JP3481070B2 - Soft rebase material mounting kit - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a soft rebase material formed on a mucosal surface of a denture base. More specifically, when mounting a soft rebase material on a denture base, a soft rebase material composed of three kinds of compositions, an adhesive agent for the denture base and the soft rebase material, a soft rebase material, and a coating material for the soft rebase material It is a kit of.

[0002]

2. Description of the Related Art At present, in dentistry, a denture base made of a polymerizable floor resin composition (hereinafter sometimes referred to as a resin) is attached to a patient who has lost teeth due to aging or the like. . In general, a denture base wearer remarkably absorbs the ridge, and thins the mucous membrane that plays a cushioning function, and causes the alveolar bone to sink due to bone resorption, etc. It has been pointed out that the compatibility with the oral cavity is reduced.

When the compatibility between the denture base and the oral cavity decreases,
Generally, the mucosal surface of the denture base called rebase (lining) is reformed to restore the compatibility with the oral cavity. Rebasing methods can be broadly divided into two types: indirect methods and direct methods. The indirect method is a method of taking an impression of the shape of the oral cavity using an impression material, reproducing an oral model of the same shape as in the oral cavity in the laboratory, and using the model to form the mucosal surface of the old denture base. Is. On the other hand, in the direct method, a rebase material is built up on the mucosal surface of the denture base, an impression operation is performed in the oral cavity in the same manner as a normal impression acquisition, and the shape of the obtained impression is retained and cured. This is a method of rebasing. Since the indirect method is performed in the laboratory as described above and requires many steps, it takes a considerable period of time for rebasing, and during that time, the patient's denture base is entrusted to the patient's daily life. Cause trouble. From this,
At present, the direct law is widely accepted.

The rebase material is generally made of a hard material having the same hardness as that of the denture base resin. However, when there is occlusal pain due to thinning of the mucous membrane of the oral cavity, even if the compatibility with the oral cavity is restored, pain may still remain. It is often done to use soft materials that have. Heretofore, a soft resin based on acrylic resin mixed with a plasticizer, a silicone resin-based lining material, etc. have been used as a soft rebase material by the direct method [Kusakari, "Tooth field outlook", Vol. 72, No. 6 Issue (1988), 1267-
See page 1272]. These soft rebase materials are composed of powder and liquid, or two pastes, and are prepared so that they are hardened when they are kneaded immediately before use.

[0005]

By the way, it has been pointed out that the above-mentioned soft rebase material has a problem that when it is inserted into the oral cavity, irritation is caused by the raw material monomer and irritation is caused by heat generation during curing. It has been greatly improved by improving the polymerization catalyst and monomers. However, in the cured product obtained from these soft rebase materials, many air bubbles are mixed,
In addition, since it has a high water absorption rate, if it is used in the oral cavity for a long period of time, not only the physical and engineering properties of the cured product are deteriorated, but also contamination of oral bacteria and strong odor are still problems. Looking at the cause of death among the elderly requiring nursing care, it is said that more than 40% is pneumonia caused by bacteria that have propagated in the oral cavity, and there is an urgent need for improvement. Further, the adhesiveness to the denture base is insufficient, and the soft rebase material often peels from the rim from the denture base during wearing. In addition to remarkably reducing the wearing feeling of the denture base due to peeling, it is also a big problem that this part also becomes a suitable breeding site for bacteria.

[0006] The present invention has been made in view of the above problems of the prior art, and maintains appropriate viscoelasticity and adhesiveness with a denture base stably in the oral cavity for a long period of time to prevent the growth of bacteria and An object of the present invention is to provide a soft rebase material mounting kit that suppresses invasion of water, which causes odor, as much as possible, and also suppresses adsorption of oily components contained in food and the like.

[0007]

The above-mentioned problems are (a) a polymerizable soft rebase material containing 30% by weight or more of a low water-absorbing elastomer having a solubility parameter of 8.0 or more and 9.0 or less; An adhesive composition between a soft rebase material and a denture base, which is a polymerizable composition containing substantially the same elastomer as the rebase material and gives a cured product having a higher elastic modulus than the soft rebase material, and (c) β-carotene discoloration This is solved by a soft rebase material mounting kit made of a polymerizable coating material of a soft rebase material that gives a cured film of low lipophilicity of 15 or less. Moreover, since the soft rebase material mounting kit of the present invention uses an essentially flexible material, it can be used without a plasticizer. In such a case, the plasticizer does not elute into the oral cavity, the softness is maintained for a long time, and the living body is not adversely affected.

