JP5956835B2 - Denture base lining adhesive - Google Patents

Description

  The present invention relates to an adhesive for denture base lining materials for the purpose of firmly lining denture lining materials against dentures made of polyamide resin as a main component.

  Usually, the intraoral mucosa and jawbone of the human body change little by little, and poor fit often occurs between the denture and the oral mucosa within a few years. Repair of the inner surface of the denture with a denture base lining material can be cited as one of the means for improving the poor conformity of the denture generated as described above. This is a means of filling the gap between the denture and the oral mucosa, which cannot be matched by placing an appropriate material on the inner surface of the denture, etc., thereby regaining the matching between the denture and the mucous membrane. A material used for filling the gap is generally called a denture base lining material, and a material made of (meth) acrylic resin or silicone rubber is widely used. This means is more widely used than 20 years ago.

  Dentures (floors) that have been used so far have mostly been (meth) acrylic resins and polycarbonate resins because of their ease of handling and low cost. ) Has spread mainly overseas, and the demand is growing in Japan (Non-patent Document 1). The greatest feature of dentures (floor) using polyamide resin is its flexibility. In the case of dentures (floor) made of conventional (meth) acrylic resin, if the denture is partially combined with natural tooth, the natural tooth with a support part called clasp separately made of metal attached to the denture The clasp's appearance is a great mental burden on the patient. On the other hand, in dentures using polyamide resin, polyamide resin is very flexible, so there is an advantage that it can be used in combination with natural teeth without using metal clasp, and it is also called non-clasp denture etc. .

  A denture using a polyamide resin has the above-mentioned excellent features, but has a drawback that the inner surface can hardly be repaired with a denture base lining material. This is a drawback that occurs because polyamide resin does not adhere to (meth) acrylate resin or silicone rubber, which is widely used as a general denture base lining material. Various denture base lining materials and adhesives for lining materials currently found are generally for dentures made of (meth) acrylic resin or polycarbonate resin (Patent Document 1, Patent Document 2), and the polyamide It cannot be used for dentures made of resin.

  That is, dentures made of polyamide resin must be repaired and repaired once a poor fit has occurred. Also, when making a denture (technical operation), no failure is allowed, and great care must be taken in the production stage. From these facts, there is a great demand for using a denture base lining material for dentures using polyamide resin.

  As a technique for adhesion to resins other than (meth) acrylic resins and polycarbonate resins widely used in industry, for example, a low-boiling solvent is contained on the surface of a high-temperature-resistant plastic molded product containing a filler. A method of treating with a conditioning agent (Patent Document 3) is known.

  Further, as an adhesive technique related to a polyamide resin, an adhesive (Patent Document 4) characterized by containing a specific solvent and copolymer nylon for the purpose of bonding polyamide resins together is known.

Japanese Patent No. 3105733 Japanese Patent No. 4398243 Special table 2010-521257 JP 2003-87783 A

Yota Takabayashi et al. “Clinical Application of Polyamide-Based Synthetic Resin Dentures” Journal of the Japan Dental Association, Vol. 61, No. 5, 503, August 10, 2008

  As described above, several techniques for bonding to polyamide resins and difficult-to-adhere resins are known, but these are all made of the (meth) acrylic resin and silicone rubber for dentures made of polyamide resin. This technique is not used when adhering denture base lining materials, and a technique that can easily and firmly bond these members has not yet been found.

  Therefore, it has been a big problem to develop such an adhesion method and to appropriately repair the denture base lining material when the denture made of polyamide resin becomes poorly compatible.

  As a result of intensive studies to solve the above problems, the present inventors have used an adhesive in which an adhesive component having reactivity with the curable composition constituting the lining material is dissolved in a specific solvent. The inventors have found that the denture base made of polyamide resin that could not be bonded so far and the lining material can be satisfactorily bonded, and have completed the present invention.

  That is, the present invention is an adhesive for a lining material for a denture base made of polyamide resin, and an adhesive component for a curable composition constituting the lining material is dissolved in a phenol solvent and / or a fluoroalcohol solvent. It is an adhesive for denture base lining materials made of an organic solution.

  By using the adhesive for denture base lining materials of the present invention, a denture base made of polyamide resin that could not be bonded so far and a denture base lining material conventionally used can be easily and firmly bonded. It became possible to make it. Therefore, even when the denture made of polyamide resin becomes incompatible, it can be appropriately repaired using the denture base lining material, which is extremely significant.

  In the adhesive for denture base lining materials of the present invention, an adhesive component for the curable composition constituting the lining material is dissolved in a phenol-based solvent and / or a fluoroalcohol-based solvent. Here, the phenol-based solvent and the fluoroalcohol-based solvent have a particularly high solubility in the polyamide resin, and the adhesive using these as a solvent is applied to the denture base made of the polyamide resin with good uniformity and quickly. It can penetrate into the surface. That is, on the application surface of the denture base made of polyamide resin, dissolution and swelling first occur in the surface layer portion due to the effect of these solvents. Next, the adhesive component with respect to the backing material contained in the adhesive penetrates well. Thus, when the backing material is placed on the adhesive application surface of the denture base, the permeating adhesive component exerts a good adhesive action on the backing material, and both members adhere firmly. It will be.

