JP2016053158A - Bonding method, orthoprosthesis material and producing method of orthoprosthesis material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bonding method achieving high adhesiveness between a polymer material having a diaryl ketone group and a curable composition containing a radical polymerizable monomer.SOLUTION: A bonding method at least includes: a reducing step of reacting polymer material having a diaryl ketone group with a reducing agent; a curable composition grant step of granting a curable composition to the surface of the polymer member having a diaryl ketone group after the reducing step; and a curing step of curing the curable composition.SELECTED DRAWING: None

Description

  The present invention relates to an adhesion method for adhering a polymer material having a diaryl ether ketone group and a curable composition containing a radical polymerizable monomer, a dental prosthesis material, and a method for producing the dental prosthesis material.

  Super engineering resins are used in a wide range of applications such as electric / electronic field, aerospace field, automobile industry, medical field, general industrial field and so on. Among these super engineering resins, in particular, polyaryl ether ketone resins, which are polymers having diaryl ketone groups, are expected to be used in various fields because they have excellent chemical properties and physical properties.

  For example, in the field of dental treatment, a technique using this polyaryl ether ketone resin as a dental material has been proposed (for example, Patent Document 1). When using a polyaryl ether ketone resin as a dental material, it is necessary to firmly bond it to a tooth or other types of dental materials. Various techniques have been proposed as a technique for adhering such a member containing a polyaryletherketone resin and a member such as a tooth or other type of dental material (for example, Patent Document 2, Non-Patent Document). 1-2).

  However, since this polyaryl ether ketone resin has high chemical stability on its surface, it is generally difficult to bond it to other materials. In general, welding or adhesion with an epoxy material is often performed. In addition, studies are being made to modify the surface of the polyaryletherketone resin material to increase its adhesion. For example, Patent Document 3 proposes a technique of using an epoxy adhesive or an epoxy primer after plasma processing.

  Here, as the curable composition, a radical polymerizable curable composition is widely used because of its high polymerization rate and easy production of a high-strength cured product. Used in agents, coating agents, sealing materials, paints, etc. For example, radically polymerizable curable compositions are widely used in dental applications, and adhesive compositions for bonding dental members to each other or between dental members and teeth (dental cement, dental bonding materials, etc.) In addition, dental restoration applications (such as dental composite resins) and dental prostheses and dentures (such as dental hard resins and dental immediate polymerization resins) are used.

  By bonding these radical polymerizable curable composition and the polyaryletherketone resin material, various useful members can be produced. Therefore, there is a demand for a technique that can obtain higher adhesion between a polymer having a diaryl ketone group such as a polyaryl ether ketone resin and a radical polymerizable curable composition.

  In addition, since the polyaryl ether ketone resin has high chemical stability on the surface as described above, the affinity and reactivity with other substances are low. For this reason, in addition to techniques for bonding, studies are being made to modify the surface for the purpose of introducing functional groups. For example, a method of generating a hydroxyl group on the surface of a polyaryletherketone resin by a reduction reaction is known. For example, Non-Patent Document 3 describes a method in which a carbonyl group on the surface of a polyether ether ketone resin is reduced to a hydroxyl group using sodium borohydride which is a hydride reducing agent. However, an example in which an adhesive or a radically polymerizable composition is applied to a polyaryl ether ketone resin material reduced by a reducing agent is not known. In addition, there is no known example in which a reduced polyaryl ether ketone resin material is used as a dental material.

JP 2013-144778 A Special table 2010-521257 JP-A-5-177714

DENTAL MATERIALS 26 (2010) 553-559 DENTAL MATERIALS 28 (2012) 1280-1283 Macromolecules 30 (1997) 540-548

  As described above, when a polymer material having a diaryl ketone group, in particular, a polyaryl ether ketone resin material is used, adhesion becomes a problem.

  Therefore, in the present invention, high adhesiveness is obtained between the polymer material having a diaryl ketone group, particularly a polyaryl ether ketone resin material, by performing a simple and appropriate treatment to the radical polymerizable curable composition. It is aimed at things. That is, it is suitably used for a technique for adhering a polymer material having a diaryl ketone group, particularly a polyaryl ether ketone resin material, and a curable composition containing a radical polymerizable monomer, and for a dental prosthesis. It is an object of the present invention to provide a polymer material having a diaryl ketone group and a method for producing the same.

  In order to solve the above-mentioned problem, the inventors have conducted intensive studies. As a result, a product obtained by reducing a diaryl ketone group on the surface of a polymer material having a diaryl ketone group by a specific treatment contains a radical polymerizable monomer. The present invention has been found to have good adhesiveness with the curable composition to be obtained.

  That is, the present invention provides a curable composition containing a radical polymerizable monomer and a polymer material having a diaryl ketone group, and a reduction step and a reduction step in which the polymer material having a diaryl ketone group and a reducing agent are reacted. A diaryl ketone comprising at least a curable composition applying step for applying the curable composition to a surface of a polymer member having a diaryl ketone group that has undergone a curing process, and a curing step for curing the curable composition. This is a method for bonding a polymer material having a group and a curable composition. It is particularly preferable to use a hydride reducing agent as the reducing agent. The reduction reaction is particularly preferably performed in the range of 60 ° C to 180 ° C. The radical polymerizable monomer contained in the curable composition preferably has a (meth) acryloyl group as a polymerizable functional group. The curable composition containing a polymer material having a diaryl ketone group and a radical polymerizable monomer used in the adhesion method is preferably dental.

Another embodiment of the present invention is a method for producing a dental prosthetic material, comprising a step of reacting a polymer material having a diaryl ketone group with a reducing agent.
Another embodiment of the present invention is a dental prosthesis material containing a polymer material having a diaryl ketone group, wherein the number of diaryl ketone sites on the surface of the polymer material is a, and the number of diarylmethanol sites is b. The dental prosthesis material is characterized in that 100 × b / (a + b) is 10 to 90.

  ADVANTAGE OF THE INVENTION According to this invention, high adhesiveness can be acquired in adhesion | attachment of the curable composition containing the polymer material which has a diaryl ketone group, and a radically polymerizable monomer.

  The polymer material having a diaryl ketone group of the present invention is a diaryl ketone group, that is, a functional group in which two aryl groups (which may independently have any functional group) are bonded to a carbon atom of a carbonyl group. Is a material containing 20% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more of a polymer having a repeating unit in addition to a material consisting only of a polymer having a diaryl ketone group. A material in which other resin is blended with a polymer having a polymer, a composite material in which a polymer having a diaryl ketone group or a polymer having a diaryl ketone group and another resin is blended with a filler using a resin matrix (hereinafter referred to as a resin matrix) The composite material is a polyaryl ether ketone resin composite material and Referred to), and the like. Moreover, you may add trace components, such as a pigment and a stabilizer, to these materials.

  As the polymer having a diaryl ketone group, the diaryl ketone group is preferably present in the main chain, and a polyaryl ether ketone resin is preferable from the viewpoint of strength and the like.

  The polyaryl ether ketone resin is a thermoplastic resin containing at least an aromatic group, an ether group (ether bond) and a ketone group (ketone bond) as its structural unit. In many cases, a phenylene group has an ether group and a ketone group. It has a linear polymer structure bonded through each other. Representative examples of the polyaryl ether ketone resin include polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ketone ether ketone ketone (PEKEKK) and the like. The aromatic group constituting the structural unit of the polyaryl ether ketone resin may have a structure having two or more benzene rings such as a biphenyl structure. In addition, the structural unit of the polyaryl ether ketone resin may contain a sulfonyl group or another monomer unit that can be copolymerized.

  The other resin that can be blended with the polymer having a diaryl ketone group is not particularly limited as long as it does not significantly deteriorate the physical properties of the polymer having a diphenyl aryl ketone group such as rigidity and toughness. Examples include polyarylate, polycarbonate, polyethylene terephthalate, polyphthalamide, polytetrafluoroethylene, and polyphenylene ether. When a polymer (resin) having a diaryl ketone group and another resin are blended, the polymer having a diaryl ketone group is preferably 50% by mass or more, more preferably 70% by mass or more of the total resin, 90 More preferably, it is more than 99 mass%, and more preferably more than 99 mass%.

  As the filler that can be blended in the polymer having a diaryl ketone group of the present invention, known fillers can be used without particular limitation, but inorganic fillers are suitable. For example, the filler material is silica glass, borosilicate glass, soda glass, aluminosilicate glass, and fluoroaluminosilicate glass, glass containing heavy metals (eg, barium, strontium, zirconium); Glass ceramics such as crystallized glass on which crystals such as crystallized glass, diopside, and leucite are deposited; composite inorganic oxides such as silica-zirconia, silica-titania, silica-alumina; or composite oxides thereof And oxides obtained by adding a group I metal oxide to the above; metal inorganic oxides such as silica, alumina, titania, zirconia; and the like.

  Curing which gives a curable composition containing a radically polymerizable monomer on the surface of a polymer member having a diaryl ketone group that has undergone a reduction step, a reduction step of reacting a polymer material having a diaryl ketone group and a reducing step of the present invention. The mechanism of action by which high adhesiveness can be obtained by an adhesion method that includes at least the curing composition-imparting step and the curing step of curing the postponed curable composition is not necessarily clear, but is presumed as follows.

