JP2018184504A - Method for producing adhesive polyaryletherketone resin material, and method for bonding polyaryletherketone resin material and adherend - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive polyaryletherketone resin material which thins a thickness of an adhesive layer and can obtain a high adhesive strength when a polyarylether ketone resin material and an adherend are bonded to each other.SOLUTION: A method for producing an adhesive polyaryletherketone resin material includes irradiating a polyaryletherketone resin material with light, and then applying an adhesive containing a radical polymerizable monomer to the resin material. In the production method, the maximum peak wavelength of the light used in light irradiation is preferably 400 nm to 500 nm.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing an adhesive polyaryletherketone resin material, and a method for adhering a polyaryletherketone resin material and an adherend.

  Super engineering resins are used in a wide range of applications such as electric / electronic field, aerospace field, automobile industry, medical field, general industrial field and so on. Among these super engineering resins, in particular, polyaryletherketone resins 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 has been proposed in which a polyaryl ether ketone resin material containing the polyaryl ether ketone resin as a main constituent is used as a dental material (for example, Patent Document 1). When a polyaryl ether ketone resin material is used as a dental material, it is necessary to firmly adhere to an adherend such as a tooth or another type of dental material. Various techniques have been proposed as a technique for bonding the polyaryl ether ketone resin material and the adherend (for example, Patent Document 2, Non-Patent Documents 1 and 2).

  Polyaryl ether ketone resin materials having excellent chemical properties and physical properties are widely used not only in dental applications but also in various fields. For this reason, there is a need for a technique capable of firmly bonding the polyaryl ether ketone resin material and the adherend regardless of the technical field or application.

  In the case where the polyaryl ether ketone resin material and the adherend are bonded using an adhesive, it is desired from the viewpoints of appearance and dimensional stability to make the adhesive layer thin. For example, in the dental field, when an abutment tooth and a prosthesis made of a dental polyaryletherketone resin material are bonded, if the adhesive layer is thick, the compatibility of the dental prosthesis is adversely affected and the dental prosthesis is lifted The amount of cutting and polishing of dental prosthesis increases due to occlusion adjustment, which increases the burden on dentists and patients. When a dental prosthesis is prepared by adhering an adherend such as a filling restoration material or a dental hard resin with an adhesive, if the adhesive layer is thick, it can be seen, and the prepared dental The prosthesis for use will be inferior in aesthetics.

  Typical adherends that need to adhere to polyaryletherketone resin materials are used in the dental field for composite resins used for filling and repairing dental defects, prosthetics, and dentures. Examples thereof include a hard resin, an immediate polymerization resin, and a dental cement used for bonding to another member. These composite resins, hard resins, immediate polymerization resins, dental cements and the like are almost always composed of a curable composition containing a radical polymerizable monomer and a polymerization initiator. In the case of an adherend other than the dental field, for example, an adhesive material, a coating material, a sealing material, a paint, and the like can be mentioned, and these are also constituted by a curable composition containing a radical polymerizable monomer. There are many. Therefore, in bonding the polyaryletherketone resin material and the curable composition containing the radical polymerizable monomer, a technique for bonding the adhesive layer thinly and with high strength is desired.

  As an adhesion technique between the polyaryl ether ketone resin material and the adherend, for example, in the dental field, a method of curing an adhesive containing a polymerizable monomer and a photopolymerization initiator by light irradiation is effective. There is a report. For example, Non-Patent Document 1 describes that relatively high adhesiveness was obtained by using a hydrophobic dental adhesive. After applying a photocurable adhesive to a polyaryletherketone resin material, polymerizing and curing by light irradiation, an adherend composed of a curable composition containing a radical polymerizable monomer and a polymerization initiator is formed. High adhesiveness can be obtained by curing with pressure bonding. However, when the photocurable adhesive is irradiated with light before the adherend is pressure-bonded, the adhesive is polymerized and cured at the time of light irradiation, so that an undeformable adhesive layer is formed. It is difficult to reduce the thickness of the layer.

  Although studies have been conducted to evaluate adhesiveness of polyaryletherketone resin materials using a dental adhesive (primer) that does not contain a polymerization initiator, high adhesion strength has not been obtained. . For example, Non-Patent Document 2 describes a primer composed of an acidic group-containing polymerizable monomer, a silane coupling agent, and a solvent. In the adhesion test using the primer, the primer is applied after roughening treatment and cleaning of the polyaryletherketone resin material, and the dental resin cement is used as an adherend after holding for 180 seconds. The dental resin cement contains a chemical polymerization initiator, and when the dental resin cement is pressure-bonded onto the primer, the primer is cured by the chemical polymerization initiator of the dental resin cement. In this case, since the primer can be deformed for a certain time after the dental resin cement is pressed, the thickness of the primer layer is reduced.

  Patent Document 2 discloses a conditioning agent containing an adhesive and a high-boiling solvent having a bipolar property for a molded article containing a high-temperature resistant plastic (including a polyaryl ether ketone resin material) and a filler. A conditioning technique has been proposed. Specifically, two types of conditioning agents consisting of methacryl silane and dimethyl sulfoxide (DMSO), methacryl silane, DMSO and ethanol are shown in the examples. In an adhesion test using the conditioning agent, the conditioning surface is infiltrated with the conditioning agent, soaked for 2 minutes, and a clean air stream is blown onto the conditioning agent, and then a photocurable dental plastic is pressed onto the adhesion surface. The photocurable dental plastic is cured by light irradiation. In this method, since the filler exhibits a bonding effect by being surface-modified with methacrylic silane, a high adhesive force can be obtained for a molded product containing the filler, but the filler is included. It doesn't show any effect on things that are not.

JP 2013-144778 A Special table 2010-521257

DENTAL MATERIALS 26 (2010) 553-559 DENTAL MATERIALS 28 (2012) 1280-1283

  As described above, when the polyaryl ether ketone resin material and the adherend are bonded, when the adhesive is applied to the polyaryl ether ketone resin material and then cured by polymerization, the adhesive strength is high. However, it was difficult to make the adhesive layer thin. On the other hand, in the case of an adhesive that presses the adherend without applying polymerization and curing to the polyaryletherketone resin material, it is not difficult to make the adhesive layer thin, but high adhesive strength cannot be obtained. There was a problem. Then, this invention makes it a subject to make thin the adhesive layer thickness, and to obtain high adhesive strength at the time of adhesion | attachment of a polyaryl ether ketone resin material and a to-be-adhered body.

  In the present application, the adhesive layer means a layer formed by a composition (adhesive) containing a polymerizable monomer that is first applied to the polyaryl ether ketone resin material, and the method of the present invention. In the adhesive polyaryletherketone resin material obtained in the above, it means a thin film layer formed by an adhesive containing a radical polymerizable monomer. In addition, after the adherend made of a curable composition containing a radical polymerizable monomer and a polymerization initiator is bonded to the polyaryl ether ketone resin material, the adhesive and the curable composition are Both are polymerized and cured, and the adhesive layer after bonding means a thin film layer of the cured adhesive.

  In order to solve the above-mentioned problems, the inventors have conducted intensive studies. As a result, the polyaryl ether is coated with an adhesive containing a radical polymerizable monomer after light irradiation of the polyaryl ether ketone resin material. The ether ketone resin material has high adhesion and formation of a thin adhesive layer on an adherend, particularly an adherend composed of a curable composition containing a radical polymerizable monomer and a polymerization initiator. I found out that both are compatible. In the usual case, the adhesive containing the photopolymerization initiator may be irradiated with light, but the polyaryletherketone resin material is not irradiated with light before the adhesive is applied. In other words, in the present invention, the polyaryletherketone resin material that is not normally irradiated with light is irradiated with light, and then an adhesive containing a polymerizable monomer is applied to improve adhesion and thin adhesion. It is an invention made by finding that the formation of the agent layer can be made compatible.

  That is, the present invention relates to a method for producing an adhesive polyaryletherketone resin material characterized by applying an adhesive containing a radical polymerizable monomer to a polyaryletherketone resin material after light irradiation. It is. It is preferable that the maximum peak wavelength of light used for light irradiation is 400 nm to 500 nm, and the radical polymerizable monomer contained in the adhesive contains 40% by mass or more as a polymerizable functional group having 2 or more (meta ) A radical polymerizable monomer having an acryloyl group is preferred.

  The polyaryletherketone resin material in the production method of the present invention is preferably for dental use.

  Another embodiment of the present invention is an adhesion method for adhering a polyaryl ether ketone resin material and an adherend comprising a curable composition containing a radical polymerizable monomer and a polymerization initiator, After light irradiation of the polyaryl ether ketone resin material, an adhesive containing a radical polymerizable monomer is applied, and then an adherend is applied on the polyaryl ether ketone resin material to which the adhesive is applied. This is a method of bonding a polyaryletherketone resin material and an adherend by pressure bonding and polymerizing and curing the curable composition.

  Furthermore, the present invention provides a pretreatment method for a polyaryletherketone resin material, characterized by applying an adhesive containing a radical polymerizable monomer to the polyaryletherketone resin material after light irradiation. It is.

  When the method according to the present invention is applied, an adhesive polyaryletherketone having high adhesion to an adherend, particularly an adherend composed of a curable composition containing a radical polymerizable monomer and a polymerization initiator. A resin material is obtained, and it is possible to reduce the thickness of the adhesive layer and increase the adhesive strength between the polyaryl ether ketone resin material and the adherend. Therefore, for example, in dental use, when a dental prosthesis made of a polyaryletherketone resin material is attached to an abutment tooth, a treatment with high adhesion and high compatibility can be obtained, or a polyaryletherketone resin Since an adhesive layer can be made thin when producing a dental prosthesis using a material and a dental curable composition, it becomes possible to produce a dental prosthesis with higher aesthetics.

  In addition, if the method according to the present invention is applied, the polyaryletherketone resin material can be sufficiently irradiated with light without considering the curing of the adhesive containing the radical polymerizable monomer. Irradiation conditions can be easily set, and the versatility is excellent.

  Radiation polymerization is performed by using an adhesive polyaryletherketone resin material produced by applying light-irradiated polyaryletherketone resin material and then applying an adhesive containing a radically polymerizable monomer. High adhesiveness can be obtained in bonding with a curable composition containing a polymerizable monomer and a polymerization initiator, for example, a dental curable composition such as a dental resin cement or a dental hard resin.

  In addition, if the method according to the present invention is applied, the polyaryletherketone resin material can be sufficiently irradiated with light without considering the curing of the adhesive containing the radical polymerizable monomer. Irradiation conditions can be easily set, and the versatility is excellent.