The soft rebase material used in the present invention contains 30% by weight or more of a low water absorbing elastomer having a solubility parameter of 8.0 or more and 9.0 or less. The solubility parameter is a constant derived from the attractive force between molecules in the Hildebrand-Scatchard solution theory [Akiyama et al., “Polymer blend”, CMC (19
81), pp. 124-144], the higher the value, the higher the polarity and the higher the water absorption. However, if this value is too low, the solubility with respect to the (meth) acrylate-based monomer is significantly lowered, which is not preferable. Conventionally,
Polyethylmethacrylate used as a soft rebase material is 9.1 and polymethylmethacrylate is 9.
3, polydimethylsiloxane is 7.3. When a low water-absorbing elastomer having a solubility parameter of 8.0 to 9.0 is used, the physical properties of the cured product do not deteriorate, and a rebase material having an excellent impression is obtained.

As the low water-absorbing elastomer having a solubility parameter of 8.0 or more and 9.0 or less, polyisoprene,
Polybutadiene, polyisobutylene, butadiene-styrene copolymer, isoprene-butadiene copolymer,
Examples thereof include solid rubbers such as isobutylene-isoprene copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, and thermoplastic elastomers containing these solid rubber components. Among them, those containing the thermoplastic polymer block (A) made of an aromatic vinyl monomer and the elastomer polymer block (B) have a high affinity with the (meth) acrylate-based monomer, and by mixing the two, the oral cavity It is suitable in that a paste-like product having excellent internal impression can be obtained. Further, one block (A) and one block (B) may be present in the thermoplastic elastomer, but a plurality of each may be present.

The thermoplastic polymer block (A) which is a constituent of the thermoplastic elastomer is preferably composed of aromatic vinyl monomer units and has a number average molecular weight of 3,000 or more. As the aromatic vinyl monomer unit, for example, styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene,
4-cyclohexylstyrene, 4-dodecylstyrene,
2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene and the like can be mentioned. Of these, styrene is preferable. The bonding mode of these monomer units is not particularly limited and may be a structure in which one of these monomer units is polymerized alone, or a structure in which two or more kinds of monomer units are copolymerized. .

The number average molecular weight of the thermoplastic polymer block (A) of the aromatic vinyl monomer unit must be 3,000 or more, and 3,000 to 1,000,0.
00 is preferable. The block A has a number average molecular weight of 3,0.
If it is less than 00, a paste having excellent impression cannot be obtained.

The content of the thermoplastic polymer block (A) in the thermoplastic elastomer is preferably in the range of 5 to 70% by weight. More preferably, 5 to 30% by weight
Is. The content of the thermoplastic polymer block (A) is 5
When it is up to 70% by weight, the compatibility with the (meth) acrylate-based monomer described later is good, and a paste having desirable properties can be obtained.

The elastomer polymer block (B) in the thermoplastic elastomer is composed of the monomer units constituting the known thermoplastic elastomer. There is no particular limitation on the binding mode of the monomer unit, and it is possible to
One of them may be polymerized alone, or 2
It may have a structure in which one or more monomer units are copolymerized.

Above all, a thermoplastic elastomer polymer composed of at least one monomer unit selected from isoprene, isobutylene and butadiene, a hydrogenated product of the polymer, and an unsaturated carboxylic acid of the polymer or the acid thereof. Derivative adducts are preferred. The block (B) composed of these polymers may have one of the above-mentioned elastomer polymer, its hydrogenated product and its adduct as a constituent component, or a plurality of them as a constituent component. It may be one.

Further, the block (B) is composed of at least one selected from polyisoprene and isoprene-butadiene copolymer, and is a thermoplastic elastomer polymer having a vinyl bond content of 40 mol% or more,
Hydrogenated products of the polymers and adducts of unsaturated carboxylic acids of the polymers or derivatives of the acids are also preferred. Similar to the above, these may also have one of the elastomer polymer, its hydrogenated product and its adduct as a constituent, or may have a plurality of constituents. Here, the vinyl bond content means, among all carbon-carbon double bonds contained in the elastomer polymer block of polyisoprene or isoprene-butadiene, an ethylenic double bond in a side chain generated by the following bonding mode. Is the ratio (mol%).

The elastomer polymer block (B) containing isoprene or butadiene monomer produces 1,2 bonds or 3,4 bonds depending on the polymerization mode, and forms an ethylenic double bond in the side chain. This ethylenic double bond is 1,
It is more reactive than the double bond of the main chain formed by 4 bonds and can be copolymerized with a (meth) acrylate-based monomer. Therefore, the low water-absorbing elastomer having the polymer block having the bond provides a paste excellent in polymerization curability, and the polymerization cured product is suitable because it has less permanent set because of chemical cross-linking.

The content of the elastomer polymer block (B) in the thermoplastic elastomer is preferably 30 to 95% by weight, more preferably 70 to 95% by weight.

Examples of such thermoplastic elastomers include diblock, triblock, multiblock having a polystyrene block, star type, and taper type polystyrene type in which the boundaries of blocks are gradually changed by random copolymerization. Styrene-isoprene elastomer, styrene-butadiene elastomer, styrene-isoprene-butadiene elastomer, styrene- which is a thermoplastic elastomer containing a block copolymer.
Examples include isobutylene-based elastomers and styrene-butyl acrylate-based elastomers.