  That is, by reacting the surface of a polymer material having a diaryl ketone group with a reducing agent, the carbonyl group of the polymer having a diaryl ketone group is reduced to a hydroxyl group. By reduction to a hydroxyl group, a carbon atom having two arylene groups, a hydroxyl group, and a hydrogen atom as substituents is present on the surface of the polymer material having a diaryl ketone group. Since this carbon atom has a structure that easily generates radicals, a curable composition containing a radical polymerizable monomer is provided, and when the radical polymerizable monomer is cured by radical polymerization, the carbon atom A reaction occurs between the monomer and the radically polymerizable monomer, and a bond can be formed. As a result, a chemical bond is generated between the polymer material having a diaryl ketone group and the composition containing the radical polymerizable monomer imparted thereon, and it is assumed that high adhesiveness can be obtained.

  As a reducing agent for reacting such a polymer material having a diaryl ketone group, any reducing agent capable of reducing a carbonyl group to a hydroxyl group can be used without particular limitation, but a hydride reducing agent can be used from the viewpoint of its reactivity. Something is preferable. A hydride reducing agent is a reducing agent that reduces a carbonyl group to a hydroxyl group by nucleophilic attack by generating a highly nucleophilic hydride ion. Examples of the hydride reducing agent include sodium borohydride, sodium cyanoborohydride, sodium triethylborohydride, lithium triethylborohydride, lithium tri (sec-butyl) borohydride, trihydride (sec -Butyl) potassium boron, lithium borohydride, zinc borohydride, sodium acetoxyborohydride, lithium aluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, diisobutylaluminum hydride, diborane, borane / tetrahydrofuran complex , Borane / dimethyl sulfide complex, borane / trimethylamine complex, trimethylsilane and the like. From the viewpoint of ease of handling, sodium borohydride, sodium cyanoborohydride and sodium bis (2-methoxyethoxy) aluminum hydride are preferable, and sodium borohydride is most preferable.

  The method for reducing the polymer material having a diaryl ketone group with a reducing agent is not particularly limited. For example, a method in which a polymer material having a diaryl ketone group is added to a solution in which the reducing agent is dissolved and heated, and the reducing agent is dissolved. Examples thereof include a technique in which a polymer material having a diaryl ketone group is immersed in the solution and then taken out and heated, and a technique in which a solution in which a reducing agent is dissolved is applied to the surface of the polymer material having a diaryl ketone group and heated. Among these methods, a solution in which a reducing agent is dissolved is applied to the surface of a polymer material having a diaryl ketone group and heated, for example, because it can be easily carried out or only a desired deposition surface can be reduced. The technique of doing is preferable. When the surface other than the desired surface is reduced, the surface reacted with the reducing agent has improved hydrophilicity compared to the non-reduced surface. A method capable of reducing only the salt is preferable.

  The solvent of the solution in which the reducing agent is dissolved is not particularly limited as long as the reaction proceeds. For this reason, it is sufficient if the amount of reducing agent necessary for the reaction can be dissolved and the reducing agent is not deactivated or does not inhibit the function of the reducing agent. Examples of such solvents are dimethyl sulfoxide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, n-pentane, n-hexane, cyclohexane, n-heptane, benzene, toluene, xylene. , Mesitylene, dichloromethane, chloroform, 1,2-dichloroethane, diethyl ether, dibutyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether , Diethylene glycol butyl methyl ether, tripropylene glycol di Such as chill ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, t-butyl methyl ether, dioxane, acetonitrile, propionitrile, etc. Can be mentioned.

  In the case of a method in which a solution in which a reducing agent is dissolved is applied to a polymer material having a diaryl ketone group and heated, in order for the reaction to proceed appropriately, if the solvent quickly evaporates during heating, Since the field is lost and the reaction efficiency is lowered, it is preferable that the solvent has a high boiling point. In addition, the amount of solution that can be applied in one operation is limited, and it is not preferable from the viewpoint of work efficiency to apply a solution having a low concentration of reducing agent in a plurality of times in order to obtain a necessary amount of reducing agent. Therefore, it is desirable to use a solvent in which the amount of reducing agent dissolved is high. Therefore, it is particularly preferable to use dimethyl sulfoxide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone or the like as the solvent for dissolving the reducing agent, and dimethyl sulfoxide is most preferable.

  When the reducing agent is dissolved in a solvent, the concentration of the reducing agent is preferably higher in order to sufficiently proceed with the reaction, preferably 0.1 mol / l or more, more preferably 0.5 mol / l or more. . However, when the reducing agent is not completely dissolved, especially when a solvent in which the reducing agent is dissolved is applied to a polymer material having a diaryl ketone group, the polymer having a diaryl ketone group is added by the undissolved reducing agent. There is a possibility that a reducing agent layer is formed on the surface of the material and the reaction efficiency is lowered. The step of applying the solvent in which the reducing agent is dissolved to the polymer material having a diaryl ketone group may be performed while the polymer material having the diaryl ketone group or the reducing agent solution is warmed. It is preferable to carry out at a temperature of from 35C to 35C, more preferably from 17C to 28C. For this reason, the reducing agent is preferably completely dissolved in the solvent at 10 ° C. to 35 ° C., more preferably completely dissolved in the solvent at 17 ° C. to 28 ° C.

  Further, when the reducing agent is dissolved in a solvent, it becomes difficult to completely dissolve the reducing agent when used in a large amount. In addition, even if it is completely dissolved during coating, a reducing agent may be deposited on the surface of the polymer material having a diaryl ketone group after coating, or a large amount of reaction residue may be deposited during the reaction. There is a risk of affecting the reduction reaction. Therefore, the reducing agent is preferably 30 mol / l or less, more preferably 10 mol / l or less, and most preferably 5.0 mol / l or less.

  The solution in which the reducing agent is dissolved has a viscosity adjusting filler, a color adjusting colorant, a stabilizer for improving storage stability, and a pH adjusting agent as long as the reduction reaction is not greatly affected. You may add arbitrary components, such as.

  The temperature at which the reduction reaction is performed is not particularly limited as long as the reduction reaction occurs, but is preferably 60 ° C to 180 ° C, more preferably 90 ° C to 150 ° C. When reacting at low temperatures, the reaction efficiency is usually low and the reaction does not proceed sufficiently to contribute to improved adhesion, or it takes a long time to proceed sufficiently or the reaction must be performed in multiple steps. There is a risk of having to. When the reaction temperature is high, the polymer material having a diaryl ketone group may be deteriorated in strength or discolored.

  The heating method is not particularly limited as long as a reaction occurs and the physical properties of the polymer material having a diaryl ketone group are not significantly deteriorated. In the case of a technique in which a solution in which a reducing agent is dissolved is applied to a polymer material having a diaryl ketone group and heated, for example, the reducing agent is dissolved on a desired surface of the polymer material having a diaryl ketone group that has been formed into a desired shape. After applying the solution, it can be performed by a method of leaving it in an oven maintained at a predetermined temperature. This method can be mentioned as a preferred method because the reduction reaction can be carried out easily and heating can be performed uniformly.

  By reacting the polymer material having a diaryl ketone group with a reducing agent, the carbonyl group on the surface of the polymer material having a diaryl ketone group is reduced to generate a hydroxyl group. Confirmation of the progress of this reaction can be easily performed by infrared spectroscopy. In addition, the progress of the reaction near the surface, which is strongly involved in adhesion, can be confirmed by infrared spectroscopy.

In infrared spectroscopy, a peak derived from a carbonyl group that appears in the vicinity of 1650 cm ⁻¹ when a polymer material having a massive diaryl ketone group is measured by a single reflection ATR method using a Fourier transform infrared spectrophotometer. the peak area (ν1650cm ^-1) and 1490cm ^-1 aromatic ring of the peak area of the peak appearing in the vicinity (ν1490 ^-1) peak area ratio of (ν1650cm ^-1 / ν1490cm ^-1), when compared with before and after reduction, Since the aromatic ring is not changed by the reduction reaction, the reaction rate of the carbonyl group is required. That is, when the peak area ratio before the reduction reaction is νb and the peak area ratio after the reduction reaction is νa, the following general formula (I) is the reaction rate obtained by infrared spectroscopy.

Reaction rate R _IR [%] = 100− (νa / νb × 100) (I)
In this reaction, since the carbonyl group is reduced to form a hydroxyl group, there is a correlation between the reaction rate of the carbonyl group and the degree of hydroxyl group generation.

Since R _IR is taking place hydroxyl generation is much higher, it is advantageous for the adhesive. The value of _RIR is preferably 10% or more, more preferably 30% or more.

  High adhesion by applying a curable composition containing a radical polymerizable monomer to the surface of a polymer member obtained by reacting a polymer material having a diaryl ketone group and a reducing agent as described above and curing You can get sex. This is on the carbon atom adjacent to the hydroxyl group formed on the surface of the polymer material having a diaryl ketone group obtained by reacting with the reducing agent, that is, on the carbon atom having two arylene group, hydroxyl group and hydrogen atom as substituents. Because radicals are easily generated by hydrogen abstraction, when the attached radical polymerizable monomer is cured, the radical polymerizable property laminated with the carbon atom adjacent to the hydroxyl group formed on the polymer surface having a diaryl ketone group. A bond is formed with the monomer. As a result, it is speculated that high adhesiveness can be obtained.