  In the present invention, as described above, the polyaryletherketone resin material is subjected to light irradiation that is not normally performed, and then an adhesive containing a radical polymerizable monomer is applied to the polyaryletherketone resin material. It is an invention that has found that the adhesion to an adherend of a ketone resin material, particularly a curable composition having a radical polymerizable monomer, is improved.

  The reason why the adhesion of the polyaryletherketone resin material is improved is that the carbonyl group bonded to the two aromatic rings on the surface of the polyaryletherketone resin is activated by light irradiation to generate radicals, and the radicals and adhesion applied thereafter It is presumed that the surface of the polyaryletherketone resin material is modified by the reaction with the radical polymerizable monomer in the agent. By this reaction, the adhesive force at the interface between the adhesive and the polyaryletherketone resin material is dramatically improved. In addition, the adhesive polyaryletherketone resin material produced in this way is not the one in which the radical polymerizable monomer of the entire adhesive is polymerized and cured to form an adhesive layer with a certain thickness. Only the radical polymerizable monomer existing near the surface of the polyaryl ether ketone resin material contributes to the reaction based on radical generation by the activation of the ketone group, and radical polymerization in most adhesives The polymerizable monomer does not polymerize after coating and remains as the polymerizable monomer. Further, even if the adhesive contains a chemical polymerization initiator, it does not immediately reach a high polymerization rate. Therefore, the adhesive itself exists on the adhesive polyaryletherketone resin material as an easily deformable layer, and an adherend made of a curable composition is laminated and pressure-bonded to the adhesive polyaryletherketone resin material. When doing so, the adhesive is easily deformed and thinned by the pressure during lamination and pressure bonding. Therefore, when the adherend and the adhesive polyaryletherketone resin material are bonded, the adhesive layer between the adherend and the adhesive polyaryletherketone resin material becomes thin. Since the adherend contains a polymerization initiator, the radical polymerization monomer in the adhesive and the radical polymerization in the curable composition even if the polymerization initiator is not contained in the adhesive. The polymerizable monomer is polymerized, and the adhesion between the adhesive and the curable composition is also strengthened. Of course, if the adhesive contains a chemical polymerization initiator, the polymerizability of the adhesive is also improved, and the adhesive strength is further improved.

<Polyaryl ether ketone resin material>
The polyaryl ether ketone resin material that can be used in the present invention contains a polyaryl ether ketone resin in a blending amount that provides the advantage of using a polyaryl ether ketone resin such as high strength. The polyaryl ether ketone resin is preferably contained in an amount of 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more.

  Such a polyaryletherketone resin material is preferably composed only of a polyaryletherketone resin, but a polyaryletherketone resin blended with another resin, a polyaryletherketone resin or a polyarylether A composite material in which a blend of a ketone resin and other resin is used as a resin matrix and mixed with a filler (hereinafter, the composite material is also referred to as a polyaryl ether ketone resin composite material) may be used. Moreover, trace components, such as a pigment and a stabilizer, may be added to these materials.

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

  The other resin that can be blended with the polyaryl ether ketone resin is not particularly limited as long as it does not significantly deteriorate the physical properties of the polyaryl ether ketone resin such as rigidity and toughness. For example, polyarylate, Examples include polycarbonate, polyethylene terephthalate, polyphthalamide, polytetrafluoroethylene, and polyphenylene ether. The other resin is preferably less than 50% by mass of the total resin, more preferably less than 30% by mass, more preferably less than 10% by mass, and more preferably less than 1% by mass.

  As the filler that can be blended in the polyaryl ether ketone resin material, known fillers can be used without particular limitation, but inorganic fillers such as amorphous inorganic compound particles are suitable. For example, as a material of the filler composed of amorphous inorganic compound particles, silica glass, borosilicate glass, soda glass, aluminosilicate glass, and fluoroaluminosilicate glass, glass containing heavy metals (for example, barium, strontium, zirconium); Composite inorganic oxides such as silica-zirconia, silica-titania, silica-alumina; or oxides obtained by adding group I metal oxides to these composite inorganic oxides; metal inorganic oxides such as silica, alumina, titania, zirconia And so on.

  The polyaryl ether ketone resin composite material preferably contains 15% by mass or more, and preferably contains 25% by mass or more of the inorganic filler. Further, the blending ratio of the inorganic filler in the polyaryl ether ketone resin composite material is preferably 70% by mass or less, and more preferably 50% by mass or less.

  Among these fillers, in particular, by blending amorphous inorganic compound particles having a volume average particle diameter of 0.1 μm to 3.0 μm, higher adhesiveness can be obtained by the method of the present invention, which is more preferable. . Although the cause is not understood in detail, when light irradiation is performed, a part of the light reaching the surface of the polyaryletherketone resin material is scattered by the amorphous inorganic compound particles, so that polyaryl by light described later is scattered. It is estimated that the activation of the ether ketone resin is performed more efficiently.

  The volume average particle diameter of the amorphous inorganic compound particles is more preferably 0.5 μm to 2.5 μm, more preferably 0.7 μm to 2.0 μm, and 0.8 μm to 1.2 μm. It is more preferable that

  Here, the volume average particle diameter of the filler to be blended with the polyaryl ether ketone resin material is measured using a laser scattering method (using LS230 manufactured by Beckman Coulter as a measuring device and ethanol as a dispersion medium). I can do it. In measurement, 0.01 to 1 g of a measurement sample is added to 5 ml of ethanol as a dispersion medium. The liquid in which the sample is suspended is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 5 minutes, and the particle size distribution of particles having a particle size in the range of 0.04 to 2000 μm is measured. For the particle size range (channel) divided based on the particle size distribution measured in this manner, the volume is drawn from the small diameter side to the cumulative distribution, and the particle size that becomes 50% cumulative is the volume average particle size (D50). ).

  The blending amount of the amorphous inorganic compound particles in the polyaryl ether ketone resin composite material is preferably in the range of 10% by mass to 50% by mass from the viewpoint of efficient light scattering in order to obtain higher adhesion. The range of 20% by mass to 40% by mass is more preferable, and the range of 25% by mass to 35% by mass is still more preferable.

  As the amorphous inorganic compound particles, amorphous silica is preferable because it has a high effect of improving adhesiveness by applying light to the polyaryletherketone resin material and then performing light irradiation. The purity of the amorphous silica particles is preferably 99.5% or more, more preferably 99.9% or more, excluding the water content. In addition, the shape of the amorphous silica particles is not particularly limited, and for example, a spherical shape, an indefinite shape, or the like can be appropriately selected. The method for producing the amorphous silica particles is not particularly limited, but the vapor phase melting method is preferable because it is suitable for producing amorphous silica particles having high purity and high sphericity.

  The method for mixing the polyaryl ether ketone resin and the filler is not particularly limited, and a known method can be used. Generally, the filler and the polyaryletherketone resin are mixed by heating, melting and kneading (melt kneading). The apparatus used for performing melt kneading is not particularly limited, and a known melt kneading apparatus can be used. For example, a mixer with a heating device, a single-axis melt kneading apparatus, a biaxial melt kneading apparatus, or the like can be used.

<Adhesive>
In the present invention, the adhesive containing a radical polymerizable monomer is used to adhere a polyaryl ether ketone resin material and an adherend composed of a curable composition containing a radical polymerizable monomer and a polymerization initiator. Furthermore, it is applied to the adherend surface of the polyaryletherketone resin material, and is applied after light irradiation to the adherend surface of the polyaryletherketone resin material. In other words, the adhesive is not polymerized and cured to the extent that it cannot be deformed. Therefore, it is easy to make the adhesive layer thin when contacting and press-bonding an adherend comprising a curable composition containing a radical polymerizable monomer and a polymerization initiator.

  The pressure bonding in the present invention is an adhesion made of a curable composition further containing a radical polymerizable monomer and a polymerization initiator on the adhesive layer applied to the adhesion surface of the polyaryl ether ketone resin material. The body is installed and force is applied to the adhesive layer through the adherend before curing. It is pressed by using a hand or a machine from above the adherend before curing. An adherend composed of a curable composition containing a radically low-paste radically polymerizable monomer and a polymerization initiator is placed on an adhesive before the adherend is cured and no longer deforms. And then applying an adherend made of a curable composition containing a radically polymerizable monomer and a polymerization initiator having a relatively low viscosity on the surface of the solid. For example, the surface is brought into contact with the adhesive layer and pressed. In addition, when an adherend composed of a curable composition containing a radical polymerizable monomer and a polymerization initiator is placed on an adhesive, force is applied to the adhesive layer before curing by the gravity, As compared with the case of pressing, the effect is small, but the effect of the present invention is obtained and included in the pressure bonding in the present invention.

  As the adhesive containing a radical polymerizable monomer in the present invention, any composition containing a radical polymerizable monomer can be used.

  The radical polymerizable monomer contained in the adhesive in the present invention is a compound having a radical polymerizable functional group in the molecule, and any known one can be used without any limitation. Examples of the radical polymerizable functional group include a vinyl group, a styryl group, an allyl group, a (meth) acryloyl group, and the like, and a (meth) acryloyl group is particularly preferable from the viewpoint of polymerization rate and biosafety. . Examples of preferable radical polymerizable monomers include, for example, radical polymerizable monomers having a (meth) acryloyl group represented by the following (I) to (IV).

(I) Monofunctional radically polymerizable monomer methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, 2-methacryloyloxyethyl dihydrogen phosphate, 2-methacryloyloxyethylphenyl Hydrogen phosphate, 6-methacryloyloxyhexyl dihydrogen phosphate, 10-methacryloyloxyhexyl dihydrogen phosphate, 2-methacryloyloxyethyl 2-bromoethyl hydrogen phosphate, methacrylic acid, N-methacryloylglycine, N-methacryloyl aspartic acid N-methacryloyl-5-aminosalicylic acid, 2-methacryloyl Xylethyl hydrogen succinate, 2-methacryloyloxyethyl hydrogen phthalate, 2-methacryloyloxyethyl hydrogen maleate, 6-methacryloyloxyethyl naphthalene-1,2,6-tricarboxylic acid, O-methacryloyl tyrosine, N-methacryloyl tyrosine N-methacryloylphenylalanine, N-methacryloyl-p-aminobenzoic acid, N-methacryloyl-O-aminobenzoic acid, 2-methacryloyloxybenzoic acid, 3-methacryloyloxybenzoic acid, 4-methacryloyloxybenzoic acid, N-methacryloyl -5-aminosalicylic acid, N-methacryloyl-4-aminosalicylic acid, 11-methacryloyloxyundecane-1,1-dicarboxylic acid, 10-methacryloyloxyde 1,1-dicarboxylic acid, 12-methacryloyl oxide decane-1,1-dicarboxylic acid, 6-methacryloyloxyhexane-1,1-dicarboxylic acid, 4- (2-methacryloyloxyethyl) trimellitate, 4-methacryloyloxy Ethyl trimellitate, 4-methacryloyloxybutyl trimellitate, 4-methacryloyloxyhexyl trimellitate, 4-methacryloyloxydecyl trimellitate, 6-methacryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid anhydride, 6-methacryloyloxyethylnaphthalene-2,3,6-tricarboxylic anhydride, 4-methacryloyloxyethylcarbonylpropionoyl-1,8-naphthalic anhydride, 4-methacryloyloxyethylnaphthalene-1,8-to Methacrylates such as recarboxylic acid anhydrides, and acrylates corresponding to these methacrylates.

