JP6541184B2 - Bonding method - Google Patents

Description

  The present invention relates to a bonding method for bonding a polymer material having a diaryl ether ketone group and a curable composition containing a radically 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 the electric and electronic fields, aerospace fields, automotive industry, medical fields, and general industrial fields. Among these super engineering resins, polyaryl ether ketone resins, which are polymers having a diaryl ketone group, in particular, 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 polyaryletherketone 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 dentin and other kinds of dental materials. Various techniques have been proposed as techniques for adhering such a member containing a polyaryl ether ketone resin to a member such as dentin or another kind of dental material (for example, Patent Document 2, Non-Patent Document) 1-2).

  However, since this polyaryl ether ketone resin has high surface chemical stability, it is generally difficult to bond with other materials. In general, welding or bonding with an epoxy material is often performed. In addition, studies are also being made to modify the surface of the polyaryl ether ketone resin material to improve its adhesion. For example, in patent document 3, after performing a plasma processing, the technique which uses an epoxy-type adhesive material and an epoxy-type primer is proposed.

  Here, as a curable composition, a radically polymerizable curable composition is widely used because of its high polymerization rate and easiness of producing a high-strength cured product, and, for example, an adhesive composition, adhesion Used in coatings, coatings, sealants and paints. For example, in dental applications, radically polymerizable curable compositions are widely used, and adhesive composition applications for bonding dental members or between dental members and teeth (dental cement, dental bonding material, etc.) , The filling restoration use of dentin defects (dental composite resin etc.), preparation of dental prostheses and dentures (hard dental resin, immediate dental polymerization resin etc) are used.

  By bonding these radically polymerizable curable compositions with the polyaryletherketone resin material, it becomes possible to produce various useful members. Therefore, there is a demand for a method for obtaining higher adhesion between a polymer having a diaryl ketone group such as a polyaryl ether ketone resin and a radically polymerizable curable composition.

  In addition, since the polyaryl ether ketone resin has high surface chemical stability as described above, it has low affinity and reactivity with other substances. Therefore, studies are also being made to modify the surface for the purpose of introducing functional groups, etc., other than the method aiming at adhesion. One of the methods is known a method of forming a hydroxyl group on the surface of a polyaryl ether ketone resin by a reduction reaction. For example, Non-Patent Document 3 describes a method of reducing the carbonyl group on the surface of a polyetheretherketone resin to a hydroxyl group using sodium borohydride which is a hydride reducing agent. However, no example is known in which an adhesive or a radically polymerizable composition is applied to a polyaryl ether ketone resin material reduced by a reducing agent. There is also no known example of using a reduced polyaryletherketone resin material as a dental material.

Unexamined-Japanese-Patent No. 2013-144778 Japanese Patent Publication No. 2010-521257 Unexamined-Japanese-Patent No. 5-177714

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

  As described above, when using a polymer material having a diaryl ketone group, particularly a polyaryl ether ketone resin material, adhesion is a problem.

  Therefore, in the present invention, high adhesiveness is obtained between a radically polymerizable curable composition by carrying out a simple and appropriate treatment on a polymer material having a diaryl ketone group, particularly a polyaryl ether ketone resin material. The purpose is to do things. That is, it is suitably used for a method of adhering a polymer material having a diaryl ketone group, particularly a polyaryl ether ketone resin material, and a curable composition containing a radically polymerizable monomer, and for dental prostheses An object is to provide a polymer material having a diaryl ketone group and a method for producing the same.

  The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, those obtained by reducing the diaryl ketone group on the surface of the polymer material having a diaryl ketone group by a specific treatment contain a radically polymerizable monomer. The present invention has been found to have good adhesion to curable compositions.

That is, the present invention provides a polymeric material having a di-aryl ketone group, a radical polymerizable having a hydroxyl group in the radical polymerizable monomer and (b) in the molecule having two or more polymerizable functional groups in (a) molecule A curable composition containing a radically polymerizable monomer containing a monomer, wherein 50% by mass or more of all radically polymerizable monomers contained in the curable composition is the above (a) or (b) preparing) a curable composition is, and the surface of the port Rimmer material, the reducing agent by applying a solution obtained by dissolving at a concentration of at least 0.1 mol / l in a solvent, heating to 60 to 180 ° C. it allows to reduce the carbonyl group of the diaryl ketone group present in the surface, reducing step of generating a hydroxyl group on the surface of the polymeric material which a hydroxyl group is generated in the reduction step, imparts the curable composition Curable composition Application step, and characterized in that it comprises a curing step of curing the curable composition, said polymeric material, and a cured product of the curable composition, a method for bonding. It is particularly preferable to use a hydride reducing agent as the reducing agent. Radical-polymerizable monomer contained in the hardening composition preferably has a (meth) acryloyl group as a polymerizable functional group. The curable composition containing the polymer material having a diaryl ketone group and the radically polymerizable monomer used in the adhesion method is preferably for dental use.

  According to the present invention, high adhesion can be obtained in the adhesion of a polymer composition having a diaryl ketone group and a curable composition containing 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 (each independently having any functional group) may be 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 diaryl ketone group Composite material mixed with filler, using as a resin matrix a material obtained by blending another resin with a polymer having a polymer, a polymer having a diaryl ketone group or a polymer having a diaryl ketone group and another resin as a resin matrix Combining the composite material with a polyaryl ether ketone resin composite material Referred to), and the like. In addition, minor components such as pigments and stabilizers may be added to these materials.

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

  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, and in many cases, a phenylene group is an ether group and a ketone group It has a linear polymer structure linked via 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, a sulfonyl group or another copolymerizable monomer unit may be contained in the structural unit of the polyaryl ether ketone resin.

  Other resins that can be blended with the polymer having a diaryl ketone group are not particularly limited as long as they do not significantly deteriorate the physical properties of the polymer having a diphenyl aryl ketone group such as rigidity and toughness, for example, There may be mentioned polyarylate, polycarbonate, polyethylene terephthalate, polyphthalamide, polytetrafluoroethylene and polyphenylene ether. When a polymer (resin) having a diaryl ketone group is blended with another resin, the polymer having a diaryl ketone group is preferably 50% by mass or more of the total resin, more preferably 70% by mass or more, and 90 It is more preferable that it is mass% or more, and it is more preferable that it is 99 mass% or more.

  Although a well-known thing can be utilized without a restriction | limiting especially as a filler which can be mix | blended with the polymer which has the diaryl ketone group of this invention, An inorganic filler is suitable. For example, as the material of the filler, silica glass, borosilicate glass, soda glass, aluminosilicate glass, fluoroaluminosilicate glass, glass containing heavy metals (for example, barium, strontium, zirconium); Glass ceramics such as crystallized glass, crystallized glass in which crystals such as diopside and leucite are precipitated; complex inorganic oxides such as silica-zirconia, silica-titania, silica-alumina, or complex oxides thereof Oxides to which a Group I metal oxide is added; metal inorganic oxides such as silica, alumina, titania and zirconia; and the like.