  As the curable composition to be applied to the surface of the polymer member obtained by reacting the polymer material having a diaryl ketone group and the reducing agent as described above, those containing a radical polymerizable monomer can be used without any particular limitation. .

  Since the curable composition usually has low consistency and can be easily deformed at first, it can be polymerized and cured after it is transformed into a desired shape and placed at a desired location. Radical polymerizable curable compositions containing radical polymerizable monomers are used in, for example, adhesive compositions, dental materials, adhesives, coating agents, sealing materials, paints, and the like.

As the radically polymerizable monomer contained in the curable composition, known ones can be used without particular limitation. The polymerizable functional group of the radically polymerizable monomer includes functional groups such as vinyl group, styryl group, allyl group, (meth) acryloyl group from the viewpoint of low biotoxicity and high polymerization activity. A (meth) acryloyl group is particularly preferred from the viewpoint of polymerization rate and biosafety. In general, examples of the radically polymerizable monomer preferably used include those shown in the following (I) to (IV).
(I) Monofunctional radically polymerizable monomer Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, 2-methacryloyloxyethyl dihydrogen phosphate, 6-methacryloyloxyhexyl dihydrogen Methacrylates such as phosphate, 10-methacryloyloxyhexyl dihydrogen phosphate, and acrylates corresponding to these methacrylates

(II) Bifunctional radically polymerizable monomer 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, 2,2- Bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4- Methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxy) Citriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytriethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-Methacryloyloxyisopropoxyphenyl) propane, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4 -Butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, glycerin dimethacrylate Bis (2-methacryloyloxyethyl) hydrogen phosphate, bis (6-methacryloyloxyhexyl) hydrogen phosphate and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro Methacrylates such as 2-hydroxypropyl methacrylate or vinyl monomers having —OH groups such as acrylates corresponding to these methacrylates, and diisocyanate methylbenzene, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate Methylcyclohexane, isophorone diisocyanate, methylenebis (4-cyclohex Diadducts obtained from adducts with diisocyanate compounds such as 1,2 bis (3-methacryloyloxy-2-hydroxypropoxy) ethyl, 1,6-bis (methacryloylethyloxycarbonylamino) 2,2 , 4-trimethylhexane and the like.

(III) Trifunctional radically polymerizable monomer: Methacrylates such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, and acrylates corresponding to these methacrylates.

(IV) Tetrafunctional radically polymerizable monomer Pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate and diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), Diaducts obtained from adducts of diisocyanate compounds such as 4,4-diphenylmethane diisocyanate and tolylene-2,4-diisocyanate and glycidol dimethacrylate.

  These (meth) acrylate radically polymerizable monomers may be used in combination of a plurality of types as required. Moreover, you may use radically polymerizable monomers other than the said (meth) acrylate type monomer.

  As the radical polymerizable monomer, it is preferable to use a radical polymerizable monomer having two or more polymerizable functional groups in the molecule at least 50% by mass of the total polymerizable monomer. By using a radically polymerizable monomer having two or more polymerizable functional groups in the molecule, the polymer can form a network structure, and the strength of the cured curable composition is increased. The strength of the cured product of the curable composition is high, and in particular, the strength of the cured product of the curable composition in the vicinity of the interface with the polymer material having a diaryl ketone group is advantageous for obtaining high adhesiveness. is there.

  As the radical polymerizable monomer, a radical polymerizable monomer having a hydroxyl group is preferably used in an amount of 30% by mass or more, more preferably 50% by mass or more of the total polymerizable monomers. By using a radically polymerizable monomer having a hydroxyl group, the affinity between the polymer material having a diaryl ketone group in which the hydroxyl group is generated by the reduction reaction and the curable composition is improved, and the adhesiveness is improved. The hydroxyl group contained in the radical polymerizable monomer is more preferably an alcoholic hydroxyl group.

  Any method may be used for the curing step of the curable composition, and it is generally performed by blending a polymerization initiator into the curable composition and activating it at an arbitrary timing. In addition, when the curable composition is a primer-type curable composition containing no polymerization initiator (hereinafter sometimes referred to as “primer”), the primer is added to a polymer material having a diaryl ketone group that has undergone a reduction process. After that, a composition containing a radically polymerizable monomer and a polymerization initiator (hereinafter sometimes referred to as “second curable composition”) is further provided, and this second curable composition is added. The primer may be polymerized and cured at the same time when the product is polymerized and cured. However, when the conditions other than the presence or absence of the polymerization initiator in the curable composition (such as the composition of the radical polymerizable monomer) are the same, the curable composition containing the polymerization initiator is more adhesive than the primer. It becomes easier to increase the strength of the layer of the curable composition in the vicinity of the interface, and higher adhesiveness is easily obtained.

  When the curable composition contains a polymerization initiator, a photopolymerization initiator, a chemical polymerization initiator or a thermal polymerization initiator can be used as the polymerization initiator, and two or more polymerization initiators can be used in combination. You can also. It should be noted that a photopolymerization initiator and / or a chemical polymerization initiator should be used because it can be easily carried out when the curable composition is cured after application to a polymer material having a diaryl ketone group that has undergone a reduction process. Is preferred. Hereinafter, these three kinds of polymerization initiators will be described in more detail.

  As the photopolymerization initiator, known ones can be used without any limitation. Representative photopolymerization initiators include a combination of α-diketone and tertiary amine, a combination of acylphosphine oxide and tertiary amine, a combination of thioxanthone and tertiary amine, α-aminoacetophenone And photopolymerization initiators such as combinations of amines and tertiary amines, combinations of aryl borates and photoacid generators.

  Examples of various compounds suitably used for the above various photopolymerization initiators include camphorquinone, benzyl, α-naphthyl, acetonaphthene, naphthoquinone, p, p′-dimethoxybenzyl, p, p. Examples include '-dichlorobenzylacetyl, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, and 9,10-phenanthrenequinone.

  Tertiary amines include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N , N-diethyl-p-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethyl Aminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylanthranilic acid methyl ester, N, N-dihydroxyethylaniline, N, N-dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol p-dimethylaminostilbene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine, tributylamine, tripropylamine , Triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate, N, N- Examples include diethylaminoethyl methacrylate and 2,2 ′-(n-butylimino) diethanol. These can be used individually or in mixture of 2 or more types.

  Acylphosphine oxides include benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5, Examples include 6-tetramethylbenzoyldiphenylphosphine oxide.

  Examples of thioxanthones include 2-chlorothioxanthone and 2,4-diethylthioxanthone.

  Examples of α-aminoacetophenones include 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -butanone-1,2. -Benzyl-dimethylamino-1- (4-morpholinophenyl) -propanone-1,2-benzyl-diethylamino-1- (4-morpholinophenyl) -propanone-1,2-benzyl-dimethylamino-1- ( 4-morpholinophenyl) -pentanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -pentanone-1, and the like.

  The photopolymerization initiators may be used alone or in combination of two or more.

  The chemical polymerization initiator is a polymerization initiator that is composed of two or more components and generates polymerization active species near room temperature by mixing all the components immediately before use. Such chemical polymerization initiators are typically amine compound / organic peroxide type. Specific examples of the amine compound include aromatic amine compounds such as N, N-dimethyl-p-toluidine, N, N-dimethylaniline, and N, N-diethanol-p-toluidine.

  Representative organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, diaryl peroxides, and the like.

  Specific examples of organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanoperoxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide.

  Peroxyketals include 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t- Butylperoxy) 3,3,5-trimethylcyclohexanone, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclodecane, 2,2-bis (t-butyl Peroxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane and the like.

  Hydroperoxides include P-methane hydroperoxide, diisopropylbenzene peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydro A peroxide etc. are mentioned.

  Dialkyl peroxides include α, α-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, and t-butylcumi. Examples include ruperoxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane-3, and the like.

  Diacyl peroxides include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, succinic acid peroxide. Examples thereof include oxides, m-toluoyl benzoyl peroxide, and benzoyl peroxides.

  Peroxydicarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di- Examples include 2-ethylhexyl peroxydicarbonate, di-2-methoxybutyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, and the like.

  Peroxyesters include α, α-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1- Cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, , 1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethyl Peroxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate , T-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3.5 , 5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylper Oxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate , T-butylperoxybenzoate, bis ( - butylperoxy) isophthalate.

  Further, t-butyltrimethylsilyl peroxide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and the like can also be used as suitable organic peroxides.

  The organic peroxide to be used may be appropriately selected and used, and it may be used alone or in combination of two or more. Among them, hydroperoxides, ketone peroxides, peroxyesters and diacyl Peroxides are particularly preferred from the viewpoint of polymerization activity. Furthermore, among these, it is preferable to use an organic peroxide having a 10-hour half-life temperature of 60 ° C. or higher from the viewpoint of storage stability of the curable composition.