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

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

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

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

  The radical polymerizable monomer to be blended in the adhesive is such that the radical polymerizable monomer having two or more radical polymerizable functional groups in the molecule is 40% by mass or more of the total radical polymerizable monomer. However, it is more preferable to set it as 50 mass% or more, and it is still more preferable to set it as 60 mass% or more. By using a radically polymerizable monomer having two or more radically polymerizable functional groups in the molecule at least 40% by mass of the total radically polymerizable monomer, a uniform and strong adhesive layer can be obtained more easily. Therefore, higher adhesiveness can be obtained.

  The radical polymerizable monomer preferably has one or more hydrogen bondable functional groups in the molecule. Adhesive layer cured on the surface of the polyaryletherketone resin material by the radically polymerizable monomer having one or more hydrogen bondable functional groups in the molecule and hydrogen bonds between the hydrogen bond functional groups. The strength of the resin becomes stronger and higher adhesion can be obtained. The radical polymerizable monomer having one or more hydrogen bonding functional groups in the molecule preferably contains 5% by mass or more, more preferably 20% by mass or more, and more preferably 30% by mass of the total polymerizable monomers. % Or more is more preferable, and it is further more preferable that it is 50 mass% or more.

  Furthermore, some or all of the polymerizable monomers having one or more hydrogen-bonding functional groups in the molecule may have two or more radical-polymerizable functional groups and one or more hydrogen-bonding functional groups in the molecule. It is preferably a radically polymerizable monomer having In this case, the radical polymerizable monomer having two or more radical polymerizable functional groups and one or more hydrogen bondable functional groups in the molecule should contain 5% by mass or more based on the total radical polymerizable monomers. It is preferable to contain 20% by mass or more, more preferably 30% by mass or more, and more preferably 50% by mass or more.

  The hydrogen bond referred to here is an electrically negative hydrogen atom (donor) that is bonded to an atom (O, N, S, etc.) having a high electronegativity and is electrically positively polarized and has a lone electron pair. This indicates a bonding interaction formed with a simple atom (acceptor). The hydrogen-bonding functional group in the present invention is a substituent that can function as a donor and acceptor in the hydrogen bond, and specifically includes a hydroxyl group, a thiol group, an amino group, a urethane group, an amide group, and the like.

  As such radical polymerizable monomers having two or more radical polymerizable functional groups and hydrogen bonding functional groups in the molecule, known ones including those exemplified above can be used without particular limitation. 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, glycerol dimethacrylate, bis (2-methacryloyloxyethyl) hydrogen phosphate, bis (6-methacryloyloxyhexyl) hydrogen Phosphate, 2-methacryloyloxyethyl-3′-methacryloyloxy-2 ′-(3,4-dicarboxybenzoyloxy) propyl succinate, N, O-dimethacryloyltyrosine and acrylates corresponding to these methacrylates; 2-hydroxy Ethyl methacrylate, -Vinyl monomers having -OH groups such as methacrylates such as hydroxypropyl methacrylate and 3-chloro-2-hydroxypropyl methacrylate or acrylates corresponding to these methacrylates, diisocyanate methylbenzene, 4,4'-diphenylmethane diisocyanate, hexamethylene Diadducts obtained from adducts with diisocyanate compounds such as diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate); 1,2-bis (3-methacryloyloxy-2-hydroxy Propoxy) ethyl, 1,6-bis (methacryloylethyloxycarbonylamino) 2,2, - it includes trimethyl hexane.

  Some or all of the radical polymerizable monomers having two or more radical polymerizable functional groups and hydrogen bonding functional groups in the molecule have two or more radical polymerizable functional groups and hydrogen bonding functional groups in the molecule. And having an aromatic ring is more preferable. By having an aromatic ring in the molecule, the aromatic ring of the radical polymerizable monomer of the adhesive and the aromatic ring of the polyaryletherketone resin material form a stack, and the polyaryletherketone resin material and the adhesive layer It is inferred that the interaction will be higher.

  Such radically polymerizable monomers having two or more radically polymerizable functional groups, hydrogen-bonding functional groups, and aromatic rings in the molecule, including those exemplified above, can be used without particular limitation, Examples include 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, 2-methacryloyloxyethyl-3′-methacryloyloxy-2 ′-(3,4-dicarboxybenzoyl) Oxy) propyl succinate, N, O-dimethacryloyl tyrosine and acrylates corresponding to this methacrylate; methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, or these methacrylates Acrylate A vinyl monomer having a -OH group such diisocyanates methylbenzene, diadduct and the like obtained from the addition of the diisocyanate compound having an aromatic group such as 4,4'-diphenylmethane diisocyanate. The radical polymerizable monomer having two or more radical polymerizable functional groups, hydrogen bondable functional groups and aromatic rings in the molecule is preferably used in an amount of 15% by mass or more of the total radical polymerizable monomers, and 25% by mass. It is more preferable to use the above. On the other hand, the radical polymerizable monomer having two or more radical polymerizable functional groups, hydrogen bondable functional groups and aromatic rings in the molecule is preferably 70% by mass or less of the total radical polymerizable monomers, More preferably, it is 50 mass% or less. By making the radical polymerizable monomer having two or more radical polymerizable functional groups, hydrogen bondable functional groups and aromatic rings in the molecule 15% by mass or more, a polyaryl ether ketone resin material and an adhesive layer It is possible to strengthen the interaction of On the other hand, when more than 70% by mass of a radical polymerizable monomer having two or more radical polymerizable functional groups, a hydrogen bondable functional group, and an aromatic ring in the molecule, hydrogen bondable functional groups or aromatic rings Due to the mutual interaction, it becomes difficult to handle the radical polymerizable monomer, and it may be difficult to add it to the adhesive from the viewpoint of workability.

  In addition, polyaryl ether ketone resin material as a filler, polyaryl ether containing a metal inorganic oxide, a composite inorganic oxide, a metal oxide such as an oxide obtained by adding a group I metal oxide to the composite inorganic oxide In the case of a ketone resin composite material, it is also preferable to add a coupling agent having a radical polymerizable functional group as a radical polymerizable monomer.

  A coupling agent is a material having a reactive group chemically bonded to an inorganic compound and a reactive group chemically bonded to an organic compound. By blending a coupling agent with the adhesive, higher adhesion to the polyaryl ether ketone resin composite material can be obtained. This is presumably because the coupling agent forms bonds with both the metal oxide of the polyaryletherketone resin composite material and the radically polymerizable monomer of the adhesive.

  As the coupling agent having a radical polymerizable functional group used in the present invention, known coupling agents can be used without limitation. Examples of the coupling agent include a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent. A silane coupling agent is particularly preferable from the viewpoint of adhesiveness and handleability. It is.

  As a coupling agent having a radical polymerizable functional group that is particularly preferably used, for example, a silane coupling agent in which the radical polymerizable functional group is a (meth) acryloyl group, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyltriisopropylsilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloyloxypropyltris (methoxyethoxy) silane, γ-methacryloxypropylmethyldiethoxysilane, ω -Methacryloyloxydecyltrimethoxysilane, (methacryloxymethyl) methyldimethoxysilane, (methacryloxymethyl) methyldiethoxysilane, methacryloxymethyltrimethoxysila , O- (methacryloyloxyethyl) -N- (triethoxysilylpropyl) carbamate, N- (3-methacryloyl-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 3- (n-methacryloyloxyphenyl) propyl Examples include trimethoxysilane and 3- (3-methoxy-4-methacryloyloxyphenyl) propyltrimethoxysilane.

  The above-mentioned coupling agents having a radical polymerizable functional group can be used alone or in combination of two or more.

  The blending amount of the coupling agent having a radical polymerizable functional group is not particularly limited, but from the viewpoint of adhesiveness, it is 1 for all radical polymerizable monomers including a coupling agent having a radical polymerizable functional group. The range of -30 mass% is preferable, the range of 2-20 mass% is more preferable, and the range of 3-10 mass% is still more preferable.

  In addition, when a coupling agent having a radical polymerizable functional group is added to the adhesive, the adhesive contains a radical polymerizable monomer having two or more radical polymerizable functional groups in the molecule as described above. It is particularly preferable to blend 40% by mass or more with respect to the polymerizable monomer in order to obtain higher adhesiveness.

  The adhesive containing the radical polymerizable monomer in the present invention may contain a polymerization initiator.

  In the present invention, since no light irradiation is performed on the adhesive, the adhesive may or may not contain a photopolymerization initiator, but the adhesive containing the photopolymerization initiator is light. Is likely to cause gelation and deteriorate storage stability, it is preferable not to blend substantially. The term “substantially” means that the photopolymerization initiator is 0.005 parts by mass or less, more preferably 0.001 parts by mass or less, and 100% by mass of the radical polymerizable monomer. Most preferred.

  The thermal polymerization initiator may or may not be contained in the adhesive, but if the adhesive containing the thermal polymerization initiator is heated, it causes gelation and the storage temperature is low. However, it is more preferable not to mix substantially because it may cause a deterioration in storage stability. The term “substantially” means that the photopolymerization initiator is 0.005 parts by mass or less, more preferably 0.001 parts by mass or less, and 100% by mass of the radical polymerizable monomer. Most preferred.

  The chemical polymerization initiator is composed of two or more components, and is a polymerization initiator that generates a polymerization active species near room temperature by mixing all the components immediately before use, and may or may not be contained in the adhesive. Although it is good, it is preferable to contain from the surface of improvement of adhesive strength and stability. When the chemical polymerization initiator is included in the adhesive, it is usually stored by dividing the adhesive packaging into two or more, mixing all the components just before use to generate chemical polymerization initiator activity and applying it. Is done. In this case, the reaction proceeds slowly from the time of mixing, but immediately loses fluidity and does not become indestructible. The adhesive containing a chemical polymerization initiator is such that the polymerization proceeds very slowly under the influence of oxygen that inhibits polymerization before the adherend is pressure-bonded, and oxygen is blocked after the adherend is pressure-bonded. Polymerization is accelerated. Accordingly, since the adhesive containing the chemical polymerization initiator becomes undeformable after the adherend is pressure-bonded, a thin adhesive layer can be formed. The compounding amount of the chemical polymerization initiator is not particularly limited, but if it is too small, it cannot contribute to sufficient polymerization of the adhesive, and if it is too large, the amount of non-polymerized components in the adhesive layer increases. Leading to a decline. Accordingly, the chemical polymerization initiator is preferably 0.002 parts by mass or more with respect to 100 parts by mass of the radical polymerizable monomer, more preferably in the range of 0.02 to 12 parts by mass, Most preferably, it is in the range of ˜7 parts by mass.