Among these, JP-A-2-102212
Thermoplastic elastomer disclosed in Japanese Patent Publication, that is,
Two or more blocks of aromatic vinyl monomer having a number average molecular weight of 3,000 or more and 40,000 or less in the molecule and one block of isoprene and / or isoprene-butadiene having a vinyl bond content of 40 mol% or more. Containing 40 or more and having a molecular weight of 40,000 or more and 300,0
The block copolymer having a number of 00 or less has
Since the vibration-damping performance is excellent, there is little discomfort when the cured and cured product of the present invention is placed in the oral cavity and occluded, which is particularly preferable.

Creep recovery generally tends to occur in a paste containing an elastomer. This phenomenon indicates that when the impression is taken in the oral cavity and then taken out, it is likely to return to the pre-impression form with time, which means that the impression is not suitable. However, by having the thermoplastic elastomer block made of an aromatic vinyl monomer, creep recovery hardly occurs and a composition having excellent impression can be obtained.

The rubber hardness of the thermoplastic elastomer is not particularly limited, but is preferably in the range of 30 to 90 in general. Here, the rubber hardness is a value measured using a durometer A type according to JIS K6253.

The rebase material used in the present invention must contain a low water-absorbing elastomer in an amount of 30% by weight or more.
If it is less than 30% by weight, the property before curing becomes close to a liquid state and the operability is deteriorated.

The rebase material is preferably a composition comprising the above low water-absorbing elastomer, a (meth) acrylate-based monomer and a polymerization initiator. As the (meth) acrylate-based monomer, either a monofunctional (meth) acrylic acid ester or a polyfunctional (meth) acrylic acid ester can be used. Examples of the monofunctional (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, Alkyl (meth) acrylates such as myristyl (meth) acrylate and stearyl (meth) acrylate (having 1 to 20 carbon atoms in the alkyl group);

Methoxyethyl (meth) acrylate, 2
-Phenoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate (polymerization degree 2
-10), tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, undecenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate (HE
MA), dimethylaminoethyl (meth) acrylate and the like.

Examples of polyfunctional (meth) acrylic acid esters include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol. Di (meth) acrylate,
Alkylene glycol di (meth) acrylates (having 1 to 20 carbon atoms in the alkylene group) such as 1,6-hexanediol di (meth) acrylate and 1,10-decanediol di (meth) acrylate,

Polyalkylene glycol di (meth) acrylates such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate (carbon of alkylene group) Number 2-4 and degree of polymerization 2-20
0), glycerin di (meth) acrylate, 2,2'-
Bis [p- (γ-methacryloxy-β-hydroxypropoxy) phenyl] propane (Bis-GMA), bisphenol A dimethacrylate, 2,2′-bis (4
-Methacryloxypolyethoxyphenyl) propane (1
2-10 ethoxy groups in the molecule),

1,2-bis (3-methacryloxy-2-
Examples thereof include hydroxypropoxy) butane, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and urethane (meth) acrylate. These (meth) acrylate-based monomers are used alone or in combination of two or more.

Of these, alkyl (meth) acrylates and alkylene glycol di (meth) acrylates are suitable because they have a particularly high compatibility with the thermoplastic elastomer used in the present invention. These alkyl (meth) acrylates or alkylene glycol di (meth) acrylates are preferably contained in the (meth) acrylate-based monomer in an amount of 40% by weight or more.

As the (meth) acrylate-based monomer, an alkyl group having a large number of carbon atoms (having 6 or more carbon atoms) such as n-hexyl (meth) acrylate, n-lauryl (meth) acrylate and n-stearyl (meth) acrylate,
When a monofunctional (meth) acrylate having an alkenyl group is mainly used, a soft cured product is obtained. on the other hand,
As the (meth) acrylate-based monomer, a monofunctional (meth) acrylate or a polyfunctional (meth) acrylate having an alkyl group or an alkenyl group having a small number of carbon atoms such as methyl (meth) acrylate or n-butyl (meth) acrylate is blended. Then, a relatively hard cured product tends to be obtained.

Examples of the polymerization initiator include a photopolymerization initiator, a thermal polymerization initiator and a room temperature polymerization initiator. Examples of the photopolymerization initiator include camphorquinone, diacetyl,
Α-diketones such as 2,3-pentanedione, benzyl, acenaphthenequinone and phenanthraquinone, 2,
Examples thereof include acylphosphine oxides such as 4,6-trimethylbenzoyldiphenylphosphine oxide, benzoin methyl ether, benzyl dimethyl catal, benzophenone, and 2-ethylthioxanthone.