The greatest feature of the adhesive for denture base lining materials of the present invention is that a phenol solvent and / or a fluoroalcohol solvent is adopted as a solvent component. These solvents are generally high in solubility in the polyamide resin as described above, but those having a solubility at 20 ° C. in the polyamide resin, which is a material of the denture base to be bonded, of 5% by mass or more are preferable, The above is particularly preferable.
Specific examples of the phenol solvent include m-cresol, o-ethylphenol, m-ethylphenol, o-propylphenol, m-propylphenol, p-propylphenol, o-isopropylphenol, m-isopropylphenol, 5- Examples include isopropyl-2-methylphenol (also referred to as carvacrol), 2-methoxy-4-ethylphenol, 2-methoxy-4-propylphenol, 2-methoxy-4- (2-oxopropyl) phenol, and the like.

  On the other hand, specific examples of the fluoroalcohol solvent include 1,1,1,3,3,3-hexafluoroisopropanol, 1,1,1-trifluoroethanol, and 3-trifluoromethylphenol.

  Both the phenol solvent and the fluoroalcohol solvent tend to have higher solubility in polyamide resins than general organic solvents, and are familiar to polyamide resins. Is a silicone-based curable composition to be described later, a higher adhesive effect is exhibited particularly when a fluoroalcohol-based solvent is used as the solvent component of the denture base lining adhesive. The reason for this is not clear, but it is thought that the fluoroalcohol solvent is more familiar with the silicone curable composition. When the curable composition constituting the lining material is not a silicone-based curable composition [specifically, in the case of a (meth) acrylic resin-based curable composition], any solvent may be used. Usually there is no significant difference in the adhesive effect.

  In the adhesive for denture base lining materials of the present invention, an adhesive component for the curable composition constituting the lining material is dissolved in the phenol solvent and / or the fluoroalcohol solvent. There are several types of curable compositions that constitute the backing material, but generally there are silicone-based curable compositions and (meth) acrylic resin-based curable compositions. Therefore, the adhesive for denture base lining materials of the present invention includes an adhesive for silicone lining materials in which an adhesive component for the silicone curable composition is dissolved, and adhesion to a (meth) acrylic resin curable composition. It can be roughly divided into adhesives for (meth) acrylic resin-based lining materials in which components are dissolved.

  Therefore, first, an adhesive component used in the adhesive for the silicone-based lining material will be described. Examples of the silicone-based curable composition constituting the lining material include a room temperature curable silicone rubber that cures at room temperature up to 50 ° C. and a low temperature curable silicone rubber that cures at a temperature of about 50 to 150 ° C. The curable composition particularly usefully used as a denture base lining material is a low-temperature curing type, which is often cured by a hydrosilylation reaction. The silicone-based curable composition that is cured by a hydrosilylation reaction includes a composition including a hydrogen siloxane compound, a siloxane compound having an unsaturated bond, and a catalyst typified by platinum.

  Such silicone-based curable compositions are known from, for example, Japanese Patent No. 3040297, Japanese Patent No. 3447425, Japanese Patent No. 3478521, and the like. As described above, in the adhesive for denture base lining materials of the present invention, when a fluoroalcohol solvent is used as a solvent, the curable composition constituting the lining material is such a silicone curable composition. If it exists, since the outstanding improvement effect of especially adhesiveness is exhibited, it is preferable.

  As the adhesive component for the backing material of such a silicone-based curable composition, an adhesive component having an affinity for the cured product of the silicone-based curable composition may be used. It has reactivity to be incorporated into the structural unit of silicone and can be dissolved in the phenol solvent or fluoroalcohol solvent. Specifically, if the silicone-based curable composition is cured by a hydrosilylation reaction, a compound having a reactive functional group of the hydrosilylation reaction is applicable. Here, the hydrosilylation reaction is a reaction that occurs when a hydrogensilyl group (Si-H group) is added to a group having an unsaturated double bond such as a vinyl group or an allyl group. The reactive functional group of the reaction corresponds to a functional group having an unsaturated carbon double bond at the terminal or a Si—H group. Among these, a vinyl group, an allyl group, and a Si—H group are preferable, and a Si—H group is particularly preferable.

  In view of the high reactivity of the hydrosilylation reaction, the reactive functional group of the hydrosilylation reaction is preferably bonded to siloxane. Moreover, since it is desirable that the adhesive component has good affinity with the denture base side as well as high adhesiveness with the lining material side, the reactive functional groups of these hydrosilylation reactions are included. The siloxane having is preferably bonded to a polymer having a high affinity for the polyamide resin. Examples of such a polymer having a high affinity for the polyamide resin include polymers having an ester bond, a carbonyl bond, a peptide bond, and the like, and a (meth) acrylic resin is particularly preferable. In addition, the siloxane having a reactive functional group for the hydrosilylation reaction and the high affinity polymer for the polyamide resin can exhibit the effect of improving the adhesiveness to some extent even if they are used in combination. However, since both materials are difficult to disperse uniformly, it is effective to bond them to the same molecule as described above.