  Curing to apply a curable composition containing a radically polymerizable monomer to the surface of a polymer member having a diaryl ketone group which has been subjected to a reduction step of reacting the polymer material having a diaryl ketone group of the present invention with a reducing agent and the reduction step. Although the action mechanism by which high adhesiveness is obtained by the adhesion method including at least the property composition application step and the curing step of curing the delayed curing composition is not necessarily clear, it is presumed as follows.

  That is, by reacting the surface of the 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, two arylene groups, a hydroxyl group, and a carbon atom having a hydrogen atom as a substituent are present on the surface of the polymer material having a diaryl ketone group. Since this carbon atom has a structure that easily generates a radical, the carbon atom is provided with a curable composition containing a radically polymerizable monomer, and the radically polymerizable monomer is cured by radical polymerization. And a radical polymerizable monomer may react to form a bond. As a result, it is surmised that a chemical bond will occur between the polymer material having a diaryl ketone group and the composition containing a radically polymerizable monomer provided thereon, and high adhesion can be obtained.

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

  The method for reducing the polymer material having a diaryl ketone group with a reducing agent is not particularly limited. For example, the polymer material having a diaryl ketone group is introduced into a solution in which the reducing agent is dissolved and heated, and the reducing agent is dissolved The method of dipping, taking out and heating the polymer material which has diaryl ketone group in the solution, and the method of apply | coating and heating the solution which dissolved the reducing agent on the surface of the polymer material which has diaryl ketone group are mentioned. Among these methods, in particular, 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, from the viewpoint that it can be easily carried out and that only a desired adhesion surface can be reduced. Method is preferred. When reduction treatment is performed on a surface other than the desired adhesion surface, the surface reacted with the reducing agent is more hydrophilic than the non-reduction surface, and thus adhesion of contaminants and the like is likely to occur. The method which can reduce only is preferable.

  The solvent of the solution in which the reducing agent is dissolved is not particularly limited as long as the reaction proceeds. Therefore, it is only necessary to be able to dissolve the reducing agent in an amount necessary for the reaction and not to inactivate the reducing agent or to inhibit the function of the reducing agent. Examples of such solvents include dimethylsulfoxide, 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 Ethyl 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. It 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 heating is performed, in order for the reaction to proceed properly, if the solvent evaporates quickly at the time of heating, the reaction It is preferable that the boiling point of the solvent is high because the reaction is lost due to the loss of space. Also, the amount of solution that can be applied in a single operation is limited, and it is not preferable from the viewpoint of work efficiency to apply a solution with a low concentration of reducing agent in multiple times to obtain the necessary amount of reducing agent. Therefore, it is desirable to use a solvent in which the amount of dissolution of the reducing agent is high. Therefore, it is particularly preferable to use dimethyl sulfoxide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone etc. as a solvent for dissolving the reducing agent, and dimethyl sulfoxide is most preferable.

  In the case of dissolving the reducing agent in the solvent, the concentration of the reducing agent is preferably high to be sufficient for the reaction to proceed sufficiently, preferably 0.1 mol / l or more, and more preferably 0.5 mol / l or more . However, when the reducing agent is not completely dissolved, particularly when the solvent in which the reducing agent is dissolved is applied to the polymer material having a diaryl ketone group, the polymer having a diaryl ketone group is obtained by the undissolved reducing agent. A layer of reducing agent may be formed on the surface of the material to reduce the reaction efficiency. 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 in a state where the polymer material having a diaryl ketone group or the reducing agent solution is warmed, but from the viewpoint of workability C. to 35.degree. C. is preferable, and 17 C. to 28.degree. C. is more preferable. Therefore, the reducing agent is preferably completely dissolved in the solvent at 10 ° C. to 35 ° C., and more preferably completely dissolved in the solvent at 17 ° C. to 28 ° C.

  When the reducing agent is dissolved in a solvent, when a large amount of the reducing agent is used, complete dissolution is difficult. In addition, even if the coating is completely dissolved, a reducing agent may precipitate on the surface of the polymer material having a diaryl ketone group after coating, or a large amount of reaction residue may precipitate during the reaction. And may affect 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.

  In the solution in which the reducing agent is dissolved, a filler for viscosity adjustment, a coloring agent for color tone adjustment, a stabilizer for improving storage stability, and a pH adjuster, as long as the reduction reaction is not significantly affected. And other optional components may be added.

  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., and more preferably 90 ° C. to 150 ° C. When the reaction is carried out at a low temperature, the reaction efficiency is usually low, and the reaction does not proceed sufficiently to contribute to the improvement of adhesion, or it takes a long time to proceed the reaction sufficiently, or the reaction must be divided into plural times. There is a risk that When the reaction temperature is high, deterioration such as strength reduction or discoloration of the polymer material having a diaryl ketone group may occur.

  The method of heating is not particularly limited as long as the reaction takes place and the physical properties of the polymer material having a diaryl ketone group are not significantly deteriorated. In the case of applying a solution in which a reducing agent is dissolved to a polymer material having a diaryl ketone group and heating, for example, the reducing agent is dissolved in the desired surface of the polymer material having a diaryl ketone group formed into a desired shape. After applying the solution, it can be carried out by leaving it in an oven maintaining a predetermined temperature. This method is mentioned as a preferable method because the reduction reaction can be carried out simply and heating can be carried out uniformly.

  By reacting the polymer material having a diaryl ketone group with the reducing agent, the carbonyl group on the surface of the polymer material having a diaryl ketone group is reduced to form a hydroxyl group. The confirmation of the progress of this reaction can be conveniently performed by infrared spectroscopy. In addition, infrared spectroscopy can confirm the progress of the reaction near the surface that is strongly involved in adhesion.

In infrared spectroscopy, when a polymer material having bulky diaryl ketone groups is measured by a single reflection ATR method using a Fourier transform infrared spectrophotometer, a peak derived from a carbonyl group that appears near 1650 cm ⁻¹ 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 determined. That is, when the peak area ratio before the reduction reaction is bb and the peak area ratio after the reduction reaction is νa, the following general formula (I) is the reaction rate determined 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 generation degree of the hydroxyl group.

As R _IR is higher, more hydroxyl groups are generated, which is advantageous for adhesion. The value of R _IR is preferably 10% or more, more preferably 30% or more.

  High adhesion is achieved by applying and curing a curable composition containing a radically polymerizable monomer to the surface of a polymer member obtained by reacting a polymer material having a diaryl ketone group with a reducing agent as described above You can get sex. This is on a carbon atom adjacent to a hydroxyl group formed on the surface of a polymer material having a diaryl ketone group obtained by reaction with a reducing agent, that is, on a carbon atom having two arylene groups, a hydroxyl group and a hydrogen atom as a substituent In this case, radicals are easily generated by hydrogen abstraction, so that when the imparted radical polymerizable monomer is cured, radical polymerization is obtained by laminating with a carbon atom adjacent to a hydroxyl group generated on the surface of the polymer having a diaryl ketone group. A bond is formed with the monomer. As a result, it is presumed that high adhesion can be obtained.

  As a curable composition to be imparted to the surface of a polymer member obtained by reacting a polymer material having a diaryl ketone group with a reducing agent as described above, one containing a radically polymerizable monomer can be used without particular limitation. .

