JP2000312689A - Denture base lining material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve contamination resistance and to prevent the degradation in the toughness of cured matter by incorporating an acrylic resin, specific fluorine-containing (meth)acrylate, polyfunctional (meth)acrylate, and a polymerization initiator into the lining material. SOLUTION: The fluorine-containing (meth)acrylate expressed by the formula: CH2=C(R1)COO.R2.Rf is compounded with the acrylic resin. In the formula, R2 denotes an alkylene group; Rf denotes a perfluoroalkyl group and may be straight chain, branched or cyclic and its hydrogen atom may be replaced with a hydroxy group. Further, R2+Rf is specified to 4-10 C and the ratio at which the number of fluorine atoms occupies in the atoms bonded to carbon atoms is specified to >=50%. For example, 1H,1H,3H-hexafluorobutyl methacrylates are used. Further, the polyfunctional (meth)acrylate, for example, alkylene glycol di(meth)acrylate and the polymerization initiator, for example, diacyl per-oxide, etc., are incorporated therein. As a result, the contamination resistance may be improved and the degradation in the toughness of the cured matter may be prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a denture lining material.

[0002]

2. Description of the Related Art In dental treatment, a denture base made of acrylic, polysulfone, or polycarbonate is currently used for patients who have lost teeth due to, for example, the elderly. In general, the denture base wearer absorbs the jaw remarkably, thins the oral mucosa responsible for cushioning, and dentures of the alveolar bone due to jaw bone resorption, etc. It has been pointed out that the compatibility with the oral cavity gradually decreases over time.

When the compatibility between the denture base and the oral cavity is reduced,
Generally, the denture base mucosal surface is reformed using a denture base lining material (denture base rebase material) to restore compatibility with the oral cavity. The method of using such a denture base material is as follows. In other words, the lining material before polymerization hardening (paste) is applied to the mucosal surface of the denture base, which has become incompatible.
Is built up again, brought back into the patient's mouth and engaged and brought into contact with the oral mucosa, and polymerized and cured after the backing formed an impression of the mucosal surface. The polymerization and curing may be carried out in a state where the film is brought into contact with the oral mucosa at the time of taking an impression and then polymerized and cured in a state in which the impression is taken, or in a state where the film is taken out of the oral cavity after the impression is taken.

[0004] However, the conventional denture base lining material is very different from the denture base body in that it tends to color, smell, absorb water, etc. over time while worn in the oral cavity. It has a problem that it is easily stained. In general, the older the elderly, the less the care of the denture becomes, the more the dentures lined with the conventional lining material increase, and the oral condition of the elderly deteriorates. Further, the conventional lining material has a strong irritancy to the oral mucosa when it comes into contact with the oral mucosa of the patient in a state before polymerization, and the patient suffers a great deal of pain during treatment.

[0005] To reduce such contamination of the denture base material, a dental material using a fluorine-based material has been proposed. In particular, a (meth) acrylate monomer having a fluorine atom in a molecule is used as a component. Some have been disclosed. In JP-A-62-33110, α
A dental material comprising a polymer containing an acrylate having a fluorine atom at the position is disclosed. From this composition, a dental material having excellent mechanical strength can be obtained. However, the coloring resistance of this composition is not sufficient, and odor and water absorption are not improved. Further, although excellent in mechanical strength, the toughness is low and the cured product is hard and brittle.

Further, Dental Materials and Instruments, Vol. 9, N
o. 2,257-264 (1990). In the soft lining material for denture base, as a polymer component, vinylidene fluoride-hexafluoropropylene copolymer or fluorovinylidene-tetrafluoroethylene-hexafluoropropylene copolymer as a polymer component, as a monomer component A composition using a fluorinated methacrylate having 2 to 5 carbon atoms in the side chain is disclosed. The water absorption and the monomer elution rate of the polymerized and cured product are lower than those of a conventional soft lining material, but coloring and bad breathing are disclosed. The odor of the components has not been improved yet.

Dental Materials and Instruments, Vol. 2, No. 1,
50-57 (1983). In, a dental resin using polymethyl methacrylate as a polymer component and 2,2,2-trifluoroethyl methacrylate as a monomer component is disclosed, and although the amount of attached protein is slightly reduced, the effect is small, Coloring, water absorption and odor still have problems.

[0008] As described above, it is difficult to impart sufficient coloring resistance to the denture base lining material and to reduce the absorption and adsorption of odorous components and water in the above-mentioned prior art. Further, the obtained polymerized cured product has a drawback that it has hardness but is brittle. Further, when used as a denture base lining material, there is no improvement in that irritation to the oral mucosa is large when the composition before polymerization is brought into contact with the oral mucosa to take an impression.

[0009]

As described above, the conventional denture base lining material has a problem that it is very easily soiled as compared with the denture base body. To reduce this problem, dental materials containing fluorine (meth) acrylate have been tried, but the stain resistance is not sufficient, and the cured product becomes brittle. Therefore, an object of the present invention is to provide a denture base lining material which is excellent in stain resistance and does not cause a decrease in toughness of a cured product. Still another object of the present invention is to provide a denture base lining material that has low irritation to the oral mucosa at the time of impression acquisition and does not cause pain to the patient.

[0010]

Means for Solving the Problems As a result of intensive search for solving the above problems, the present inventors surprisingly found that a fluorine-containing (meth) acrylate having a specific side chain structure as a monomer component and a specific amount of The present inventors have found that a denture base lining material containing a multifunctional (meth) acrylate shows a remarkable improvement over the above-mentioned problems, and have completed the present invention. That is, the present invention provides (a) an acrylic resin, (b)
Fluoro (meth) acrylate represented by the following general formula _{(I), CH 2 = C} (R 1) COO-R 2 -Rf (I) ( wherein, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group, Rf represents a perfluoroalkyl group, the carbon number of R ² + Rf has from 4 to 10 and, the proportion of the number of fluorine atoms out of the atoms bonded to the carbon atoms of R ² + Rf 50% It is a lining material for denture bases, characterized by containing (c) a polyfunctional (meth) acrylate and (d) a polymerization initiator.

In the denture base lining material of the present invention, the addition of the fluorinated (meth) acrylate (b) represented by the general formula (I) contributes to the improvement of the resistance to discoloration and coloring. Also,
It has been found that by blending the fluorinated (meth) acrylate (b), it is possible to reduce the irritation of the composition before polymerization to the oral mucosa at the time of impression acquisition. (I)
In the formula, R ² represents an alkylene group and Rf represents a perfluoroalkyl group. The alkylene group and the perfluoroalkyl group may be linear, branched or cyclic.
Further, a part of hydrogen atoms may be substituted with a hydroxyl group. In order to suppress the discoloration resistance of the cured product and the irritation to the oral mucosa of the composition, the carbon number of R ² + Rf needs to be 4 or more, more preferably 6 or more, and R ² + R
It is necessary that the ratio of the number of fluorine atoms to the number of atoms bonded to the carbon atom of f is 50% or more. R ²
+ Rf may be any ratio of the number of fluorine atoms out of the atoms attached to carbon atoms of 50% or more, the improved resistance to deformation discoloration with increasing number of carbon atoms, but irritation is low, R ² When the carbon number of + Rf exceeds 10, the toughness of the polymerized and cured product of the composition decreases.