Thus, when the backing material is a silicone-based curable composition that is cured by a hydrosilation reaction, the adhesive component that is preferably used is modified with a siloxane having a reactive functional group for the hydrosilation reaction. (Meth) acrylic polymer (hereinafter also referred to as “reactive siloxane-modified (meth) acrylic copolymer”). Specifically, in the (meth) acrylic polymerizable monomer, a structural unit A based on an unmodified product and a structural unit B based on a modified product by a polysiloxane having a reactive functional group for hydrosilylation reaction, A random copolymer of
The structural unit A has the following formula (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 13 carbon atoms or an aryl group having 6 to 14 carbon atoms)
On the other hand,
The structural unit B is
The following formula (2a) or (2b)

(Wherein R ³ represents a hydrogen atom or a methyl group, R ^{4 to} R ¹⁵ each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms, and Y represents a main chain) C1-C18 bivalent organic residue which may have an ether bond or an ester bond, a-c shows the average number of repeating units, a is 1, b is 1-100, c is 0 To 100, and 10 ≦ b + c ≦ 100, 0 ≦ c / b ≦ 10)
Si—H group-containing structural unit represented by the following formula (3)

(Wherein R ¹⁶ represents a hydrogen atom or a methyl group, R ^{17 to} R ¹⁹ each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms, and Y represents a main chain) A C1-C18 divalent organic residue which may have an ether bond or an ester bond, m represents the average number of repeating units, is 1 to 100, and n is 1, 2, or 3. )
A reactive silicone-modified (meth) acrylic random copolymer comprising a structural unit selected from unsaturated carbon double bond-containing structural units represented by In this reactive silicone-modified (meth) acrylic random copolymer, the structural unit A and the structural unit B are structural unit A / (structural unit A + structural unit B) = 99.9 to 10%, more preferably It is preferable that the copolymerization is performed at a unit number ratio of 98.5 to 50%.

  Furthermore, the reactive silicone-modified (meth) acrylic random copolymer is a structural unit C represented by the following general formula (4) instead of a part of the structural unit A.

(In the formula, R ²⁰ represents a hydrogen atom or a methyl group, and Y represents a C 1-18 divalent organic residue that may have an ether bond or an ester bond in the main chain.)
Are copolymerized. Specifically, the copolymerization amount is (structural unit A + structural unit C) / (structural unit A + structural unit B + structural unit C) = 99.9 to 10%, and structural unit A / (structural unit A + structure). Unit B + structural unit C)> 10%, more preferably 98.5-50%, and proportion of copolymerization at a unit number ratio of structural unit A / (structural unit A + structural unit B + structural unit C)> 30% It is.

  In the structural unit B, the Si—H group-containing structural unit represented by (2a) or (2b) and the unsaturated carbon double bond-containing structural unit represented by (3) are included together. May be. Furthermore, in the Si—H group-containing structural unit, each structural unit (2a) or (2b) may be included together.

In the general formulas (2a), (2b), (3), and (4), R ¹ , R ³ , R ¹⁶ , and R ²⁰ are each a hydrogen atom or a methyl group. In addition, a hydrogen atom and a methyl group may coexist in one polymer.

R ² is an alkyl group having 1 to 13 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group or a tridecyl group, a phenyl group, a benzyl group, a naphthyl group, or the like. Selected from among aryl groups having 6 to 14 carbon atoms, and alkyl groups having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and an n-propyl group are most suitable. Or the mixed system which used 2 or more types of group together is preferable.

R ^{4 to} R ¹⁵ and R ^{17 to} R ¹⁹ are each independently an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, or an n-hexyl group, or a phenyl group, a benzyl group, or a naphthyl group. Selected from aryl groups having 6 to 14 carbon atoms such as a group, synthesis of polysiloxane having a SiH reaction point as a synthesis raw material, availability, and high reactivity of the resulting copolymer Therefore, a methyl group, a phenyl group, or a mixed system using these in combination is preferable.

Y is a C1-C18 divalent hydrocarbon group which may have an ether bond or an ester bond in the main chain, and may have an ether bond or an ester bond for ease of synthesis. A divalent hydrocarbon group having 1 to 10 carbon atoms is preferred. Specifically, an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a heptamethylene group, an octamethylene group, a —CH ₂ CH ₂ OCH ₂ CH ₂ — group, Derivative groups of alkylene glycol groups such as CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ — group, —CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ — group, —CH ₂ CH ₂ OC (═O) CH _{A 2} CH ₂ CH ₂ — group and the like can be mentioned as a suitable group.

  In the above general formulas (2a) and (2b), a to c represent the number of units of each siloxane unit (—SiO—), a is 1, b is 1 to 100, c is 0 to 100, and 10 ≦ b + c ≦ 100, 0 ≦ c / b ≦ 10, and within this range, the units may be arranged in any order. Usually, from the request | requirement on a synthesis | combination, although obtained as a mixture from which said b and c differ, the average value of b and c in these mixtures should just be in the said range. Particularly preferred is a compound having an average value of c of 3 or more.

  These copolymers preferably have a weight average molecular weight of 5,000 to 1,000,000. Copolymerization of b and c, and structural unit A, structural unit B and structural unit C is within this range. The ratio and the total number of polymerizations may be determined.

  Furthermore, the ratio of the molecular weight of the siloxane part to the molecular weight of the (meth) acrylic polymer part is 1: because of compatibility with the polyamide resin of the denture base and the silicone rubber part, reactivity, and ease of synthesis. It is preferable to select a combination of 0.1 to 2.

  If the typical thing of the reactive siloxane modified (meth) acrylic copolymer in the present invention is specifically shown by the structure of the structural unit and the average number of repeating units,

  (Wherein Ph represents a phenyl group). These polymers are generally white powdered solids.

  The order of bonding of these copolymers and the structural units and siloxane units in the copolymers used in Examples and Comparative Examples to be described later is completely arbitrary, and the number of repeating units shown in the structural formula is simply each structural unit. As well as the average total amount of each siloxane unit. Moreover, the terminal of the (meth) acrylic polymer part in the said copolymer is determined depending on the polymerization catalyst which superposes | polymerizes the (meth) acrylic acid ester used as a raw material.