  A system obtained by further adding a sulfinic acid such as benzenesulfinic acid, p-toluenesulfinic acid and its salt to an initiator system comprising the organic peroxide and the amine compound, and a barbituric acid system such as 5-butylbarbituric acid Even if an initiator is blended, it can be used without any problem.

  Also included are transition metal compound / organic peroxide based chemical polymerization initiators. Specific examples of the transition metal compound include divanadium tetroxide (IV), vanadium oxide acetyl acetate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl-1, 3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium oxide (V), sodium metavanadate (V), vanadium compounds such as ammonium metavanadate (V), scandium iodide ( Scandium compounds such as III), titanium compounds such as titanium (IV) chloride, titanium (IV) tetraisopropoxide, chromium compounds such as chromium (II) chloride, chromium (III) chloride, chromic acid, chromate, acetic acid Manganese compounds such as manganese (II) and manganese (II) naphthenate, Iron compounds such as iron (II) acid, iron (II) chloride, iron (III) acetate, iron (III) chloride, cobalt compounds such as cobalt (II) acetate and cobalt (II) naphthenate, nickel (II) chloride Nickel compounds such as copper chloride (I), copper bromide (I), copper chloride (II), copper compounds such as copper (II), zinc compounds such as zinc chloride (II) and zinc acetate (II) Illustrated. Among these transition metal compounds, + IV and / or + V vanadium compounds are preferably used because high adhesiveness is easily obtained. Examples of the organic peroxide include those exemplified above.

  An aryl borate compound / acidic compound polymerization initiator that utilizes the fact that an aryl borate compound is decomposed by an acid to generate a radical can also be used.

  The aryl borate compound is not particularly limited as long as it is a compound having at least one boron-aryl bond in the molecule, and known compounds can be used, but among them, three in one molecule are considered in view of storage stability. Alternatively, an aryl borate compound having four boron-aryl bonds is preferably used, and an aryl borate compound having four boron-aryl bonds is more preferable from the viewpoint of easy handling, synthesis, and availability.

  As aryl borate compounds having three boron-aryl bonds in one molecule, monoalkyltriphenylboron, monoalkyltris (p-chlorophenyl) boron, monoalkyltris (p-fluorophenyl) boron, monoalkyltris (3 , 5-bistrifluoromethyl) phenyl boron, monoalkyltris [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, monoalkyltris (P-nitrophenyl) boron, monoalkyltris (m-nitrophenyl) boron, monoalkyltris (p-butylphenyl) boron, monoalkyltris (m-butylphenyl) boron, monoalkyltris (p-butyloxyphenyl) ) Boron, monoalkyltris (m-buty Oxyphenyl) boron, monoalkyltris (p-octyloxyphenyl) boron, monoalkyltris (m-octyloxyphenyl) boron (wherein alkyl is n-butyl, n-octyl or n-dodecyl in any compound) Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, tributylamine salt, triethanolamine salt, methylpyridinium salt, ethylpyridinium salt, Examples thereof include butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, and butylquinolinium salt.

  As aryl borate compounds having four boron-aryl bonds in one molecule, tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl) phenyl Boron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis (m- Nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis (p-octyloxyphenyl) ) Boron, Tetrakis (m- Octyloxyphenyl) boron (wherein alkyl represents any of n-butyl, n-octyl or n-dodecyl in any compound), sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt Tetramethylammonium salt, tetraethylammonium salt, tributylamine salt, triethanolamine salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, etc. Can be mentioned.

  Two or more of the various aryl borate compounds exemplified above may be used in combination. It is also preferable to use an organic peroxide and / or a transition metal compound in combination with the above-described aryl borate compound / acidic compound polymerization initiator. The organic peroxide is as described above. The transition metal compound is preferably a + IV and / or + V vanadium compound. Specific examples of the + IV and / or + V vanadium compounds include divanadium tetraoxide (IV), vanadium oxide acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis ( 1-phenyl-1,3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), ammon metavanadate (V), etc. A vanadium compound is mentioned.

  Examples of the thermal polymerization initiator include benzoyl peroxide, p-chlorobenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydicarbonate, and diisopropyl peroxydicarbonate. Peroxide, azo compounds such as azobisisobutyronitrile, tributylborane, tributylborane partial oxide, sodium tetraphenylborate, sodium tetrakis (p-fluorophenyl) borate, tetraphenylborate triethanolamine salt, etc. Boron compounds, 5-barbituric acid, barbituric acids such as 1-benzyl-5-phenylbarbituric acid, sulfinates such as sodium benzenesulfinate, sodium p-toluenesulfinate, and the like.

  The blending amount of these polymerization initiators is preferably in the range of 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the polymerizable monomer. When the amount of the polymerization initiator is less than 0.01 parts by mass, the curing of the curable composition becomes insufficient and the adhesiveness tends to decrease particularly immediately after curing. On the other hand, when the polymerization initiator exceeds 10 parts by mass, the cured product strength of the curable composition is lowered particularly at the bonding interface portion, and the adhesiveness tends to be lowered.

  In addition, the curable composition may contain components such as a filler, a solvent, a polymerization inhibitor, a polymerization inhibitor, a dye, a pigment, and a fragrance, as necessary.

  The curable composition preferably has a low viscosity. The lower the viscosity of the curable composition, the better the familiarity between the curable composition and the polymer material having a diaryl ketone group, and the reduction process when the radical polymerizable monomer in the curable composition was polymerized. Bond formation with a polymer material having a diaryl ketone group is performed uniformly and at a high density, and higher adhesion can be obtained. However, when the viscosity is too low, it is difficult to uniformly apply the curable composition onto the polymer material having a diaryl ketone group. Therefore, the viscosity of the curable composition is preferably in the range of 0.3 cP to 100,000 cP, more preferably in the range of 0.3 cP to 10,000 cP, and in the range of 0.4 cP to 3000 cP at 23 ° C. More preferably, it is more preferably in the range of 0.4 cP to 500 cP, still more preferably in the range of 0.5 cP to 30 cP, and most preferably in the range of 0.5 cP to 10 cP. Viscosity is measured using a cone plate viscometer in a temperature-controlled room kept at 23 ° C. under a red lamp to prevent viscosity change due to polymerization during measurement when a photopolymerization initiator is used. Just do it.

  Here, a filler may be blended for the purpose of improving the strength of the curable composition. However, when a large amount of filler is blended, the viscosity of the curable composition becomes high. Therefore, the filler blended in the curable composition of the present invention is preferably 300 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 50 parts by mass or less, per 100 parts by mass of the polymerizable monomer. Most preferred is less than or equal to parts by weight. In addition, when there is too much compounding quantity of a filler, the ratio which the polymer material which has the diaryl ketone group which passed through the radically polymerizable monomer in a curable composition and the reduction process will also fall, and high adhesiveness will be reduced. From the viewpoint of reducing the density of bonds necessary for obtaining, it is preferable that the amount of filler in the curable composition is small.

  In addition, as a filler, a well-known inorganic filler, an organic filler, and an organic-inorganic composite filler are used without a restriction | limiting at all.

  Examples of the inorganic filler include quartz, silica, silica-alumina, silica-titania, silica-zirconia, lanthanum glass, barium glass, strontium glass, fluoroaluminosilicate glass, and the like. In addition, when using these inorganic fillers, it is preferable to treat with a surface treatment agent typified by a silane coupling agent. In this case, the affinity between the inorganic filler and the radical polymerizable monomer is improved, and the mechanical strength and water resistance of the cured product can be improved. The surface treatment can be performed by a known method. As the silane coupling agent, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyl Triacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyl Dimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylate Silane, N- phenyl--γ- aminopropyltrimethoxysilane, 11-methacryloyloxy undecyl trimethoxysilane, 11-methacryloyloxy such acryloyloxy undecyl methyl dimethoxy silane.

  Examples of organic fillers include polymethyl methacrylate, polymethyl methacrylate-polyethyl methacrylate copolymer, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene. Examples thereof include particles made of an organic polymer such as a copolymer.

  Examples of the organic-inorganic composite filler include granular organic-inorganic composite filler obtained by mixing the above-described inorganic particles and a polymerizable monomer, polymerizing, and pulverizing.

  The particle diameter of these fillers is not particularly limited, and generally used fillers having an average particle diameter of 0.01 μm to 100 μm (particularly preferably 0.01 to 5 μm) can be appropriately used depending on the purpose. Further, the refractive index of the filler is not particularly limited. For example, when used as a dental application, those having a range of 1.4 to 1.7 that a general dental inorganic filler has can be suitably used. What is necessary is just to set suitably according to the objective. A plurality of fillers having different particle size ranges and different refractive indexes may be used in combination.