  Since the curable composition usually has a low viscosity and is easily deformable at the beginning, it can be deformed into a desired shape, placed at a desired location, and then polymerized and cured. Radically polymerizable curable compositions containing radically polymerizable monomers are used, for example, in adhesive compositions, dental materials, adhesives, coatings, sealants, 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 and (meth) acryloyl group from the viewpoint of low biotoxicity and high polymerization activity, etc. From the viewpoint of polymerization rate and biological safety, (meth) acryloyl group is particularly preferable. As a radically polymerizable monomer generally used suitably, the thing shown by following (I)-(IV) is mentioned, for example.
(I) Monofunctional Radically Polymerizable Monomer Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, 2-methacryloyloxyethyl dihydrogen phosphate, 6-methacryloyloxyhexyl dihydrogen Phosphate, methacrylates such as 10-methacryloyloxyhexyl dihydrogen phosphate, and acrylates corresponding to these methacrylates

(II) Difunctional 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-) Methacryloyloxy tetraethoxyphenyl) 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-methacryloyl oxyhexyl) 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 group such as acrylate corresponding to these methacrylates, diisocyanate methylbenzene, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate Methylcyclohexane, isophorone diisocyanate, methylene bis (4-cyclohexene Diaducts obtained from adducts with diisocyanate compounds such as diisocyanates); 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethyl, 1,6-bis (methacryloylethyloxycarbonylamino) 2,2 , 4-trimethylhexane and the like.

(III) Trifunctional Radically Polymerizable Monomers Methacrylates such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate and acrylates corresponding to these methacrylates and the like.

(IV) Tetrafunctional Radical Polymerizable Monomer Pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate and diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), The diaduct etc. obtained from the adduct of glycidol dimethacrylate with diisocyanate compounds, such as 4, 4- diphenylmethane diisocyanate and tolylene 2,4- diisocyanate.

  These (meth) acrylate-based radically polymerizable monomers may be used in combination of two or more types, if necessary. Moreover, you may use radically polymerizable monomers other than the said (meth) acrylate type monomer.

  As the radically polymerizable monomer, it is preferable to use 50% by mass or more of all polymerizable monomers of the radically polymerizable monomer having two or more polymerizable functional groups in the molecule. 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 becomes high. An increase in the strength of the cured product of the curable composition, in particular, a high strength of the cured product of the curable composition near the interface with the polymer material having a diaryl ketone group is advantageous for obtaining high adhesion. is there.

  As a radically polymerizable monomer, it is preferable to use the radically polymerizable monomer which has a hydroxyl group 30 mass% or more among all the polymerizable monomers, and it is more preferable to use 50 mass% or more. By using the radically polymerizable monomer having a hydroxyl group, the affinity between the curable composition and the polymer material having a diaryl ketone group in which a hydroxyl group is formed by the reduction reaction is improved, and the adhesiveness is improved. The hydroxyl group contained in the radical polymerizable monomer is more preferably an alcoholic hydroxyl group.

  The curing process of the curable composition may be performed by any method, and generally, it is carried out by blending a polymerization initiator into the curable composition and activating it at any time. In addition, in the case where the curable composition is a primer type curable composition containing no polymerization initiator (hereinafter sometimes referred to as "primer"), this primer is a polymer material having a diaryl ketone group which has been subjected to a reduction step. The second curable composition is further applied with a composition containing a radically polymerizable monomer and a polymerization initiator (hereinafter sometimes referred to as "second curable composition"). When polymerizing and curing a substance, it is sufficient to simultaneously polymerize and cure the primer. However, when the conditions other than the presence or absence of the polymerization initiator of the curable composition (such as the composition of the radically polymerizable monomer) are the same, the curable composition containing the polymerization initiator has better adhesion than the primer. The strength of the layer of the curable composition in the vicinity of the interface is likely to be further enhanced, and higher adhesion is likely to be 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 a polymerization initiator, and two or more kinds of polymerization initiators may be used in combination. You can also. In addition, since it can carry out simply when hardening a curable composition after apply | coating to the polymer material which has the diaryl ketone group which passed through the reduction process, using a photoinitiator and / or a chemical polymerization initiator Is preferred. These three types of polymerization initiators will be described in more detail below.

  As the photopolymerization initiator, known ones can be used without any limitation. Representative photopolymerization initiators include combinations of α-diketones and tertiary amines, combinations of acyl phosphine oxides and tertiary amines, combinations of thioxanthones and tertiary amines, α-aminoacetophenone And photoinitiators such as combinations of arylamines and photoacid generators.

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

  As tertiary amines, 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-dimethylanthralic 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, 2,2 '-(n-butylimino) diethanol and the like. These can be used singly or in combination of two or more.

  Acyl phosphine oxides include benzoyl diphenyl phosphine oxide, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2,6-dimethoxy benzoyl diphenyl phosphine oxide, 2,6-dichloro benzoyl diphenyl phosphine oxide, 2,3,5, 6- tetramethyl benzoyl diphenyl phosphine oxide etc. are mentioned.

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

  As α-aminoacetophenones, 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.

  A chemical polymerization initiator is a polymerization initiator which consists of two or more components and which generates polymerization active species at around room temperature by mixing all the components immediately before use. An amine compound / organic peroxide system is typical as such a chemical polymerization initiator. 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, peroxy dicarbonates, peroxy esters, diaryl peroxides and the like.

  Specific examples of the organic peroxide include methyl ethyl ketone peroxide, cyclohexano peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide and the like as ketone peroxides.

  As peroxyketals, 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 can be mentioned.

  As hydroperoxides, P-methane hydroperoxide, diisopropyl benzene peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide Peroxide etc. are mentioned.

  As dialkyl peroxides, α, α-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl Luper peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane-3 and the like can be mentioned.

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

  Examples of peroxydicarbonates include di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethylperoxydicarbonate, and di-2-ethoxyethylperoxydicarbonate. -2-ethylhexyl peroxydicarbonate, di-2-methoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate and the like.

  Examples of peroxy esters include α, α-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1- Cyclohexyl-1-methylethyl peroxy neodecanoate, t-hexyl peroxy neo decanoate, t-butyl peroxy neo decanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, 1 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 3,5-trimethylhexanoate, t-butylperoxy laurate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butyl peroxy Oxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5 bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate , T-Butyl peroxybenzoate, bis ( - butylperoxy) isophthalate.

  Also, t-butyltrimethylsilyl peroxide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and the like can 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, but 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 in which a sulfinic acid such as benzenesulfinic acid or p-toluenesulfinic acid and a salt thereof is further added to an initiator system comprising the organic peroxide and the amine compound, and a barbituric acid such as 5-butyl barbituric acid Even when the initiator is blended, it can be used without any problem.