  Reactive siloxane-modified (meth) acrylic copolymers comprising structural units represented by the above formulas (1), (2a), (2b), and (3) are disclosed in Japanese Patent No. 3105733 and Japanese Patent No. 3107702, etc. The polymer can be produced by a method according to the method described in the above publication.

  Next, the adhesive component used in the adhesive for (meth) acrylic resin backing materials will be described. The (meth) acrylic resin-based curable composition constituting the backing material includes a (meth) acrylic polymerizable monomer, a radical polymerization initiator, and an appropriate resin and / or filler as necessary. In general, a polymerizable composition is used. Such (meth) acrylic resin-based curable compositions are cured by normal polymerization or chemical polymerization by heating or photopolymerization.

  As the adhesive component for such a (meth) acrylic resin-based curable composition, those having an affinity for the (meth) acrylic resin of the cured product may be used. It has reactivity to be incorporated into the structural unit and can be dissolved in the phenol solvent or fluoroalcohol solvent. Specifically, a radical polymerizable monomer can be preferably used. That is, the radical polymerizable monomer is obtained by polymerizing together with the (meth) acrylic polymerizable monomer component when the (meth) acrylic resin curable composition is cured. It becomes a structural unit of resin.

    Such radically polymerizable monomers can be used without any limitation as long as they have radically polymerizable groups. Specifically, ethylene-based polymerizable monomers, vinyl chloride-based polymerizable monomers , Vinyl acetate polymerizable monomer, styrene polymerizable monomer, vinylamine polymerizable monomer, vinylamide polymerizable monomer, (meth) acrylic polymerizable monomer, (meth) acrylamide Examples thereof include a polymerizable monomer, a fumaric acid polymerizable monomer, and a butadiene polymerizable monomer. Among them, the (meth) acrylate polymerizable monomer is the same system as the polymerizable monomer contained in the (meth) acrylic resin-based curable composition constituting the backing material, and has higher reactivity. This is preferable because it exerts high adhesiveness.

  As the (meth) acrylic polymerizable monomer to be used, known (meth) acrylic polymerizable monomers that can be generally used in dental restoration materials can be used without any limitation. Specific examples of such polymerizable monomers include the monomers shown in the following a) to d).

A) Monofunctional (meth) acrylic polymerizable monomers Methacrylates such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, and acrylates corresponding to these methacrylates; or acrylic Acid, methacrylic acid, p-methacryloyloxybenzoic acid, N-2-hydroxy-3-methacryloyloxypropyl-N-phenylglycine, 4-methacryloyloxyethyl trimellitic acid, and its anhydride, 6-methacryloyloxyhexamethylenemalon Acid, 10-methacryloyloxydecamethylenemalonic acid, 2-methacryloyloxyethyl dihydrogen phosphate, 10-methacryloylo Xidecamethylene dihydrogen phosphate etc.

B) Bifunctional (meth) acrylic polymerizable monomer (I) Aromatic compound type 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane (hereinafter abbreviated as bis-GMA), 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane (hereinafter referred to as “2-hydroxypropoxyphenyl” propane) , D-26E), 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane), 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- Methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropo) Xylphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxydiethoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxyditriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytriethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyiso) Propoxyphenyl) propane and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate Vinyl monomers having a methacrylate or -OH group such as the corresponding acrylates to these methacrylates bets like

(II) Aliphatic compound type ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate (hereinafter abbreviated as 3G), butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, propylene glycol dimethacrylate, 1, 3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2 -Having -OH groups such as methacrylates such as hydroxypropyl methacrylate or acrylates corresponding to these methacrylates Nirumonoma, acrylic anhydride, methacrylic anhydride, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethyl, di (2-methacryloyloxy propyl) phosphate and the like

C) Trifunctional (meth) acrylic polymerizable monomers Trimethylol propane trimethacrylate, trimethylol ethane trimethacrylate, pentaerythritol trimethacrylate, trimethylol methane trimethacrylate and other methacrylates and acrylates corresponding to these methacrylates

D) Tetrafunctional (meth) acrylic polymerizable monomers Tetramethylolmethane tetramethacrylate, pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate and acrylates corresponding to these methacrylates.

  These radically polymerizable monomers can be used alone or in combination of two or more.

  In the adhesive for denture base lining materials of the present invention, the amount of these adhesive components varies depending on the type of adhesive component used, and thus cannot be limited unconditionally, but from the viewpoint of applicability, uniformity, etc., preferably phenolic The amount is 0.05 to 30 parts by weight with respect to 100 parts by weight of the solvent and / or the fluoroalcohol solvent. Furthermore, it is preferably 0.1 to 20 parts by weight because it has low viscosity and better operability.

  In the case where the adhesive component has a reactivity incorporated into the structural unit of the cured body of the curable composition constituting the backing material, the organic solution has a catalyst or polymerization start in order to increase the reactivity. An agent may be included. More specifically, the curable composition constituting the lining material is a silicone rubber-based curable composition that is cured by a hydrosilylation reaction, and the adhesive component has a reactive functional group for the hydrosilylation reaction. In the case of a compound, the organic solution preferably contains a noble metal catalyst (platinum, palladium, ruthenium, rhodium, etc.) that is a catalyst for hydrosilylation reaction.

