JP6602163B2 - Method for producing adhesive polyaryletherketone resin material and adhesion method - Google Patents

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 such a polyaryletherketone resin material and an 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.

  When the polyaryletherketone resin material and the adherend are bonded using an adhesive composition, it is necessary to make the adhesive composition layer thin (adhesive layer) from the viewpoint of appearance and dimensional stability. It is desired. For example, in the dental field, when an abutment tooth and a prosthesis made of a dental polyaryletherketone resin material are bonded, if the layer of the adhesive composition is thick, the compatibility of the dental prosthesis is adversely affected. As a result, the amount of cutting and polishing of the dental prosthesis increases to increase the burden on the dentist / patient. In another example in the dental field, when a polyaryletherketone resin material and an adherend such as a dental filling restorative material or a dental hard resin are bonded with an adhesive composition, a dental prosthesis is produced. When the layer of the adhesive composition is thick, the layer of the adhesive composition is visible, and the produced dental prosthesis is 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, there is an urgent need for a technique for bonding a polyaryletherketone resin material and a curable composition containing the radical polymerizable monomer with a thin adhesive layer and high strength.

  As a method for bonding the polyaryl ether ketone resin material and the adherend, for example, in the dental field, it has been reported that the use of an adhesive composition containing a polymerizable monomer and a polymerization initiator is effective. For example, Non-Patent Document 1 describes that relatively high adhesiveness was obtained by using a hydrophobic dental bonding material. High adhesiveness can be obtained by applying the adhesive composition to a polyaryletherketone resin material followed by polymerization and curing. However, when an adhesive composition that is cured after application is used, a layer resulting from the adhesive composition is formed by polymerization and curing of the polymerizable monomer in the adhesive composition, so that generally adhesion It is difficult to reduce the thickness of the composition layer.

  On the other hand, it is not an adhesive composition that contains a polymerization initiator and a polymerizable monomer and forms a film by curing immediately after coating, but generally does not contain a polymerization initiator (pretreatment agent) Is used, the other adherend is pressure-bonded without being cured after the primer application, so that it is easier to reduce the film thickness as compared with the adhesive composition to be pressure-bonded after curing.

  However, studies have been made to evaluate adhesiveness of a polyaryletherketone resin material using a dental primer that does not contain a polymerization initiator, but 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. However, it is not disclosed to irradiate the primer with light, and it does not suggest that the adhesion with the adherend is improved by irradiating with light.

  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 DMSO and methacryl silane, DMSO and ethanol are shown in the examples. In the adhesion test using the conditioning agent, the conditioning agent is infiltrated into the adherend surface, soaked for 2 minutes, a clean air stream is sprayed on the conditioning agent, and then a photocurable dental plastic is used. There is no description or suggestion of direct light irradiation on the conditioning agent (primer).

JP 2013-144778 A Special table 2010-521257

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

  As described above, in the case where the polyaryl ether ketone resin material and the adherend are bonded, the adhesive composition is applied to the polyaryl ether ketone resin material and then cured by polymerization, and the adherend is bonded. Although it was easy to obtain adhesive strength, it was difficult to make the adhesive layer thin. On the other hand, in the case of a primer that pressure-bonds an adherend without polymerizing and curing the adhesive composition after applying it to a 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 obtain high adhesive strength in the case of the adhesion | attachment of a polyaryl ether ketone resin material and a to-be-adhered body using the primer which can make the thickness of an adhesive bond layer thin easily. .

  In the present application, the adhesive layer means a layer formed by a composition containing a polymerizable monomer that is first applied to the polyaryletherketone resin material. In the case of an aryl ether ketone resin material, it means a thin film layer obtained by curing a primer containing a radical polymerizable monomer.

  In order to solve the above-mentioned problems, the inventors have conducted intensive studies. As a result, after applying a primer containing a radical polymerizable monomer to the polyaryletherketone resin material, The irradiated polyaryletherketone resin material has high adhesion to an adherend, particularly an adherend composed of a curable composition containing a radical polymerizable monomer and a polymerization initiator. I found out. In addition, since the primer is not polymerized and cured by light irradiation, in general, the primer is not irradiated with light after the primer is applied. That is, in the present invention, a primer containing a radically polymerizable monomer that is not normally irradiated with light is applied on the polyaryl ether ketone resin material and then light irradiation is performed, whereby the polyaryl ether ketone resin material is obtained. It is an invention that has been found to improve the adhesion to an adherend. That is, by applying the present invention, it was found that the polyaryletherketone resin material and the adherend can be bonded with high adhesive strength while thinning the adhesive layer, and the present invention has been achieved.

  That is, the present invention is a method for producing an adhesive polyaryletherketone resin material, characterized in that a polyaryletherketone resin material is coated with a primer containing a radical polymerizable monomer and then irradiated with light. . 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 primer has 40% by mass or more as a polymerizable functional group having 2 or more (meth) in the molecule. 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 applying a primer containing a radical polymerizable monomer to the polyaryletherketone resin material, light irradiation is performed, and then the adherend is pressure-bonded onto the polyaryletherketone resin material coated with the primer, This is a method for bonding a polyaryletherketone resin material and an adherend by polymerizing and curing the curable composition.

  Furthermore, the present invention is a pretreatment method for a polyaryletherketone resin material, wherein a light-irradiation is performed after a primer containing a radical polymerizable monomer is applied to the polyaryletherketone resin material. .

  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 of 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.

  By applying a primer containing a radical polymerizable monomer to a polyaryl ether ketone resin material, and then using an adhesive polyaryl ether ketone resin material produced by light irradiation, a radical polymerizable monomer is obtained. High adhesion can be obtained in adhesion between a curable composition containing a monomer and a polymerization initiator, for example, a dental curable composition such as dental resin cement or dental hard resin.