  In order to make the curable composition have a low viscosity, a solvent may be added to the curable composition. It becomes easy to make a curable composition low viscosity by mix | blending a solvent, and it is preferable. Here, the solvent is preferably removed from the system after the curable composition is applied to the polymer material having a diaryl ketone group that has undergone the reduction step, and is preferably a volatile solvent. Here, the volatile solvent means that the vapor pressure at 20 ° C. is 1.0 KPa or more. However, since it is preferable that the volatile solvent volatilizes sufficiently and does not adversely affect the volatile solvent, the vapor pressure at 20 ° C. is more preferably 2.0 KPa or more, and further preferably 5.0 KPa or more. On the other hand, when the volatilization of the volatile solvent is too fast, it needs to be applied quickly at the time of use, and in addition, the storage stability of the curable composition is deteriorated. Therefore, the vapor pressure at 20 ° C. of the volatile solvent is preferably 60 KPa or less, and more preferably 50 KPa or less. In addition, the boiling point of the volatile solvent is not particularly limited, but the lower boiling point is easier to remove after applying the curable composition to the polymer material having a diaryl ketone group that has undergone the reduction step. Therefore, the volatile solvent at 760 mmHg The boiling point is preferably 100 ° C. or lower, and more preferably 80 ° C. or lower. Examples of such a preferable volatile solvent include acetone, methyl ethyl ketone, diethyl ketone, methyl n-propyl ketone, methyl isobutyl ketone, acetonitrile, tetrahydrofuran, diethyl ether, pentane, hexane, toluene, ethyl acetate, methanol, ethanol, 1 -Propanol, isopropanol, water and the like. These volatile solvents may be used alone, or a plurality of them may be mixed when they can be mixed uniformly.

  In the bonding method of the present invention, it is more preferable to roughen the adherend surface of the polymer material having a diaryl ketone group before the reduction step. The polymer material having a diaryl ketone group with a roughened adherend surface has higher surface irregularities, and therefore, by applying the curable composition after reducing the adherend surface, higher adhesion is obtained. I can do it. The roughening treatment method is not particularly limited, and a known roughening treatment method can be used. From the viewpoint of simplicity and safety, sandblasting is preferable. In the sandblasting treatment, alumina particles having a particle size of several μm to several hundred μm are generally sprayed onto the adherend surface of a polymer material having a diaryl ketone group at a pressure of several tens KPa to several MPa using a sandblasting device. Can be implemented.

  Further, in the bonding method of the present invention, in the curable composition application step, the curable composition is applied to the surface of the polymer material having a diaryl ketone group that has undergone the reduction step in a mixture state mixed with another composition. In the curing step, the adhesive composition may be cured in the form of a mixture mixed with another composition. Moreover, the form in particular which provides a curable composition to the surface of the polymer material which has the diaryl ketone group which passed through the reduction process is not restrict | limited, For example, the polymer material which has the diaryl ketone group which passed through the reduction process After applying the curable composition to the surface of other members other than the polymer material having a diaryl ketone group that has been directly applied to the surface of the material or having undergone a reduction process, the other member has a diaryl ketone group that has undergone the reduction process. By making it contact with polymer material, a curable composition can be made to contact the surface of the polymer material which has the diaryl ketone group which passed through the reduction process.

  In the bonding method of the present invention, it is also possible to bond polymer materials having a diaryl ketone group to each other using a curable composition. In that case, for example, a reduction process is performed on both one end and the other end of the polymer material having a ring-shaped diaryl ketone group provided with a joint, and the same curable composition is applied and cured. The one end and the other end of the polymer material having a diaryl ketone group can be bonded together.

  As another example, the surface of the polymer material having a diaryl ketone group is cured by applying a curable composition to the polymer material having a diaryl ketone group that has undergone a reduction process and curing the composition. A structure coated with a cured product of the product can be produced.

  In addition, when the curable composition has adhesiveness with other members (hereinafter sometimes referred to as “second member”), by using the bonding method of the present invention, the diaryl is bonded via the curable composition. It is also possible to adhere the polymer material having a ketone group and the second member. Here, the second member may be, for example, a member that is in a solid state before the start of the bonding operation (hereinafter, may be referred to as “solid second member”). Is a curable member that forms a paste or liquid and cures during the bonding operation to form a solid after completion of the bonding operation (hereinafter sometimes referred to as a “curable second member”). There may be.

  The solid second member may be a polymer material having a diaryl ketone group that has undergone a reduction process, or may be a member that does not contain any polymer material having a diaryl ketone group that has undergone a reduction process in the vicinity of the adherend surface. Good.

  The curable second member may function as an adhesive. In this case, the hardened | cured material of the curable composition provided to the polymer material which has the diaryl ketone group which passed through the reduction | restoration process, and the hardened | cured material of a curable 2nd member can be adhere | attached firmly. In addition to this, the curable second member can also be used for adhesion to other solid members (hereinafter sometimes referred to as “third member”). For example, if the curable second member is a member having a property of firmly adhering to the surface of the third member, a polymer material having a diaryl ketone group and a radical polymerizable monomer are bonded by the bonding method of the present invention. The polymer material having a diaryl ketone group and the third member are firmly bonded by adhering the curable composition contained and applying the second curable second member before curing to the third member side. be able to. The third member can be used without particular limitation as long as it is a known solid member, but it is usually preferable to use a member that is not a polymer having a diaryl ketone group in the vicinity of the adherend surface that has undergone a reduction process. Details of the second member and the third member will be described later.

  In addition, when using the primer which does not contain a polymerization initiator as a curable composition provided to the polymer material which has the diaryl ketone group which passed through the reduction | restoration process, the curable 2nd member containing the radically polymerizable monomer and the polymerization initiator The primer can be cured by using (corresponding to the above-mentioned second curable composition).

  In that case, for example, after a primer is applied to the surface of the polymer material having a diaryl ketone group that has undergone the reduction step, a curable second member may be further applied, and then the curable second member may be cured. The timing of the curing treatment and the curing method (thermal curing, photocuring, chemical curing) can be appropriately selected according to the type of polymerization initiator compounded in the curable second member.

  When the third member is further used, for example, a primer is applied to the surface of the polymer material having a diaryl ketone group that has undergone a reduction step, and a curable second member is applied to the surface of the third member, and then reduced. The surface of the polymer material having a diaryl ketone group that has undergone the process is brought into contact with the surface of the third member provided with the curable second member, and then the curable second member may be cured. . Moreover, after providing the primer and the curable second member in this order on the surface of the polymer material having a diaryl ketone group that has undergone the reduction step, the primer and the curable second member having a diaryl ketone group that has undergone the reduction step The surface to which is given may be brought into contact with the third member, and then the curable second member may be cured. Alternatively, a polymer having a diaryl ketone group that has been subjected to a reduction step after the surface of the third member having been provided with the curable second member and the primer after the curable second member and the primer have been provided in this order. The surface of the material may be contacted, and then the curable second member may be cured. In addition, the member and timing which provide a primer and a curable 2nd member, and the timing which hardens | cures a curable 2nd member can be selected suitably.

  The solid second member is not particularly limited as long as it is a member made of a known solid material. Regarding the material composition and structure of the member, the polymer material having a diaryl ketone group and the solid second member may be the same. May be different. When the solid second member is made of a polymer material having a diaryl ketone group that has undergone a reduction process, the curable composition of the present embodiment can adhere to the solid second member with high adhesion. It is. Examples of the material constituting the solid second member include: a) Various resins such as polymers having a diaryl ketone group, materials mainly composed of organic substances other than resins (pulp materials, etc.), metals, inorganic compounds, and the like. It may be an artificially manufactured or purified material, b) a composite material using two or more materials shown in a), or c) a non-artificial biomaterial such as a tooth or bone.

  The curable second member includes at least a polymerization initiator and a polymerizable monomer. As each component constituting the curable second member, materials that can be used in the curable composition that can be imparted to the polymer material having a diaryl ketone group that has undergone the reduction step by the bonding method of the present invention are used in appropriate combination. it can. However, the composition of the curable second member is usually selected from a composition different from the curable composition to be applied to the polymer material having a diaryl ketone group that has undergone the reduction step in the bonding method of the present invention actually used for bonding. Is done. In addition, since the curable second member contains a polymerizable monomer, the curable composition imparted to the curable second member and the polymer material having a diaryl ketone group that has undergone the reduction process by the bonding method of the present invention is strong. Glued to. When the third member is also used, the polymerizable monomer contained in the curable second member interacts with the surface of the third member to bond the curable second member and the third member. it can. In addition, it is preferable to select a composition with high affinity with the adherend part constituent material of the third member as the composition of the curable second member.

  The third member is not particularly limited as long as it is a member made of a known solid material, and the same member as the solid second member can be used. However, as the third member, it is usually preferable to use a member that does not contain a polymer having a diaryl ketone group as a material for the adherend portion.

  The bonding method of the present invention is particularly preferably applied to a polymer material having a diaryl ketone group used for dental use. In dental applications, radically polymerizable curable compositions are widely used. By using the bonding method of the present invention, a polymer material having a diaryl ketone group and a radically polymerizable dental curable composition are used. Adhesion is preferable because higher adhesion than before can be obtained. Further, in dental use, it is necessary to have strong adhesiveness in a harsh environment such as the oral cavity, and in particular, it is a field where high adhesiveness is required. Since it becomes easy to satisfy | fill, it is preferable.

  In addition, since dental applications, particularly dental prosthetic materials, have high aesthetic requirements, a solution in which a reducing agent is dissolved is applied to the surface of a polymer material having a diaryl ketone group in a reduction process at 60 to 180 ° C. The method of heating with is particularly preferred.