  On the other hand, when the curable composition constituting the lining material is a (meth) acrylic resin-based curable composition and the adhesive component is the radical polymerizable monomer, the organic solution contains: It is preferable to contain a radical polymerization initiator. As such a radical polymerization initiator, it is required to match a polymerization method similar to that contained in the (meth) acrylic resin-based curable composition, and (meth) acrylic resin-based curability. If the radical polymerization initiator of the composition is of the chemical polymerization type, the chemical polymerization type is adopted for the one contained in the organic solution, and the radical polymerization initiator of the (meth) acrylic resin-based curable composition is of the photopolymerization type. If it is a thing, what is contained in an organic solution will also employ a photopolymerization type.

  As the chemical polymerization initiator, an organic peroxide is preferable, and specific examples include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, dilauroyl peroxide, and the like. These organic peroxides generate radicals by heating to accelerate the polymerization reaction. Moreover, in combination with a tertiary amine compound, radicals are actively generated even at room temperature, so that the tertiary amine compound is blended with the (meth) acrylic resin-based curable composition constituting the backing material. If the polymerization initiator of the adhesive is only an organic peroxide, radical polymerization proceeds satisfactorily even at room temperature due to the migration of the tertiary amine compound on the backing material side.

  As the photopolymerization initiator, a known initiator system such as α-diketone-reducing agent, ketal-reducing agent, thioxanthone-reducing agent is preferably used. Examples of ジ -diketones include camphorquinone, benzyl, 2,3-pentadione, and 3,4-heptadione. Examples of the ketal include benzyl dimethyl ketal, benzyl diethyl ketal, and benzyl (2-methoxyethyl ketal). Examples of thioxanthone include thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2-chlorothioxanthone. The reducing agent as one component of the photopolymerization initiator includes tertiary amines such as 2- (dimethylamino) ethyl methacrylate, ethyl 4-dimethylaminobenzoate and N-methyldiethanolamine, lauryl aldehyde, dimethylaminobenzaldehyde, terephthalate Examples include aldehydes such as aldehyde, 2-mercaptobenzoxazole, 1-decanethiol, thiosalicylic acid, and thiobenzoic acid.

  In the organic solution, the content of such a polymerization initiator is not limited as long as it is an effective amount, but is usually preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the radical polymerizable monomer. 05-2 mass parts is more preferable.

  Furthermore, in the adhesive for denture base lining materials of the present invention, dissolving the film-forming resin improves the applicability of the denture base surface and has particularly high adhesion between the denture base and the lining material. From the viewpoint of making it. Examples of suitable film forming resins include poly (methyl methacrylate), poly (ethyl methacrylate), poly (isopropyl methacrylate), poly (butyl methacrylate), poly (methyl methacrylate-ethyl methacrylate) copolymer, poly (Methyl methacrylate-propyl methacrylate) copolymer, poly (methyl methacrylate-butyl methacrylate) copolymer, methacrylate (co) polymer such as poly (ethyl methacrylate-butyl methacrylate) copolymer, polystyrene, polycarbonate-poly (Methyl methacrylate) block copolymer, polycarbonate-poly (ethyl methacrylate) block copolymer, polystyrene, polysulfone-poly (methyl methacrylate) block copolymer, Risuruhon - poly (ethyl methacrylate) block copolymer and the like are suitably used.

  The molecular weight of these film forming resins is preferably in the range of 5,000 to 1,000,000, and more preferably in the range of 50,000 to 800,000 in terms of weight average molecular weight.

  In the organic solution, the content of the resin for forming a film is preferably 0.1 to 10% by weight with respect to 100 parts by weight of the phenol-based solvent and / or fluoroalcohol-based solvent from the viewpoints of coatability and uniformity. Parts, more preferably 0.5 to 5 parts by weight.

  In addition, the adhesive for denture base lining materials of the present invention includes additives such as fillers, colorants, and fragrances for improving applicability to denture bases made of polyamide resin within the range that does not impair the effects of the present invention. May be used in combination.

  The adhesive of the present invention is used for bonding a denture base made of polyamide resin and a lining material. Here, the polyamide resin used as the material for the denture base is not limited as long as it is a known linear polymer in which the main chain is constituted by repeating amide bonds (—CONH—). Includes an aliphatic polyamide compound called nylon containing an aliphatic skeleton and an aramid compound composed only of an aromatic skeleton, and the former nylon compound is preferable as a material for a denture base in terms of flexibility and the like. . Examples of such a nylon compound include nylon 6, nylon 11, nylon 12, nylon 66, and the like. Among these, nylon 12 is preferably used.

  Such a polyamide resin denture base can be used in a well-known manner, but in general, the adhesive material of the present invention is applied to the oral mucosa side of the denture base surfaced with a stamp bar or the like with a brush or brush. After thinly applying and drying, the denture lining material may be stacked, shaped, and then cured.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

  The phenol solvents and / or fluoroalcohol solvents, polymer polymers, polymerizable monomers, polymerization initiators, and reactive cyclohexane-modified (meth) acrylic polymers used in Examples and Comparative Examples are as follows. It is as follows.