These photopolymerization initiators are appropriately used as a photopolymerization initiator system in combination with a reducing agent such as a tertiary amine, an aldehyde or a mercaptan. Examples of such a tertiary amine include N, N-dimethylaminoethyl methacrylate, ethyl N, N-dimethylaminobenzoate, bis-N, N-dimethylaminobenzophenone,
N, N-dimethylaminobenzaldehyde, N-phenylglycine, morpholinomethacrylate, triethanolamine, N-methyldiethanolamine, 2-n-butoxyethyl N, N-dimethylaminobenzoate, isoamyl N-dimethylaminobenzoate, and the like. be able to.

Examples of the aldehyde include citronellal, lauryl aldehyde, o-phthaldialdehyde,
p-octyloxybenzaldehyde etc. can be mentioned. Examples of mercaptans include 1-decanethiol, thiosalicylic acid, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 4-mercaptoacetophenone, and 4-t-butylthiophenol. it can. Furthermore, a system in which an organic peroxide such as benzoyl peroxide is added to the photopolymerization initiator is also suitably used.

Examples of the thermal polymerization initiator include peroxides such as benzoyl peroxide, di-t-butyl peroxide and cumene hydroperoxide, azo compounds such as azobisisobutyronitrile, and tetramethylthiuram disulfide. Initiators such as

Further, as the room temperature polymerization initiator, redox type initiators such as organic peroxide / aromatic tertiary amine type and organic peroxide / aromatic tertiary amine / aromatic sulfinic acid type are used. It When a combination of an oxidizing agent and a reducing agent is contained as the polymerization initiator (c), from the viewpoint of storage stability, it is necessary to use a divided packaging form so that they are not mixed, and to mix them immediately before use. is there.

The compounding amounts of the low water-absorbing elastomer, the (meth) acrylate-based monomer and the polymerization initiator in the soft rebase material of the present invention are determined by the type and molecular weight of the low-water-absorbing elastomer used, the type of the (meth) acrylate-based monomer and the like. The amount of the low-water-absorbing elastomer, the (meth) acrylate-based monomer, and the polymerization initiator is usually 30 to 80% by weight, and the (meth) acrylate-based monomer is 60 to 20% by weight. % And a polymerization initiator in the range of 0.05 to 5% by weight,
Preferably, the low water-absorbing elastomer component is 50 to 60% by weight, and the (meth) acrylate-based monomer component is 50 to 40.
% By weight, and 0.1 to 3% by weight of the polymerization initiator component.

The adhesive between the soft rebase material and the denture base used in the present invention is a polymerizable composition containing substantially the same elastomer as the soft rebase material, and among them, a (meth) acrylate monomer. , And a composition comprising a polymerization initiator are preferred. As the respective components, those described as the components of the soft rebase material can be mentioned as they are. However, in order to improve the adhesiveness, it is necessary to increase the elastic modulus of the polymerized cured product as compared with the soft rebase material, and it is preferable to add a polyfunctional (meth) acrylate monomer. Above all, it is preferable to add 50% by weight or more of a polyfunctional (meth) acrylate-based monomer to all (meth) acrylate-based monomers. Further, a relatively volatile organic solvent such as methyl acetate, ethyl acetate, butyl acetate, methylene chloride, chloroform, acetone, methyl ethyl kentone, toluene, ethyl alcohol, methyl alcohol or ethyl ether may be added. Among them, methylene chloride has a strong property of swelling and dissolving polymethylmethacrylate, which is most used as a resin for denture base, increasing the adhesive area and infiltrating the (meth) acrylate monomer in the adhesive to enhance the adhesiveness. It has an effect to do and is suitable.

The elastic modulus higher than that of the polymerized and cured product of the soft rebase material specifically means that the 100% elastic modulus in the tensile test according to JIS K6251 (1993 edition) is preferably 10 MPa or more, More preferably, it is 20 MPa or more. The 100% elastic modulus of the soft rebase material is 8MP to obtain cushioning properties.
It is based on the fact that it is preferably about a or less.

The low water-absorbing elastomer, the (meth) acrylic monomer, the polymerization initiator and the organic solvent in the adhesive composition used in the present invention are compounded in such amounts that the type and molecular weight of the low water-absorbing elastomer used and the organic solvent are used. Depending on the type, etc., the low water-absorbing elastomer, the (meth) acrylate-based monomer, the polymerization catalyst, and the organic solvent are usually contained in an amount of 1 to 40% by weight of the low-water-absorbing elastomer and the (meth) acrylate-based monomer. 1 to 90% by weight, polymerization catalyst 0.05 to 5% by weight and organic solvent 4
It is 0 to 90% by weight.

The cured film obtained from the coating material of the present invention exhibits low lipophilicity with a β-carotene discoloration degree of 15 or less. The β-carotene discoloration referred to in the present invention means the change in color tone before and after immersion in a 0.1% by weight olive oil solution of β-carotene for 24 hours in the discoloration test described in the section of the present specification (Δ). E * value). If this value exceeds 15, discoloration in the oral cavity becomes large, which is not desirable.