  Furthermore, a part of the components forming the chemical polymerization initiator system (hereinafter also referred to as a part of the chemical polymerization initiator component) is blended in the adhesive, and a part of the chemical polymerization initiator component is combined with A curable composition containing a component that forms a chemical polymerization initiator system may be used as an adherend. That is, after light-irradiating the adherend surface of the polyaryl ether ketone resin material, an adhesive containing a part of the chemical polymerization initiator component is applied, and one of the chemical polymerization initiator components mixed in the adhesive is applied. An adherend containing a chemical polymerization initiator component forming a chemical polymerization initiator system with a partial component is pressure-bonded from above the adhesive. Thereby, the polymerizability of the radically polymerizable monomer in the adhesive containing a part of the chemical polymerization initiator component is improved, and the adhesiveness is improved.

  As such a chemical polymerization initiator, known chemical polymerization initiators can be used without limitation, but those using a redox reaction comprising an oxidizing agent and a reducing agent are typical.

  Examples of the oxidizing agent for the chemical polymerization initiator using the redox reaction include inorganic peroxides and organic peroxides. For example, specific examples of the inorganic peroxide include sodium persulfate, potassium persulfate, aluminum persulfate, ammonium persulfate, potassium chlorate, potassium bromate, and potassium perphosphate.

  Typical organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, diaryl peroxides. Examples thereof include oxides.

  As an oxidizing agent mix | blended with the adhesive agent of this invention, an organic peroxide is preferable.

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

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

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

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

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

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

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

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

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

  Examples of such organic peroxides include P-methane hydroperoxide, diisopropylbenzene peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide. Hydroperoxides, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, t- Hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxymaleic acid , T-butylperoxy-3,5,5-tri Tylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5 Peroxyesters such as bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, octanoyl peroxide, lauroyl peroxide, succinic Examples include diacyl peroxides such as acid peroxide, m-toluoyl benzoyl peroxide, and benzoyl peroxide.

  Further, t-butyltrimethylsilyl peroxide is also exemplified as an organic peroxide having a 10-hour half-life temperature of 60 ° C. or higher.

  Examples of the reducing agent for the chemical polymerization initiator using a peroxide as the oxidizing agent for the redox reaction include amine compounds, sulfinic acid compounds, thiourea compounds, oxime compounds, and transition metal compounds.

  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.

  As the sulfinic acid compound, a sulfinic acid compound or a salt thereof can be used. Specific examples include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, Calcium p-toluenesulfinate, benzenesulfinate, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinate, 2,4,6-trimethylbenzene Sodium sulfinate, potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6 Triethylbenzenesulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, 2,4,6-triethylbenzenesulfin Calcium, 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, 2,4,6-triisopropylbenzene Examples thereof include lithium sulfinate, calcium 2,4,6-triisopropylbenzene sulfinate, and the like. Sodium p-toluenesulfinate, sodium benzenesulfinate, sodium 2,4,6-triethylbenzenesulfinate Masui.

  Examples of thiourea compounds include thiourea, methylthiourea, ethylthiourea, N, N′-dimethylthiourea, N, N′-diethylthiourea, N, N′-di-n-propylthiourea, N, N′— Dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, tetracyclohexylthiourea, 1- (2-pyridyl) ) -2-thiourea and the like.

  Examples of oxime compounds include methyl ethyl ketone oxime, methyl isobutyl ketone oxime, acetophenone oxime, P, P′-dibenzoylquinone dioxime, and the like.

  Especially as a transition metal compound, the transition metal compound of the 4th period can be used conveniently. The transition metal compound of the fourth period is a metal compound of Group 3-12 of the fourth period of the periodic table, and specifically, scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr). , Manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn). Each of the above transition metal elements can have a plurality of valences, but can be incorporated into the primer or curable composition of the present invention as long as it can function as a reducing agent with a valence that can exist stably. is there. Representative examples of such compounds include: vanadium tetroxide (IV), vanadium oxide acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl-1) , 3-butanedionate) vanadium (IV), + IV valent vanadium compounds such as bis (maltolate) oxovanadium (IV), + II valent chromium compounds such as chromium (II) chloride, manganese (II) acetate, naphthenic acid + II-valent manganese compounds such as manganese (II), + II-valent iron compounds such as iron (II) acetate, iron (II) chloride, iron (II) sulfate, cobalt (II) acetate, cobalt (II) naphthenate, etc. + II cobalt compounds, nickel naphthenate, nickel chloride (II) + II valent nickel compounds, copper (I) chloride, bromide (I) + I-valent copper compound such as and the like.

  As the reducing agent of the chemical polymerization initiator compounded in the adhesive, a transition metal compound of the fourth period is preferable, and among the stable vanadium compounds, a + IV valent vanadium compound having a low oxidation number and high reducing ability is most preferable.

  In addition, the adhesive of the present invention includes other components such as a solvent, a filler, a polymerization inhibitor, a polymerization inhibitor, a dye, a pigment, and a fragrance as long as they do not significantly impair the effects of the present invention. It may be.

  The solvent to be contained in the adhesive is preferably a volatile solvent. Mixing volatile solvents reduces the viscosity of the adhesive, making it easier for radically polymerizable monomers to enter the fine irregularities on the surface of the polyaryletherketone resin material, and a uniform adhesive layer It becomes easy to form. In addition, due to the volatility, after the adhesive is applied to the adherend surface of the polyaryletherketone resin material, it is removed from the surface of the polyaryletherketone resin material by an operation such as air blow, and adhesion due to residual solvent It can suppress the adverse effect on

  Here, the volatile solvent means that the boiling point at 760 mmHg is 100 ° C. or lower and the vapor pressure at 20 ° C. is 1.0 KPa or higher. However, since it is preferable that the volatile solvent is sufficiently volatilized and does not adversely affect the volatile solvent, the vapor pressure at 20 ° C. is more preferably 2.0 KPa or more, and further preferably 5.0 KPa or more. . On the other hand, when the volatilization of the volatile solvent is too fast, it is difficult to sufficiently obtain the effect of blending the volatile solvent. Therefore, the vapor pressure at 20 ° C. of the volatile solvent is preferably 60 KPa or less, and more preferably 50 KPa or less. Further, since the lower boiling point is easier to remove from the surface of the polyaryletherketone resin material, the boiling point at 760 mmHg of the volatile solvent is more preferably 85 ° C. or lower.

  Examples of such a preferable volatile solvent include acetone, methyl ethyl ketone, diethyl ketone, methyl n-propyl ketone, methyl isobutyl ketone, acetonitrile, tetrahydrofuran, diethyl ether, pentane, hexane, toluene, ethyl acetate, methanol, ethanol, 1 -Propanol, isopropanol, water and the like. These volatile solvents may be used alone, or a plurality of them may be mixed when they can be mixed uniformly.

  The blending amount of the volatile solvent is preferably 10 parts by mass or more, more preferably 50 parts by mass or more, and 100 parts by mass or more with respect to 100 parts by mass of the total radical polymerizable monomer. More preferably, it is more preferably 300 parts by mass or more. Moreover, it is preferable that it is 3000 mass parts or less with respect to 100 mass parts of all radically polymerizable monomers, It is more preferable that it is 2000 mass parts or less, It is more preferable that it is 1500 mass parts or less, 1000 masses More preferably, it is at most parts. By setting the volatile solvent to 10 parts by mass or more, it is easy to obtain an effect that the adhesive easily enters the fine irregularities on the surface of the polyaryletherketone resin material or forms a uniform adhesive layer. Become. By setting the volatile solvent to 3000 parts by mass or less, the radically polymerizable monomer component of the adhesive is reduced. As a result, when the adhesive is applied to the surface of the polyaryletherketone resin material, the polyaryletherketone The amount of radically polymerizable monomer present on the surface of the resin material is not insufficient, and a uniform and strong adhesive layer is sufficiently formed, and the advantage of blending a volatile solvent is easily obtained.

  The volatile solvent may be used in combination with a low volatility solvent having a vapor pressure of less than 1.0 KPa at 20 ° C. However, if a large amount of low-volatility solvent is contained, the interaction between the polyaryletherketone resin material and the radical-polymerizable monomer of the adhesive may be inhibited, or the radical-polymerizable monomer of the adhesive may be polymerized. There is a possibility that the adhesiveness may be lowered by inhibiting the curing. Therefore, the low volatility solvent contained in the adhesive is preferably 40% by mass or less, more preferably 20% by mass or less, and more preferably 10% by mass or less with respect to the blending amount of the volatile solvent. More preferably, it is more preferably 1% by mass or less.

  As the filler that may be contained in the adhesive in the present invention, known inorganic fillers, organic fillers, organic-inorganic composite fillers and the like can be used without particular limitation. By containing the filler, the strength of the adhesive is increased, and higher adhesiveness is easily obtained.

  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, those subjected to silane coupling treatment are preferable. As the silane coupling agent, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyl Triacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyl Dimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylate Silane, N- phenyl--γ- aminopropyltrimethoxysilane, 11-methacryloyloxy undecyl trimethoxysilane, 11-methacryloyloxy such acryloyloxy undecyl methyl dimethoxy silane.

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

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

  On the other hand, when the adhesive contains a large amount of a filler, the viscosity of the adhesive tends to increase and the adhesiveness tends to decrease, and the adhesive layer tends to become thicker. Therefore, the blending amount of the filler in the adhesive is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 2 to 5 parts by mass with respect to 100 parts by mass of the adhesive. .

  The particle size and shape of the filler are not particularly limited, but are preferably small from the viewpoint of forming a uniform adhesive layer. As the particle size of the filler, the average primary particle size of any 100 particles measured with a transmission electron microscope is preferably 100 μm or less, more preferably 0.01 to 10 μm, further 0.01 μm to 1 μm. preferable.