The incorporation of a polyfunctional (meth) acrylate (c) slightly improves the toughness but is not sufficient.
In addition, when the amount of the monomer (c) increases, the coloring resistance decreases. From this point, the number of carbon atoms of R ² + Rf must 10 or less, the number of carbon atoms in R ² + Rf in the component (b) is required to be 4 to 10.

The compounding of the above-mentioned fluorinated (meth) acrylate (b) is effective in suppressing coloring and reducing irritation to the oral mucosa, but as a monomer component,
When the component (b) is used alone, the polymerized cured product does not have a crosslinked structure, so that it is difficult to prevent odor components and water from entering the cured product. Therefore, the compounding of a polyfunctional (meth) acrylate was effective in suppressing water absorption and odoration. The amount of the monomer is preferably in the range of 0.1 to 20% by weight, more preferably 2 to 15% by weight. When the content is less than 0.1% by weight, water absorption and odor tend to increase. Further, when it is blended in an amount of 20% by weight or more, the coloring resistance of the polymerized cured product may decrease. Further, among the monomers, one kind of alkylene glycol di (meth) acrylate having 3 to 20 alkylene carbon atoms between two (meth) acryloyl groups (the alkylene group may have a linear, branched or cyclic structure) It has been found that the use of the above-mentioned monomers further enhances the effect of suppressing water absorption and odor, and improves the toughness of the polymer cured product.

The main components in the composition of the present invention are a polymer component composed of an acrylic resin, a monomer component containing a fluorinated (meth) acrylate and a polyfunctional (meth) acrylate, and a polymerization initiator. Acrylic resin is a necessary component as a matrix of a denture base lining material. Fluorine-containing (meth) acrylate and polyfunctional (meth) acrylate are used for coloring,
It is blended in order to improve problems such as large water absorption and odor.

The acrylic resin used in the denture base lining material of the present invention is a polymer comprising at least one (meth) acrylate unit and another monomer unit copolymerizable therewith. For example, examples of the methacrylate include methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, pentyl methacrylate, and cyclohexyl methacrylate. In addition, acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, and benzyl acrylate are exemplified. These (meth) acrylates are used alone or in combination.

As other copolymerizable monomers, 1,3-
Butadiene, 2,3-dimethylbutadiene, diene compounds such as isoprene, styrene, vinyltoluene, α-
Aromatic vinyl compounds such as methylstyrene, N-cyclohexylmaleimide, N-O-chlorophenylmaleimide, N-substituted maleimides such as N-tert-butylmaleimide, acrylonitrile, vinyl cyanide compounds such as methacrylonitrile, and the like. Are used alone or in combination.

Further, a crosslinkable monomer may be contained as another copolymerizable monomer. Examples of such a crosslinkable monomer include allyl methacrylate, allyl acrylate and triallyl cyanurate. Allyl cinnamate, allyl sorbate, diallyl maleate, diallyl phthalate, triallyl trimetate, diallyl fumarate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, divinylbenzene, 1,3
-Butylene glycol di (meth) acrylate, 1,6
And polyfunctional monomers such as hexanediol di (meth) acrylate, which are used alone or in combination.

Among the components constituting the above-mentioned acrylic resin, polymethyl methacrylate, polyethyl methacrylate, polymethyl methacrylate-polyethyl methacrylate copolymer, etc. are preferred in view of the mechanical strength and transparency of the polymerized and cured product. It is preferably used. Among them, it is preferable to use polyethyl methacrylate, a polymethyl methacrylate-polyethyl methacrylate copolymer having excellent compatibility with the monomer components (b) and (c), or a mixture of these polymers and other polymers.

For the purpose of improving the mechanical strength of the polymerized and cured product, a resin composite comprising a core-shell type resin and a (meth) acrylic resin may be added to the acrylic resin. The core-shell type resin has at least one
It is a multi-layered resin composed of the above hard layer and at least one soft layer and having an outermost hard layer. Here, the hard layer is made of resin having a Tg of 40 ° C. or higher, and the soft layer is made of Tg.
Of a resin having a temperature of less than 20 ° C. The (meth) acrylic resin that forms the resin composite with the core-shell type resin is
It consists of resin whose Tg is 40 ° C. or higher. The core-shell type resin and the (meth) acrylic resin forming the resin composite with the core-shell type resin are adjusted to have a desired Tg from the monomers constituting the acrylic resin. It was done.

The acrylic resin in the present invention has a molecular weight of 1
It is preferably from 10,000 to 1,000,000, and particularly preferably from 100,000 to 700,000. If the molecular weight is less than 10,000, the toughness of the cured polymer may be insufficient, and if it exceeds 1,000,000, the solubility of the acrylic resin in fluorinated (meth) acrylate may decrease.

The commercial form of the denture lining material of the present invention comprises a powder component composed of an acrylic resin powder and a liquid component composed mainly of a fluorinated (meth) acrylate and a polyfunctional (meth) acrylate. Powder-liquid type, and paste type obtained by mixing an acrylic resin with a liquid component mainly containing a fluorinated (meth) acrylate and a polyfunctional (meth) acrylate with an acrylic resin in advance. .

When the acrylic resin in the present invention is in the form of a powder, the preferred range of the average particle size varies depending on the commercial form of the composition. That is, it is composed of a powder component composed of an acrylic resin powder and a liquid component composed mainly of a fluorinated (meth) acrylate and a polyfunctional (meth) acrylate. When applied inside, after mixing the powder and liquid, the powder component swells and dissolves with the liquid component, so that the viscosity of this mixture increases with time. Since the particle size of the acrylic resin affects the change in viscosity over time of the mixture, the average particle size of the acrylic resin is preferably from 1 to 150 μm, particularly preferably from 10 to 100 μm. .

If the average particle size is less than 1 μm, the acrylic resin powder dissolves readily in the monomer and the viscosity of the composition rises rapidly, so that the impression in the oral cavity may be poor. When the average particle diameter exceeds 150 μm,
The acrylic resin powder does not easily dissolve in the monomer, the viscosity of the composition does not increase, and the composition does not easily become a paste. Further, in terms of workability, when the average particle diameter is 1 μm or less, the acrylic resin powder is easily scattered. On the other hand, the acrylic resin is made of fluorine-containing (meth) acrylate and polyfunctional (meth)
In the case of adopting a commercial form in which a monomer component containing acrylate as a main component is previously dissolved and provided as a paste-like composition, the average particle diameter of the acrylic resin powder is not particularly limited.