  The dental material using the polymer material having a diaryl ketone group used in the present invention for dental applications includes a denture, an artificial tooth, a denture base, and a dental implant partially or entirely made using a polymer having a diaryl ketone group. And dental prosthetic materials such as crown restoration materials and abutment construction materials.

  When the adhesion method of the present invention is applied to a polymer material having a diaryl ketone group used for dental use, the curable composition includes a curable composition containing a radical polymerizable monomer used for dental use. Things can be used. Examples of such a dental curable composition include a dental composite resin, a dental hard resin, a dental resin cement, a dental bonding material, a dental immediate polymerization resin, a dental primer, and the like.

  In addition, as described above, radical polymerizable curable compositions are widely used in dental applications, and radical polymerizable curable compositions are also widely used as adhesive compositions. By using a polymer material having a diaryl ketone group obtained through the reduction step of the method as a dental prosthesis, it is firmly attached to the tooth via a radical polymerizable adhesive composition widely used in dental applications. It becomes easy to adhere. Therefore, a method for producing a dental prosthesis including at least a step of reacting a polymer material having a diaryl ketone group and a reducing agent can be mentioned as a preferred embodiment.

  When a polymer material having a diaryl ketone group is used as a dental prosthesis, a polyaryl ether ketone resin is preferable because physical properties necessary for dental use such as strength can be easily obtained. Among them, in particular, as a polyaryl ether ketone resin used as a dental restorative material, from the viewpoint of color tone and physical properties, an ether group and a ketone group constituting a main chain are arranged in the order of ether, ether, and ketone. It is preferable to use polyether ether ketone having a repeating unit or polyether ketone ketone having repeating units arranged in the order of ether, ketone, and ketone.

  The dental prosthetic material obtained from the polymer material having such a diaryl ether ketone group through the above-described reduction step is partially reduced on the surface thereof, so that 1 part of the carbon atom has 1 diaryl ketone group (diaryl ketone part). There will be a diarylmethanol moiety in which one hydroxyl group, one hydrogen atom and two arylene groups are present as substituents. When the number of diaryl ketone sites is a and the number of diarylmethanol sites is b, 100 × b / (a + b) is preferably in the range of 10 to 90, more preferably in the range of 30 to 70. preferable. By setting 100 × b / (a + b) to 10 or more, it becomes easy to obtain high adhesion between the dental prosthetic material and a dental curable composition such as an adhesive composition. On the other hand, by setting 100 × b / (a + b) to 90 or less, adhesion to dental prostheses such as plaques and contaminants due to hydrophilic hydroxyl groups is suppressed, and coloring is suppressed to increase the dental prosthesis. It becomes easy to maintain aesthetics.

The value of 100 × b / (a + b) can be determined by infrared spectroscopy as with the reaction rate R _{IR of the} polymer material having a diaryl ketone group in the reduction step described above. By this method using infrared spectroscopy, it is possible to confirm the state of the surface several μm site that is strongly related to adhesion. Specifically, when a polymer material having a diaryl ketone group is measured by a single reflection ATR method using a Fourier transform infrared spectrophotometer, the peak area of a peak derived from a carbonyl group appearing in the vicinity of 1650 cm ^−1. (ν1650cm ^-1) and 1490cm ^-1 aromatic ring of the peak area of the peak appearing in the vicinity (ν1490 ^-1) peak area ratio of the (ν1650cm ^-1 / ν1490cm ^-1), when compared with before and after reduction, aromatic ring Since there is no change due to the reduction reaction, the amount of diaryl ketone moiety reduced and the amount of diarylmethanol moiety produced can be determined. That is, as described above, when the peak area ratio before the reduction step is νb and the peak area ratio after the reduction step is νa, 100 × b / (a + b) according to the following general formula (II): ) Value can be obtained.

100 × b / (a + b) = 100 × (νb−νa) / νb (II)
The value of 100 × b / (a + b) is the same value as the _RIR obtained by the general formula (I). That is, the following general formula (III) is established.

100 × b / (a + b) = R _IR [%] (III)
When a polymer material having a diaryl ketone group that has undergone the reduction process as described above is used as a dental prosthesis material, the dental resin is a radical polymerizable curable composition using the material itself as a dental prosthesis. It can be used to prepare dental prosthesis by attaching cement to tooth using cement or laminating dental hard resin.

  When a dental prosthesis is produced by laminating a dental hard resin or the like, the surface of the polymer material having a diaryl ketone group molded into a desired shape is reacted with a reducing agent. Thus, the dental prosthesis material of the present invention can be obtained. Then, the dental hard resin may be directly applied to the surface, or after the dental bonding material treatment or the dental primer treatment is performed before the dental hard resin is applied, the dental hard resin may be laminated. .

  When the material itself is used as a dental prosthesis, for example, in a dental laboratory, a dental prosthesis having a desired shape is made of a polymer material having a diaryl ketone group, and a dental resin cement is used to attach the dental prosthesis to a tooth. The surface to which is applied is reacted with a reducing agent to provide the dental prosthesis material of the present invention. After that, the dentist uses a dental resin cement to attach to the patient's dental defect, or the surface treated with the reducing agent of the polymer material having a diaryl ketone group before applying the dental resin cement. After the dental bonding material treatment and the dental primer treatment, the dental resin cement can be used to attach the dental defect to the patient. When the dental prosthesis material of the present invention is attached to a dental defect as described above, the polymer material having a reduced diaryl ketone group can be slowly oxidized by oxygen in the air or the like, but for at least one week. It is possible to maintain a surface state with a high degree of adhesion. Therefore, a dental prosthesis is produced with a polymer material having a diaryl ketone group at a dental laboratory, and a reduction reaction is performed as it is at a dental laboratory where facilities such as a heating device are provided. It is an example of a method for producing and using a dental prosthesis that is preferably packed in a box so as not to be contaminated by adhesion of the material, covered with a cloth or aluminum foil, and sent to a dental clinic.

  A dental treatment kit comprising a dental curable composition containing a radically polymerizable monomer and a polymerization initiator, a dental prosthesis material obtained by reacting a polymer material having a diaryl ketone group and a reducing agent, is suitable. It can also be mentioned as a special dental treatment kit. The dental curable composition constituting the kit means any dental material containing a radical polymerizable monomer, specifically, a dental bonding material, a dental resin cement, a dental filling restorative material, a dental It means hard resin, dental immediate polymerization resin, dental primer and the like. In addition, this dental treatment kit includes two components: a dental curable composition containing a radically polymerizable monomer, a polymer material having a diaryl ketone group, and a reducing agent, and a dental prosthetic material. In other cases, for example, when a dental primer that does not contain a polymerization initiator is used as a dental curable composition, the dental primer is further laminated on the dental primer. It may contain a resin cement for use.

  Further, a dental curable composition containing a radically polymerizable monomer, a polymer material having a diaryl ketone group for a dental prosthesis, and a reducing agent solution for reducing a polymer material having a diaryl ketone group for a dental prosthesis Can also be cited as a suitable dental treatment kit. This dental treatment kit reduces a dental curable composition containing a radically polymerizable monomer, a polymer material having a diaryl ketone group for a dental prosthesis, and a polymer material having a diaryl ketone group for a dental prosthesis. The kit may be composed of only three components of the reducing agent solution to be used, or other components such as a dental primer that does not contain a polymerization initiator as a dental curable composition. It may include a dental resin cement that is further laminated on the primer for use.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not restrict | limited to these Examples. The abbreviations and titles shown in the examples are as follows.

[Radically polymerizable monomer]
BisGMA: 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane 3G: triethylene glycol dimethacrylate UDMA: 1,6-bis (methacrylethyloxycarbonylamino) 2, 2,4-trimethylhexane, PM1: 2-methacryloyloxyhexyl dihydrogen phosphate, PM2: bis (2-methacryloyloxyethyl) hydrogen phosphate, HEMA: 2-hydroxyethyl methacrylate [polymerization initiator]
CQ: camphorquinone DMBE: p-dimethylaminobenzoic acid ethyl ester BPO: benzoyl peroxide DMPT: N, N-dimethyl-p-toluidine DMAn: 9,10-dimethylanthracene IMPDI: 4-isopropyl- 4-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate [filler]
F1: Spherical silica-zirconia (average particle size 0.4 μm) surface-treated with γ-methacryloyloxypropyltrimethoxysilane F2: Amorphous silica-zirconia (average particle size 3 μm) γ-methacryloyloxypropyltrimethoxy Surface treatment with silane [solvent]
DMSO: dimethyl sulfoxide DMI: 1,3-dimethyl-2-imidazolidinone DMF: N, N-dimethylformamide [cationically polymerizable monomer]
・ OX-1

・ EP-1

  As the adherend, a polyether ether ketone resin material, which is a polymer material having two types of diaryl ketone groups, D1 and D2, was used. D1 is VESTAKEEEP MC4420 (manufactured by Daicel Evonik), and D2 is VESTAKEEEP M2G (manufactured by Daicel Evonik).

  Each test method is as follows.