<Viscosity of adhesive>
The viscosity of the adhesive is preferably low. The low viscosity of the adhesive makes it easier for the adhesive to penetrate into the fine irregularities on the surface of the polyaryl ether ketone resin material, making it easier to apply the adhesive evenly on the surface of the polyaryl ether ketone resin material. , It becomes easier to obtain higher adhesiveness. On the other hand, when the viscosity of the adhesive is too low, the adhesive is evenly applied to the adherend surface of the polyaryletherketone resin material, which may have a complicated structure due to causes such as dripping. Things can be difficult. Therefore, the viscosity of the adhesive is preferably in the range of 0.3 cP to 3000 cP at 23 ° C., more preferably in the range of 0.4 cP to 500 cP, and in the range of 0.5 cP to 30 cP. Is more preferable, and the range of 0.5 cP to 10 cP is most preferable. The viscosity may be measured using a cone plate viscometer in a thermostatic chamber maintained at 23 ° C. The viscosity of the adhesive containing the chemical polymerization initiator and the radical polymerizable monomer may be measured by adjusting the composition not containing the chemical polymerization initiator.

<Light irradiation method>
In the present invention, an adhesive polyaryletherketone resin material is produced by irradiating light onto the adherend surface of the polyaryletherketone resin material and then applying an adhesive containing the above-mentioned radical polymerizable monomer. To do. The atmosphere in performing the light irradiation is not particularly limited and may be performed in the air. In addition, since the radical generated by light irradiation is captured by oxygen molecules, the effect of obtaining the high adhesiveness of the present invention can be more effectively obtained by performing light irradiation under the condition without oxygen. By irradiating the surface of the polyaryletherketone resin material with light, the ketone group of the polyaryletherketone resin material having two aromatic rings as substituents in the polyaryletherketone resin is activated, generating radicals. To do. The generated radical reacts with the radical polymerizable functional group of the radical polymerizable monomer contained in the adhesive, whereby a bond is formed between the polyaryl ether ketone resin material and the adhesive. Next, by pressing a curable composition containing a radical polymerizable monomer and a polymerization start time from above the adhesive, oxygen is blocked and inhibition of polymerization of the adhesive is suppressed. Further, when the adhesive contains a chemical polymerization initiator, the polymerization is accelerated here. Then, by curing and curing this curable composition, the radical polymerizable functional group of the radical polymerizable monomer of the adhesive reacts with the radical polymerizable functional group of the radical polymerizable monomer of the curable composition. By doing so, a bond is formed between the adhesive and the curable composition. In this way, it is presumed that high adhesiveness can be obtained between the polyaryl ether ketone resin material and the radical polymerizable curable composition.

  The light used for the light irradiation on the surface of the polyaryletherketone resin material before applying the adhesive of the present invention may be any wavelength, but is preferably visible light, particularly blue It is preferably light. As the visible light, those having a maximum peak wavelength in the range of 400 nm to 500 nm are preferable, and those in the range of 450 nm to 500 nm are particularly preferable. When light having a maximum peak wavelength of 400 nm or less is used, there is a concern that an adverse effect on the health of an operator or the like may occur, or the polyaryl ether ketone resin material itself may be damaged and its strength may be reduced. When light having a maximum peak wavelength of 500 nm or more is used, it is difficult to obtain an effect of improving adhesiveness to the polyaryl ether ketone resin material.

Here, since the ketone group having two aromatic rings as substituents has a very small blue light absorption ability compared to ultraviolet light, when light having a maximum peak wavelength in the range of 400 nm to 500 nm is used, In order to obtain the effects of the invention, it is preferable to give a large amount of light energy. The light energy can be represented by the product (mJ / cm ² ) of the light intensity (mW / cm ² ) and the light irradiation time (sec). Preferably the light energy is 8000 mJ / cm ² or more, more preferably 15,000 mJ / cm ² or more, further preferably 30000mJ / cm ² or more, and most preferably 45000mJ / cm ² or more .

Moreover, it is more preferable to give a large amount of the light energy in a short time in order to obtain the effect of the present invention. Therefore, it is preferable that the light intensity using a 200 mW / cm ² or more light, more preferable to use a 400 mW / cm ² or more light, it is most preferable to use a 800 mW / cm ² or more light.

  In addition, the light intensity of the light used for this invention is measurable by using the measuring apparatus which can measure the light intensity of the light of the range of 400 nm-500 nm. As such a measuring apparatus, for example, Demetron L. E. D. RADIOMETER (manufactured by Kerr), OPTILUX RADIOMETER (manufactured by Kerr) and the like can be used.

  The polyaryl ether ketone resin material in the present invention is more preferably roughened on the adherend surface. The roughened polyaryletherketone resin material has increased surface irregularities and can obtain higher adhesion without variation. Roughening may be performed on the surface on which the adhesive of the polyaryletherketone resin material is to be applied by a technique that can be carried out simply and safely before light irradiation. As a roughening treatment method, it is preferable to sandblast the surface of the polyaryl ether ketone resin material. Sand blasting can easily and safely roughen the adherend surface of the polyaryletherketone resin material and contribute to the improvement of adhesion. The sand blasting process may be carried out by a conventional method. In general, alumina particles having a particle size of several μm to several hundreds of μm are made of polyaryl at a pressure of several tens of KPa to several MPa using a sand blasting apparatus. It is carried out by spraying on an ether ketone resin material. That is, by applying light to the roughened polyaryletherketone resin material and applying an adhesive containing a radical polymerizable monomer, higher adhesion can be obtained without variation. It becomes easy.

  The effect of light irradiation on the adherend surface of the polyaryletherketone resin material is about 20 minutes, and after the light irradiation is performed on the adherend surface of the polyaryletherketone resin material, the radically polymerizable monomer is as quickly as possible. It is preferable to apply an adhesive containing the monomer (a).

<Method for producing adhesive polyaryletherketone resin>
The adhesive polyaryletherketone resin of the present invention is applied with an adhesive containing the radical polymerizable monomer (a) after irradiating light onto the adherend surface of the polyaryletherketone resin material as described above. It is obtained by doing. The method of applying the adhesive is not particularly limited, but it is easy to apply the adhesive uniformly by soaking it in a dental microbrush or cotton ball. When the adhesive contains a solvent, it is desirable to dry the solvent from the viewpoint of adhesive strength. The drying method is not particularly limited, but a method of spraying compressed air is simple.

<Adherent>
In the present invention, the adherend bonded to the polyaryl ether ketone resin material is composed of a curable composition containing a radical polymerizable monomer and a polymerization initiator.

  The adhesive polyaryletherketone resin material obtained by the production method of the present invention comprises an adherend composed of a curable composition containing a radical polymerizable monomer and a polymerization initiator on the adherend surface. When bonded, high adhesion can be obtained, and the adhesive layer can be thin. Therefore, after light irradiation is performed on the polyaryl ether ketone resin material, an adhesive containing a radical polymerizable monomer is applied, and then radical polymerization is performed on the polyaryl ether ketone resin material to which the adhesive is applied. A polyaryletherketone resin material characterized by pressure-bonding an adherend comprising a curable composition containing a curable monomer and a polymerization initiator, and polymerizing and curing the adherend (curable composition) A method of bonding the substrate and the adherend is also suitable.

  A curable composition containing a radically polymerizable monomer and a polymerization initiator is initially low in consistency and easily deformable, so after it is transformed into a desired shape and placed in a desired location The function is exhibited by completing the polymerization and curing.

  The curable composition containing a radical polymerizable monomer and a polymerization initiator can be used without particular limitation as long as it contains a radical polymerizable monomer and a radical polymerization initiator. In the bonding operation with respect to the polyaryl ether ketone resin material, pressure bonding is applied to the adherend surface of the polyaryl ether ketone resin material. By pressure-bonding a curable composition containing a radical polymerizable monomer and a polymerization initiator, the thickness of the adhesive layer that has been previously applied and has not yet been sufficiently polymerized and cured is reduced, and oxygen By blocking, inhibition of polymerization of the adhesive is suppressed. At this time, when the adhesive contains a chemical polymerization initiator, the polymerization of the adhesive is accelerated. Thereafter, by completing the polymerization and curing of the curable composition, it is presumed that the adhesive is also polymerized and cured, and high adhesiveness is obtained.

  The radical polymerizable monomer contained in the curable composition containing the radical polymerizable monomer and the polymerization initiator is a compound having a radical polymerizable functional group in the molecule, and any known one can be used without any limitation. it can. Examples of the radical polymerizable functional group include a vinyl group, a styryl group, an allyl group, a (meth) acryloyl group, and the like, and a (meth) acryloyl group is particularly preferable from the viewpoint of polymerization rate and biosafety. . As an example of a preferable radical polymerizable monomer, what was shown to said (I)-(IV) is mentioned as an example of the radical polymerizable monomer mix | blended with an adhesive agent, for example.

  These radically polymerizable monomers may be used in combination of a plurality of types as required. Moreover, you may use radically polymerizable monomers other than the said (meth) acrylate type monomer. The compounding amount of these radical polymerizable monomers is preferably in the range of 6 to 60 parts by mass and more preferably in the range of 9 to 55 parts by mass with respect to 100 parts by mass of the curable composition.

  As a polymerization initiator contained in the curable composition containing a radical polymerizable monomer and a polymerization initiator, a photopolymerization initiator, a chemical polymerization initiator, or a thermal polymerization initiator can be used, and two or more types can be used. Combinations of polymerization initiators can also be used. In addition, since a curable composition containing a radical polymerizable monomer and a polymerization initiator is pressure-bonded to a polyaryl ether ketone resin material, the curable composition can be easily cured, so that photopolymerization can be performed. It is preferable to use an initiator and / or a chemical polymerization initiator. Hereinafter, these three kinds of polymerization initiators will be described in more detail.

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

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

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

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

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

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

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

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

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

  The photoacid generator used in the present invention generates Bronsted acid or Lewis acid by light irradiation. Even if a sensitizer is required, it decomposes under visible light irradiation and generates an acid. A well-known thing can be used without any limitation.

  Examples of the photoacid generator include halomethyl group-substituted s-triazine derivatives, diphenyliodonium salt compounds, sulfonium salt compounds, sulfonic acid ester compounds, disulfone compounds, diazonium salt compounds and the like.

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

  The chemical polymerization initiator is a polymerization initiator that is composed of two or more components and generates polymerization active species near room temperature by mixing all the components immediately before use. Examples of such a chemical polymerization initiator include those exemplified for some components of the chemical polymerization initiator to be blended in the adhesive. Including these, examples of usable chemical polymerization initiators include, for example, amine compounds / organic peroxides. Specific examples of the amine compound include aromatic amine compounds such as N, N-dimethyl-p-toluidine, N, N-dimethylaniline, and N, N-diethanol-p-toluidine.