  Moreover, the chemical polymerization initiator of a transition metal compound / organic peroxide type | system | group is also mentioned. Specific examples of the transition metal compound include, for example, divanadium tetraoxide (IV), vanadium oxide acetyl acetate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl-1, Vanadium compounds such as 3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV), alternate vanadium (V), metavanadate sodium (V), ammonium metavanadate (V), scandium iodide ( Scandium compounds such as III) etc., titanium compounds such as titanium (IV) chloride, titanium (IV) tetraisopropoxide, chromium (II) chloride, chromium (III) chloride, chromium compounds such as chromate, chromate, acetic acid Manganese compounds such as manganese (II), manganese naphthenate (II), etc. Iron compounds such as iron (II) acid, iron (II) chloride, iron (III) acetate, iron (III) chloride, cobalt compounds such as cobalt (II) acetate, cobalt (II) naphthenate, nickel (II) chloride Copper compounds such as copper (I) chloride, copper (I) bromide, copper (I) bromide, copper (II) chloride, copper (II) acetate, zinc compounds such as zinc (II) chloride and zinc (II) acetate It is illustrated. Among these transition metal compounds, it is preferable to use a + IV-valent and / or + V-valent vanadium compound because high adhesion is easily obtained. As an organic peroxide, what was illustrated above is mentioned, for example.

  Moreover, the polymerization initiator of the aryl borate compound / acidic compound type | system | group which also utilized that an aryl borate compound decomposes | disassembles with an acid and produces 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. Among them, three are considered in one molecule in consideration of storage stability. Alternatively, it is preferable to use an aryl borate compound having four boron-aryl bonds, and more preferably an aryl borate compound having four boron-aryl bonds in terms of handling, synthesis and availability.

  Examples of aryl borate compounds having three boron-aryl bonds in one molecule include monoalkyltriphenylboron, monoalkyltris (p-chlorophenyl) boron, monoalkyltris (p-fluorophenyl) boron, monoalkyltris (3) 5,5-Bistrifluoromethyl) phenylboron, 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, monoalkyl tris (m-buty Oxyphenyl) boron, monoalkyltris (p-octyloxyphenyl) boron, monoalkyltris (m-octyloxyphenyl) boron, provided that the alkyl in any compound is n-butyl, n-octyl or n-dodecyl Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutyl ammonium salt, tetramethyl ammonium salt, tetraethyl ammonium salt, tributyl amine salt, triethanolamine salt, methyl pyridinium salt, ethyl pyridinium salt) Examples include butyl pyridinium salts, methyl quinolinium salts, ethyl quinolinium salts or butyl quinolinium salts.

  As an aryl borate compound having 4 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- Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutyl ammonium salt of butyloxyphenyl) [wherein in any compounds, alkyl represents either n-butyl, n-octyl or n-dodecyl] Tetramethyl ammonium salt, tetraethyl ammonium salt, tributyl amine salt, triethanolamine salt, methyl pyridinium salt, ethyl pyridinium salt, butyl pyridinium salt, methyl quinolinium salt, ethyl quinolinium salt or butyl quinolinium salt, etc. It can be mentioned.

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

  Also, as a thermal polymerization initiator, for example, benzoyl peroxide, p-chlorobenzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxydicarbonate, diisopropylperoxydicarbonate and the like Peroxides, azo compounds such as azobisisobutyronitrile, tributylborane, tributylborane partial oxide, sodium tetraphenylborate, sodium tetrakis (p-fluorophenyl) borate, triethanolamine tetraphenylborate, etc. Boron compounds, barbituric acids such as 5-butyl barbituric acid and 1-benzyl-5-phenyl barbituric acid, and sodium sulfinates such as sodium benzenesulfinate and sodium p-toluenesulfinate.

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

  The curable composition may further contain components such as a filler, a solvent, a polymerization inhibitor, a polymerization inhibitor, a dye, a pigment, and a perfume, as necessary.

  The curable composition preferably has a low viscosity. The lower the viscosity of the curable composition, the better the compatibility of the curable composition with the polymer material having a diaryl ketone group, and the reduction step when the radically polymerizable monomer in the curable composition is polymerized. The formation of the bond with the polymer material having a diaryl ketone group is performed uniformly and at a high density, and higher adhesion can be obtained. However, if the viscosity is too low, it will be 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 at 23 ° C., more preferably in the range of 0.3 cP to 10000 cP, and in the range of 0.4 cP to 3000 cP. It is further preferable that the range is 0.4 cP to 500 cP, more preferably 0.5 cP to 30 cP, and most preferably 0.5 cP to 10 cP. The viscosity is measured using a cone-plate viscometer in a thermostatic chamber kept at 23 ° C. under a red light to prevent viscosity change due to polymerization during measurement when a photopolymerization initiator is used. It is good.

  Here, it is also possible to blend a filler for the purpose of improving the strength of the curable composition. However, when the filler is blended in a large amount, the viscosity of the curable composition becomes high. Therefore, 300 parts by mass or less is preferable, 100 parts by mass or less is more preferable, 50 parts by mass or less is more preferable, and the filler mixed in the curable composition of the present invention is preferably 100 parts by mass or less. Most preferred are parts by weight or less. In addition, when the compounding quantity of a filler is too large, the ratio which the polymer material which has the diaryl ketone group which passed through the reduction process in the curable composition and the reduction process also contacts will also fall, and it has high adhesiveness. The amount of filler in the curable composition is preferably as small as possible because the density of bonding required to obtain the viscosity decreases.

  In addition, as a filler, a well-known inorganic filler, an organic filler, and an organic-inorganic composite filler are used without any restriction.

  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 process with the surface treating agent represented by the silane coupling agent. In this case, the affinity between the inorganic filler and the radical polymerizable monomer is improved, and the mechanical strength and the water resistance of the cured product can be improved. Surface treatment can be performed by a known method. As a silane coupling agent, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyl Triacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacroyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyl Dimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl ether Silane, N- phenyl--γ- aminopropyltrimethoxysilane, 11-methacryloyloxy undecyl trimethoxysilane, 11-methacryloyloxy such acryloyloxy undecyl methyl dimethoxy silane.

  Examples of the organic filler include polymethyl methacrylate, polymethyl methacrylate-polyethyl methacrylate copolymer, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene The particle | grains which consist of organic polymers, such as a copolymer, are mentioned.

  Examples of the organic-inorganic composite filler include particulate organic-inorganic composite fillers obtained by mixing the above-mentioned inorganic particles and a polymerizable monomer, followed by polymerization and pulverization.

  The particle size of these fillers is not particularly limited, and generally used fillers having an average particle size of 0.01 μm to 100 μm (particularly preferably 0.01 to 5 μm) can be suitably used according to the purpose. In addition, the refractive index of the filler is not particularly limited, and, for example, when it is used as a dental application, the filler in the range of 1.4 to 1.7 possessed by general inorganic fillers can be suitably used, etc. It may be set appropriately according to the purpose. A plurality of fillers having different particle diameter ranges and different refractive indices may be used in combination.

  A solvent may be added to the curable composition in order to make the curable composition have a low viscosity. By blending a solvent, it is easy to lower the viscosity of the curable composition, which is preferable. Here, the solvent is preferably removed from the system after applying the curable composition 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 give an adverse effect, the vapor pressure at 20 ° C. is more preferably 2.0 KPa or more, further preferably 5.0 KPa or more. On the other hand, when the volatilization of the volatile solvent is too fast, it must be applied quickly at the time of use, and in addition, the storage stability of the curable composition also deteriorates. Therefore, the vapor pressure of the volatile solvent at 20 ° C. is preferably 60 KPa or less, more preferably 50 KPa or less. Also, the boiling point of the volatile solvent is not particularly limited, but the lower the boiling point, the easier to remove the curable composition after being applied to the polymer material having a diaryl ketone group that has undergone the reduction step, the volatile solvent at 760 mmHg The boiling point is preferably 100 ° C. or less, more preferably 80 ° C. or less. Such preferred volatile solvents include, for example, 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 etc. are mentioned. These volatile solvents may be used alone or in combination of two or more if uniform mixing is possible.