The compatibility between the acrylic resin and the fluorine-containing (meth) acrylate in the present invention greatly affects the operability as described above. This compatibility can be evaluated by measuring the viscosity of a solution obtained by dissolving the acrylic resin in a fluorine-containing (meth) acrylate.
In order to obtain good operability of the composition, the viscosity (25 ° C.) of a solution in which the acrylic resin is dissolved at a concentration of 5% by weight is
It is preferably at least 100 cp. When the above-mentioned acrylic resin having a solution viscosity of less than 100 cp is used, the toughness of the polymerized cured product may be reduced.

Specific examples of preferred fluorine-containing (meth) acrylates represented by the general formula (I) used in the denture base lining material of the present invention include 1H, 1
H, 2H, 2H-nonylfluorohexyl (meth) acrylate, 1H, 1H, 2H, 2H-tridecafluorooctyl (meth) acrylate, 1H, 1H, 2H, 3
H, 3H-2-hydroxy-tridecafluorononyl (meth) acrylate, 1H, 1H, 2H, 2H-undecafluoro-5-methylhexyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) Acrylate, 1H, 1H, 6H-decafluorohexyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1
H, 9H-hexadecafluorononyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, 1H, 1H, 2H, 2H, 7H-decafluoroheptyl (meth) acrylate, 1H, 1
H, 2H, 4H, 7H-decafluoroheptyl methacrylate and the like.

Among the above-mentioned fluorine-containing (meth) acrylates, particularly preferred are 1H, 1H, 3H-hexafluorobutyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 6H-
Decafluorohexyl methacrylate and 1H, 1H,
Among the four kinds of 7H-dodecafluoroheptyl methacrylate, among these four kinds of compounds, particularly preferable one is 1
H, 1H, 6H-decafluorohexyl methacrylate and 1H, 1H, 7H-dodecafluoroheptyl methacrylate. The denture base lining material containing one or more compounds selected from these compounds is more effective than the composition using other fluorinated (meth) acrylate.
Furthermore, it is excellent in suppressing coloring, water absorption and odoration, and has particularly low irritation to the oral mucosa.

Specific examples of the polyfunctional (meth) acrylate (c) suitable for the present invention as the polyfunctional (meth) acrylate (c) used in the denture base lining material of the present invention include ethylene glycol di (meth) acrylate and 1,3. -Propanediol di (meth) acrylate, 1,4-butanediol di (meth)
Acrylate, 1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,11-undecanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate 1,13 -Tridecanediol di (meth) acrylate, 1,14-tetradecanediol di (meth) acrylate, 1,15-pentadecanediol di (meth)
Acrylate, 1,16-hexadecanediol di (meth) acrylate, 1,17-heptanedecanediol di (meth) acrylate, 1,18-octadecanediol di (meth) acrylate, 1,19-nonadecanediol di (meth) Acrylate, 1,20-eicosandiol di (meth) acrylate, alkylene glycol di (meth) acrylate such as neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate
Acrylates, polyalkylene glycol di (meth) acrylates such as dipropylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate, glycerin di (meth) acrylate, 2,2
'-Bis {p- (γ-methacryloxy-β-hydroxypropoxy) phenyl} propane, bisphenol A di (meth) acrylate, 2,2′-di (4-methacryloxypolyethoxyphenyl) propane (in one molecule) (Ethoxy groups 2 to 10), 1,2-bis (3-methacryloxy-2-hydroxypropoxy) butane, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, urethane (meth) acrylate and the like. . These (meth) acrylate monomers can be used alone or in combination of two or more.

Particularly preferred among the above-mentioned polyfunctional (meth) acrylates are alkylene glycol di (meth) acrylates having 3 to 20 alkylene carbon atoms between two (meth) acryloyl groups. Here, the alkylene group may have a linear, branched or cyclic structure. When one or more of these compounds are blended, the effect of suppressing the water absorption and odor of the polymerized and cured product is particularly excellent as compared with the case where another polyfunctional (meth) acrylate is used. It has also been found that the addition of the monomer improves the toughness of the cured product.

In the denture base lining material of the present invention, the blending amount of the acrylic resin with the fluorinated (meth) acrylate and the polyfunctional (meth) acrylate is as follows: (a) 25 to 85 wt. %, (B) the fluorine-containing (meth)
15 to 75% by weight of acrylate, (c) 0.1 to 20% by weight of polyfunctional (meth) acrylate
It is preferred that

In a preferred embodiment of the present invention, (a) an acrylic resin having a weight average molecular weight of 10,000 to 1,000,000
85% by weight, (b) 1H, 1H, 3H-hexafluorobutyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 6H-decafluorohexyl methacrylate and 1H, 1H, 1H, 3H-hexafluorobutyl methacrylate 15 to 75% by weight of one or more compounds selected from 1H, 7H-dodecafluoroheptyl methacrylate, (c) as a polyfunctional (meth) acrylate, wherein the number of alkylene carbon atoms between two (meth) acryloyl groups is One or more compounds of 3 to 20 alkylene glycol di (meth) acrylates (where the alkylene group may have a linear, branched or cyclic structure)
２０20% by weight, the composition has excellent stain resistance and good toughness as a denture base lining material,
It is particularly preferable because it has good operability.

The primary feature of the denture base lining material of the present invention is that the polymerized cured product has excellent stain resistance.
In particular, coloring with an edible pigment, water absorption (which is one of the causes of odor of dentures), and adsorption of odor components can be reduced as compared with conventional denture base lining materials. More specifically, turmeric (curry powder), a conventional denture base lining material
The degree of coloring in the aqueous solution was ΔE * of 40 or more, and the water absorption was about 15 μg / mm ³ .
The degree of coloring by turmeric is less than the conventional level with ΔE *,
The water absorption was 10 μg / mm ³ or less, and the adsorption of methyl mercaptan could be suppressed to about ／ or less of the level of the conventional commercially available lining material. Other polymerizable monomers copolymerizable with the fluorinated (meth) acrylate and the polyfunctional (meth) acrylate represented by the general formula (I), if necessary, as long as the stain resistance can be maintained. Functional monomer components can be included.

As the polymerizable monofunctional monomer component, generally, a monofunctional (meth) acrylate is preferable.
For example, methyl (meth) acrylate, ethyl (meth)
Acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, myristyl ( (Meth) acrylate, stearyl (meth) acrylate, cetyl (meth) acrylate and the like.