(Tensile bond strength measurement)
The polyether ether ketone resin material was molded into a plate having a thickness of about 2 mm by injection molding to obtain an adherend. After the adherend surface of this adherend was polished with a # 800 water-resistant abrasive paper, sandblasting (alumina particles having a particle size of about 50 μm were sprayed at a pressure of about 0.2 MPa for 10 seconds using a sandblasting apparatus). Roughening was performed. Thereafter, the substrate was immersed in water and exposed to ultrasonic waves for 5 minutes, and then washed by being immersed in acetone and exposed to ultrasonic waves for 5 minutes. Subsequently, based on each method shown in M1 to M5 described later, the surface of the polyether ether ketone resin material that had been sandblasted was subjected to a treatment such as reacting with a reducing agent. A double-sided tape having a hole with a diameter of 3 mm was attached to the surface of the obtained polyether ether ketone resin material that had been subjected to a treatment such as a reduction reaction.

Thereafter, when the curable composition is B1, B2, B3, the curable composition (B1, B2, B3) is applied to the holes, left for 10 seconds, and then dried by blowing compressed air for about 10 seconds. The curable composition was irradiated with light for 30 seconds with a dental irradiator (Tokuso Power Light, manufactured by Tokuyama Dental Co., Ltd .; light output density 700 mW / cm ² ) to be cured. A dental resin cement (Bistite II, manufactured by Tokuyama Dental Co., Ltd.) was applied thereon, and a stainless steel attachment was further pressed onto it to prepare an adhesion test piece.

  When a primer was used as the curable composition (P1), the primer (P1) was applied to the hole, allowed to stand for 10 seconds, and then dried by blowing compressed air for about 10 seconds. A dental resin cement (Bistite II, manufactured by Tokuyama Dental Co., Ltd.), which is a dental curable composition, was applied thereon, and a stainless steel attachment was pressed onto the dental cement, thereby preparing an adhesion test piece.

  When the curable composition was C1, the adhesive test piece was prepared by applying the curable composition (C1) on the hole and then pressing the stainless steel attachment thereon.

When the curable composition was R1, a simulated cavity was formed by fixing a paraffin hook having a hole with a thickness of 0.5 mm and a diameter of 8 mm so as to be concentric with the hole of the double-sided tape. The simulated cavity is filled with the curable composition (R1), pressed with a polyester sheet, and cured for 30 seconds with a dental irradiator (Tokuso Power Light, manufactured by Tokuyama Dental Co., Ltd .; light output density 700 mW / cm ² ). The composition was cured by light irradiation. A dental resin cement (Bistite II, manufactured by Tokuyama Dental Co., Ltd.) was applied on top of it, and a stainless steel attachment was pressed on top of it. When the composition (O1) was used, a simulated cavity was formed by fixing paraffin wax having a hole with a thickness of 0.5 mm and a diameter of 8 mm so as to be concentric with the hole of the double-sided tape. The simulated cavity was filled with a cationic polymerizable composition (O1), pressed with a polyester sheet, and cationized for 30 seconds with a dental irradiator (Tokuso Power Light, manufactured by Tokuyama Dental Co .; light output density 700 mW / cm ² ). The polymerizable composition was cured by light irradiation. A dental resin cement (Bistite II, manufactured by Tokuyama Dental Co., Ltd.) was applied thereon, and a stainless steel attachment was further pressed onto it to prepare an adhesion test piece.

  After holding the above-mentioned adhesion test piece at 37 ° C. for 24 hours, using a tensile tester (Autograph, manufactured by Shimadzu Corporation), pulling it at a crosshead speed of 2 mm / min, the polyether ether ketone resin material and The tensile adhesive strength with the curable composition was measured. The tensile bond strength between the polyether ether ketone resin material and the curable composition was measured for each of the four test specimens for each example or each comparative example, and the average value and standard deviation (SD )

(Measurement of reaction rate _RIR of reduction reaction)
The polyether ether ketone resin material was molded into a plate having a thickness of about 2 mm by injection molding to obtain an adherend. Thereafter, the substrate was immersed in water and exposed to ultrasonic waves for 5 minutes, and then washed by being immersed in acetone and exposed to ultrasonic waves for 5 minutes. After thoroughly drying the surface of the polyether ether ketone resin material thus obtained, an IR spectrum is obtained by a single reflection ATR method using a Fourier transform infrared spectrophotometer (Spectrum One, manufactured by Perkin Elmer). Te, 1650 cm ^-1 peak of the peak area derived from a carbonyl group appearing in the vicinity (ν1650cm ^-1) and 1490cm ^-1 calculates the peak area of the peak of the aromatic ring (ν1490 ^-1) appearing near the peak area ratio before the reaction νb (= ν1650 cm ⁻¹ / ν1490 cm ⁻¹ ) was determined.

  Then, based on each method shown to M1-M5 mentioned later, the process which made the sample react with the reducing agent with respect to the surface which calculated | required the peak area ratio of the polyether ether ketone resin material was performed.

The IR spectrum was obtained by a single reflection ATR method using a Fourier transform infrared spectrophotometer, and the peak of the peak derived from the carbonyl group appearing in the vicinity of 1650 cm ⁻¹ was obtained on the surface that had been thoroughly dried after the treatment. The area (ν1650 cm ⁻¹ ) and the peak area (ν1490 ⁻¹ ) of the peak of the aromatic ring appearing in the vicinity of 1490 cm ⁻¹ were calculated, and the peak area ratio νa (= ν1650 cm ⁻¹ / ν1490 cm ⁻¹ ) after the reaction was determined.
Using the peak area ratio thus determined, the reaction rate R _IR (= 100−νa / νb × 100) determined by infrared spectroscopy was calculated.

(Reaction between polyether ether ketone resin material and reducing agent)
The polyether ether ketone resin material and the reducing agent were reacted by the following methods.

  M1: Sodium borohydride was dissolved in DMSO to prepare a 0.7 mol / l sodium borohydride / DMSO solution. A sodium borohydride / DMSO solution was applied with a brush to the surface of the polyether ether ketone resin material washed after sandblasting, and was left in an oven maintained at 120 ° C. for 3 hours. The polyether ether ketone resin material was taken out of the oven, cooled to room temperature, then immersed in water and exposed to ultrasonic waves for 5 minutes, and then immersed in acetone and exposed to ultrasonic waves for 5 minutes for cleaning.

  M2: Sodium borohydride was dissolved in DMI to prepare a 0.7 mol / l sodium borohydride / DMI solution. A sodium borohydride / DMI solution was applied to the surface of the polyether ether ketone resin material washed after sandblasting with a brush and allowed to stand in an oven maintained at 120 ° C. for 3 hours. The polyether ether ketone resin material was taken out of the oven, cooled to room temperature, then immersed in water and exposed to ultrasonic waves for 5 minutes, and then immersed in acetone and exposed to ultrasonic waves for 5 minutes for cleaning.

  M3: Sodium borohydride was dissolved in DMF to prepare a 0.7 mol / l sodium borohydride / DMF solution. A sodium borohydride / DMF solution was applied to the surface of the polyetheretherketone resin material washed after sandblasting with a brush and allowed to stand in an oven maintained at 120 ° C. for 3 hours. The polyether ether ketone resin material was taken out of the oven, cooled to room temperature, then immersed in water and exposed to ultrasonic waves for 5 minutes, and then immersed in acetone and exposed to ultrasonic waves for 5 minutes for cleaning.

(Other processing methods)
M4: The polyether ether ketone resin material washed after sandblasting was thoroughly dried.
M5: DMSO was applied to the surface of the polyetheretherketone resin material washed after sandblasting with a brush and allowed to stand in an oven maintained at 120 ° C. for 3 hours. The polyether ether ketone resin material was taken out of the oven, cooled to room temperature, then immersed in water and exposed to ultrasonic waves for 5 minutes, and then immersed in acetone and exposed to ultrasonic waves for 5 minutes for cleaning.

<Example 1>
Using a polymer D1 having a diaryl ketone group and a 0.7 mol / l sodium borohydride / DMSO solution prepared by dissolving 0.26 g of sodium borohydride in 10 ml of DMSO, the diaryl was prepared according to the procedure of M1. A reduction step of reacting a polymer material having a ketone group with a reducing agent was performed. 5 g of bisGMA as a radical polymerizable monomer component, 5 g of 3G are mixed, 0.2 g of CQ and 0.2 g of DMBE are added as a polymerization initiator component, and 10 g of acetone as a solvent is further added and stirred to cure. Composition B1 was produced. The composition of the curable composition is shown in Table 1. The reaction rate of the reduction process of the polymer material having the diaryl ketone group and the tensile adhesive strength between the polymer material having the diaryl ketone group adhered by the method and the curable composition were measured. The results are shown in Table 3.

<Examples 2 to 4>
In accordance with Example 1, a reduction process was performed in which a polymer material having a diaryl ketone group and a reducing agent were reacted. A curable composition was prepared according to Example 1 except that the composition shown in Table 1 was changed. The composition of the curable composition is shown in Table 1. The reaction rate of the reduction process of the polymer material having the diaryl ketone group and the tensile adhesive strength between the polymer material having the diaryl ketone group adhered by the tooth method and the curable composition were measured. The results are shown in Table 3.