  In the bonding method of the present invention, it is more preferable to roughen the adhesion surface of the polymer material having a diaryl ketone group before the reduction step. A polymer material having a roughened diaryl ketone group on the adhesion surface obtains higher adhesiveness by applying the curable composition after reducing the adhesion surface because the surface unevenness is increased. I can do things. The roughening method is not particularly limited, and any known roughening method can be used, but sandblasting is preferable from the viewpoint of simplicity and safety. Sandblasting generally sprays alumina particles having a particle diameter of several μm to several hundreds of μm onto a deposition surface of a polymer material having a diaryl ketone group at a pressure of several tens KPa to several MPa using a sandblasting apparatus Can be implemented by

  Further, in the adhesive 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 which has been subjected to the reduction step in the state of a mixture mixed with other compositions. Alternatively, in the curing step, the adhesive composition may be cured in the form of a mixture with other compositions. Further, the form in which the curable composition is applied to the surface of the polymer material having a diaryl ketone group through the reduction step is not particularly limited. For example, the polymer material having a diaryl ketone group through the reduction step of the curable composition The curable composition is applied to the surface of the other member other than the polymer material having the diaryl ketone group which has been directly applied to the surface of the polymer or which has undergone the reduction step, and then the other member has the diaryl ketone group which has undergone the reduction step. By contacting the polymer material, the curable composition can be brought into contact with the surface of the polymer material having a diaryl ketone group that has undergone the reduction step.

  In the adhesion method of the present invention, it is also possible to adhere polymer materials having a diaryl ketone group using a curable composition. In that case, for example, a reduction step is performed on both one end and the other end of the polymer material having a ring-shaped diaryl ketone group provided with an inlet, and the same curable composition is applied and cured. And one end of the polymer material having a diaryl ketone group can be bonded to the other end.

  As another example, the surface of the polymer material having a diaryl ketone group has a curable composition by applying a curable composition to the polymer material having a diaryl ketone group that has undergone a reduction step and curing the composition. It is possible to make a structure coated with a cured product of the product.

  In addition, when the curable composition has adhesiveness to another member (hereinafter sometimes referred to as "second member"), the diaryl compound can be obtained via the curable composition by using the adhesion method of the present invention. It is also possible to bond the polymer material having a ketone group to the second member. Here, the second member may be, for example, a member which forms a solid before the start of the bonding operation (hereinafter, may be referred to as a “solid second member”), before the start of the bonding operation. Is in the form of a paste or liquid, and is a curable member (hereinafter sometimes referred to as a “curable second member”) that forms a solid after completion of the bonding operation by being cured during the bonding operation. It may be.

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

  The curable second member may function as an adhesive. In this case, the cured product of the curable composition applied to the polymer material having a diaryl ketone group which has undergone the reduction step can be firmly adhered to the cured product of the curable second member. 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 has a property of firmly adhering to the surface of the third member, a polymer material having a diaryl ketone group and a radically polymerizable monomer by the adhesion method of the present invention A curable composition containing is adhered, and a curable second member before curing is applied to the third member side to perform adhesion, whereby the polymer material having a diaryl ketone group and the third member are firmly adhered. be able to. The third member can be used without particular limitation as long as it is a known solid member, but in general, it is preferable to use a member which is not a polymer having a diaryl ketone group in which a portion near the deposition surface has undergone a reduction step. The 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 process, the curable 2nd member containing a radically polymerizable monomer and a polymerization initiator The primer can be cured by using (corresponding to the second curable composition described above).

  In that case, for example, after the 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 (heat curing, light curing, chemical curing) can be appropriately selected according to the type of the polymerization initiator to be blended 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 the reduction step, and a curable second member is applied to the surface of the third member, followed by reduction. The surface of the polymer material having a diaryl ketone group through the process may be brought into contact with the surface of the third member to which the curable second member is applied, and then the curable second member may be cured. . After the primer and the curable second member are applied in this order to the surface of the polymer material having the diaryl ketone group which has undergone the reduction step, the primer and the curable second member of the polymer material having the diaryl ketone group which has undergone the reduction step The third member may be brought into contact with the surface on which the second member is applied, and then the curable second member may be cured. Alternatively, after the curable second member and the primer are applied in this order to the surface of the third member, the curable second member of the third member and the polymer having the surface to which the primer is applied and the diaryl ketone group subjected to the reduction step The surface of the material may be brought into contact and then the curable second member may be cured. In addition, the member which provides a primer and a curable 2nd member, the timing, and the timing which hardens 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, and the polymer material having a diaryl ketone group and the solid second member are the same in material composition and structure of the member. It may be different. When the solid second member is made of a polymer material having a diaryl ketone group that has undergone the reduction step, the curable composition of the present embodiment can be adhered with high adhesion to the solid second member as well. 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, etc. Materials artificially produced or purified, b) composite materials using two or more kinds of materials shown in a), or c) non-artificial biomaterials such as teeth and bones may be used.

  Moreover, a curable 2nd member contains at least a polymerization initiator and a polymerizable monomer. As each component which comprises a curable 2nd member, it is used combining suitably the material which can be used with the curable composition which can be provided to the polymer material which has the diaryl ketone group which passed through the reduction process by the adhesion method of this invention it can. However, the composition of the curable second member is selected from a composition different from the curable composition applied to the polymer material having a diaryl ketone group which has been subjected to the reduction step by the adhesion method of the present invention which is actually used for adhesion. Be done. In addition, since the curable second member contains a polymerizable monomer, the curable second member and the curable composition to be applied to the polymer material having a diaryl ketone group which has been subjected to the reduction step by the adhesion method of the present invention are strong Glued to. When the third member is further used, the polymerizable monomer contained in the curable second member may also interact with the surface of the third member to bond the curable second member to the third member. it can. Preferably, the composition of the curable second member is selected to have a high affinity to the material constituting the adhered portion of the third 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, in general, it is preferable to use a member in which the deposition part constituting material does not contain a polymer having a diaryl ketone group.

  It is particularly preferred to apply the bonding method of the invention to polymeric materials having diaryl ketone groups for use in dental applications. In dental applications, radically curable curable compositions are widely used, and by using the adhesion method of the present invention, a polymer material having a diaryl ketone group and a radically polymerizable dental curable composition Adhesion is preferable because higher adhesion than before can be obtained. Moreover, in dental applications, it is necessary to have strong adhesion in severe environments such as the oral cavity, especially in areas where high adhesion is required, but according to the adhesion method of the present invention, such a demand is required. Is preferable because it is easy to satisfy

  In addition, since dental use, in particular, dental prosthesis materials have high aesthetic requirements, in the reduction step, a solution in which a reducing agent is dissolved is applied to the surface of a polymer material having a diaryl ketone group to 60 to 180 ° C. Particularly preferred is the method of heating by

  As dental materials using the polymer material having a diaryl ketone group used in the present invention in dental applications, a denture, an artificial tooth, a denture base, a dental implant partially or entirely produced using a polymer having a diaryl ketone group And dental prosthesis 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 in dental applications, as the curable composition, a curable composition containing a radically polymerizable monomer used in dental applications Can be used. Examples of such dental curable compositions include dental composite resins, dental hard resins, dental resin cements, dental bonding materials, dental immediate polymerization resins, dental primers and the like.