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

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

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

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

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

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

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

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

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

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

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

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

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

  As an aryl borate compound, what can be used as a photoinitiator can be used. Two or more aryl borate compounds may be used in combination.

  The acidic compound is used as a proton source, and is a component used to react with the aryl borate compound to generate aryl borane.

  Examples of such acidic compounds include inorganic acids and organic acids generally known as Bronsted acids, and acidic groups containing polymerizable monomers that themselves contain polymerizable groups together with acidic groups. A mer is used.

  In such acidic compounds, examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc., and examples of organic acids include acetic acid, propionic acid, maleic acid, fumaric acid, phthalic acid, benzoic acid , Carboxylic acids such as trichloroacetic acid, trifluoroacetic acid, citric acid and trimellitic acid; sulfonic acids such as p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid; methylphosphonic acid, phenylphosphonic acid, dimethyl Typical examples include phosphoric acids such as phosphinic acid and diphenylphosphinic acid. In addition to phenols and thiols, solid acids such as acidic ion exchange resins and acidic alumina can also be used as acidic compounds in the present invention.

  In addition, an acidic group-containing polymerizable monomer is a compound having at least one acidic group and at least one polymerizable unsaturated group in one molecule. In the present invention, it is most preferably used as an acidic compound.

  It is also preferable to use an organic peroxide and / or a transition metal compound in combination with the above-described aryl borate compound / acidic compound polymerization initiator. The organic peroxide and the transition metal compound are as described above.

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

  The blending amount of these polymerization initiators is preferably in the range of 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the polymerizable monomer. When the polymerization initiator is 0.01 part by mass or more, the curable composition containing the radical polymerizable monomer and the polymerization initiator is sufficiently cured even after the curing, and the physical properties are not deteriorated. Moreover, when a polymerization initiator is 10 mass parts or less, the operativity of this curable composition is favorable.

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

  For example, a curable composition using a filler can suppress polymerization shrinkage of the curable composition, improve the operability of the curable composition, or improve the mechanical properties of the cured product. Can do. In particular, the polymerization shrinkage ratio is such that, for example, when a large amount of the curable composition is used, the polymerization shrinkage of the curable composition increases, and the curable composition and the polyarylether are caused by the polymerization shrinkage stress generated by the polymerization shrinkage. Peeling may occur between the adhesive applied to the surface of the ketone resin material or between the curable composition and the adhesive applied to the surface, which may make it difficult to obtain high adhesiveness. is there.

  As the filler, known inorganic fillers and organic-inorganic composite fillers can be used without any limitation. Examples of the inorganic filler include metal oxides such as quartz, silica, alumina, silica-titania, silica-zirconia, lanthanum glass, barium glass, and strontium glass. Moreover, silicate glass, fluoroaluminosilicate glass, etc. can also be used as needed as a cation elution inorganic filler. These inorganic fillers may be used alone or in combination of two or more.

  In addition, as the organic-inorganic composite filler, a granular material obtained by adding a polymerizable monomer to the inorganic filler exemplified above to form a paste and then polymerizing and pulverizing the obtained polymer is used. be able to.

  The particle diameters of these fillers are not particularly limited, and fillers having an average particle diameter of 0.01 μm to 100 μm (particularly preferably 0.01 to 5 μm) can be appropriately used depending on the purpose. Further, the refractive index of the filler is not particularly limited, and may be appropriately set according to the purpose. You may use together several inorganic fillers from which a particle size range and refractive index differ.

  The inorganic filler is preferably treated with a surface treatment agent typified by a silane coupling agent. In this case, the affinity between the inorganic filler and the radical polymerizable monomer is improved, and the mechanical strength and water resistance of the cured product can be improved. The surface treatment can be performed by a known method. As silane coupling agents, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ- Methacryloyloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, hexamethyldisilazane and the like are preferably used.

  The blending amount of these fillers may be appropriately determined in consideration of the viscosity when mixed with the radical polymerizable monomer and the mechanical properties of the cured product, depending on the purpose of use. The range of 50-1500 mass parts is preferable with respect to 100 mass parts of radically polymerizable monomers, and the range of 70-1000 mass parts is more preferable.

<Adhesion method>
A method for adhering the adhesive polyaryletherketone resin material obtained by the production method of the present invention to an adherend comprising a curable composition containing a radical polymerizable monomer and a polymerization initiator is not particularly limited. The form in which the curable composition containing the radical polymerizable monomer and the polymerization initiator is applied to the surface of the adhesive polyaryletherketone resin material of the present invention is not particularly limited. For example, the radical polymerizable monomer And a curable composition containing a polymerization initiator are directly applied to the surface of the adhesive polyaryletherketone resin material of the present invention, or on the surface of other members other than the adhesive polyaryletherketone resin material of the present invention. After applying a curable composition containing a radically polymerizable monomer and a polymerization initiator, another member is brought into contact with the adhesive polyaryletherketone resin material of the present invention so that the polyaryletherketone resin material and the radical are brought into contact with each other. A curable composition containing a polymerizable monomer and a polymerization initiator can be contacted.

  In addition, the adhesive polyaryletherketone resin materials obtained by the production method of the present invention are bonded to each other through the curable composition containing the radical polymerizable monomer and the polymerization initiator, or the production of the present invention. The adhesive polyaryletherketone resin material obtained by the method and the third member can be bonded together.

  When adhering the adhesive polyaryletherketone resin materials obtained by the production method of the present invention via a curable composition containing a radical polymerizable monomer and a polymerization initiator, for example, holes, grooves, etc. The curable composition is filled with a curable composition containing a radical polymerizable monomer and a polymerization initiator in the concave portion of the adhesive polyaryletherketone resin material obtained by the production method of the present invention provided with the concave portion. The composition may be bonded to a polyaryl ether ketone resin material. In this case, the concave portion is embedded, and the curable composition filled in the concave portion is bonded to the inner wall surface of the concave portion of the adhesive polyaryletherketone resin material obtained by the production method of the present invention.

  For example, when the curable composition containing the radically polymerizable monomer and the polymerization initiator as the adherend has a property of firmly adhering to the surface of another member (third member) The adhesive polyaryl ether ketone resin material of the present invention and the third member can be firmly bonded by bringing the third member into contact with the adherend and polymerizing and curing the adherend. The third member can be used without particular limitation as long as it is a known solid member.

  A curable composition comprising a radically polymerizable monomer and a polymerization initiator when the adherend is bonded to the polyaryletherketone resin material by the method for bonding the polyaryletherketone resin material and the adherend of the present invention. The adherend made of is polymerized and cured to form a cured body.

  A laminated body can be produced by the above-described bonding method of the present invention. After the polyaryl ether ketone resin material is irradiated with light, an adhesive containing the radical polymerizable monomer (a) is applied, and the radical polymerizable property is applied onto the polyaryl ether ketone resin material coated with the adhesive. When an adherend composed of a curable composition containing a monomer and a polymerization initiator is pressure-bonded, the adherend is polymerized and cured, and the polyaryletherketone resin material and the adherend are bonded together, A laminate having an adhesive (cured adhesive) layer and an adherend (cured adherend) can be formed on the ketone resin material. Further, when the polyaryl ether ketone resin material and the third member are bonded using the bonding method of the present invention, an adhesive (cured adhesive) layer and an adherend (cured) are cured on the polyaryl ether ketone resin material. An adherend) and a laminate having a third member.

<Use in the dental field>
The adhesive polyaryletherketone resin material obtained by the production method of the present invention can be used for any application, but is preferably used in the dental field.

  In the dental field, there is a great demand for a shortened treatment time and a member with high aesthetics, and the advantage of thinning the adhesive layer is particularly great. In dental applications, in consideration of safety to the living body, blue light is often used instead of ultraviolet light, and dental laboratories and other facilities are equipped with the corresponding maximum peak wavelength. Is preferably used in the dental field because it can be widely implemented using existing equipment by using light of 400 nm to 500 nm.

  The adhesive polyaryletherketone resin obtained by the production method of the present invention is used as a dental polyaryletherketone resin material using the adhesive polyaryletherketone resin material obtained by the production method of the present invention for dental use. Dentures, artificial teeth, denture bases, dental implants, crown restoration materials, abutment construction materials, etc., partially or wholly made using

  In addition, as a curable composition containing a radical polymerizable monomer and a polymerization initiator that can be used as a dental member, a dental curable composition can be used. A dental curable composition is a curable composition used for dental treatment. At first, it has low consistency and can be easily deformed, so it can be transformed into a desired shape and installed at a desired location. After that, the function is exhibited by polymerizing and curing. Examples of the dental curable composition include a dental composite resin, a dental hard resin, a dental cement, a dental bonding material, a dental immediate polymerization resin, and the like. In addition, the third member includes dental teeth such as natural teeth, dentures made of metal materials / ceramic materials / resin materials, artificial teeth, denture bases, dental implants, crown restoration materials, abutment building materials, etc. A member etc. are mentioned.

  As an example of the method of using the adhesive dental polyaryletherketone resin material obtained by the production method of the present invention, a dental hard resin is used as a dental curable composition, and a dental polyaryletherketone resin material is used. And a dental hard resin are laminated to prepare a dental prosthesis. Specifically, for example, by applying light to a desired surface of a dental polyaryletherketone resin material molded into a desired shape and applying an adhesive containing a radical polymerizable monomer, An aryl ether ketone resin material is obtained. Thereafter, a hard resin is laminated thereon, arranged in a desired shape, and then cured to produce a desired dental prosthesis. The dental prosthesis can be easily broken because of its high adhesiveness, and the adhesive layer can be thinned, so that it becomes easy to obtain a dental prosthesis having high aesthetics.

  Another example includes a step of using a dental cement as a dental curable composition and mounting a prosthesis made of a polyaryletherketone resin material on a tooth defect. Specifically, for example, by applying light to the adherend surface of a prosthesis made of a polyaryl ether ketone resin material prepared in advance and applying an adhesive containing a radical polymerizable monomer thereto, An aryl ether ketone resin material is obtained. The dental polyaryletherketone resin prosthesis can be attached to the teeth by applying dental cement to the adherend surface. At that time, it is possible to make the adhesive layer thin while obtaining high adhesiveness, so that the prosthesis made of the dental polyaryletherketone resin material obtained by the production method of the present invention has high compatibility. It becomes easy to be.

  In addition, as a polyaryl ether ketone resin used as a dental material, particularly a dental restorative material, an ether group and a ketone group constituting the 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 polyether ether ketone having repeating units, or polyether ketone ketone having repeating units arranged in the order of ether, ketone, and ketone.