  As described above, the present invention provides a polyaryletherketone resin material by irradiating a primer containing a radical polymerizable monomer coated on the polyaryletherketone resin material, which is not usually performed. This is an invention in which the adhesion to an adherend, 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 two aromatic rings on the surface of the polyaryletherketone resin is activated by light irradiation to generate radicals, and radical polymerization in the radicals and primer It is presumed that the surface of the polyaryletherketone resin material is modified by the reaction with the functional monomer. By this reaction, the adhesive force at the interface between the primer and the polyaryletherketone resin material is improved. In addition, the adhesive polyaryletherketone resin material produced in this way does not have an adhesive layer of a certain thickness formed by the polymerization and curing of the radical polymerizable monomer of the entire primer. Only the radical polymerizable monomer present in the vicinity of the aryl ether ketone resin material surface only contributes to the reaction based on the generation of radicals by the activation of the ketone group, and the radical polymerizable monomer in most primers. Does not polymerize after light irradiation and remains as a polymerizable monomer. Therefore, even after light irradiation, the primer itself exists on the adhesive polyaryl ether ketone resin material as a fluidly easy-to-deform layer, and is composed of a curable composition for the adhesive polyaryl ether ketone resin material. When the adherend is laminated and pressure bonded, the primer is easily deformed and thinned by the pressure at the time of lamination and pressure bonding. Therefore, when the curable composition is cured and the adherend and the adhesive polyaryletherketone resin material are bonded, the adhesion between the adherend and the adhesive polyaryletherketone resin material The layer is thinned. Since the curable composition contains a polymerization initiator, the radical polymerizable monomer in the primer and the curability are then activated by activating the polymerization initiator, for example, by performing light irradiation again. The radical polymerizable monomer in the composition is polymerized, and the adhesion between the primer and the curable composition is also strengthened.

<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 may be composed only of a polyaryletherketone resin, but a material obtained by blending another resin with a polyaryletherketone resin, a polyaryletherketone resin or a polyaryletherketone resin And other resins blended 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). Moreover, you may add trace components, such as a pigment and a stabilizer, 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. When blending a polyaryl ether ketone resin and another resin, the polyaryl ether ketone resin is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more of the total resin. Is more preferable, and it is more preferable that it is 99 mass% or more.

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

  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 known in detail, when light is applied after the primer is applied to the polyaryletherketone resin material, part of the light that reaches the polyaryletherketone resin material surface by the amorphous inorganic compound particles By scattering, it is presumed that the activation of the polyaryletherketone resin by light described later 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 blended in the polyaryletherketone resin material including the amorphous inorganic compound particles is determined by the laser scattering method (LS230 manufactured by Beckman Coulter, Inc. is used as a measuring device, and ethanol is used as a dispersion medium. Can be used to measure. 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 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 adhesiveness. The range of mass% to 40 mass% is more preferable, and the range of 25 mass% to 35 mass% is still more preferable.

  The amorphous inorganic compound particles are preferably amorphous silica because the effect of improving adhesion by applying light to the polyaryl ether ketone resin material after applying a primer to the polyaryl ether ketone resin material is high. 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.

<Primer>
The primer containing the radical polymerizable monomer of the present invention is a polyaryl ether ketone in order to bond a polyaryl ether ketone resin material to a curable composition containing a radical polymerizable monomer and a polymerization initiator. It is applied to the surface of the resin material and is used without being polymerized and cured before being brought into contact with the curable composition. In other words, after applying a primer containing a radical polymerizable monomer to the polyaryl ether ketone resin material and before contacting the curable composition on the applied primer, the primer is irradiated. Does not polymerize and cure. By making contact and pressure bonding of the curable composition without polymerizing and curing the primer, it becomes easy to thin the adhesive layer.

  The pressure bonding in the present invention means that a curable composition is further placed on the primer layer applied to the adherend surface of the polyaryletherketone resin material, and the primer layer is forced through the curable composition before curing. The curable composition before being cured by pressing with a hand or a machine, and placing the paste-like curable composition having a relatively low viscosity on the primer. Before the material hardens and no longer deforms, place and press a solid on it, apply a paste-like curable composition with a relatively low viscosity to the surface of the solid, and bring the surface into contact with the primer layer. Includes pressing. In addition, when a curable composition is placed on a primer and force is applied to the primer layer before curing due to its gravity, the effect of the present invention is obtained, although the effect is smaller than in the case of pressing as described above. And included in the crimping in the present invention.

  The radical polymerizable monomer contained in the primer of 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 compounded in the primer may be 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. Preferably, 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. Using a radical polymerizable monomer having two or more radical polymerizable functional groups in the molecule makes it possible to obtain a uniform and strong primer layer more easily by using 40% by mass or more of the total radical polymerizable monomer. Higher adhesion can be obtained.

  The radical polymerizable monomer preferably has one or more hydrogen bondable functional groups in the molecule. Since the radical polymerizable monomer has one or more hydrogen-bonding functional groups in the molecule, the primer layer cured on the surface of the polyaryletherketone resin material by hydrogen bonding between the hydrogen-bonding functional groups. Strength becomes stronger and higher adhesiveness 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 hydrogen bonding functional groups in the molecule is preferably contained in an amount of 5% by mass or more based on the total radical polymerizable monomers. It is more preferable to include at least 30% by mass, more preferably at least 30% by mass, and even more preferably at least 50% by mass.

  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 primer and the aromatic ring of the polyaryletherketone resin material form a stack, and the interaction between the polyaryletherketone resin material and the primer layer Is estimated to 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 setting the radical polymerizable monomer having two or more radical polymerizable functional groups, hydrogen bondable functional groups and aromatic rings in the molecule to 15% by mass or more, the polyaryl ether ketone resin material and the primer layer It is possible to strengthen the interaction. 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 The interaction between them makes it difficult to handle the radically polymerizable monomer, and it may be difficult to mix it with the primer from the viewpoint of workability.

  In the case where the polyaryl ether ketone resin material is a polyaryl ether ketone resin composite material containing a metal oxide as a filler, a coupling agent having a radical polymerizable functional group is blended as a radical polymerizable monomer. It is also suitable.

  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 adding a coupling agent to the primer, 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 polyaryl ether ketone resin composite material and the radical polymerizable monomer of the primer.

  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 coupling agents include silane coupling agents, titanate coupling agents, aluminate coupling agents, and zirconate coupling agents, but silane coupling agents are particularly preferred from the viewpoints of adhesiveness and handleability. is there.

  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 blended in the primer, the radical polymerizable monomer having two or more radical polymerizable functional groups in the molecule is added to the primer. It is particularly preferable to blend 40% by mass or more with respect to the monomer in order to obtain higher adhesiveness.