The polymerization initiator to be incorporated in the denture base lining material of the present invention can be used without any limitation as long as it is known. Examples of the polymerization initiator include a photopolymerization initiator and / or a heat polymerization initiator. And / or a chemical polymerization initiator. Examples of the photopolymerization initiator include α-diketone /
And reducing agents, ketals / reducing agents, thioxanthone / reducing agents, and the like. Examples of α-diketones include camphorquinone, benzyl, 2,3-pentanedione and the like. Examples of ketals include benzyl dimethyl ketal, benzyl diethyl ketal, and the like. Examples of thioxanthone include 2-chlorothioxanthone,
2,4-diethylthioxanthone and the like.

Examples of the reducing agent include 2- (dimethylamino) ethyl methacrylate, N, N-bis [(meth) acryloyloxyethyl] -N-methylamine, ethyl 4-dimethylaminobenzoate, 4-dimethylamino Tertiary such as butyl benzoate, butoxyethyl 4-dimethylaminobenzoate, N-methyldiethanolamine, 4-dimethylaminobenzophenone, N, N-di (2-hydroxyethyl) -p-toluidine, dimethylaminophenanthol Amines, dimethylaminobenzaldehyde,
Examples include aldehydes such as terephthalaldehyde, and compounds having a thiol group such as 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, and thiobenzoic acid.

In the case of performing photopolymerization by irradiation with ultraviolet light, benzoin alkyl ether, benzyl dimethyl ketal and the like are preferable. Further, an acylphosphine oxide-based photopolymerization initiator is also preferably used. Such acyl phosphine oxides include, for example, 2, 4,
6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6- Dimethylphenyl) phosphonate,
2,4,6-trimethylbenzoylethoxyphenylphosphine oxide and the like. These acylphosphine oxide-based photopolymerization initiators can be used alone or in combination with various amines, aldehydes or mercaptans, sulfinic acid salts and other reducing agents. These photopolymerization initiators are used singly or in combination. The compounding amount of these photopolymerization initiators is usually in the range of 0.001 to 15% by weight, preferably 0.1 to 1%, based on the entire denture base lining material (100% by weight).
It is used in the range of 0% by weight.

The product form of the denture base lining material includes a powder-liquid type and a paste type. When a photopolymerization initiator is used as the polymerization initiator of the denture base lining material of the present invention, the powder-liquid type is used. in the case of,
A method is adopted in which a paste-like composition obtained by mixing a powder component and a liquid component at the time of use is applied to the oral cavity and then polymerized. The photopolymerization initiator can be blended into only one of the powder / liquid components or divided into two components. In the case of the paste type, it is a one-paste type containing a photopolymerization initiator.

As the heat polymerization initiator, for example,
Organic peroxides such as diacyl peroxides, peroxy esters, dialkyl peroxides, peroxy ketals, ketone peroxides, and hydroperoxides can also be blended. Examples of the peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide and the like.

As peroxyesters, for example,
t-butylperoxybenzoate, bis-t-butylperoxyisophthalate, 2,5-dimethyl-2,5
-Bis (benzoylperoxy) hexane, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisopropyl carbonate and the like. Examples of the dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, and the like. Examples of the peroxyketals include 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane. Ketone peroxides include, for example, methyl ethyl ketone peroxide and the like.

The hydroperoxides include, for example, t-butyl hydroperoxide and the like. These thermal polymerization initiators are used singly or in combination. The amount of these oxidizing agents is usually 0.1% based on the whole denture base lining material (100% by weight).
It is used in the range of from 01 to 15% by weight, preferably in the range of from 0.1 to 10% by weight.

When a heat polymerization initiator is used as the polymerization initiator for the denture base lining material of the present invention, in the case of the powder-liquid type, the paste component obtained by mixing the powder component and the liquid component at the time of use is used. The approach is to apply the composition into the oral cavity and then polymerize. The heat polymerization initiator can be blended into only one of the powder / liquid components, or can be blended into two components. In the case of the paste type, it is a one-paste type in which a heat polymerization initiator is blended.

As the chemical polymerization initiator, for example,
Redox-based polymerization initiators such as organic peroxide / amine and organic peroxide / amine / sulfinic acid (or salts thereof) are preferably used. When a redox-based polymerization initiator is used, the denture base lining material of the present invention needs to take a packaging form in which an oxidizing agent and a reducing agent are separately packaged.

As the oxidizing agent, those similar to the above-mentioned thermal polymerization initiator can be mentioned. These oxidizing agents are used singly or in combination. The amount of these oxidizing agents is usually in the range of 0.01 to 15% by weight, preferably in the range of 0.1 to 10% by weight, based on the entire denture base lining material (100% by weight). used

As the reducing agent, a tertiary amine is usually used. For example, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-amine Diethyl-p-toluidine, N, N-
Dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4
-Ethylaniline, N, N-dimethyl-4-i-propylaniline, N, N-dimethyl-4-t-butylaniline, N, N-dimethyl-3,5-di-tert-butylaniline, N, N- Di (2-hydroxyethyl) -p-toluidine, N, N-di (2-hydroxyethyl) -3,5-
Dimethylaniline, N, N-di (2-hydroxyethyl) -3,4-dimethylaniline, N, N-di (2-hydroxyethyl) -4-ethylaniline, N, N-di (2-hydroxyethyl) -4-i-propylaniline, N, N-di (2-hydroxyethyl) -4-t-butylaniline, N, N-di (2-hydroxyethyl)-
3,5-dii-propylaniline, N, N-di (2-hydroxyethyl) -3,5-di-tert-butylaniline,
-Ethyl dimethylaminobenzoate, n-butoxyethyl 4-dimethylaminobenzoate, (2-methacryloyloxy) ethyl 4-dimethylaminobenzoate, trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn- Butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, (2-dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine Trimethacrylate and the like.

These reducing agents are used alone or in combination. The amount of these reducing agents is
Usually in the range of 0.01 to 15% by weight, preferably 0.1 to 10% by weight, based on the entire denture base lining material (100% by weight).
Used in the range of weight percent. When a chemical polymerization initiator is used as a polymerization initiator for the denture base lining material of the present invention, in the case of a powder-liquid type, an oxidizing agent such as an organic peroxide and a reducing agent such as a tertiary amine are used. It is necessary to separately mix the liquid components. In addition, a method of mixing and polymerizing a paste in which an oxidizing agent and a reducing agent are separately mixed at the time of use is used.