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

[Radically polymerizable monomer]
<Polymerizable monomer having two or more polymerizable functional groups in the molecule>
BisGMA: 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane 3G: triethylene glycol dimethacrylate PM2: bis (2-methacryloyloxyethyl) hydrogen phosphate <intramolecular Polymerizable monomer having only one polymerizable functional group>
PM1: 2-methacryloyloxyhexyl dihydrogen phosphate HEMA: 2-hydroxyethyl methacrylate [chemical polymerization initiator]
BPO: benzoyl peroxide DMBE: p-dimethylaminobenzoic acid ethyl ester [photoinitiator]
CQ: camphorquinone DMBE: p-dimethylaminobenzoic acid ethyl ester [adhesive containing a radical polymerizable monomer]
As an adhesive containing a radical polymerizable monomer, an adhesive having a composition shown in Table 1 was used.

(Preparation of adhesive)
The adhesive containing a radical polymerizable monomer was prepared by mixing the radical polymerizable monomer shown in Table 1, a solvent, and a polymerization initiator, and stirring until all components were uniform. In addition, about the adhesives (B4, B5, B6) containing a chemical polymerization initiator, the final adhesive (TOTAL) was prepared by dividing into two (A and B) and mixing immediately before. . A and B show the composition of each package, and TOTAL shows the composition after mixing.

(Measurement of viscosity of adhesive layer)
The viscosity of the adhesive described in Table 1 was measured using a cone plate viscometer in a thermostatic chamber maintained at 23 ° C. The viscosity of the adhesive containing the chemical polymerization initiator and the radical polymerizable monomer was measured by separately adjusting the composition not containing the chemical polymerization initiator.

[Polyaryl ether ketone resin material]
As polyaryl ether ketone resin materials, the following two types of polyaryl ether ketone resin materials C1 and C2 were used.

  Polyaryletherketone resin material C1: Polyetheretherketone resin (manufactured by Daicel Evonik Co., Ltd .: VESTAKEEEP M2G) and spherical silica (gaseous phase melt) surface-treated with γ-methacryloyloxypropyltrimethoxysilane as amorphous silica particles Polyaryletherketone prepared by the above method and having a purity of 99.9% or more and an average particle size of 1.0 μm mixed with 70 parts by mass of polyetheretherketone resin so that amorphous silica particles are 30 parts by mass A resin composite material was used. The mixing method is as follows. First, a predetermined amount of polyetheretherketone resin and amorphous silica particles are weighed and put into a kneading lab plast mill (manufactured by Toyo Seiki Co., Ltd.) for 5 minutes under conditions of a test temperature of 370 ° C. and a rotation speed of 100 rpm. After the melt-kneading, the melt-kneaded product was recovered to obtain a polyaryl ether ketone resin material C1.

  Polyaryl ether ketone resin material C2: VESTAKEEEP M2G (manufactured by Daicel Evonik), which is a polyaryl ether ketone resin, was used.

(Measurement of tensile adhesive strength between polyaryl ether ketone resin material and cured product of curable composition)
The polyaryl ether ketone resin material was molded into a 2 mm × 13 mm × 13 mm plate by injection molding. After polishing the 13 mm × 13 mm adherent surface with # 800 water-resistant abrasive paper, it was roughed by sandblasting (alumina particles having a particle size of about 50 μm were sprayed at a pressure of about 0.2 MPa for 10 seconds using a sandblasting apparatus). Elephantized. Thereafter, the substrate was immersed in water and exposed to ultrasonic waves for 5 minutes, and then washed by being immersed in acetone and exposed to ultrasonic waves for 5 minutes. Next, a double-sided tape having a thickness of 0.2 μm having a hole with a diameter of 3 mm was attached to the adherend surface.

  Thereafter, the hole was subjected to light irradiation and application and drying of an adhesive containing a radical polymerizable monomer. The order of application and drying of the adhesive containing light irradiation and the radical polymerizable monomer is as shown in Tables 2 and 3. Light irradiation was performed on the aforementioned holes using a dental visible light irradiator under the conditions shown in Tables 2 and 3. Application and drying of an adhesive containing a radical polymerizable monomer is performed by applying an adhesive containing a radical polymerizable monomer, and then allowing to stand for 10 seconds after application, followed by blowing compressed air for about 10 seconds and drying. It was done by doing. Thus, the adhesive polyaryl ether ketone resin material of the present invention was obtained. A dental cement material (Bistite II, manufactured by Tokuyama Dental Co., Ltd.), which is a curable composition containing a radical polymerizable monomer and a polymerization initiator as an adherend, on the adherend surface portion (hole portion of the double-sided tape). The adhesive test piece was produced by applying and pressing a cylindrical stainless steel attachment having a diameter of 8 mm and a height of 2 mm thereon. After holding the above-mentioned adhesion test piece at 37 ° C. for 24 hours, using a tensile tester (Autograph, manufactured by Shimadzu Corporation), it is pulled at a crosshead speed of 2 mm / min, and produced by the production method of the present invention. The tensile adhesive strength between the cured adhesive polyaryletherketone resin material, the cured material of the dental cement material which is a curable composition containing a radical polymerizable monomer and a polymerization initiator was measured. Tensile bond strength was measured for each of the five test pieces for each example or each comparative example, and the average value and standard deviation (SD) were determined.

  As a dental visible light irradiator, L.L. E. Demetron II (manufactured by Kerr, LED irradiator) and Optilux 500 (manufactured by Kerr, halogen irradiator) were used as L2. Both of these light irradiators have a maximum peak wavelength of light irradiated between 450 nm and 500 nm. The light intensity was measured by Demetron L. E. D. Using RADIOMETER (manufactured by Kerr), the light intensity of 400 nm to 500 nm was measured. In addition, the desired light intensity was obtained by changing the distance between the light guide tip and the irradiated surface, and used for the test.

(Measurement of adhesive layer thickness)
The polyaryl ether ketone resin material was molded into a 2 mm × 13 mm × 13 mm plate by injection molding. The adherend surface of the polyaryl ether ketone resin material was polished with a # 800 water-resistant abrasive paper, and then sandblasted (alumina particles having a particle size of about 50 μm were sprayed at a pressure of about 0.2 MPa for 10 seconds using a sandblasting apparatus. ). Thereafter, the substrate was immersed in water and exposed to ultrasonic waves for 5 minutes, and then washed by being immersed in acetone and exposed to ultrasonic waves for 5 minutes.

  Thereafter, light irradiation and application of an adhesive containing a radical polymerizable monomer and drying were performed on the adherend surface of the polyaryl ether ketone resin material. The order of application and drying of the adhesive containing light irradiation and the radical polymerizable monomer is as shown in Tables 2 and 3. The light irradiation was performed using a dental visible light irradiator under the conditions shown in Tables 2 and 3. The application and drying of the adhesive containing the radical polymerizable monomer is performed by applying the adhesive containing the radical polymerizable monomer, and then allowing it to stand for 10 seconds and then blowing it with compressed air for about 10 seconds to dry it. It went by. Thereafter, a dental cement material (made by Tokuyama Dental Co., Ltd .: Bistight II), which is a curable composition containing a radical polymerizable monomer and a polymerization initiator, is applied as an adherend on the adherend surface, and further A test piece was prepared by pressing a cylindrical attachment having a diameter of 8 mm and a height of 2 mm, which was prepared by curing a dental hard resin (made by Tokuyama Dental Co., Ltd .: Pearl Este). The above-mentioned test piece was held at 37 ° C. for 24 hours, and then cut perpendicularly to the adherend surface using a diamond cutter to expose the cross section of the bonded portion. After this bonded part was polished with # 3000 water-resistant abrasive paper, the thickness of the adhesive layer was measured with a laser microscope (manufactured by Keyence Corporation).

<Example 1>
5 g of bisGMA as a radical polymerizable monomer component having two or more radical polymerizable functional groups in the molecule, 5 g of 3G, 50 g of acetone as a solvent component, and stirring and mixing until uniform, radical polymerizable monomer An adhesive B1 containing was obtained. Table 1 shows the composition and viscosity of the adhesive. A double-sided tape having a hole with a diameter of 3 mm is attached to the surface of the polyaryl ether ketone resin material C1, and L. as a dental visible light irradiator L1. E. Demetron II (manufactured by Kerr, LED irradiator) is used to adjust the distance between the light guide tip and the light irradiation surface under the condition that the light intensity of the light irradiation surface is 800 mW / cm ^2, and performs light irradiation for 10 seconds. Next, the adhesive B1 containing the aforementioned radical polymerizable monomer was applied to this surface, and the solvent was removed by applying compressed air. Using the adhesive polyaryletherketone resin material thus obtained, measurement of tensile adhesion strength of the curable composition containing the polyaryletherketone resin material, the radical polymerizable monomer, and the polymerization initiator, The thickness of the adhesive layer was measured. Table 2 shows the conditions and measurement results.

<Examples 2 to 19>
In accordance with Example 1, except that the adhesive containing the radical polymerizable monomer, the light irradiator, the light intensity at the time of light irradiation, the light irradiation time, and the light energy were changed as shown in Table 2. The tensile adhesive strength measurement of the ketone resin material, the curable composition containing the radical polymerizable monomer and the polymerization initiator, and the thickness of the adhesive layer were measured. Table 1 shows the composition and viscosity of the adhesive containing the radical polymerizable monomer, and Table 2 shows the conditions and measurement results. The adhesives B4, B5, and B6 containing the chemical polymerization initiator were prepared by being divided into two parts A and B, and mixed immediately before use to prepare a final adhesive.

<Comparative Examples 1-3>
Polymerization with a polyaryletherketone resin material, a radically polymerizable monomer, and polymerization according to Examples 1, 12, and 16, respectively, except that the adhesive applied to the polyaryletherketone resin material was not irradiated with light. The tensile adhesive strength with the curable composition containing the initiator and the thickness of the adhesive layer were measured. Table 2 shows the conditions and measurement results.

<Comparative example 4>
Curing containing polyaryletherketone resin material, radical polymerizable monomer and polymerization initiator according to Example 19 except that the order of light irradiation, adhesive application and drying was changed as shown in Table 2. The tensile adhesive strength with the adhesive composition and the thickness of the adhesive layer were measured. Table 1 shows the composition of the adhesive, and Table 2 shows the conditions and measurement results.

<Examples 20 to 26>
Except for changing the polyaryl ether ketone resin material to C2, in accordance with Examples 1, 3, 8, 12, 15, 16, and 19, respectively, the polyaryl ether ketone resin material and the radical polymerizable monomer were polymerized. Measurement of tensile adhesive strength with the curable composition containing the initiator and measurement of the thickness of the adhesive layer were performed. Table 3 shows the conditions and measurement results.