As a specific example of the coating material, a composition comprising a low lipophilic polymer, a (meth) acrylate-based monomer, and a polymerization initiator is mentioned as a preferable example. Examples of low lipophilic polymers include acrylic polymers and fluorine-containing elastomers. As the acrylic polymer, methyl polymethacrylate (hereinafter referred to as P
MMA), ethyl polymethacrylate (hereinafter abbreviated as PEMA), butyl polymethacrylate (hereinafter abbreviated as PBMA), and PMMA-PEMA,
Examples of these copolymers include PMMA-PBMA,
As the fluorine-containing elastomer, vinylidene fluoride-hexafluoropropylene copolymer,

Vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-pentafluoropropylene copolymer, vinylidene fluoride-pentafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-perfluoro Methyl vinyl ether-tetrafluoroethylene copolymer, vinylidene fluoride-
Examples thereof include fluororubber such as chlorotrifluoroethylene copolymer.

As the (meth) acrylate-based monomer and the polymerization catalyst, those described as the components of the soft rebase material can be mentioned. Further, a relatively highly volatile organic solvent such as methyl acetate, ethyl acetate, butyl acetate, methylene chloride, chloroform, acetone, methyl ethyl ketone, toluene, ethyl alcohol, methyl alcohol or ethyl ether can be added.

The coating material has a viscosity of 1 to 25 ° C.
A range of 10,000 centipoise is suitable for easy application. A more preferable viscosity is in the range of 1 to 2,000 poise.

The compounding amounts of the low lipophilic polymer, the (meth) acrylic monomer, the polymerization initiator and the organic solvent in the coating material vary depending on the type and molecular weight of the low lipophilic polymer used and the type of organic solvent. Usually, the low lipophilic polymer, the (meth) acrylic monomer, the polymerization initiator, and the organic solvent are contained in an amount of 2 to 40% by weight of the low lipophilic polymer and 2 to 98% of the (meth) acrylate monomer. % By weight, 0.05 to 5% by weight of polymerization catalyst and 10 to 95% by weight of organic solvent. A small amount of hydroquinone, hydroquinone monomethyl ether, butylhydroxyl toluene, etc. may be added as a polymerization inhibitor to each composition of the soft rebase material, the adhesive and the coating material used in the present invention. Further, in order to enhance the stability of the elastomer, a small amount of an antioxidant, a light stabilizer or the like can be added. Furthermore, various lubricants, surfactants, inorganic fillers, plasticizers and the like may be added in small amounts in order to adjust the properties of the paste and the cured product to a more suitable one, and it also gives the composition a gum color. Therefore, pigments, dyes, and fibers for artificial blood vessels can be added.

The soft rebase material composition of the present invention is usually provided as a paste by mixing the respective components. As a method of mixing each component, a known method is used without particular limitation, and examples thereof include kneading with a solvent and melt kneading. Specifically, a low water-absorbing elastomer, a (meth) acrylate-based monomer, and a polymerization initiator are dissolved in a solvent such as toluene or methylene chloride, and the mixture is uniformly mixed, and then the solvent is removed. There is a method such as batch kneading or biaxial continuous kneading using a kneader such as that manufactured by Brabender Co., etc., whereby a uniform paste can be prepared. The obtained paste is preferably subjected to defoaming treatment. On the other hand, the adhesive and the coating material are usually provided as uniformly dissolved solutions.

The procedure for forming a rebase material from the composition of the present invention is as follows. That is, an adhesive is applied to the mucosal surface of the denture base and then dried, and then a soft rebase material is built up. After that, an impression is taken in the oral cavity. Then, it is removed from the oral cavity, and while maintaining the impression after collection, it is polymerized and cured by a method such as light irradiation and room temperature polymerization, and a coating material is applied and polymerized and cured to rebase the denture base. It is also possible to perform the above steps on a gypsum model as well.

[0047]

【Example】

(1) Rubber hardness of the cured product is filled with a soft rebase material in a mold having a diameter of 10 mm and a thickness of 10 mm, and the dental light irradiator [α-light, manufactured by Kuraray Co., Ltd.] is irradiated with light for 10 minutes for polymerization and curing. Then, a coating material was applied to the obtained cured product, which was dried and similarly irradiated with light for 3 minutes to polymerize and cure, to obtain a test piece. 3 test pieces
After soaking in water at 7 ° C. for 1 day, the rubber hardness was measured using a Durometer A type (manufactured by Kobunshi Keiki Co., Ltd.) according to JIS K6253.