(A) Organic solvent <phenolic solvent>
o-Ethylphenol (abbreviated as o-EP) Tokyo Chemicals m-propylphenol (abbreviated as m-PP) Tokyo Chemicals 5-Isopropyl-2-methylphenol (abbreviated as i-PMP) Tokyo Chemical product <Fluoroalcohol solvent>
Hexafluoroisopropanol (abbreviated as HFIP) Tokyo Chemicals Trifluoroethanol (abbreviated as TFE) Tokyo Chemicals <Other organic solvents>
Methylene chloride Tokuyama Corporation Ethyl acetate Wako Pure Chemicals Acetone Wako Pure Chemicals

(B) Radical polymerizable monomer triethylene glycol dimethacrylate (abbreviated as 3G) Trimethylolpropane trimethacrylate (abbreviated as TMPT) Shin-Nakamura Chemical Co., Ltd. Tetramethylolmethane tetramethacrylate (TMMT) Abbreviation) Shinnakamura Chemical Co., Ltd.

(C) radical polymerization initiator benzoyl peroxide (abbreviated as BPO)
1-cyclohexyl-5-ethylpyrimidinetrione (abbreviated as Barbi)

(D) High molecular weight polymer polymethyl methacrylate (Mw = 500,000, abbreviated as PMMA) Sekisui Plastics polyethyl methacrylate (Mw = 500,000, abbreviated as PEMA) Sekisui Chemicals methyl methacrylate-ethyl methacrylate (Mw = 500,000, MMA / EMA molar ratio = 30/70, abbreviated as P (MMA-EMA)). } Sekisui Plastics Further, the reactive siloxane-modified (meth) acrylic polymers used in each example and comparative example are as shown in the following table, and each production example is shown below.

Production 1 <Synthesis of Copolymer a>
Place 25 g of methyl methacrylate, 0.63 g of allyl methacrylate, 0.26 g of azobisisobutyronitrile, and 30 ml of toluene in a flask, and heat and stir to 70 ° C. while bubbling nitrogen, and mix methyl methacrylate and allyl methacrylate. A copolymer having a polymerization ratio of 50: 1 (molar ratio) (weight average molecular weight of 120,000) was obtained.

  Flask with the following chemical formula

27.7g of hydrogen siloxane compound DMS-M20H20 (TSL9586, Toshiba Silicone) shown in Fig. 3, 300ml of toluene, 0.33g of platinum / divinylsiloxane complex solution adjusted to 1000ppm of platinum, and heated to 80 ° C while bubbling nitrogen. , Stir. A solution prepared by dissolving 5 g of a copolymer (weight average molecular weight 120,000) of 50: 1 (molar ratio) of methyl methacrylate and allyl methacrylate synthesized in the above method in 100 ml of toluene is added dropwise over 1 hour. Then, after completion of dropping, the mixture was further heated and stirred for 6 hours, toluene was removed under reduced pressure, excess DMS-M20H20 was washed with a methanol / ethanol mixed solvent, and then filtered and dried to obtain a copolymer (1). . The weight average molecular weight of the obtained polymer was 180,000 as a polystyrene standard.

Production Example 2 <Synthesis of Copolymer b>
Place 25 g of methyl methacrylate, 0.63 g of allyl methacrylate, 0.31 g of azobisisobutyronitrile, and 30 ml of toluene in a flask, and heat and stir at 70 ° C. while bubbling nitrogen, and both methyl methacrylate and allyl methacrylate are mixed. A copolymer having a polymerization ratio of 50: 1 (molar ratio) (weight average molecular weight 100,000) was obtained.

  The following chemical formula

And a copolymer (weight average molecular weight 100000) having a copolymerization ratio of 50: 1 (molar ratio) of methyl methacrylate and allyl methacrylate synthesized by the above method and hydrogen siloxane compound DHS-P30H30 (manufactured by Asmax Co.) shown in FIG. Synthesis was performed in the same manner as the synthesis of copolymer (1) to obtain copolymer (2). The weight average molecular weight of the obtained polymer was 200000 by polystyrene standard.

Production Example 3 <Synthesis of Copolymer c>
Flask 25g methyl methacrylate, chemical formula below

The reactive siloxane compound MTVDS (manufactured by Azmax Co.) shown in 2.3 g, 0.26 g of azobisisobutyronitrile, 30 ml of toluene was added, and the mixture was heated and stirred at 80 ° C. for 5 hours while bubbling nitrogen. . The weight average molecular weight of the obtained copolymer was 100,000 on a polystyrene standard. Moreover, the ¹ H-NMR spectrum of the obtained product is as follows: proton absorption of Si—CH ₃ group at 0.1 ppm, proton absorption derived from acrylic chain at 0.5 to 2.0 ppm, and COO—CH _{3 at} 3.5 ppm. The absorption of double bond protons of Si—CH═CH ₂ group appeared at 5.5 to 6.1 ppm.

  Moreover, the evaluation methods of various physical properties in each example and comparative example are as follows.

(1) Evaluation of adhesion strength between polyamide resin plate and (meth) acrylic lining material Resin plate (10 × 10 × 2 mm) using a denture base material made of polyamide resin (product name: Valplast) ), The resin plate was polished with water-resistant abrasive paper # 320, and then immersed in water for 24 hours was compared with the denture base model to compare the adhesive strength.