<Comparative Examples 5-7>
Polymerization with a polyaryletherketone resin material, a radical polymerizable monomer, and polymerization according to Examples 20, 23 and 25, respectively, except that the adhesive applied to the polyaryletherketone resin material was not irradiated with light. The tensile adhesive strength with the curable composition containing the initiator and the thickness of the adhesive layer were measured. Table 3 shows the conditions and measurement results.

<Comparative Example 8>
Curing containing polyaryletherketone resin material, radical polymerizable monomer and polymerization initiator according to Example 26 except that the order of light irradiation, adhesive application and drying was changed as shown in Table 3 The tensile adhesive strength with the adhesive composition and the thickness of the adhesive layer were measured. Table 3 shows the conditions and measurement results.

  From the examination results (Table 2) using C1 as the polyaryl ether ketone resin material, the following can be said.

  Examples 1-8 and Comparative Example 1 use the same adhesive B1. In Examples 1 to 8, the polyaryl ether ketone resin material was irradiated with light, while in Comparative Example 1, the polyaryl ether ketone resin material was not irradiated with light. By comparing these results, it can be confirmed that the adhesive strength is improved by light irradiation.

  In addition, Examples 12 and 15 and Comparative Example 2 and Examples 16 and 19 and Comparative Example 3 are all under the same conditions in Comparative Examples 2 and 3 except that the polyaryl ketone resin material is not irradiated with light. is there. From these comparisons, it can be confirmed that the adhesive strength is improved by light irradiation.

  In Example 19 and Comparative Example 4, an adhesive containing a photopolymerization initiator was used, and all conditions were the same except for the order of application and drying of the adhesive and light irradiation. In Example 19, the adhesive was applied and dried after light irradiation, and the adhesive layer was thin. On the other hand, in Comparative Example 4, the adhesive is applied and dried before light irradiation, and the adhesive layer is thick. From these results, it can be confirmed that the thickness of the adhesive layer can be reduced by applying and drying the adhesive after the light irradiation. This is because the application and drying of the adhesive is performed before the light irradiation, so that the adhesive is irradiated with light, and the adhesive containing the photopolymerization initiator is polymerized and cured, and cannot be deformed. This is thought to be because of In addition, adhesive strength did not change a lot by the order of application | coating and drying of an adhesive agent, and light irradiation differing.

Comparing Examples 1 to 8 using the same adhesive and the same light irradiator, and different in light intensity and light irradiation time, Examples 2 to 8 having a light energy of 15000 mJ / cm ² or more are 15000 mJ. From Example 1 which is less than / cm ² , it can be confirmed that a high adhesive strength is exhibited. In Examples 3-8 the light energy is 30000mJ / cm ² or more can be confirmed to exhibit high adhesive strength than Examples 1 and 2 is less than 30000mJ / cm ^2. Furthermore, it can confirm that Examples 4-8 whose optical energy is 45000 mJ / cm < ² > or more show higher adhesive strength than Examples 1-3 which are less than 45000 mJ / cm < ² >.

Comparing Examples 4 to 7 in which the same adhesive and the same light irradiator were used, and light irradiation was performed under the same light energy but different light intensity and light irradiation time, the light intensity was 400 mW / cm ^2. It can be confirmed that Examples 4, 5, and 7 described above show higher adhesive strength than Example 6 which is less than 400 mW / cm ² . Furthermore, it can confirm that Example 4, 7 whose light intensity is 800 mW / cm < ² > or more shows higher adhesive strength than Example 5, 6 which is less than 800 mW / cm < ² >.

  Comparing Examples 4 and 9 in which the same adhesive and different light irradiators were used, and the light irradiation was performed with the same light intensity and the same light irradiation time, in both the LED irradiator and the halogen type irradiator, It can be confirmed that the adhesive strength is equivalent.

  Comparing Examples 1, 10, and 11 in which the adhesives having different monomer compositions and the same light irradiator were used and the light irradiation was performed under the same conditions, the radical polymerizable monomers contained in the used adhesives were compared. Among them, Examples 1 and 10 containing 40 parts by mass or more of radically polymerizable monomers having two or more radically polymerizable functional groups in the molecule have higher adhesive strength than Example 10 containing less than 40 parts by mass. It was confirmed that

  When Examples 1, 12, 13, and 14 in which light irradiation was performed under the same light irradiation condition using the same light irradiator with different amounts of chemical polymerization initiator contained, the chemical polymerization initiator was compared. From Example 1 using an adhesive not containing, it can be confirmed that Examples 12, 13, and 14 using an adhesive containing a chemical polymerization initiator of 0.002 parts by mass or more show high adhesive strength. Furthermore, Example 12 in which the content of the chemical polymerization initiator is in the range of 0.5 to 7% by mass is higher in adhesive strength than Examples 13 and 14 in which the content is less than 0.5 parts by mass or greater than 7 parts by mass. This was confirmed.

  When Examples 1, 16, 17, and 18 in which light irradiation was performed under the same light irradiation conditions using different adhesives and the same light irradiator contained, the photopolymerization initiators were compared. Regardless of the content, it was confirmed that the adhesive strength was comparable. Even if an adhesive containing a photopolymerization initiator is used, it is considered that the adhesive strength was not affected because the adhesive was not irradiated with light.

  From the examination results (Table 3) using C2 as the polyaryl ether ketone resin material, the following can be said.

  Examples 20-22 and Comparative Example 5 use the same adhesive B1. In Examples 20 to 22, the polyaryl ether ketone resin material was irradiated with light, while in Comparative Example 1, the polyaryl ether ketone resin material was not irradiated with light. By comparing these results, it can be confirmed that the adhesive strength is improved by light irradiation.

  Moreover, Examples 23 and 24 and Comparative Example 6 and Examples 25 and 26 and Comparative Example 7 are all under the same conditions in Comparative Examples 6 and 7, except that the polyaryl ketone resin material is not irradiated with light. is there. From these comparisons, it can be confirmed that the adhesive strength is improved by light irradiation.

  Example 26 and Comparative Example 8 all have the same conditions except the order of application and drying of the adhesive and light irradiation. In Example 26, the adhesive was applied and dried after light irradiation, and the adhesive layer was thin. On the other hand, in Comparative Example 8, the adhesive is applied and dried before light irradiation, and the adhesive layer is thick. From these results, it can be confirmed that the thickness of the adhesive layer can be reduced by applying and drying the adhesive after the light irradiation. This is because the application and drying of the adhesive is performed before the light irradiation, so that the adhesive is irradiated with light, and the adhesive containing the photopolymerization initiator is polymerized and cured, and cannot be deformed. This is thought to be because of In addition, adhesive strength did not change a lot by the order of application | coating and drying of an adhesive agent, and light irradiation differing.

Comparing Examples 20 to 22 using the same adhesive and the same light irradiator and having different light intensity and light irradiation time, Examples 21 and 22 having a light energy of 45000 mJ / cm ² or more are 45000 mJ. It can be confirmed that the adhesive strength is higher than that of Example 20 which is less than / cm ² .

  A comparison of Examples 20 and 23 in which light was irradiated under the same light irradiation conditions using the same light irradiator with different presence or absence of the chemical polymerization initiator. From Example 20 used, it can be confirmed that Example 23 using an adhesive containing a chemical polymerization initiator in an amount of 0.002 parts by mass or more exhibits high adhesive strength.

  Comparing Examples 20 and 25 in which light was irradiated under the same light irradiation conditions using different adhesives and the same light irradiator with or without a photopolymerization initiator, regardless of whether or not a photopolymerization initiator was contained It was confirmed that the adhesive strength was comparable. Even if an adhesive containing a photopolymerization initiator is used, it is considered that the adhesive strength was not affected because the adhesive was not irradiated with light.

  By comparing the study results using C1 as the polyaryl ether ketone resin material (Table 2) and the study results using C2 as the polyaryl ether ketone resin material (Table 3), the following can be said.

  Example 1 and Example 20, Example 4 and Example 21, Example 8 and Example 22 in which the same adhesive was used for different polyaryl ether ketone resin materials and light irradiation was performed under the same conditions. When Example 12 and Example 23, Example 15 and Example 24, Example 16 and Example 25, Example 19 and Example 26 are compared, respectively, the polyaryletherketone resin material has amorphous inorganic compound particles. Examples 1, 4, 8, 12, 15, 16, and 19 in which amorphous silica is blended are examples 20, 21, 22, 23, in which amorphous inorganic compound particles are not blended, respectively. Compared with 24, 25, and 26, it was confirmed that the adhesive strength was slightly higher.

Claims (10)

  A method for producing an adhesive polyaryletherketone resin material comprising applying an adhesive containing the radical polymerizable monomer (a) after light irradiation of the polyaryletherketone resin material.   The method for producing an adhesive polyaryletherketone resin material according to claim 1, wherein the maximum peak wavelength of light used for light irradiation is 400 nm to 500 nm.   3. The radical polymerizable monomer of the adhesive is a radical polymerizable monomer having 40% by mass or more having two or more (meth) acryloyl groups in the molecule as a polymerizable functional group. Of producing an adhesive polyaryletherketone resin material.   Furthermore, the said adhesive agent contains a chemical polymerization initiator (b), The manufacturing method of the adhesive polyaryl ether ketone resin material as described in any one of Claims 1-4.   The method for producing an adhesive polyaryletherketone resin material according to any one of claims 1 to 5, wherein the adhesive polyaryletherketone resin material is for dental use.   A pretreatment method for a polyaryl ether ketone resin material, comprising: applying an adhesive containing the radical polymerizable monomer (a) after light irradiation of the polyaryl ether ketone resin material.   The pretreatment method for a polyaryletherketone resin material according to claim 7, wherein the adhesive further contains a chemical polymerization initiator (b).   An adhesion method for adhering a polyaryl ether ketone resin material and an adherend comprising a curable composition containing a radical polymerizable monomer and a polymerization initiator, wherein the polyaryl ether ketone resin material is irradiated with light. After that, an adhesive containing the radical polymerizable monomer (a) is applied, the adherend is pressure-bonded onto the polyaryl ether ketone resin material to which the adhesive is applied, and the adherend is polymerized and cured. A method for adhering a polyaryletherketone resin material and an adherend, characterized by comprising:   The method for adhering a polyaryletherketone resin material and an adherend according to claim 8, wherein the adhesive further contains a chemical polymerization initiator (b).   After the polyaryl ether ketone resin material is irradiated with light, an adhesive containing the radical polymerizable monomer (a) is applied, and the radical polymerizable property is applied onto the polyaryl ether ketone resin material coated with the adhesive. A method for producing a laminate, comprising: bonding an adherend comprising a curable composition containing a monomer and a polymerization initiator, and polymerizing and curing the adherend.