  Further, as described above, radically polymerizable curable compositions are widely used in dental applications, and radically 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, the tooth is firmly fixed via a radically polymerizable adhesive composition widely used in dental applications. It becomes easy to make it adhere. Therefore, a method for producing a dental prosthesis at least including the step of reacting a polymer material having a diaryl ketone group with 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, polyaryl ether ketone resin is preferable from the viewpoint that physical properties necessary for dental use such as strength can be easily obtained. Among them, as a polyaryl ether ketone resin used as a dental restorative material, a repeating unit in which an ether group and a ketone group constituting a main chain are arranged in the order of ether, ether, and ketone from the viewpoint of color tone and physical properties. It is preferable to use a polyetheretherketone having a repeating unit or a polyetherketoneketone having repeating units arranged in the order of ether, ketone and ketone.

  From the polymer material having such a diaryl ether ketone group, a dental prosthesis material obtained through the above-mentioned reduction step has a portion of the diaryl ketone group (diaryl ketone moiety) on the surface thereof reduced to 1 carbon atom 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 moieties is a and the number of diarylmethanol moieties is b, those in which 100 × b / (a + b) is in the range of 10 to 90 are preferable, and 30 to 70 are more preferable. preferable. By setting 100 × b / (a + b) to 10 or more, it becomes easy to obtain high adhesiveness between the dental prosthesis 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 of a plaque, a contaminant, or the like to a dental prosthesis due to hydrophilic hydroxyl groups is suppressed or coloring is suppressed to enhance the dental prosthesis high. It becomes easy to maintain aesthetics.

The value of 100 × b / (a + b) can be determined by infrared spectroscopy, as is the conversion R _{IR of the} polymer material having a diaryl ketone group in the reduction step described above. By the method using this infrared spectroscopy, it is possible to confirm the state of several μm of the surface strongly involved in 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, a 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 the amount does not change by the reduction reaction, the amount of diaryl ketone site reduction and the amount of diarylmethanol site generated can be determined. That is, as described above, when the peak area ratio before performing the reduction step is bb and the peak area ratio after performing the reduction step is νa, 100 × b / (a + b) is given by the following general formula (II) The value of) can be determined.

100 × b / (a + b) = 100 × (νb−νa) / νb (II)
The value of 100 × b / (a + b) indicates the same value as R _IR obtained by the above general formula (I). That is, it becomes the relationship of the following general formula (III).

100 × b / (a + b) = R _IR [%] (III)
When a polymer material having a diaryl ketone group which has undergone the reduction step as described above is used as a dental prosthesis material, a dental resin which is a curable composition which is radically polymerizable using the material itself as a dental prosthesis The cement can be used to attach to dentin or used to make a dental prosthesis by laminating a dental hard resin or the like.

  In addition, in the case of producing a dental prosthesis 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 on which the dental hard resin or the like is laminated is reacted with a reducing agent. Thus, the dental prosthesis material of the present invention can be obtained. After that, the dental hard resin may be directly applied to the surface, or the dental bonding material treatment or the dental primer treatment may be performed before applying the dental hard resin, and then the dental hard resin may be laminated. .

  When the material itself is used as a dental prosthesis, a dental resin cement is prepared to make a dental prosthesis of a desired shape with a polymer material having a diaryl ketone group in, for example, a dental laboratory and attach it to the dental substance The dental prosthesis material of the present invention can be obtained by reacting the surface to which it is applied with a reducing agent. Thereafter, the dental resin cement is used to attach it to the patient's dentin defect portion, or the surface treated with the reducing agent of the polymer material having a diaryl ketone group before applying the dental resin cement After treatment with a dental bonding material or treatment with a dental primer, the dental resin cement can be used to attach to a patient's dentate defect portion. When the dental prosthesis material of the present invention is attached to the tooth defect as described above, the polymer material having the reduced diaryl ketone group can be slowly oxidized by oxygen or the like in the air, but at least one week It is possible to maintain the surface condition to obtain high adhesion. Therefore, a dental prosthesis is made of a polymer material having a diaryl ketone group at a dental laboratory, and a reduction reaction is carried out at the dental laboratory where the equipment such as a heating device is ready as it is, and the reduction surface is dust etc. It is an example of a method for producing and using a dental prosthesis that it is preferable to pack it in a box so as not to be contaminated due to the adhesion of the product, cover it with a cloth or aluminum foil and send it to a dental clinic.

  A dental treatment kit comprising a dental curable composition containing a radical polymerizable monomer and a polymerization initiator, a dental prosthesis material in which a polymer material having a diaryl ketone group and a reducing agent are reacted, is suitable It can also be mentioned as a new dental treatment kit. The dental curable composition constituting the kit means any dental material containing a radically polymerizable monomer, and specifically, a dental bonding material, a dental resin cement, a dental filling repair material, a dental Hard resin, dental immediate polymerization resin, dental primer etc. In addition, this kit for dental treatment comprises two components of a dental curable composition containing a radical polymerizable monomer, a dental prosthesis material in which a polymer material having a diaryl ketone group and a reducing agent are reacted. The kit may be a kit consisting only of, or other components, for example, in the case where a dental primer containing no polymerization initiator is used as a dental curing composition, the dental primer is used by further laminating on the dental primer. For example, resin cement may be included.

  Also, a dental curable composition containing a radical 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 And a dental treatment kit containing the same may be mentioned as a suitable dental treatment kit. This dental treatment kit reduces a dental curable composition containing a radical 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 a kit consisting of only three components of the reducing agent solution to be used, or other components, such as the dental hardener if the dental primer containing no polymerization initiator is used as the dental hardenable composition. It may be one including a dental resin cement or the like which is used by further laminating on the primer.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The abbreviations and titles shown in the examples are as follows.

[Radical 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: camphor quinone DMBE: p-dimethylaminobenzoic acid ethyl ester BPO: benzoyl peroxide DMPT: N, N-dimethyl-p- toluidine DMAn: 9, 10-dimethyl anthracene 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-methacryloyloxypropyl trimethoxy Surface-treated with silane [solvent]
・ DMSO: dimethyl sulfoxide ・ DMI: 1,3-dimethyl-2-imidazolidinone ・ DMF: N, N-dimethylformamide [cationic polymerizable monomer]
・ OX-1

・ EP-1

  As the adherend, a polyetheretherketone resin material which is a polymer material having two kinds of diaryl ketone groups D1 and D2 was used. D1 is VESTAKEEP MC 4420 (manufactured by Daicel Evonik), and D2 is VESTAKEEP M2G (manufactured by Daicel Evonik).

  Each test method is as follows.