  As described above, the primer in the present invention is used without being polymerized and cured before being brought into contact with the curable composition. By not polymerizing and curing, the radically polymerizable monomer of the primer applied to the surface of the polyaryletherketone resin material maintains fluidity and can be easily deformed. When the curable composition is pressure-bonded, the primer This layer (adhesive layer) can be easily thinned. As the primer of the present invention, a primer having a specific value measured in Raman spectroscopic measurement before and after light irradiation can be suitably used as follows.

  It can be confirmed by micro Raman spectroscopic measurement that the radical polymerizable monomer of the primer is not polymerized and cured.

For example, when the radical polymerizable monomer contained in the primer is a radical polymerizable monomer having a (meth) acryloyl group, the consumption of the radical polymerizable functional group by light irradiation can be obtained by the following method. It can be confirmed that the polymer is not cured. The primer in a storage state is applied onto a slide glass using a dental bonding material collecting brush. When air blow is performed at the time of use, air blow is performed to form a primer layer on the slide glass. On the formed primer layer, a primer in a storage state is further applied. When air blowing is performed at the time of use, air blowing is performed, and the primer layer is formed nine times. The primer for measurement on the slide glass Form a layer. A Raman spectrum of the primer layer is measured, and a peak height ratio H ₁ before light irradiation is obtained according to the following formula I. In addition, when the storage form of the primer is divided into two or more packaging, and these are mixed and used immediately before use, the above operation is performed for each packaging, and after obtaining the peak height ratio according to the formula I, each packaging According to the mixing ratio, the peak height ratio is averaged to obtain the peak height ratio before light irradiation.

In formula I, the peak near 1640 cm ⁻¹ is derived from a double bond, and the peak near 1715 cm ⁻¹ is derived from a ketone group.

Next, apply the primer on the slide glass using a brush for collecting dental bonding material according to the method of using the primer (for example, mix when mixing two or more liquids). To form a primer layer. On the formed primer layer, a primer is further applied according to the method of use. When air blow is performed during use, air blow is performed, and the primer layer is formed nine times. The primer for measurement on the slide glass Form a layer. Thereafter, a polypropylene film having a thickness of about 100 μm is placed on the primer layer, and a dental visible ray irradiator having a maximum peak wavelength of irradiation light in the range of 450 nm to 500 nm is used, and light in the range of 400 nm to 500 nm is used. The primer layer is irradiated for 60 seconds from above the polypropylene film with light having a light intensity of 800 mW / cm ² measured using a measuring apparatus capable of measuring the light intensity of the film. The polypropylene film is removed, the Raman spectrum of the primer layer is measured, and the peak height ratio H ₂ after light irradiation is obtained according to the following formula II.

Thus, the operation of obtaining H ₁ and H ₂ is performed five times or more, the respective average values H _1a and H _2a are calculated, and the peak attenuation rate is calculated from the following formula III.

  Here, it is known that the double bond of the (meth) acryloyl group affects the peak height of the ketone group of the (meth) acryloyl group due to the resonance action with the double bond (C. Pianelli et al., J Biomed Mater Res Vol. 48 p675-681), the peak attenuation value obtained by this method does not match the polymerization rate value of the radical polymerizable monomer, but this peak attenuation rate is correlated with the polymerization rate. It is assumed that there is. Therefore, when the double bond is consumed by polymerization curing, the peak attenuation rate increases. When the peak attenuation rate is 15% or less, the adhesive layer can be made thin. In addition, since the radically polymerizable monomer of the primer maintains higher fluidity as the peak attenuation rate is smaller and it is easier to reduce the thickness of the adhesive layer, the peak attenuation rate is 10% or less. More preferably, it is 5% or less.

  Although the primer of the present invention contains a polymerizable monomer, the polymerizable monomers are polymerized and cured by light irradiation performed after the primer is applied to the polyaryl ether ketone resin material to form a thick adhesive layer. It is not a thing. That is, an adhesive composition containing a radical polymerizable monomer and a certain amount of a photopolymerization initiator forms a thick adhesive layer by irradiating light, but the primer of the present invention has such an adhesive composition. Is different. Accordingly, the primer of the present invention does not substantially contain a photopolymerization initiator that polymerizes and cures the polymerization initiators by light irradiation. 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. Some amount of the photopolymerization initiator is acceptable because it does not form a thick adhesive layer by light irradiation.

  The thermal polymerization initiator may be blended if it is not polymerized and cured before being brought into contact with the curable composition without performing an operation for generating radical polymerization initiator activity such as not heating, but is not blended substantially. It is more preferable. 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. By blending a thermal polymerization initiator, even in the case of no heating, compared to the case where it is not substantially blended, the radically polymerizable monomer contained in the primer is more easily cured during operation, and the primer There is a possibility that the thickness of the layer is slightly increased. Further, from the viewpoint of storage stability of the primer, it is preferable that a thermal polymerization initiator is not substantially blended.

  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. When a chemical polymerization initiator is added to a primer, it is usually used by storing the primer package in two or more parts, mixing all the components just before use to generate chemical polymerization initiator activity, and applying it quickly. The In this case, since the reaction proceeds gradually from the time of mixing, there are cases where it can be used without being polymerized and cured before being brought into contact with the curable composition by performing a quick operation. Usage methods such as standing time and light irradiation time are limited. Therefore, it is preferable not to mix all the components of the chemical polymerization initiator.

  On the other hand, a part of the components forming the chemical polymerization initiator system (hereinafter, also referred to as a partial component of the chemical polymerization initiator component) is blended with the primer, and the chemical component initiator is partially combined with the chemical component. It is particularly preferable to use a curable composition containing a component that forms a polymerization initiator system as an adherend. That is, a primer for a polyaryl ether ketone resin material containing a part of the chemical polymerization initiator component is applied to the adherend surface of the polyaryl ether ketone resin material, irradiated with light, and then the chemical polymerization compounded in the primer A curable composition containing a chemical polymerization initiator component that forms a chemical polymerization initiator system with a portion of the initiator component is used over the primer. As a result, in the primer for the polyaryl ether ketone resin material, which does not form a chemical polymerization initiator system and contains a part of the chemical polymerization initiator component, the chemical polymerization is initiated by the chemical polymerization initiator component of the curable composition. Since the agent system is formed, the polymerizability of the radically polymerizable monomer in the primer layer is improved, and the curability of the primer layer is improved, so that the adhesion is improved. On the other hand, since no chemical polymerization initiator system is formed in the primer layer until immediately before the curable composition is pressure-bonded, the primer can be used without being polymerized and cured before contacting with the curable composition. Since the fluidity that can be easily deformed can be maintained, the thickness of the adhesive layer can be reduced.