(2) Discoloration test A mold having a diameter of 20 mm and a thickness of 1 mm was filled with a soft rebase material and irradiated with α-light for 10 minutes to be polymerized and cured,
Further, the coating material was applied, dried, and then irradiated again with α-light for 3 minutes to obtain a cured product, which was used as a test piece. The color tone of the cured sample was measured using a color difference meter (Nippon Denshoku)
The reflection measurement was performed under the condition that the background color was white. L * for each measured value
₀ , a * ₀ , b * ₀ . Subsequently, the sample was immersed in a 2% by weight aqueous solution of coffee (manufactured by Nescafe) at 37 ° C. and a 0.1% by weight olive oil (manufactured by Wako Pure Chemical Industries) solution of β-carotene (manufactured by Wako Pure Chemical Industries) for 24 hours, The color tone after immersion is measured in the same manner, and L * ₁ , a * ₁ , and b * ₁ are set.
The degree of color change (ΔE *) was calculated from the following formula.

[0049]

[Equation 1]

(3) Water Absorption and Dissolved Amount of Hardened Material The method was as described in ISO1567. That is, a mold having a diameter of 20 mm and a thickness of 1 mm was filled with the soft rebase material composition, irradiated with α-light for 10 minutes to be polymerized and cured, further coated with a coating material, dried, and then again used with α-light. A cured product obtained by light irradiation for 3 minutes was used as a test piece. The test piece was placed in a desiccator and kept in an oven at 37 ± 2 ° C for 23 hours, then transferred to a desiccator kept at 23 ± 2 ° C, and after 1 hour, the test piece was taken out from the desiccator, and the mass of the test piece was measured. Weigh to an accuracy of 0.2 mg. The measured weight value of the test piece is 0.
This operation is repeated until a constant weight within a range of 2 mg is reached, and the weight value at this time is taken as the mass of the test piece (W ₁ ). Next, the test piece is immersed in distilled water at 37 ± 2 ° C. for 7 days, taken out with tweezers, the surface water is wiped off, and the mass of the test piece is weighed (W ₂ ).

Then, the test piece after the above operation was put in 37 ± 2.
The test piece is placed in a desiccator kept at 37 ° C. and kept in an oven at 37 ± 2 ° C. for 23 hours, then transferred to a desiccator kept at 23 ± 2 ° C., and after 1 hour, the test piece is taken out from the desiccator. This operation is repeated until the measured value of the mass of the test piece reaches a constant value within a range of 0.2 mg within 24 hours (measured value at this time:
W ₃ ). When the volume of the test piece is V (mm ³ ), the amount of water absorption (μg / mm ³ ) and the amount of dissolution (μg / mm ³ ) were obtained from the following formulas.

[0052]

[Equation 2]

(4) Tensile Shear Adhesion Test According to the method for preparing an anti-deflection test sample of ISO1567 (1988 edition), powder and liquid of PMMA-based denture base material Akron (manufactured by GC) were mixed at a ratio of 65:35 to prepare a rice cake. The paste having the above shape was filled in a mold of 65 × 10 × 2.5 mm, sandwiched between glass plates, gradually heated, and heat-polymerized in boiling water for 60 minutes. After polymerization and curing, let it cool naturally and then # 1 the adhesive surface.
Polish with 500 sandpaper. The adhesive composition is applied and naturally dried. The bonding area is defined as a circle of 8 mm in diameter,
P with a thickness of 1 mm filled with an adherend and similarly coated with an adhesive
The adherend on which the MMA-based denture base material plate is superposed is irradiated with light of α-light for 5 minutes to be polymerized and cured. After storing in 37 ° C water for 24 hours, under the condition of 25 ° C, Universal Material Testing Machine Model 11
Using 75 (manufactured by Instron), a tensile shear adhesion test was performed at a displacement rate of 10 mm / min, and an average value of 5 pieces was obtained and used as the adhesion strength.

Example 1 S which is a styrene-isoprene thermoplastic elastomer
IS5000 (Nippon Synthetic Rubber) 60 g, n-lauryl methacrylate (Kyoeisha Chemical Co., Ltd.) 38 g, 1,10-
Decanediol dimethacrylate (manufactured by Kyoeisha Chemical) 2
g, camphorquinone (Wako Pure Chemical Industries, Ltd.) 1.0 g, dimethylaminoethyl methacrylate (Wako Pure Chemical Industries, Ltd.) 0.
5 g, benzoyl peroxide (hereinafter abbreviated as BPO) 0.
2 g was dissolved in 100 ml of methylene chloride and the methylene chloride was distilled off to form a paste, which was used as a soft rebase material.

30 g of Hybler VS-1 (manufactured by Kuraray), which is a styrene-isoprene thermoplastic elastomer,
10 g of 1,4-butanediol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd.), 1.0 g of camphorquinone, 0.5 g of dimethylaminoethyl methacrylate and 60 g of methylene chloride (manufactured by Wako Pure Chemical Industries) were uniformly dissolved to obtain an adhesive. .
HYPERAL D-250E which is polyethylmethacrylate
(Negami Kogyo Co., Ltd.) 14 g, triethylene glycol dimethacrylate (Shin Nakamura Co., Ltd.) 1.0 g, camphorquinone 0.3 g, dimethylaminoethyl methacrylate 0.1 g, ethyl acetate (Wako Pure Chemical Industries, Ltd.) 75 g Was dissolved into a coating material. Using the soft rebase material mounting kit composed of these, a cured product was prepared according to the above-described test method and subjected to the test. The test results are shown in Tables 1 and 2.