(Measurement of tensile bond strength)
The above-mentioned polyetheretherketone resin material was formed into a plate having a thickness of about 2 mm by injection molding to obtain an adherend. The adherend surface of this adherend was polished with # 800 water-resistant abrasive paper and sandblasted (Alumina particles with a particle size of about 50 μm were sprayed for 10 seconds at a pressure of about 0.2 MPa using a sandblasting apparatus) It was coarsened. Then, it was immersed in water and exposed to ultrasonic waves for 5 minutes, and subsequently, it was immersed in acetone and washed by ultrasonic waves for 5 minutes. Subsequently, based on each method shown to M1-M5 mentioned later, the process of making it react with a reducing agent etc. was performed with respect to the surface which performed the sandblasting of polyetheretherketone resin material. A double-sided tape having a hole of 3 mm in diameter was attached to the surface of the obtained polyetheretherketone resin material on which the reduction reaction and the like were performed.

Thereafter, when the curable composition is B1, B2 or B3, the curable composition (B1, B2 or B3) is applied to the hole and left for 10 seconds, and then compressed air is sprayed for about 10 seconds for drying. The curable composition was irradiated with light for 30 seconds using a dental irradiator (Tokso Power Light, manufactured by Tokuyama Dental Co., Ltd .; light output density 700 mW / cm ² ) for curing. A resin cement for dental use (Bistite II, manufactured by Tokuyama Dental Co., Ltd.) was applied thereon, and a stainless steel attachment was pressure-welded thereon, to prepare an adhesion test piece.

  When a primer was used as a curable composition (P1), the primer (P1) was applied to the hole, left for 10 seconds, and 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 resin cement to prepare an adhesion test piece.

  When the curable composition was C1, the curable composition (C1) was applied onto the hole, and a stainless steel attachment was further pressed onto the hole to produce an adhesion test piece.

When the curable composition was R1, a simulated cavity was formed by fixing paraffin fuchs having a hole of 0.5 mm in thickness and 8 mm in diameter 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 (Tokso Power Light, manufactured by Tokuyama Dental Co., Ltd .; light output density 700 mW / cm ² ) The composition was irradiated with light to cure it. A resin cement for dental use (Bistite II, manufactured by Tokuyama Dental Co., Ltd.) is applied thereon, and a stainless steel attachment is pressed against the resin cement to form an adhesive test piece. Instead of the radically polymerizable composition, it is cationically polymerizable. When using the composition (O1), a simulated cavity was formed by fixing paraffin wax having a hole of 0.5 mm in thickness and 8 mm in diameter so as to be concentric with the hole of the double-sided tape. This simulated cavity is filled with a cationic polymerizable composition (O1), pressed with a polyester sheet, and cationized for 30 seconds with a dental irradiator (Tokso Power Light, manufactured by Tokuyama Dental Co., Ltd .; light output density 700 mW / cm ² ) The polymerizable composition was irradiated with light to be cured. A resin cement for dental use (Bistite II, manufactured by Tokuyama Dental Co., Ltd.) was applied thereon, and a stainless steel attachment was pressure-welded thereon, to prepare an adhesion test piece.

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

(Measurement of reaction rate R _IR of reduction reaction)
The above-mentioned polyetheretherketone resin material was formed into a plate having a thickness of about 2 mm by injection molding to obtain an adherend. Then, it was immersed in water and exposed to ultrasonic waves for 5 minutes, and subsequently, it was immersed in acetone and washed by ultrasonic waves for 5 minutes. The surface of the polyetheretherketone resin material thus obtained is thoroughly dried, and 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 ν b (= 16 1650 cm ^-1 / 14 1490 cm ^-1 ) was determined.

  Thereafter, the surface of the polyether ether ketone resin material for which the peak area ratio was determined was subjected to a treatment such as reaction with a reducing agent, based on each method described in M1 to M5 described later.

An IR spectrum was obtained by a single reflection ATR method using a Fourier transform infrared spectrophotometer, and the peak of a peak derived from a carbonyl group appeared in the vicinity of 1650 cm ^-1 for a surface which was thoroughly dried after treatment and treated. and calculating the area (ν1650cm ^-1) and 1490cm ^-1 aromatic ring of the peak area of the peak appearing in the vicinity (ν1490 ^-1), the peak area was determined ratio νa after the reaction ^{(= ν1650cm -1 / ν1490cm -1)} .
The reaction ratio R _IR (= 100−νa / νb × 100) obtained by infrared spectroscopy was calculated using the peak area ratio obtained in this manner.

(Reaction of polyetheretherketone resin material and reducing agent)
The polyetheretherketone resin material and the reducing agent were reacted by each method shown below.

  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 using a brush to the surface of the washed polyetheretherketone resin material after sandblasting, and was left in an oven maintained at 120 ° C. for 3 hours. The polyetheretherketone resin material was removed from the oven, cooled to room temperature, immersed in water and exposed to ultrasound for 5 minutes, and subsequently immersed in acetone and exposed to ultrasound for 5 minutes to perform washing.

  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 using a brush to the surface of the washed polyetheretherketone resin material after sand blasting, and was left in an oven maintained at 120 ° C. for 3 hours. The polyetheretherketone resin material was removed from the oven, cooled to room temperature, immersed in water and exposed to ultrasound for 5 minutes, and subsequently immersed in acetone and exposed to ultrasound for 5 minutes to perform washing.

  M3: Sodium borohydride was dissolved in DMF to prepare a 0.7 mol / l sodium borohydride / DMF solution. After sand blasting, a sodium borohydride / DMF solution was applied to the surface of the washed polyetheretherketone resin material using a brush, and was allowed to stand in an oven maintained at 120 ° C. for 3 hours. The polyetheretherketone resin material was removed from the oven, cooled to room temperature, immersed in water and exposed to ultrasound for 5 minutes, and subsequently immersed in acetone and exposed to ultrasound for 5 minutes to perform washing.

(Other processing method)
M4: After sand blasting, the washed polyetheretherketone resin material was thoroughly dried.
M5: After sand blasting DMSO was applied using a brush on the surface of the washed polyetheretherketone resin material, and left in an oven maintained at 120 ° C. for 3 hours. The polyetheretherketone resin material was removed from the oven, cooled to room temperature, immersed in water and exposed to ultrasound for 5 minutes, and subsequently immersed in acetone and exposed to ultrasound for 5 minutes to perform washing.