  As a partial component of such a chemical polymerization initiator, it is possible to use any component out of a combination of two or more components forming a chemical polymerization initiator system. A typical radical polymerizable chemical polymerization initiator system is one using a redox reaction comprising an oxidizing agent and a reducing agent.

  In the case of a chemical polymerization initiator system using a redox reaction, either an oxidizing agent or a reducing agent can be used as a partial component of the chemical polymerization initiator to be blended in the primer. When using a primer containing an oxidizing agent, a curable composition containing a reducing agent, or when using a primer containing a reducing agent, a curable composition containing an oxidizing agent is used together for higher adhesion. You can get sex.

  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 the oxidizing agent to be blended in the primer of the present 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 primer or the curable composition.

  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.

  In particular, as a partial component of the chemical polymerization initiator component, it is preferable to mix a primer that can function as a reducing agent from the viewpoint of improving adhesiveness. The reason why this improves adhesion is not known in detail, but when this primer is applied to the surface of the polyaryletherketone resin material by blending the reducing agent with the primer, the reducing agent in the primer is polyaryl. By acting on the resin on the surface of the ether ketone resin material and reducing a part of the ketone group, carbon atoms having two arylene groups, hydroxyl groups and hydrogen atoms as substituents on the surface of the polyaryl ether ketone resin material Generate. On the carbon atom having two arylene groups, a hydroxyl group and a hydrogen atom as substituents, radicals are easily generated by hydrogen abstraction. Therefore, when the primer is polymerized and cured, the surface of the polyaryletherketone resin material is A bond is formed between the carbon atom adjacent to the generated hydroxyl group and the laminated radical polymerizable monomer. As a result, it is estimated that the adhesiveness is improved.

  In addition, as a part of the chemical polymerization initiator component, the high activity as the chemical polymerization initiator, the fluidity as high as possible until just before the primer layer comes into contact with the curable composition, and the storage stability From the balance of properties and the like, it is preferable to blend the transition metal compound of the fourth period with the primer. The transition metal compound in the fourth period blended in the primer is more preferably a vanadium compound.

  Considering these points, a part of the chemical polymerization initiator component blended in the primer is preferably a transition metal compound in the fourth period that can function as a reducing agent. Particularly, among the stable vanadium compounds, the oxidation number is low. Highly active + IV valent vanadium compounds are most preferred.

  The compounding amount of a part of the chemical polymerization initiator component is 0.002 to 10 parts by mass with respect to 100 parts by mass of the total polymerizable monomer, particularly from the balance between the adhesion immediately after adhesion and the storage stability of the primer. The range is preferably 0.007 to 2 parts by mass, and most preferably 0.01 to 1 part by mass.

  In addition, the primer of the present invention contains 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. May be.

  It is also preferable to mix a volatile solvent with the primer. By adding a volatile solvent, the viscosity of the primer decreases, making it easier for radically polymerizable monomers to penetrate into the fine irregularities on the surface of the polyaryletherketone resin material and forming a uniform primer layer. It becomes easy to do. In addition, due to the volatility, after the primer is applied to the adherend surface of the polyaryl ether ketone resin material, it is removed from the surface of the polyaryl ether ketone resin material by an operation such as air blowing, and adhesion due to residual solvent is achieved. Can suppress the adverse effect of.

  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 becomes easy to obtain an effect that the primer easily enters the fine irregularities on the surface of the polyaryletherketone resin material or that a uniform primer layer is formed. When the volatile solvent is more than 3000 parts by mass, the radical polymerizable monomer component of the primer is reduced, and as a result, when the primer is applied to the surface of the polyaryl ether ketone resin material, the surface of the polyaryl ether ketone resin material is reduced. The amount of the radically polymerizable monomer present is insufficient, the formation of a uniform and strong primer layer is insufficient, and the advantage of blending a volatile solvent is difficult to obtain.

  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 primer is inhibited, or the polymerization and curing of the radical polymerizable monomer of the primer is inhibited. There is a risk that the adhesiveness may be reduced due to inhibition. Therefore, the low volatility solvent contained in the primer 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 most preferably 1% by mass or less.

  The primer of the present invention may contain a filler as necessary. As the filler, 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 primer entering the fine irregularities present on the surface of the polyaryletherketone resin material 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, if the primer contains a large amount of filler, the viscosity of the primer 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 primer is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less with respect to 100 parts by mass of the primer.

  The particle size and shape of the filler are not particularly limited, but are preferably small from the viewpoint of forming a uniform primer 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.

<Primer properties>
The viscosity of the primer is preferably low. The low viscosity of the primer makes it easier for the primer to penetrate into the fine irregularities on the surface of the polyaryletherketone resin material, making it easier to apply the primer uniformly on the surface of the polyaryletherketone resin material, and higher Adhesiveness is easily obtained. On the other hand, when the viscosity of the primer is too low, it is difficult to uniformly apply the primer to the adherend surface of the polyaryletherketone resin material, which may have a complicated structure due to causes such as dripping of the primer It may become. Therefore, the viscosity of the primer 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. More preferably, 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 primer is preferably highly transparent. When the transparency of the primer is low, the light irradiated from above the primer does not reach the polyaryletherketone resin material, and it becomes difficult to obtain the effect of improving the adhesiveness due to the light irradiation. Therefore, it is preferable that the primer has a low contrast ratio.

  Here, the contrast ratio in the present invention is a scale representing transparency, and is calculated using the Y value related to brightness among the tristimulus values of the XYZ color system defined in JIS Z8701, It can be measured by using a simple color difference meter. Specifically, the black value or white background is brought into contact with the sample, and the Y value in the reflected light when the standard light C is irradiated is read. The contrast ratio can be obtained from Yb / Yw, where Yb for a black background is Yb and Y for a white background is Yw. The closer the contrast ratio value is to 1, the more opaque the material is, and the closer to 0 the transparent material.

  The contrast ratio of the primer is measured by applying a primer to a polypropylene film having a thickness of about 100 μm according to a predetermined method including mixing, air blowing, etc., covering the polypropylene film with a thickness of about 100 μm, and then pressing the primer. It can be performed by calculating Yb / Yw by the above method using the prepared measurement sample.