The denture base lining material of the present invention may optionally contain a filler. The filler may be organic or inorganic, but as the inorganic filler, for example, silica or kaolin, clay, mica,
Minerals based on silica such as mica, silica based, Al2O3, B2O3, TiO2, ZrO2, Ba
Ceramics and glasses containing O, La2O3, SrO2, CaO, P2O5, etc., especially lanthanum glass,
Examples include barium glass, strontium glass, soda glass, lithium borosilicate glass, zinc glass, fluoroaluminum borosilicate glass, borosilicate glass, and bioglass. Furthermore, crystal quartz,
Hydroxyapatite, alumina, titanium oxide, yttrium oxide, zirconia, calcium phosphate, barium sulfate, aluminum hydroxide and the like are also suitably used.

In order to improve the hardness and abrasion resistance after polymerization, an inorganic filler is dispersed in an organic resin,
An inorganic / organic composite filler obtained by coating an inorganic filler with an organic resin, a fibrous reinforcing agent, and the like can also be added.
Further, polymerization inhibitors (for example, hydroquinone, hydroquinone monomethyl ether, butylhydroxyl toluene, etc.), oxidation stabilizers, ultraviolet absorbers (for example, benzophenone), pigments, dyes, and fibers for mimic blood vessels can also be added.

As a more preferable product form of the denture base lining material of the present invention, a chemical polymerization initiator composed of a combination of a peroxide and a reducing agent is used as a polymerization catalyst, and it comprises two packages of an acrylic resin powder and a monomer liquid. There is a powder-liquid type. Such a powder-liquid chemical polymerization type lining material has excellent operability and is clinically useful. In particular, a powder is prepared by adding a peroxide to an acrylic resin powder, and a liquid is prepared by mixing a tertiary amine with a fluorinated (meth) acrylate and a polyfunctional (meth) acrylate. A mode of polymerization and curing is particularly preferred.

In such a powder-liquid chemical polymerization type soft lining material for a denture base, a more preferable polymerization catalyst is a combination of an organic peroxide and a tertiary amine. Benzoyl and tertiary amines are preferably aromatic tertiary amines, for example, N, N-dimethylaniline, N, N-dimethyl-p-toluidine,
N, N-di (2-hydroxyethyl) aniline, N, N
-Di (2-hydroxyethyl) -p-toluidine and the like are particularly preferred.

When an acrylic resin powder having a spherical particle shape and a particle size in the range of 10 to 100 microns is used as the acrylic resin powder, the operability of the powder and the properties of the paste when mixed with a liquid agent are improved. It is easy to make it suitable for taking impressions in the oral cavity. As such acrylic resin powder,
Particularly preferred are polymers of methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate. These acrylic resin powders with spherical particles are
It can be obtained by a method such as suspension polymerization.

As a component of such a powder comprising an acrylic resin powder and a peroxide, a particle size range of 0.001
Addition of a fine inorganic oxide powder having a specific surface area of from 0.1 to 0.1 micron and a specific surface area of from 20 to 500 m ² / g significantly improves the fluidity of the powder, and has a great merit in clinical operation. In other words, when the dentist measures the powder, the powder is measured with a measuring cup or a spoon, but at this time, if the fluidity of the powder is poor or the powder adheres to the wall of the container, the operability is reduced. Gets worse. When the acrylic resin powder alone was used, the fluidity of the powder was not so good in some cases. However, it was found that the fluidity of the acrylic resin powder was significantly improved by adding a small amount of the fine inorganic oxide. Examples of such fine inorganic oxides include silica, alumina, titanium oxide, and zirconia. Among them, highly dispersible silica represented by the trade name “Aerosil” is particularly preferable. The addition amount of these fine inorganic oxide powders is usually in the range of 0.01 to 5% by weight, preferably 0.05 to 1% by weight, based on the acrylic resin powder.

An example of an actual method of using such a denture base lining material will be described below. That is, the powder containing the peroxide and the liquid containing the tertiary amine are mixed in appropriate amounts so that the curing time is appropriate. When the acrylic resin powder is dissolved to some extent in the liquid agent to form a soft rice cake-like paste, the paste is built up on the mucosal surface of the denture base to be rebased. It is set in the patient's mouth, engaged to take an impression, and polymerized and cured in the engaged state for several minutes to ten and several minutes. In order to improve the adhesiveness between the mucosal surface of the denture base to be rebased and the lining material of the present invention, an adhesive primer may be applied in advance to the surface of the denture base. After curing, remove the denture base in the oral cavity,
If the backing material protruding from the mucosal surface is removed and polished as required, a denture base rebase is completed by the backing material for a denture base of the present invention.

[0052]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Abbreviations and abbreviations shown in Examples and Comparative Examples are as follows. 6FMA: 1H, 1H, 3H-hexafluorobutyl methacrylate 5F / 4H-BMA: 1H, 1H, 2H, 2H-pentafluorobutyl methacrylate 8FMA: 1H, 1H, 5H-octafluoropentyl methacrylate 10FMA: 1H, 1H, 6H- Decafluorohexyl methacrylate 12FMA: 1H, 1H, 7H-dodecafluoroheptyl methacrylate 16FMA: 1H, 1H, 9H-hexadecafluorononyl methacrylate 5FMA: 2,2,3,3,3-pentafluoropropyl methacrylate 19FMA: 1H, 1H , 2H, 2H-nonadecafluoroundecyl methacrylate 7F / 12H-NMA: 7,7,8,8,8,8-pentafluorononyl methacrylate α-FMA: α-fluoro-methyl acrylate G BMA: butyl methacrylate NMA: nonyl methacrylate EHMA: 2-ethylhexyl methacrylate

PMMA: polymethyl methacrylate PEMA: polyethyl methacrylate PBMA: polybutyl methacrylate 1,6-HD: 1,6-hexanediol dimethacrylate 1,10-DD: 1,10-decanediol dimethacrylate 3G: triethylene Glycol dimethacrylate TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide BPO: benzoyl peroxide DMPT: N, N-dimethyl-p-toluidine DEPT: N, N-dihydroxyethyl-p-toluidine

In this example, various tests were performed by the following methods. (1) Food coloring test for cured polymerized product [Tataka, “Journal of the Japanese Society of Prosthodontics”, Vol. 35, No. 3
No. 542-555 (1991). That is, the paste-like composition was filled into a disk-shaped mold having a thickness of 1 mm and a diameter of 2 cm, and the paste was cured. Using the obtained cured product as a test piece,
It was immersed in a 0.05% by weight aqueous solution of turmeric at 37 ° C. for 7 days, and the change in color tone before and after immersion was measured using a color difference meter (manufactured by Nippon Denshoku) and expressed as ΔE ^* . ΔE ^* was measured according to the following procedure. That is, the chromaticity of the cured product test piece was measured before and after immersion in a turmeric aqueous solution, and this was coordinated as a point on the color space coordinates according to the L ^* a ^* b ^* color system defined in JIS-Z-8729, The distance between these two points was defined as ΔE ^* . That is, the degree of discoloration ΔE ^* is defined by the following equation. ΔE ^* = ｛(L ₁ ^* −L ₂ ^* ) ² + (a ₁ ^* −a ₂ ^* )
² + (b ₁ ^* -b ₂ ^* ) ² ｝ ^1/2 where (L ₁ ^* , a ₁ ^* , b ₁
^* ) Are the color coordinate values measured before immersion, and (L ₂ ^* , a ₂ ^* , b ₂
^* ) Are color coordinate values measured after immersion. In the measurement, a standard white plate was placed behind the cured product test piece.
The larger the ΔE ^* , the greater the degree of discoloration.