<Example 5>
In accordance with Example 1, a reduction process was performed in which a polymer material having a diaryl ketone group and a reducing agent were reacted. As a radical polymerizable monomer component, 3 g of bisGMA, 2 g of 3G, 1.5 g of PM1, 1.5 g of PM2, and 2 g of HEMA are mixed, and 10 g of acetone as a solvent is added and stirred to obtain a primer composition ( Curable composition) P1 was produced. The composition of the primer composition is shown in Table 1. The reaction rate of the reduction process of the polymer material having the diaryl ketone group and the tensile adhesive strength between the polymer having the diaryl ketone group adhered by the method and the curable composition were measured. The results are shown in Table 3.

<Example 6>
In accordance with Example 1, a reduction process was performed in which a polymer material having a diaryl ketone group and a reducing agent were reacted. 3 g of bisGMA as a radical polymerizable monomer component, 2 g of 3G, 1.5 g of PM1, 1.5 g of PM2, and 2 g of HEMA are mixed, and 0.05 g of DEPT is added as a polymerization initiator component, and further a filler As ingredients, 16 g of F1 and 10 g of F2 were added and mixed to form a paste. 1 g of the paste was taken on a straight line, and 9.7 mg of BPO was added and mixed with the paste to obtain a curable composition C1, which was quickly used for the test. The composition of the curable composition is shown in Table 1. The reaction rate of the reduction process of the polymer material having the diaryl ketone group and the tensile adhesive strength between the polymer material having the diaryl ketone group adhered by the method and the curable composition were measured. The results are shown in Table 3.

<Example 7>
In accordance with Example 1, a reduction process was performed in which a polymer material having a diaryl ketone group and a reducing agent were reacted. As a radical polymerizable monomer component, 5 g of bisGMA and 5 g of 3G are mixed, 0.2 g of CQ and 0.2 g of DMBE are added as a polymerization initiator component, and 16 g of F1 and 10 g of F2 are added as a filler component. It mixed and paste-ized and produced curable composition R1. The composition of the curable composition is shown in Table 1. The reaction rate of the reduction process of the polymer material having the diaryl ketone group and the tensile adhesive strength between the polymer material having the diaryl ketone group adhered by the method and the curable composition were measured. The results are shown in Table 3.

<Examples 8 and 9>
As a method for reacting the polymer material having the diaryl ketone group shown in Table 1 with the reducing agent, the polymer material having the diaryl ketone group and the reducing agent were changed according to Example 1 except that the solution of the reducing agent solvent was changed. A reduction step for reacting was carried out. The reaction rate of the reduction process of the polymer material having the diaryl ketone group and the tensile adhesive strength between the polymer material having the diaryl ketone group adhered by the method and the curable composition were measured. The results are shown in Table 3.

<Example 10>
Except having changed the polymer material which has a diaryl ketone group into D2, the reduction process which reacts the polymer material which has a diaryl ketone group, and a reducing agent according to Example 1 was performed. The reaction rate of the reduction process of the polymer material having the diaryl ketone group and the tensile adhesive strength between the polymer material having the diaryl ketone group adhered by the method and the curable composition were measured. The results are shown in Table 3.

<Comparative Example 1>
The polymer material having a diaryl ketone group was treated according to the M4 procedure without reacting with a reducing agent. The tensile bond strength between the reaction rate of the polymer and the curable composition B1 produced in Example 1 was measured. The results are shown in Table 3.

<Comparative Example 2>
The polymer material having a diaryl ketone group was treated according to the M5 procedure without reacting with a reducing agent. The tensile adhesive strength between the reaction rate of the polymer material having the diaryl ketone group and the curable composition B1 produced in Example 1 was measured. The results are shown in Table 3.

<Comparative Example 3>
The polymer material having a diaryl ketone group was treated according to the M4 procedure without reacting with a reducing agent. 6 g of OX-1 and 4 g of EP-1 are mixed as a cationic polymerizable monomer component, 0.06 g of CQ, 0.02 g of DMAn and 0.15 g of IMDPI are added as a polymerization initiator component, and a filler 16 g of F1 and 10 g of F2 were added and mixed as components, and the mixture was made into a paste to produce a curable composition O1. Table 2 shows the composition of the curable composition containing the cationic polymerizable monomer. The reaction rate of the polymer material having the diaryl ketone group and the tensile adhesive strength between the curable composition were measured. The results are shown in Table 3.

<Comparative example 4>
In accordance with Example 1, a reduction process was performed in which a polymer material having a diaryl ketone group and a reducing agent were reacted. The tensile adhesive strength between the reaction rate of the polymer material having the diaryl ketone group and the curable composition O1 produced in Comparative Example 3 was measured. The results are shown in Table 3.

(Evaluation results)
Table 3 shows the measurement results of the tensile adhesive strength of the polymerizable composition of each Example and each Comparative Example with respect to the polyether ether ketone resin material.

  Regarding the evaluation results, Examples 1 to 10 using the curable composition containing the radical polymerizable monomer after reacting the polyether ether ketone resin material with the reducing agent were used as the reducing agent. The adhesive strength was higher than those of Comparative Examples 1 and 2 in which the curable composition was applied without being reacted.

  In Comparative Examples 3 and 4 using a curable composition prepared so that a cationic polymerization reaction occurs instead of a radical polymerization reaction, the adhesive strength differs depending on whether or not the polyether ether ketone resin material is reacted with a reducing agent. Did not appear. This is because the effect of improving the adhesive strength by reacting the polyether ether ketone resin material with the reducing agent requires a radical polymerizable composition, and the polyether ether ketone resin material and the radical polymerizable monomer are This shows that it supports the theory that the bond strength is improved by forming a bond by radical reaction.

  After reacting the polyether ether ketone resin material with a reducing agent, comparing Examples 1 to 4 using curable compositions that differ only in the composition of the radical polymerizable monomer, the radical polymerizable monomer having a hydroxyl group Examples 1, 3 and 4 using a curable composition containing a body (bisGMA, HEMA, PM1, PM2) are examples using a curable composition containing no radical polymerizable monomer having a hydroxyl group. Compared with 2, it showed high adhesive strength. In addition, Examples 1 and 3 using a curable composition containing a radically polymerizable monomer having an alcoholic hydroxyl group (bisGMA, HEMA) are radically polymerizable having a hydroxyl group but having no alcoholic hydroxyl group. Compared with Example 4 which used the curable composition containing a monomer (PM1, PM2), the high adhesive strength was shown.

  In Examples 3, 5 and 6 in which the curable composition having the same radical polymerizable monomer composition was used for the polyaryl ether ketone resin material reacted with the reducing agent, the polymerization initiator was low in viscosity. Example 3 to which the curable composition contained was applied, Example 5 using a primer having a low viscosity but not containing a polymerization initiator, and a curable composition containing a polymerization initiator but containing a filler and having a high viscosity Compared with Example 6 which gave, high adhesive strength was shown.

  Similarly, in Examples 1 and 7 in which the curable composition having the same radical polymerizable monomer composition was used for the polyaryl ether ketone resin material reacted with the reducing agent, the polymerization initiator was low in viscosity. Example 1 which provided the curable composition to contain showed high adhesive strength compared with Example 7 which contained the curable composition which contains a filler and is high-viscosity.

  Among the curable compositions used in this example, B1, B2, B3, B4, and P1 are viscosities measured using a cone plate viscometer in a thermostatic chamber maintained at 23 ° C. under a red light. Is included in the range of 0.5 cP to 10 cP, and the viscosity of C1 and R1 exceeds 3000 cP. Comparing Examples 1 to 7 in which the reduction reaction was performed on the same adherend by the same method, implementation using B1, B2, B3, B4, and P1, which are lower viscosity curable compositions Examples 1-5 showed high adhesive strength compared with Example 6 and 7 which used C1 and R1 which are curable compositions with higher viscosity.

Claims (7)

Preparing a curable composition containing a radical polymerizable monomer and a polymer material having a diaryl ketone group;
A reduction step of reacting the polymer material having the diaryl ketone group with a reducing agent;
A curable composition application step for applying the curable composition to the surface of the polymer member having a diaryl ketone group that has undergone the reduction step;
A curing step for curing the curable composition;
A method for adhering a polymer material having a diaryl ketone group and a curable composition, comprising at least   The bonding method according to claim 1, wherein the reducing agent is a hydride reducing agent.   The adhesion method according to claim 1 or 2, wherein the reduction step is performed at 60 to 180 ° C.   The adhesion method according to any one of claims 1 to 3, wherein the radical polymerizable monomer is a radical polymerizable monomer having a (meth) acryloyl group.   The adhesion method according to any one of claims 1 to 4, wherein the polymer material having a diaryl ketone group and the curable composition containing a radical polymerizable monomer are both dental.   The manufacturing method of the dental prosthesis material characterized by including the process with which the polymeric material which has a diaryl ketone group, and a reducing agent are made to react.   A dental prosthesis material containing a polymer material having a diaryl ketone group, where the number of diaryl ketone sites on the surface of the polymer material is a and the number of diarylmethanol sites is 100 × b / (a + b) A dental prosthesis material characterized in that is 10 to 90.