  The contrast ratio of the primer of the present invention measured by the above method is preferably 0.5 or less, more preferably 0.3 or less, and further preferably 0.1 or less.

<Light irradiation method>
In the present invention, a primer containing the above-mentioned radical polymerizable monomer is applied to the adherend surface of the polyaryl ether ketone resin material, and then light irradiation is performed on the primer. By irradiating the surface of the polyaryl ether ketone resin material after the primer application, the ketone group having two aromatic rings as substituents in the polyaryl ether ketone resin material of the polyaryl ether ketone resin material is activated. , Radicals are generated. By reacting the generated radical with the radical polymerizable functional group of the radical polymerizable monomer contained in the primer, a bond is formed between the polyaryl ether ketone resin material and the primer. Next, the curable composition is pressure-bonded from above the primer, and then the curable composition is polymerized and cured, whereby the radical polymerizable functional group of the radical polymerizable monomer of the primer and the radical of the curable composition are obtained. The radical polymerizable functional group of the polymerizable monomer reacts to form a bond between the primer and the curable composition. Therefore, 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 light irradiation on the surface of the polyaryletherketone resin material coated with the primer of the present invention may be any wavelength, but is preferably visible light, particularly blue light. It is preferable. 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 light irradiation of the surface of the polyaryletherketone resin material coated with the primer of the present invention includes a volatile solvent in the primer, and when it is necessary to remove this by air blow or the like, the light irradiation is performed before air blow. Although it may be performed or may be performed later, it is more preferably performed after removal of the volatile solvent by air blow or the like. By performing light irradiation after removing the volatile solvent by air blow or the like, it becomes possible to operate without worrying about changes in the surface state due to the volatilization of the solvent, and it becomes easier to obtain stable quality every time. . In addition, by performing light irradiation after removal of the volatile solvent by air blow or the like, the radical polymerizable monomer contained in the primer is compared with the case of performing light irradiation with the volatile solvent remaining. In the vicinity of the polyaryletherketone resin of the polyaryletherketone resin material, it becomes easy to be present at a high concentration, and the effect of improving adhesiveness is easily obtained.

  The polyaryletherketone resin material of the present invention is produced by applying light to a polyaryletherketone resin material having a roughened coating surface after applying a primer containing a radical polymerizable monomer. More preferably. The roughened polyaryletherketone resin material has increased surface irregularities and can achieve higher adhesion. Roughening is a technique that can be carried out simply and safely before applying a primer containing a radical polymerizable monomer, and roughening is performed on the surface on which the primer of the polyaryletherketone resin material is to be applied. What is necessary is just to implement a process. 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, it is easy to obtain higher adhesion by applying a primer containing a radical polymerizable monomer to the thus roughened polyaryletherketone resin material and then performing light irradiation. It becomes.

<Curable composition>
The adhesive polyaryletherketone resin material obtained by the production method of the present invention has high adhesiveness when the curable composition is pressure-bonded to the adherend surface, and the adhesive layer is thin. Can be. Therefore, after applying a primer containing a radical polymerizable monomer to the polyaryl ether ketone resin material, light irradiation is performed, and then the radical polymerizable single monomer is applied onto the polyaryl ether ketone resin material to which the primer is applied. A polyaryletherketone resin material and an adhesion, characterized in that an adherend comprising a curable composition containing a polymer and a polymerization initiator is pressure-bonded, and the adherend (curable composition) is polymerized and cured. A method of bonding to the body is also suitable.

  The curable composition has a low viscosity and can be easily deformed at first, so that it can be deformed into a desired shape and placed at a desired location, and then polymerized and cured to exert its function. is there.

  In the present invention, the curable composition contains a radical polymerizable monomer and a radical polymerization initiator. In the bonding operation to the polyaryletherketone resin material, pressure bonding is performed to the adherend surface of the polyaryletherketone resin material. By applying pressure to the present curable composition, the primer layer that has been previously applied and has not yet been polymerized and cured is thinned, and then when the present curable composition is polymerized and cured, the radical polymerization property of the primer is reduced. It is presumed that the monomer is also polymerized and cured, the interaction between the polyaryl ether ketone resin material and the curable composition becomes stronger, and high adhesiveness can be obtained.

  The radical polymerizable monomer contained in the curable composition 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. . As an example of a preferable radical polymerizable monomer, what was shown to the said (I)-(IV) as an example of the radical polymerizable monomer mix | blended with a primer is mentioned, 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.

  As a polymerization initiator contained in the curable composition, a photopolymerization initiator, a chemical polymerization initiator, or a thermal polymerization initiator can be used, and two or more polymerization initiators can be used in combination. In addition, since a curable composition can be hardened | cured simply after crimping | bonding a curable composition to a polyaryl ether ketone resin material, it is preferable to use a photoinitiator 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-dimethyl Aminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylanthranilic acid methyl ester, N, N-dihydroxyethylaniline, N, N-dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol p-dimethylaminostilbene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine, tributylamine, tripropylamine , Triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate, N, N- Examples include diethylaminoethyl methacrylate and 2,2 ′-(n-butylimino) diethanol. These can be used individually or in mixture of 2 or more types.

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

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

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

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

  A chemical polymerization initiator is a polymerization initiator which consists 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 primer. Including these, examples of usable chemical polymerization initiators include, for example, those based on 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-butyl barbituric acid Even if an initiator is blended, it can be used without any problem.

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

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

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

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

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

  Two or more of the various aryl borate compounds exemplified above may be used in combination.

  It is also preferable to use an organic peroxide and / or a transition metal compound in combination with the above-described aryl borate compound / acidic compound polymerization initiator. The organic peroxide 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, diisopropyl peroxydicarbonate, and the like. , 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 amount of the polymerization initiator is less than 0.01 parts by mass, the curing of the curable composition becomes insufficient particularly immediately after curing, and the physical properties tend to decrease. Conversely, when the polymerization initiator exceeds 10 parts by mass, it becomes difficult to improve the operability of the curable composition.

  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, the curable composition of the present invention can suppress polymerization shrinkage of the curable composition, improve the operability of the curable composition by using a filler, or mechanical properties of the cured product. Can be improved. 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. There may be some peeling between the primer applied to the surface of the ketone resin material, or between the curable composition and the primer applied to the surface thereof, which may make it difficult to obtain high adhesiveness.