Example 2 T which is a styrene-butadiene type thermoplastic elastomer
R2825 (manufactured by Japan Synthetic Rubber) 58 g, n-stearyl methacrylate 20 g, cetyl methacrylate (manufactured by NOF Corporation) 20 g, 1,6-hexanediol dimethacrylate 2 g, camphorquinone 1.0 g, dimethylaminoethyl methacrylate 0. 5 g was kneaded at 80 ° C. for 30 minutes using a plastic coder (manufactured by Brabender) to form a paste, which was used as a soft rebase material.

20 g of TR2825, 20 g of 1,6-hexanediol dimethacrylate, 1.0 g of camphorquinone, 0.5 of dimethylaminoethyl methacrylate.
g and 60 g of methylene chloride were uniformly dissolved to obtain an adhesive. Fluorine rubber Daiel G501NK (manufactured by Daikin Industries) 20 g, trimethylpentenetrimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) 5 g, and camphorquinone 1.0
g, 0.5 g of dimethylaminoethyl methacrylate,
75 g of ethyl acetate was dissolved to obtain a coating material. Using the soft rebase material mounting kit composed of these, a cured product was prepared according to the above-described test method and subjected to the test. The test results are shown in Tables 1 and 2.

Example 3 60 g of Hybler VS-1 (manufactured by Kuraray) which is a styrene-isoprene type thermoplastic elastomer, 38 g of 1, -stearyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.), 1,10-
Decanediol dimethacrylate (manufactured by Kyoeisha Chemical) 2
g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF, hereinafter abbreviated as TMDPO) 1.0 g of plasticcoder (manufactured by Brabender)
Was kneaded for 30 minutes at 80 ° C. to form a paste, which was used as a soft rebase material.

20 g of Hybler VS-1, 20 g of triethylene glycol dimethacrylate (made by Shin Nakamura), T
1.0 g of MDPO and 60 g of methyl methacrylate (manufactured by Wako Pure Chemical Industries) were uniformly dissolved to obtain an adhesive. Fluororubber Technoflon P710 (manufactured by Zeon Corporation) 20g,
A coating material was prepared by dissolving 5 g of 1,6-hexanediol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd.), 1.0 g of TMDPO, and 75 g of ethyl acetate (manufactured by Wako Pure Chemical Industries). Using the soft rebase material mounting kit composed of these, a cured product was prepared according to the above-described test method and subjected to the test. The test results are shown in Tables 1 and 2.

Example 4 40 g of Hybler VS-1, 57 g of lauryl methacrylate, 3 g of 1,10-decanediol dimethacrylate, and 0.5 g of BPO were added to 100 m of methylene chloride.
After dissolving in 1, the methylene chloride was distilled off to give a paste (a). 40 g of Hybler VS-1, 57 g of lauryl methacrylate, 3 g of 1,10-decanediol dimethacrylate, and dihydroxyethyl-
After dissolving 0.5 g of p-toluidine in 100 ml of methylene chloride, the methylene chloride was distilled off to obtain a paste (b). A soft rebase material that is polymerized at room temperature by mixing the above two kinds of pastes was prepared.

25 g of Hybler VS-1, 15 g of ethylene glycol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd.), T
1.0 g of MDPO, methylene chloride (Wako Pure Chemical Industries) 60
g was uniformly dissolved to obtain an adhesive. 20 g of fluoroelastomer Daiel G501NK, 5 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd.), TMDPO1.
A coating material was prepared by dissolving 0 g and 75 g of ethyl acetate. Using the soft rebase material mounting kit composed of these, a cured product was prepared according to the above-described test method and subjected to the test. The test results are shown in Tables 1 and 2.

Example 5 60 g of Septon 2005 (manufactured by Kuraray Co., Ltd.), which is a hydrogenated product of a styrene-isoprene thermoplastic elastomer, 38 g of isodecyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.), 2 g of triethylene glycol dimethacrylate, 1.0 g of camphorquinone, 0.5 g of mercaptobenzoxazole (manufactured by Tokyo Kasei), Plasticorder (manufactured by Brabender)
Was kneaded at 80 ° C. for 30 minutes to form a paste, which was used as a soft rebase material.