(2) Odor test of polymerized and cured product A paste-like composition was filled into a disk-shaped mold having a thickness of 1 mm and a diameter of 2 cm, and the paste was cured. The obtained cured product was used as a test piece, and the test piece was immersed in a 0.5% by weight aqueous solution of methyl mercaptan (10 ml) at 37 ° C. for 24 hours. The amount of methyl mercaptan released per hour was measured. The method for measuring the amount of methyl mercaptan is as follows: each test piece is placed in a glass sample tube (100 ml),
The methylmercaptan concentration in the sample tube at 1 ° C. after 1 hour was determined from the length of the discolored portion of the detection tube using a gas detection tube for methylmercaptan (100 ml of suction).

(3) Water Absorption / Dissolution Test of Polymerized and Cured Product The test was carried out according to the method described in ISO 1567. That is, the paste-like composition was filled into a disk-shaped mold having a thickness of 1 mm and a diameter of 2 cm, and the paste was polymerized and cured.
Using the obtained cured product as a test piece, the test piece is put into a desiccator containing dried silica gel, dried at 37 ± 1 ° C. for 23 hours, subsequently at 25 ± 1 ° C. for 1 hour, and weighed. Repeat the above operation until the weight becomes constant (mass W
1). When the weight becomes constant, the sample is immersed in water at 37 ± 1 ° C. for 7 days, and then weighed (mass W2). After that, 3
After drying at 7 ± 1 ° C. for 23 hours, then at 25 ± 1 ° C. for 1 hour, weigh. The above steps are repeated until the weight becomes constant (mass W3). Water absorption (μg / mm ³ ) = (W2-W3) / V V; Sample volume (mm ³ ) Dissolution (μg / mm ³ ) = (W1-W3) / V

(4) Fracture toughness test of polymerized and cured product Reference [Matsumoto, "Dental Materials and Instruments", Vol. 7, No. 5, 75
6-768 (1988)]. That is, the paste-like composition was prepared as 2.5 × 5
The mold was filled into a mold having a prism shape of × 30 mm and having a notch of 2.5 mm with a razor in the center, and the paste was covered with a glass plate and polymerized and cured. Using the obtained cured product as a test piece, the fracture toughness value was measured. Measurement is # 1
After polishing the test piece with 500 water-resistant abrasive paper, place it in water at 37 ° C.
After storage for 4 hours, the test piece was placed in an Instron universal tester, and the test was carried out at room temperature at a crosshead speed of 1 mm / min and a distance between fulcrums of 20 mm.

(Curing conditions of the composition) The composition can take several polymerization forms depending on its catalyst composition. The polymerization conditions are shown below for each polymerization mode. Chemical polymerization type; 37 ° C in water for 10 minutes Photopolymerization type; Light irradiator “α-light” (manufactured by Morita Co., Ltd.) for technical use 5 minutes irradiation Heat polymerization type;

Example 1 (Powder-liquid-chemical polymerization type) 60 g of PMMA (molecular weight: 200,000, average particle diameter: 20 μm, solution viscosity: 305 cp), BPO: 2 g, fine silica (specific surface area: 130 m ² / g; 016 microns,
Nippon Aerosil Co., Ltd. product name: Aerosil 130)
A powder component containing 0.03 g, and 30 g of 6FMA,
After mixing with a liquid component containing 10 g of 1,10-DD and 2 g of DMPT, a polymerized cured product was obtained by chemical polymerization. Table 1 shows the results of the discoloration test, odor test, water absorption / dissolution test, and fracture toughness test of the cured product. The solution viscosity of the polymer shown here is the viscosity at 25 ° C. of a solution obtained by dissolving the polymer component in the fluorine monomer used in the present composition at a concentration of 5% by weight. Therefore, in the following examples, even if the polymer component is the same, the solution viscosity shows a different value if the fluorine monomer to be dissolved is different.

Examples 2 to 6 In Example 1, 8 FMA (solution viscosity: 315 cp) and 10 FMA (solution viscosity: 326 c) were used in place of 6 FMA.
p), 12 FMA (solution viscosity 370 cp), 16 FMA
(Solution viscosity 410 cp) The same test was performed using 5F / 4H-BMA (solution viscosity 300 cp), respectively. The results are shown in Table 1.

Comparative Examples 1 to 6 In Example 1, 5 FMA and 1 FMA were used instead of 6 FMA.
9FMA, BMA, 7F / 12H-NMA, NMA, α
The same test was carried out using -FMA, and the results are shown in Table 1. Here, 5FMA is a monomer containing fluorine, and R ² + Rf in the side chain has 3 carbon atoms. 19
FMA is a similar fluorinated methacrylate monomer, but the side chain R ² + Rf has 11 carbon atoms. 7F /
In 12H-NMA, the number of carbon atoms of R ² + Rf in the side chain is 9, but the ratio of the number of fluorine atoms to the number of atoms bonded to carbon atoms is low. BMA and NMA are methacrylate monomers containing no fluorine atom. α-FMA
Has one fluorine atom in the molecule, but the portion corresponding to the side chain is a methyl group, and the fluorine-containing (meth)
Different from acrylate.

Example 7 PMMA (molecular weight: 200,000, average particle diameter: 20 μm) was adjusted to 60
g, a powder component containing 2 g of BPO and 30 of 16 FMA.
g, 10 g of 3G, and a liquid component containing 2 g of DMPT, and then a polymerized cured product was obtained by chemical polymerization. (Solution viscosity 390 cp)

Comparative Example 7 PMMA (molecular weight 200,000, average particle diameter 20 μm, solution viscosity 290 cp) 60 g, powder component containing 2 g BPO, 30 g 5FMA, 10 g 3G, and 2 g DMPT
After mixing with the contained liquid components, a polymerized and cured product was obtained by chemical polymerization. In this composition, 5FMA having 3 carbon atoms of R ² + Rf in the side chain is used as the fluorinated (meth) acrylate of the liquid component.