  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. A plurality of inorganic fillers having different particle size ranges and different refractive indexes may be used in combination.

  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>
The adhesion method of the adhesive polyaryl ether ketone resin material obtained by the production method of the present invention and the curable composition is not particularly limited. The form in particular which gives a curable composition to the surface of adhesive polyaryl ether ketone resin material of the present invention is not restricted, for example, a curable composition is applied to the surface of adhesive polyaryl ether ketone resin material of the present invention. Apply the curable composition directly on the surface of another member other than the adhesive polyaryletherketone resin material of the present invention, and then contact the other member with the adhesive polyaryletherketone resin material of the present invention. By making it, a polyaryl ether ketone resin material and a curable composition can be made to contact.

  Also, the adhesive polyaryletherketone resin material of the present invention is bonded to each other through the curable composition, or the adhesive polyaryletherketone resin material of the present invention and the third member are bonded. You can also.

  When the adhesive polyaryletherketone resin materials of the present invention are bonded to each other through the curable composition, for example, one end and the other end of the ring-shaped adhesive polyaryletherketone resin material of the present invention provided with a joint. Can be adhered using a curable composition. Moreover, you may adhere | attach in the form which fills the recessed part of the adhesive polyaryl ether ketone resin material of this invention provided with recessed parts, such as a hole and a groove | channel, with a curable composition. In this case, the recess is embedded, and the curable composition filled in the recess and the inner wall surface of the recess of the adhesive polyaryletherketone resin material of the present invention are bonded.

  For example, when the curable composition has a property of firmly bonding to the surface of another member (third member), the adhesive polyaryletherketone resin material of the present invention and the third member Can be firmly bonded. The third member can be used without particular limitation as long as it is a known solid member, but it is usually preferable to use a member in which the vicinity of the adherend surface is not the adhesive polyaryletherketone resin material of the present invention.

<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.

  As a dental polyaryletherketone resin material using the adhesive polyaryletherketone resin material of the present invention for dental use, a denture partially or entirely made using the adhesive polyaryletherketone resin of the present invention, Examples include artificial teeth, denture bases, dental implants, crown restoration materials, and abutment building materials.

  In addition, as a curable composition which 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. Furthermore, as the third member, there are 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 construction materials, etc. A member etc. are mentioned.

  As an example of the method of using the adhesive dental polyaryletherketone resin material of the present invention, a dental hard resin is used as a dental curable composition, and a dental polyaryletherketone resin material and a dental hard resin are used. Laminate to make a dental prosthesis. Specifically, for example, the adhesive polyaryletherketone resin material of the present invention is obtained by applying a primer to a desired surface of a dental polyaryletherketone resin material molded into a desired shape and irradiating it with light. Get. Thereafter, a hard resin is laminated thereon, arranged in a desired shape, and then cured to produce a desired dental prosthesis. The dental prosthesis is easy to be hard to break due to high adhesiveness, and it becomes easy to obtain a dental prosthesis having high aesthetics by thinning the adhesive layer.

  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, a primer is applied to the adherend surface of a prosthesis made of a polyaryletherketone resin material prepared in advance, and the adhesive polyaryletherketone resin material of the present invention is obtained by irradiating the primer with light. . 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 it is easy to make the prosthesis made of the dental polyaryletherketone resin material of the present invention highly compatible. It becomes.

  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 a main chain are arranged in the order of ether, ether, and ketone from the viewpoint of color tone and physical properties. It is preferable to use 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 [photoinitiator]
CQ: camphorquinone DMBE: p-dimethylaminobenzoic acid ethyl ester

Table 1 shows the composition of the primer composition (P1 to P3) or the bonding material composition (B1).

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

  Polyetheretherketone resin (manufactured by Daicel Evonik: VESTAKEEEP M2G) and spherical silica surface-treated with γ-methacryloyloxypropyltrimethoxysilane as amorphous silica particles (prepared by vapor phase melting method, purity 99.9) % Or more and an average particle size of 1.0 μm) was used in which a polyaryletherketone resin material in which amorphous silica particles were 30 parts by mass with respect to 70 parts by mass of polyetheretherketone resin 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.

  As the polyaryl ether ketone resin material C2, polyaryl ether ketone resin (manufactured by Daicel Evonik Co., Ltd .: VESTAKEEEP M2G) was used.

  Each test method is as follows.

(Preparation of Adhesive Polyaryletherketone Resin Material of the Present Invention and Measurement of Tensile Adhesive Strength Between It and Curable Composition)
The polyaryl ether ketone resin material was formed into a plate shape having a thickness of about 2 mm by injection molding. After polishing the adherend surface with # 800 water-resistant abrasive paper, it was roughened 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). It was. 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 hole with a diameter of 3 mm was attached to the adherend surface.

  Thereafter, the primer composition was applied to the holes, allowed to stand for 10 seconds, and then dried by blowing compressed air for about 10 seconds. Subsequently, using the dental visible light irradiator with a predetermined light intensity, the applied primer composition was irradiated with light for a predetermined time, and the adhesive polyaryletherketone 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, is applied to the surface of the adherend, and further thereon. The adhesion test piece was produced by press-contacting the stainless steel attachment. 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 bond strength between the adhesive polyaryletherketone resin material and the curable composition 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 tensile adhesion strength to adherend of polyaryletherketone resin material that is not the adhesive polyaryletherketone resin material of the present invention)
The polyaryl ether ketone resin material was formed into a plate shape having a thickness of about 2 mm 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. Next, a double-sided tape having a hole with a diameter of 3 mm was attached to the adherend surface.
Thereafter, the primer composition or the bonding material composition was applied to the holes, allowed to stand for 10 seconds, and then dried by blowing compressed air for about 10 seconds. When the bonding material composition was applied, the applied bonding material composition was then irradiated with light for a predetermined time using a dental visible light irradiator having a predetermined light intensity. When the primer was applied, light irradiation was not performed. A dental cement material (Bistite II, manufactured by Tokuyama Dental Co., Ltd.) was applied thereon, and a stainless steel attachment was pressed onto the dental cement material, thereby preparing an adhesion test piece. After holding the above-mentioned adhesion test piece at 37 ° C. for 24 hours, using a tensile tester (Autograph, manufactured by Shimadzu Corporation), pulling at a crosshead speed of 2 mm / min, the polyaryletherketone resin material and The tensile adhesive strength with the curable composition 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.