Styrene-isoprene type thermoplastic elastomer Hybler VS-3 (manufactured by Kuraray) 25, ethylene glycol dimethacrylate 20, TMDPO0.
5 g and 55 g of chloroform (manufactured by Wako Pure Chemical Industries) were uniformly dissolved to obtain an adhesive. Fluororubber Technoflon P71
20 g of 0, 5 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd.), 1.0 g of TMDPO and 75 g of ethyl acetate were dissolved to obtain a coating material. Using the soft rebase material mounting kit composed of these, a cured product was prepared according to the above-described test method and subjected to the test. The test results are shown in Tables 1 and 2.

Comparative Example 1 A tissue recycler (manufactured by Kamemizu Kagaku Co., Ltd.), which is commercially available as an acrylic soft rebase material, was prepared as a soft rebase material mounting kit according to the attached instruction manual. That is, there are three types: a room temperature-polymerizable soft rebase material composed of a powder component and a liquid component, a liquid coating material (name "top coat"), and a liquid adhesive (name "top coat"). A cured product of each of these soft rebase material mounting kits was prepared according to the above-mentioned test method and subjected to the test. However, since the present composition does not require light irradiation,
In each test sample preparation, light irradiation by α-light was omitted. The test results are shown in Tables 1 and 2.

Comparative Example 2 Evatouch (manufactured by Neo Pharmaceutical Co., Ltd.), which is commercially available as a silicon-based soft rebase material, was prepared as a soft rebase material kit according to the attached instruction manual. That is, there are two types: a room temperature-curable soft rebase material composed of two kinds of pastes and a liquid adhesive (named “adhesive”). A cured product of each of these soft rebase material mounting kits was prepared according to the above-mentioned test method and subjected to the test. However, since neither of the present compositions requires light irradiation, the light irradiation by α-light was omitted in each test sample preparation. Also,
Since the coating material was not included in this product as a kit, the coating step was omitted in the sample preparation for each test. The test results are shown in Tables 1 and 2.

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[Table 1]

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[Table 2]

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EFFECTS OF THE INVENTION The soft rebase material mounting kit according to the present invention significantly reduces water absorption into the rebase material, has a low lipophilicity on the rebase surface, and has high adhesiveness to the denture base. A denture can be provided with a soft rebase material that has excellent stain resistance and that particularly suppresses the growth of bacteria and the attachment of contaminants such as food. Furthermore, in the case of a composition containing no plasticizer, the plasticizer does not elute into the oral cavity and maintains softness for a long period of time, and there is no adverse effect on the living body.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Eiichi Masuhara 2-5-11 Honkomagome, Bunkyo-ku, Tokyo (56) Reference JP-A-3-63205 (JP, A) JP-A-60-173058 (JP) , A) JP 52-134291 (JP, A) JP 4-134011 (JP, A) JP 2-247108 (JP, A) JP 2-188511 (JP, A) JP 1-94850 (JP, A) JP 62-340 (JP, A) JP 59-25739 (JP, A) JP 60-97911 (JP, A) JP 8-245330 (JP, A) JP-A-2-157206 (JP, A) JP-A-60-161207 (JP, A) JP-A-9-67223 (JP, A) JP-A-7-286018 (JP, A) (58) Survey Areas (Int.Cl. ⁷ , DB name) A61K 6/00

Claims (4)

(57) [Claims] 1. A number comprising (a) an aromatic vinyl monomer.
Thermoplastic polymer block having an average molecular weight of 3,000 or more
(A) and elastomer polymer block (B)
Made of thermoplastic elastomer with one or more blocks each
Ri, solubility parameter is 8.0 to 9.0 <br/> low water absorption elastomers, (meth) acrylate monomer
And a polymerization initiator.
Te, the polymerizable soft rebase material containing low water absorption elastomers 30 wt% or more, (b) low water absorption elastomers, at least 50 wt% multifunctional
A (meth) accompound consisting of a (meth) acrylate-based monomer
Includes Relate monomer and polymerization initiator, the soft <br/> in rebase material substantially polymerizable composition containing the same elastomers, soft rebase material which gives a cured product having a high elastic modulus than the soft rebase material A kit for mounting a soft rebase material, which comprises an adhesive agent for denture base and (c) a polymerizable coating material of a soft rebase material that gives a low lipophilic cured film having a β-carotene discoloration degree of 15 or less. 2. An elastomer polymer block (B) of a thermoplastic elastomer is at least one polymer block selected from polyisoprene and isoprene-butadiene copolymer, and has a vinyl bond content of 40 mol% or more. A plastic elastomer polymer
The kit for mounting the soft rebase material according to 1 . 3. (c) polymerizing the coating material of the soft rebase material, fluorine-containing elastomer, (meth) acrylate monomers and consists polymerization initiator claim 1 soft rebase material mounting kit according. 4. The (c) fluorine-containing elastomer of the polymerizable coating material of the soft rebase material comprises vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, pentafluoropropylene, perfluoromethyl vinyl ether, and chlorotrifluoroethylene. The soft rebase material mounting kit according to claim 3, which is a polymer or copolymer of one or more monomers selected from the group.