Comparative Example 8 PMMA (molecular weight: 200,000, average particle diameter: 20 μm, solution viscosity: 420 cp), 60 g, a powder component containing 2 g of BPO, 30 g of 19FMA, 10 g of 3G, and 2 g of DMPT
After mixing with the liquid component containing g, a polymerized cured product was obtained by chemical polymerization. This composition uses 19FMA having R ² + Rf in the side chain having 11 carbon atoms as the fluorinated (meth) acrylate of the liquid component.

Comparative Example 9 60 g of PMMA (molecular weight: 200,000, average particle diameter: 20 μm, solution viscosity: 350 cp), a powder component containing 2 g of BPO, 30 g of EHMA, 10 g of 3G, and 2 g of DMPT
After mixing with the contained liquid components, a polymerized and cured product was obtained by chemical polymerization. This composition contains fluorine (meth) as a liquid component.
No acrylate is used.

[0066]

[Table 1]

Comparative Example 10 A powder component composed of 60 g of PMMA (molecular weight: 200,000, average particle diameter: 20 μm, solution viscosity: 390 cp), 2 g of BPO, and a liquid component containing 40 g of 16FMA and 2 g of DMPT were mixed. A polymerization cured product was obtained by polymerization. The same evaluation was performed, and the results are shown in Table 2. This composition uses a fluorinated (meth) acrylate alone as a liquid component and does not use a polyfunctional (meth) acrylate.

Examples 8 to 14 and Comparative Examples 11 to 12 Using the same powder component as in Comparative Example 10, the monomer component of the liquid preparation was 1,10-DD as the polyfunctional methacrylate.
Using 6 FMA as a fluorinated methacrylate and liquids prepared in the amounts shown in Table 2 respectively, cured products were similarly prepared and evaluated. The results are shown in Table 2.

[0069]

[Table 2]

Example 15 (powder-liquid-chemical polymerization type) PEMA (molecular weight 250,000, average particle diameter 60 μm, solution viscosity 617 cp) 60 g, powder component containing 2 g BPO, 30 g 6FMA, 10 g 3G, DMPT 2g
After mixing with the contained liquid components, a polymerized and cured product was obtained by chemical polymerization. Similar evaluations were made and the results are summarized in Table 3.

Example 16 (Powder-liquid-chemical polymerization type) 60 g of PEMA (molecular weight: 250,000, average particle diameter: 60 μm, solution viscosity: 617 cp), a powder component containing 2 g of BPO, 30 g of 8FMA, 10 g of 3G, DEPT 2g
After mixing with the contained liquid components, a polymerized and cured product was obtained by chemical polymerization.

Example 17 (Powder-liquid-chemical polymerization type) PMMA / PEMA copolymer (molecular weight 700,000, average particle diameter 60 μm, copolymer composition 50/50, solution viscosity 284c
powder component containing 65 g of p) and 2 g of BPO, and 6FM
25 g of A, 10 g of 1,10-DD, and 2 g of DMPT
After mixing with the contained liquid components, a polymerized and cured product was obtained by chemical polymerization.

Example 18 (powder-liquid-chemical polymerization type) PMMA / PEMA copolymer (molecular weight 700,000, average particle diameter 60 μm, copolymer composition 50/50, solution viscosity 284c
powder component containing 60 g of p) and 2 g of BPO, and 6FM
A: 25 g, 1,10-DD: 10 g, EHMA: 5
g, and a liquid component containing 2 g of DEPT, followed by chemical polymerization to obtain a polymerized and cured product.

Example 19 (powder liquid-heat polymerization type) PMMA / PEMA copolymer (molecular weight 700,000, average particle diameter 60 μm, copolymer composition 50/50, solution viscosity 284c
powder component containing 65 g of p) and 2 g of BPO, and 6FM
After mixing with a liquid component containing 25 g of A and 10 g of 1,6-HD, a polymerized and cured product was obtained by heat polymerization.

Example 20 (2 pastes-chemical polymerization type) PMMA / PEMA copolymer (molecular weight 700,000, average particle diameter 60 μm, copolymer composition 50/50, solution viscosity 284c
p) 65 g, 6 FMA 25 g, 1,6-HD 10
g, A paste containing 2 g of BPO and PMMA / P
EMA copolymer (molecular weight 700,000, average particle size 60 μm,
Copolymer composition 50/50, solution viscosity 284 cp)
g, 25 g of 6FMA, 10 g of 1,6-HD, DMP
After mixing with a B paste containing 2 g of T, a polymerized and cured product was obtained by chemical polymerization.

Example 21 (2 pastes-photo-chemical polymerization type) PMMA / PEMA copolymer (molecular weight 700,000, average particle diameter 60 μm, copolymer composition 50/50, solution viscosity 284c
p) 65 g, 6 FMA 25 g, 1,6-HD 10
A, an A paste containing 2 g of BPO and 1 g of TMDPO, and a PMMA / PEMA copolymer (molecular weight 700,000, average particle diameter 60 μm, copolymer composition 50/50, solution viscosity 2
84cp) 65g, 6FMA 25g, 1,6-HD
Was mixed with B paste containing 2 g of DMPT, and then a photocured polymerized product was obtained.

Example 22 (1 paste-photopolymerization type) PMMA / PBMA copolymer (molecular weight: 400,000, average particle diameter: 30 μm, copolymer composition: 75/25, solution viscosity: 195c)
p) 65 g, 6 FMA 30 g, 1,6-HD 5
g and a paste containing 1 g of TMDPO were photopolymerized to obtain a polymerized and cured product.

Comparative Example 13 (Powder-Liquid-Chemical Polymerization Type) After mixing 65 g of the powder component and 35 g of the liquid component of a commercially available denture base lining material, Tokusori Base (manufactured by Tokuyama), polymerization and curing were performed by chemical polymerization. I got something. The same evaluation was performed, and the results are shown in Table 3.

Comparative Example 14 (Powder-Liquid-Chemical Polymerization Type) After mixing 65 g of a powder component and 35 g of a liquid component of Mildriveron (GC), which is a commercially available backing material for denture base, polymerized and cured by chemical polymerization. I got something.

[0080]

[Table 3]

Example 23 PMMA (molecular weight: 200,000, average particle size: 20 μm) was adjusted to 60
g, 0.6 g of BPO and 0.0 of colloidal silica powder (trade name: Aerosil 380, manufactured by Nippon Aerosil Co., Ltd.)
Powder component containing 2 g, 35 g of 6FMA, 1,10-
A liquid component containing 5 g of DD and 0.15 g of DEPT was mixed, and the obtained paste composition was subjected to an oral mucosal irritation test.