(Measurement of adhesive layer thickness)
The polyaryl ether ketone resin material was formed into a plate shape having a thickness of about 2 mm 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, an adhesive composition (primer composition or bonding material composition) was applied to the adherend surface of the polyaryl ether ketone resin material, allowed to stand for 10 seconds, and then dried by blowing compressed air for about 10 seconds. Next, using a dental visible light irradiator with a predetermined light intensity, the applied primer composition or bonding material composition was irradiated with light for a predetermined time. Thereafter, a dental cement material (Bistite II, manufactured by Tokuyama Dental Co., Ltd.) is applied thereon, and an attachment prepared by curing a dental hard resin (manufactured by Tokuyama Dental Co., Ltd .: Pearl Este) is further pressure-welded. Thus, a test piece was prepared. After holding the above-mentioned test piece at 37 ° C. for 24 hours, it was cut perpendicularly to the adherend surface using a diamond cutter to expose the cross section of the adhesion site. After this adhesion site was polished with # 3000 water-resistant abrasive paper, the thickness of the adhesive composition layer was measured as the adhesive layer thickness with a laser microscope (manufactured by Keyence Corporation).

(Measurement of peak attenuation rate)
A primer or a bonding material was collected on the slide glass, and air blowing was performed to remove the volatile solvent. A primer having a thickness required for measurement is repeated 10 times in total by repeating the operation of applying the primer or the bonding material again on the layer of the primer or the bonding material thus generated and performing air blowing to remove the volatile solvent. Alternatively, a bonding material layer was formed. Next, using a micro Raman spectrophotometer (NRS-7100: manufactured by JASCO Corporation), excitation wavelength 785 nm, microscope objective lens 100 times, resolution 4 cm ⁻¹ , center wave number 1500 cm ⁻¹ , exposure time 60 seconds, integration Measurement was performed under the conditions of 5 times, and a Raman spectrum of the primer or bonding material layer was obtained. In the obtained Raman spectrum, the peak height of a peak near 1640 cm ⁻¹ derived from a double bond and the peak height of a peak near 1715 cm ⁻¹ derived from a ketone group are calculated. to obtain a peak height ratio H ₁ before irradiation.

A primer or a bonding material stored on the slide glass was collected and air blown to remove the volatile solvent. A primer having a thickness required for measurement is repeated 10 times in total by repeating the operation of applying the primer or the bonding material again on the layer of the primer or the bonding material thus generated and performing air blowing to remove the volatile solvent. Alternatively, a bonding material layer was formed. The primer or bonding material layer is covered with a polypropylene film having a thickness of about 100 μm, and a dental visible light irradiator (LE Demetron II: LED irradiator manufactured by Kerr Co.) is used. Primer is used to apply light having a light intensity of 800 mW / cm ² measured on a polypropylene film using a measuring device capable of measuring the light intensity of light (Demetron LED RADIOMETER: manufactured by Kerr). Alternatively, the bonding material layer was irradiated for 60 seconds. The polypropylene film was removed and a Raman spectrum of the primer or bonding material layer was obtained. In the obtained Raman spectrum, the peak height of a peak near 1640 cm ⁻¹ derived from a double bond and the peak height of a peak near 1715 cm ⁻¹ derived from a ketone group are calculated. to obtain a peak height ratio of H ₂ after irradiation.

Thus, the operation of obtaining H ₁ and H ₂ was performed 5 times, the average values H _1a and H _2a were calculated, and the peak attenuation rate of the double bond was calculated from the following formula VI.

<Example 1>
As a radical polymerizable monomer component having two or more radical polymerizable functional groups in the molecule, 5 g of bisGMA, 5 g of 3G, and 50 g of acetone as a volatile solvent component were stirred and mixed to obtain a primer composition P1. The composition of the primer composition is shown in Table 1. This primer composition was applied to the surface of the polyaryletherketone resin material C1, and L.D. E. Demetron II (manufactured by Kerr, LED irradiator) is used under the condition that the distance between the light guide tip and the light irradiation surface is adjusted and the light intensity of the light irradiation surface is 800 mW / cm ² . The primer-coated surface is irradiated with light for 60 seconds to obtain the adhesive polyaryletherketone resin material of the present invention, and the production of the adhesive polyaryletherketone resin material of the present invention and the curable composition Tensile bond strength measurement and adhesive layer thickness measurement were performed. Further, the peak attenuation rate of the primer composition was measured. Table 2 shows the measurement results of the light intensity, light irradiation time, light energy value, tensile adhesive strength, adhesive layer thickness, and peak attenuation rate of the dental light irradiator.

<Examples 2 to 7>
Preparation of the adhesive polyaryletherketone resin material of the present invention and the curable composition according to Example 1 except that the light intensity at the time of light irradiation, the light irradiation time, and the light energy were changed as shown in Table 2. Tensile bond strength measurement, adhesive layer thickness measurement, and peak attenuation rate measurement were performed. The measurement results are shown in Table 2.

<Example 8>
Preparation and curing of the adhesive polyaryletherketone resin material of the present invention according to Example 1, except that the dental visible light irradiator used was Optilux 500 (Kerr, halogen irradiator) as L2. The tensile adhesive strength with the adhesive composition, the thickness of the adhesive layer, and the peak attenuation rate were measured. The measurement results are shown in Table 2.

<Example 9>
As a radical polymerizable monomer component having two or more radical polymerizable functional groups in the molecule, 3.5 g of bisGMA, 2.5 g of 3G, 1.5 g of PM2, and only one radical polymerizable in the molecule As a radical polymerizable monomer component having a functional group, a primer composition P2 was obtained by stirring and mixing 1.5 g of PM1, 1 g of HEMA, and 50 g of acetone as a volatile solvent component. The composition of the primer composition is shown in Table 1. This primer composition was applied to the surface of the polyaryletherketone resin material C1, and L.D. E. Demetron II (manufactured by Kerr, LED irradiator) is used under the condition that the distance between the light guide tip and the light irradiation surface is adjusted and the light intensity of the light irradiation surface is 800 mW / cm ² . The primer-coated surface is irradiated with light for 10 seconds to obtain the adhesive polyaryletherketone resin material of the present invention, and the production of the adhesive polyaryletherketone resin material of the present invention and the curable composition Tensile bond strength measurement and adhesive layer thickness measurement were performed. Further, the peak attenuation rate of the primer composition was measured. Table 2 shows the measurement results of the light intensity, light irradiation time, light energy value, tensile adhesive strength, adhesive layer thickness, and peak attenuation rate of the dental light irradiator.