  The polyamide plate was taken out of the water, and the surface moisture was wiped off with Kimwipe (manufactured by Crecia) to remove the surface moisture. The prepared adhesive for denture lining material was applied to the polished surface of the Akron plate using a brush, left to dry as it was, and then a double-sided tape with a hole having a diameter of 3 mm was applied to define the adhesion area. After that, the rust-like material obtained by kneading the powder and liquid of the (meth) acrylate-based resin lining material (Tokuyama Co., Ltd., Tokuyama Base II First Type) at the specified kneading ratio, After depositing only the amount to close, an attachment made of methyl methacrylate resin was quickly pressure-bonded, and then the sample was cured under wet conditions at 37 ° C. to obtain an adhesive sample. Thereafter, the adhesive sample was immersed in water at 37 ° C., and the strength was measured after 24 hours. The strength was measured by setting the sample in a tensile tester (manufactured by Shimadzu Corporation, Autograph) and measuring the tensile strength at a crosshead speed of 1 mm / min. In the test, 10 items were measured for one item, and the strength was evaluated by the average value.

(2) Evaluation of Adhesive Strength between Polyamide Resin Plate and Silicone Backing Material As low-temperature curable silicone rubbers cured by a hydrosilylation reaction, the following two types of pastes A and B were prepared. These abbreviations and structures are shown below. These are cured by kneading the same amount to form silicone rubber. The tensile strength of the silicone rubber prepared here is about 2.0 MPa.
A paste:
-Polydivinyldimethylsiloxane (ME91: Toshiba Silicone) 50 parts by weight-Polydivinyldimethylsiloxane (XC86-A9723: Toshiba Silicone) 50 parts by weight-Platinum / vinylsiloxane complex solution (platinum 1000 ppm, Pt / V2) 0.3 parts by weight・ Polymethylsilsesquioxane fine particles (particle size 3 μm, obtained by hydrolyzing methyltrimethoxysilane) 40 parts by weight B paste:
-Polydivinyldimethylsiloxane (ME91: Toshiba Silicone) 50 parts by weight-Polydivinyldimethylsiloxane (XC86-A9723: Toshiba Silicone) 50 parts by weight-Polyhydrogenmethylsiloxane (KF9901, Shin-Etsu Chemical) 2 parts by weight-DMS-M20H20 ( TSL9586, Toshiba Silicone) 7 parts by weight

ここで調製したシリコーンゴムの引張強度は約２．０ＭＰａである。

The tensile strength of the silicone rubber prepared here is about 2.0 MPa.

  Apply the prepared adhesive for denture base lining material to a polyamide plate (Valplast, manufactured by Valplast Co., Ltd.) whose surface has been poured and polished with water-resistant abrasive paper No. 800, and take both A and B pastes in equal amounts and mix well. And placed on an acrylic plate coated with the adhesive. This was allowed to stand at 25 ° C. for 10 minutes to cure the paste, and then the adhesive strength was evaluated.

  After curing, an attempt was made to peel off from the interface between the polyamide plate and the cured silicone rubber with a spatula, and the state of destruction at that time was observed and evaluated. Evaluation points were evaluated in four stages from A to D in accordance with the following determination.

A: Cohesive failure of all silicone rubbers (adhesive force> 2.0 MPa)
B: Mixed failure of cohesive failure and interface failure (adhesive force approximately 2.0 MPa)
C: Interface fracture (adhesive force <2.0 MPa)
D: Interfacial fracture (not bonded at all) (adhesive force of almost 0 MPa)

(3) Permeability Evaluation of Adhesive 5 minutes after applying the prepared denture base lining adhesive to a polyamide resin plate (made by Valplast, Valplast, Inc.) whose surface was poured and polished with No. 800 water-resistant abrasive paper After standing, the surface was observed with a microscope (10 magnifications), and the following classification was performed according to the properties.

    A: An adhesive layer penetrating the entire coated surface is observed.

    B: Although there is some unevenness, an adhesive layer penetrating at 80% or more of the coated surface is observed.

    C: The observed penetrated adhesive layer is less than 80% of the coated surface.

Example 1
An adhesive for a (meth) acrylic resin-based backing material was prepared by mixing with HFIP as a solvent at a compounding ratio shown in Table 1, and evaluation of the adhesive strength between the polyamide resin plate and the (meth) acrylic-based backing material And the applicability of the adhesive was evaluated.

  As shown in Table 1, when the prepared adhesive was applied to a polyamide resin plate, an adhesive layer penetrating the entire surface was observed, and the adhesiveness also showed a high value of 13.4 MPa.

Examples 2-6
Except that the type of solvent was changed to that shown in Table 1, adhesives for (meth) acrylic resin-based lining materials were prepared in the same manner as in Example 1 and tested.

  As shown in Table 1, an adhesive layer penetrating the entire surface of the polyamide resin plate was observed for any adhesive, and both showed high adhesive strength.

Examples 7-15
Except having changed the kind of adhesive component into what was shown in Table 1, the adhesive agent for (meth) acrylic-type lining materials was prepared similarly to Example 1, and each tested.

  As shown in Table 1, an adhesive layer penetrating the entire surface of the polyamide resin plate was observed for any adhesive, and both showed high adhesive strength.

Examples 16-21
Except for changing the blending amounts of the adhesive components as shown in Table 1, adhesives for (meth) acrylic resin-based lining materials were prepared in the same manner as in Example 1 and tested.

  As shown in Table 1, an adhesive layer penetrating the entire surface of the polyamide resin plate was observed with any adhesive. Moreover, although the adhesive force was somewhat varied depending on the blending amount, all showed good adhesiveness.

Comparative Examples 1-3
Except that the solvent type was changed to a type other than the phenolic solvent and / or fluoroalcohol solvent, the adhesive for the (meth) acrylic resin backing material was prepared in the same manner as in Example 1, and the test was performed for each. went.

