,S~100μ as a filler (Comparative Example 2), s~4
A dental composite material using a normal filler as a functional monomer (Comparative Example 3) and a bifunctional monomer as a binder,
It has superior mechanical properties compared to a dental composite material (Comparative Example 1) containing an inorganic powder with a particle size of 0.1 to 25 μm and amorphous silica with an average particle size of 0.04 μm as a filler.

Example 5 Creating a cavity in an extracted tooth A paste was prepared by adding iron oxide as a coloring agent to the composition shown in Table 2. When the paste was filled into the cavity, it hardened within 5 minutes.

Thus, the tooth cavity is filled and restored with the material of the invention,
The filled part blended well with the tooth.Thus, it was confirmed that the material of the present invention can be used satisfactorily as a dental material.

Patent applicant RiRashi Co., Ltd. Representative Patent Attorney Ken Honda

Claims (1)

Scope of Claims: (1) A dental composite material comprising 10 to 50 parts of a polymerizable monomer, 90 to 50 parts of a powdered inorganic filler, and a polymerization initiator, The monomer is (a)
Formula Turtle (OH, -0-(X)0.Y)
II may have a hydroxyl group as a substituent), turtle is hydrogen or methyl group, 1 is 5 or 4] 20 to 100% by weight (based on total monomers) and ←) mono or It is composed of a di(meth)acrylate polymerizable monomer in an amount of 80 to 96 (per strain rate mass), and the inorganic filler has (a) a particle size range of 0.1 to 100#, Part 2: Powder with an average particle diameter of 0.2 to 20 mm, weight 4 (
(per inorganic filler) and (b) 40 to 10% powder (per inorganic filler) having a particle size range of 10 to 100 mμ and an average particle size of 10 to 50 mμ. (2) The dental composite material according to claim 1, wherein Y is a carbide residue having 4 to 10 carbon atoms which may have a hydroxyl group as a substituent. (3) The polymerizable monomer (a) is trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolbutane tri(
The dental composite material according to claim 2, which is meth)acrylate, tetramethylolmethanetri(meth)acrylate, or tetramethylolmethanetetra(meth)acrylate. (4) The polymerizable monomer (b) has the formula R1--(CH
2:C-COO+rx [wherein, R1 is hydrogen or methyl group, X is ru group, p is 0
~20), an. -OH, -C-CM, -, Zhan Hs CB. 11. The dental composite material according to claim 1, which is a polymerizable monomer represented by 111 or a mixture of two or more thereof. (5) The dental composite material according to claim 111, wherein the polymerizable monomer (b) is a urethane di(meth)acrylate polymerizable monomer. (6) The dental composite material according to claim 1, wherein the powder (a) is one or more powders selected from quartz, fused silica, and glass ceramics. (1) The dental composite material according to claim 1, wherein the powder (b) is 111 or two or more powders selected from amorphous silica, alumina, and titanium oxide. (8) The dental composite material according to claim 1, wherein the inorganic filler is a filler whose surface has been treated with a silane treatment agent.