That is, a test was conducted using a hamster according to the method described in ISO 10993-10, which is an international standard for the oral mucosal irritation test of dental materials. As a negative control, a 1 cm square cotton containing 0.4 ml of saline was inserted into the cheek pouch on one side of the hamster, and a 1 cm square cotton containing 0.4 ml of the pasty composition of the present invention was replaced with the same hamster. The other cheek pouch was inserted and contacted for 10 minutes. Every hour, the sample was replaced with a new sample, and the above operation was performed four times in total. The site where the sample was applied was visually observed, and negative and positive evaluations were made based on whether or not red spots had occurred. Five hamsters were used for one sample. In the case of irritation, red spots were formed and judged to be positive. The results are shown in Table 4.

Examples 24 to 28 and Comparative Examples 15 to 17 In Example 23, a liquid preparation was prepared by using the methacrylate monomers shown in Table 4 instead of 6FMA, and was obtained in the same manner by combining with the same powder. The paste-like composition was subjected to an oral mucosal irritation test.

Comparative Example 18 A liquid preparation was prepared in the same manner as in Example 23 except that α-fluoro-methyl acrylate (α-FMA) was used instead of 6FMA. The product was subjected to an oral mucosal irritation test. The results are shown in Table 4. The fluorine-containing monomer contained in the liquid component of this composition is a compound different from the fluorine-containing monomer used in the present invention.

[0085]

[Table 4]

Example 29 100 g of PEMA powder (manufactured by Negami Kogyo, molecular weight 250,000, average particle diameter 60 μm, solution viscosity 680 cp), 1 g of BPO, fine silica powder (130 m ² / g specific surface area, 0.016 μm particle size) Product name: Aerosil 130) 0.05
g was uniformly mixed using a ball mill to produce a powder. The fluidity of the powder was excellent, and even when the powder was transferred to a polyethylene container and shaken, the powder did not adhere to the wall of the container. On the other hand, 86 g for 10FMA and 1 for 1,10-DD
4 g and 0.24 g of DEPT were each weighed and uniformly dissolved to prepare a liquid preparation, thereby producing a powder-liquid chemical polymerization type backing material.

On the other hand, PMM with poor compatibility with the oral cavity
A portion of the denture base made of A to be rebased was further ground at a carborundum point, and an adhesive primer was applied. The adhesive primer used was an adhesive primer (mainly dichloromethane) attached to “Toksori Base” (manufactured by Tokuyama), which is a commercially available lining material for denture base. 2.4 g of the powder prepared in the above procedure and 2.0 ml of the liquid were measured and mixed, and when the mixture became a soft paste, the paste was laid on the surface of the denture base coated with the adhesive primer. Then, the patient was set in the oral cavity of the patient and bite was performed to obtain an impression.

After 5 minutes of polymerization and curing in the engaged state, the denture base was taken out of the patient's mouth and the protruding lining material was trimmed. In order to reduce the unpolymerized layer on the surface of the cured backing material, it was immersed in warm water (about 50 ° C.) in which sodium sulfite was dissolved for 5 minutes. The trimmed portion was finely modified and the surface was polished to produce a denture base that was rebase properly fitted with the lining material of the present invention.

After using the denture base in the oral cavity of the patient for 3 weeks, the discoloration was hardly observed when the lining material was visually observed. In addition, plaque was slightly adhered to a part of the surface, but could be easily removed by ultrasonic water washing. There was almost no smell of the lining material.

Comparative Example 19 A powder-liquid type denture base lining material having exactly the same composition as in the example except that EHMA was used instead of 10FMA was prepared, and the denture base was similarly rebased. After three weeks of use in the patient's mouth, the lining material was observed to show a noticeable yellow-brown discoloration. In addition, the smell of the lining material was also recognized.

[0091]

The lining material for denture base of the present invention is obtained by blending a fluorinated (meth) acrylate having a specific side chain structure and a specific amount of a polyfunctional (meth) acrylate. The stain resistance to coloring, odor, water absorption, and the like, which are major problems in the conventional denture base lining material, can be improved without impairing the toughness of the cured product. Furthermore, the composition has low irritation to the oral mucosa.

Claims (8)

[Claims] 1. An acrylic resin, (b) a fluorinated (meth) acrylate represented by the following general formula (I), and CH ₂ ＣC (R ¹ ) COO—R ² —Rf (I) (formula ¹ ) In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group, Rf represents a perfluoroalkyl group, R ² + Rf has 4 to 10 carbon atoms, and R ² + Rf has a carbon atom The ratio of the number of fluorine atoms to the bonding atoms is 50% or more.) (C) A back for denture base, which contains a polyfunctional (meth) acrylate and (d) a polymerization initiator. Equipment. 2. The denture base lining material according to claim 1, wherein the fluorine-containing (meth) acrylate represented by the general formula (I) has 6 to 10 carbon atoms of R ² + Rf. Wood. 3. The denture base lining material according to claim 1, wherein (a) the acrylic resin is 25 to 85% by weight,
(B) 15 to 75% by weight of a fluorine-containing (meth) acrylate, (c) 0.1 to 2 of a polyfunctional (meth) acrylate
0% by weight and (d) 0.1 to 10% by weight of a polymerization initiator
Lining material for denture base. 4. The denture base lining material according to claim 1, wherein (b) the fluorinated (meth) acrylate is 1H, 1H, 3H-hexafluorobutyl methacrylate, 1H, 1H, 5H. A denture lining material which is one or more compounds selected from the group consisting of octafluoropentyl methacrylate, 1H, 1H, 6H-decafluorohexyl methacrylate and 1H, 1H, 7H-dodecafluoroheptyl methacrylate. 5. The denture base material according to claim 1, wherein (c) the polyfunctional (meth) acrylate has an alkylene carbon number between two (meth) acryloyl groups. Alkylene glycol di (meth) which is 3 to 20
A denture base lining material which is at least one compound of an acrylate (the alkylene group may have a linear, branched or cyclic structure). 6. The denture base material according to claim 1, wherein the polymerization catalyst (d) is a combination of a peroxide and a tertiary amine, and the powder component is a peroxide. Acrylic resin powder to which is added, and the liquid component is composed of a tertiary amine, a fluorinated (meth) acrylate (b) and a polyfunctional methacrylate (c), and the powder component and the liquid component are mixed. Powder-liquid chemical polymerization type soft denture base material for denture base. 7. The denture base lining material according to claim 6, wherein the acrylic resin powder has a spherical particle shape and a particle size of 10 to 10.
Denture base lining material which is acrylic resin powder in the range of 100 microns 8. The powder component further has a particle size range of 0.0
01-0.1 micron, specific surface area 10-500 m ² /
7. A denture base lining material according to claim 6, wherein g of a fine inorganic oxide powder is added.