  As shown in Table 1, almost no adhesive layer permeating the polyamide resin plate was observed with any adhesive, and the result was that the adhesive layer hardly adhered.

Example 22
The adhesive for silicone backing material is prepared by mixing with HFIP as a solvent at the blending ratio shown in Table 2, evaluation of the adhesive strength between the polyamide resin plate and the silicone backing material, and the applicability of the adhesive Evaluation was performed.

  As shown in Table 2, when the prepared adhesive was applied to a polyamide resin plate, an adhesive layer penetrating the entire surface was observed. Further, regarding the adhesion evaluation, all the silicone rubbers on the adhesion interface by the peeling test showed cohesive failure, and it was shown that the silicone rubber had high adhesion.

Examples 23-27
Except having changed the kind of solvent into what was shown in Table 2, the adhesive agent for silicone type backing materials was prepared similarly to Example 22, and each test was done.

  As shown in Table 2, although the adhesiveness slightly varied depending on the type of solvent, all showed good adhesiveness.

Examples 28-31
Except having changed the kind of adhesive component into what was shown in Table 2, the adhesive agent for silicone type lining materials was prepared similarly to Example 22, and each test was done.

  As shown in Table 2, an adhesive layer penetrating the entire surface of the polyamide resin plate was observed for any adhesive, and it was found that both showed good adhesiveness.

Examples 32-37
Except having changed the compounding quantity of the adhesive component as shown in Table 2, the adhesives for silicone backing materials were prepared in the same manner as in Example 22 and tested.

  As shown in Table 2, an adhesive layer penetrating the entire surface of the polyamide resin plate was observed with any adhesive. Moreover, although some dispersion | variation was seen by the compounding quantity about the adhesiveness, all showed favorable adhesiveness.

Comparative Examples 4-6
A silicone-based backing material adhesive was prepared in the same manner as in Example 22 except that the solvent type was changed to a type other than the phenol-based solvent and / or fluoroalcohol-based solvent, and each test was performed.

  As shown in Table 2, the adhesive layer that permeated the polyamide resin plate was hardly observed with any adhesive material, and further, the adhesive layer was hardly adhered.

Claims (4)

An adhesive for a lining material for a denture base made of polyamide resin,
In the adhesive for denture base lining materials , the adhesive component for the curable composition constituting the lining material comprises an organic solution dissolved in a phenolic solvent and / or a fluoroalcohol solvent ,
The curable composition constituting the lining material is a silicone-based curable composition that is cured by a hydrosilylation reaction,
The adhesive component dissolved in the organic solution is a (meth) acrylic polymer modified with a siloxane having a reactive group for hydrosilylation reaction, and the (meth) acrylic polymer is (meth) acrylic A random copolymer of a structural unit A based on an unmodified product of polysiloxane having a reactive functional group for hydrosilylation reaction in a system polymerizable monomer, and a structural unit B based on the modified product,
The structural unit A has the following formula (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 13 carbon atoms or an aryl group having 6 to 14 carbon atoms)
On the other hand,
The structural unit B is
The following formula (2a) or (2b)

(Wherein R ³ represents a hydrogen atom or a methyl group, R ^{4 to} R ¹⁵ each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms, and Y represents a main chain) C1-C18 bivalent organic residue which may have an ether bond or an ester bond, a-c shows the average number of repeating units, a is 1, b is 1-100, c is 0 To 100, and 10 ≦ b + c ≦ 100, 0 ≦ c / b ≦ 10)
A Si—H group-containing structural unit represented by:
Following formula (3)

(Wherein R ¹⁶ represents a hydrogen atom or a methyl group, R ^{17 to} R ¹⁹ each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms, and Y represents a main chain) A C1-C18 divalent organic residue which may have an ether bond or an ester bond, m represents the average number of repeating units, is 1 to 100, and n is 1, 2, or 3. )
Consisting of a structural unit selected from unsaturated carbon double bond-containing structural units represented by
The phenol solvent is m-cresol, o-ethylphenol, m-ethylphenol, o-propylphenol, m-propylphenol, p-propylphenol, o-isopropylphenol, m-isopropylphenol, 5-isopropyl-2. A solvent selected from methylphenol, 2-methoxy-4-ethylphenol, 2-methoxy-4-propylphenol, and 2-methoxy-4- (2-oxopropyl) phenol;
Denture base lining, wherein the fluoroalcohol solvent is a solvent selected from 1,1,1,3,3,3-hexafluoroisopropanol, 1,1,1-trifluoroethanol, and 3-trifluoromethylphenol Adhesive for equipment. The phenol solvent is a solvent selected from o-ethylphenol, m-propylphenol, and 5-isopropyl-2-methylphenol;
  The denture base lining according to claim 1, wherein the fluoroalcohol solvent is a solvent selected from 1,1,1,3,3,3-hexafluoroisopropanol and 1,1,1-trifluoroethanol. Adhesive for materials. The modified siloxane having a reactive functional group of the hydrosilylation reaction (meth) acrylic polymer is, in the structural unit A / (structural unit A + structural unit B) = 99.9 to 10% units ratio of The adhesive for denture base lining materials according to claim 1 or 2 , which is copolymerized. The denture base according to any one of claims 1 to 3, wherein the solvent is a solvent selected from 1,1,1,3,3,3-hexafluoroisopropanol and 1,1,1-trifluoroethanol. Adhesive for lining materials.