Example 1
Diaryl according to the procedure of M1, 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 A reduction step was carried out in which a polymer material having a ketone group was reacted with a reducing agent. 5g of bisGMA as a radically polymerizable monomer component and 5g of 3G are mixed, 0.2g of CQ as a polymerization initiator component and 0.2g of DMBE are added, and 10g of acetone as a solvent is further added and stirred for curing Sex composition B1 was produced. The composition of the curable composition is shown in Table 1. The reaction rate of the reduction step of the polymer material having the diaryl ketone group and the tensile adhesion 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
According to Example 1, a reduction step in which a polymer material having a diaryl ketone group and a reducing agent were reacted was performed. A curable composition was produced 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 step of the polymer material having the diaryl ketone group and the tensile adhesion 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
According to Example 1, a reduction step in which a polymer material having a diaryl ketone group and a reducing agent were reacted was performed. 3 g of bisGMA as a radically polymerizable monomer component, 2 g of 3 G, 1.5 g of PM1, 1.5 g of PM2, and 2 g of HEMA are mixed, and 10 g of acetone is further added as a solvent 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 step of the polymer material having the diaryl ketone group and the tensile adhesion 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
According to Example 1, a reduction step in which a polymer material having a diaryl ketone group and a reducing agent were reacted was performed. 3g of bisGMA as a radically polymerizable monomer component, 2g of 3G, 1.5g of PM1, 1.5g of PM2 and 2g of HEMA are mixed, 0.05g of DEPT is added as a polymerization initiator component, and a filler is further added 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 in a use straight line, to which 9.7 mg of BPO was added and mixed to obtain a curable composition C1, which was used for a quick test. The composition of the curable composition is shown in Table 1. The reaction rate of the reduction step of the polymer material having the diaryl ketone group and the tensile adhesion 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
According to Example 1, a reduction step in which a polymer material having a diaryl ketone group and a reducing agent were reacted was performed. 5g of bisGMA as a radically polymerizable monomer component and 5g of 3G are mixed, 0.2g of CQ as a polymerization initiator component and 0.2g of DMBE are added, and 16g of F1 and 10g of F2 are further added as a filler component The mixture was mixed and pasted to prepare a curable composition R1. The composition of the curable composition is shown in Table 1. The reaction rate of the reduction step of the polymer material having the diaryl ketone group and the tensile adhesion 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 of reacting a polymer material having a diaryl ketone group shown in Table 1 with a reducing agent, a polymer material having a diaryl ketone group and a reducing agent according to Example 1 except that the solution of the reducing agent solvent is changed The reduction process to make it react was performed. The reaction rate of the reduction step of the polymer material having the diaryl ketone group and the tensile adhesion 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
A reduction step of reacting a polymer material having a diaryl ketone group with a reducing agent was performed according to Example 1 except that the polymer material having a diaryl ketone group was changed to D2. The reaction rate of the reduction step of the polymer material having the diaryl ketone group and the tensile adhesion 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 polymeric material with the diaryl ketone group was treated according to the procedure of M4, without reaction with the reducing agent. The tensile bond strength between the conversion of the polymer and the curable composition B1 prepared in Example 1 was measured. The results are shown in Table 3.

Comparative Example 2
The polymeric material with the diaryl ketone group was treated according to the procedure of M5 without reaction with the reducing agent. The tensile bond strength between the conversion of the polymer material having the diaryl ketone group and the curable composition B1 prepared in Example 1 was measured. The results are shown in Table 3.

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

Comparative Example 4
According to Example 1, a reduction step in which a polymer material having a diaryl ketone group and a reducing agent were reacted was performed. The tensile bond strength between the conversion 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 bond strength of the polymerizable composition of each of the examples and the comparative examples with respect to the polyetheretherketone resin material.

  Regarding the evaluation results, in Examples 1 to 10 using the curable composition containing a radically polymerizable monomer after reacting the polyetheretherketone resin material with the reducing agent, the polyetheretherketone resin material is used as the reducing agent. It showed higher adhesive strength than Comparative Examples 1 and 2 in which the curable composition was applied without reaction.

  Comparative Examples 3 and 4 using a curable composition prepared so that a cationic polymerization reaction occurs instead of a radical polymerization reaction differ in adhesion strength between the case where the polyetheretherketone resin material is reacted with a reducing agent and the case where it is not caused to react Did not appear. This is because the effect of improving the adhesive strength by reacting the polyetheretherketone resin material with the reducing agent requires a radically polymerizable composition, and the polyetheretherketone resin material and the radically polymerizable monomer are necessary. It is shown that it supports the theory that adhesion strength is improved by generating bonds by radical reaction.

  Comparing Examples 1 to 4 using a curable composition that differs only in the composition of the radically polymerizable monomer after reacting the polyetheretherketone resin material with the reducing agent, the radically polymerizable unit having a hydroxyl group In Examples 1, 3 and 4 in which the curable composition containing the body (bisGMA, HEMA, PM1, PM2) was used, the examples using the curable composition containing no radically polymerizable monomer having a hydroxyl group It showed high adhesive strength compared with 2. In addition, in Examples 1 and 3 using the curable composition containing a radically polymerizable monomer (bisGMA, HEMA) having an alcoholic hydroxyl group, radical polymerization having a hydroxyl group but not having an alcoholic hydroxyl group It showed high adhesive strength as compared with Example 4 using a curable composition containing a monomer (PM1, PM2).

  In Examples 3, 5 and 6 in which a curable composition having the same radical polymerizable monomer composition was used for a polyaryl ether ketone resin material reacted with a reducing agent, a polymerization initiator was used at a low viscosity. A curable composition containing a curable composition and containing a low viscosity but containing no primer and a primer containing a polymerization initiator but containing a filler and having a high viscosity It showed high adhesive strength as compared with Example 6 which was applied.

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

  Among the curable compositions used in this example, B1, B2, B3, B4, and P1 were 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 is more than 3000 cP. Comparing Examples 1 to 7 in which the reduction reaction was performed on the same adherend in the same manner, it was found that B1, B2, B3, B4 and P1, which are curable compositions with lower viscosity, were used. Examples 1-5 showed high adhesive strength compared with Examples 6 and 7 which use C1 and R1 which are curable compositions with higher viscosity.

Claims (4)

Comprising a polymeric material having a di-aryl ketone group, a radical polymerizable monomer having a hydroxyl group in the radical polymerizable monomer and (b) in the molecule having two or more polymerizable functional groups in (a) molecule A curable composition containing a radically polymerizable monomer, wherein 50% by mass or more of all radically polymerizable monomers contained in the curable composition is the above (a) or (b) Preparing the composition ;
On the surface of the port Rimmer material, a solution in which a reducing agent is dissolved at a concentration of at least 0.1 mol / l in a solvent was applied by heating to 60 to 180 ° C., carbonyl diaryl ketone group present in the surface Reducing the group to form a hydroxyl group ,
Wherein the surface of the polymeric material which a hydroxyl group is generated in the reduction step, the curable composition step of applying the curable composition, and curing step of curing the curable composition,
Characterized in that it comprises a said polymeric material, and a cured product of the curable composition, the method of bonding.   The adhesion method according to claim 1, wherein the reducing agent is a hydride reducing agent. The radical polymerizable monomer, bonding method according to claim 1 or 2 is a radical polymerizable monomer having a (meth) acryloyl groups. In the reduction step, the reaction rate of the reduction defined by the following formula: R _IR The adhesion method according to any one of claims 1 to 3, wherein L is 30% to 70%.
R _IR (%) = 100− (νa / νb × 100)
{However, bb and νa in the above formula respectively measure the surface of the polymer material before and after the reduction of the reduction step by the single reflection ATR method using a Fourier transform infrared spectrophotometer. 1650 cm obtained when ^-1 Peak area of the peak derived from the carbonyl group appearing in the vicinity (ν 1650 cm ^-1 ) And 1490 cm ^-1 Peak area of the peak of the aromatic ring appearing in the vicinity (ν 1490 cm ^-1 Peak area ratio (ν 1650 cm) ^-1 / 14 1490 cm ^-1 The peak area ratio (νb) before the reduction reaction and the peak area ratio (νa) after the reduction reaction are shown. }