<Example 10>
Except that the primer composition was changed to the composition shown in Table 1, according to Example 9, preparation of the adhesive polyaryletherketone resin material of the present invention and measurement of tensile adhesive strength between the curable composition and adhesion thereof The thickness of the agent layer and the peak attenuation rate were measured. The measurement results are shown in Table 2.

<Example 11>
Except that the polyaryl ether ketone resin material was changed to C2, according to Example 3, the production of the adhesive polyaryl ether ketone resin material of the present invention and the measurement of the tensile adhesive strength between the curable composition and the adhesion The thickness of the agent layer and the peak attenuation rate were measured. Table 3 shows the measurement results.

<Example 12>
Except that the polyaryl ether ketone resin material was changed to C2, according to Example 4, the production of the adhesive polyaryl ether ketone resin material of the present invention and the measurement of the tensile adhesive strength between the curable composition and the adhesion The thickness of the agent layer and the peak attenuation rate were measured. Table 3 shows the measurement results.

<Comparative Example 1>
Using the polyaryl ether ketone resin material C1 and the primer composition prepared in Example 1, the primer composition applied to the polyaryl ether ketone resin material is not irradiated with light, and the adhesive polycrystal of the present invention is used. The tensile adhesive strength between the polyaryl ether ketone resin material that is not an aryl ether ketone resin material and the curable composition was measured, and the thickness of the adhesive layer was measured. In this system, since the light irradiation is not performed in the measurement of the tensile bond strength, the peak attenuation rate is not measured. The measurement results are shown in Table 2.

<Comparative Examples 2 and 3>
Except that the primer composition used was changed as shown in Table 2, according to Comparative Example 1, the primer composition applied to the polyaryl ether ketone resin material was not irradiated with light, and the adhesion of the present invention was performed. The tensile bond strength between the polyaryletherketone resin material and the curable composition, which is not the conductive polyaryletherketone resin material, and the thickness of the adhesive layer were measured. The measurement results are shown in Table 2.

<Comparative Example 4>
As a radical polymerizable monomer component having two or more radical polymerizable functional groups in the molecule, 5 g of bisGMA, 5 g of 3G, 50 g of acetone as a volatile solvent component, and 0.2 g of CQ as a photopolymerization initiator component Then, a bonding material composition B1 obtained by stirring and mixing 0.2 g of DMBE was obtained. The composition of the bonding material composition is shown in Table 1. This bonding material composition was applied to the surface of the polyaryletherketone resin material C1, and L.D. E. Demetron II (manufactured by Kerr, LED irradiator) is used under the condition that the distance between the light guide tip and the light irradiation surface is adjusted and the light intensity of the light irradiation surface is 800 mW / cm ² . The surface to which the bonding material is applied is irradiated with light for 60 seconds to prepare a tensile adhesion strength test specimen, and the tensile strength of the polyaryletherketone resin material that is not the polyaryletherketone resin material of the present invention and the curable composition The adhesive strength measurement and the thickness of the adhesive layer were measured. Further, the peak attenuation rate of the bonding material composition was measured. Table 2 shows the measurement results of the light intensity, light irradiation time, light energy value, tensile adhesive strength, adhesive layer thickness, and peak attenuation rate of the dental light irradiator.
<Comparative Example 5>
Except for changing the polyaryl ether ketone resin material to C2, the tensile adhesive strength between the polyaryl ether ketone resin material and the curable composition that is not the polyaryl ether ketone resin material of the present invention is the same as in Comparative Example 1. Measurement, measurement of the thickness of the adhesive layer, and measurement of the peak attenuation rate were performed. Table 3 shows the measurement results.

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

  When comparing Examples 1 to 8 and Comparative Example 1 using the same primer composition, the polyaryletherketone resin material was irradiated with light after applying the primer, and the adhesive polyaryletherketone resin material of the present invention The adhesive polyaryletherketone resin of the present invention, in which Examples 1 to 8 were evaluated for tensile adhesive strength and were not irradiated with light after applying a primer to the polyaryletherketone resin material. Compared with the comparative example 1 which evaluated tensile adhesive strength with respect to the polyaryl ether ketone resin material which is not material, all showed high adhesive strength.

  Comparing Example 9 and Comparative Example 2 using the same primer composition, the primer was applied to the polyaryletherketone resin material and then irradiated with light to obtain the adhesive polyaryletherketone resin material of the present invention. In Example 9 where the tensile adhesive strength was evaluated, the polyaryletherketone resin material was not irradiated with light after applying a primer to the polyaryletherketone resin material. Compared with the comparative example 2 which evaluated tensile adhesive strength with respect to the aryl ether ketone resin material, the high adhesive strength was shown.

  When Example 10 using the same primer composition was compared with Comparative Example 3, the primer was applied to the polyaryletherketone resin material and then irradiated with light to obtain the adhesive polyaryletherketone resin material of the present invention. In Example 10 where the tensile adhesive strength was evaluated, the polyaryletherketone resin material of the present invention was not irradiated with light after the primer was applied to the polyaryletherketone resin material. Compared with the comparative example 3 which evaluated tensile adhesive strength with respect to the aryl ether ketone resin material, the high adhesive strength was shown.

  Examples 1 to 10, which were evaluated using the adhesive polyaryletherketone resin material of the present invention obtained by irradiating light to the primer, started photopolymerization with respect to the polyaryletherketone resin material It was possible to make the adhesive layer thinner as compared with Comparative Example 4 in which light irradiation was performed after the bonding material containing the agent was applied. The peak attenuation rates of the primer compositions used in Examples 1 to 10 are all 15% or less, the radical polymerizable monomer is not polymerized and cured, and the primer radical polymerizable monomer flows. It is easy to deform. On the other hand, the peak decay rate of the bonding material used in Comparative Example 4 exceeds 15%, and the radical polymerizable monomer is polymerized and cured, and the radical polymerizable monomer does not maintain fluidity, so it is easy. It is not deformable.

The same primer was used, and the same light irradiator was used. However, when the light intensity and the light irradiation time were different, the light energy was 15000 mJ / cm ² or more when comparing Examples 1 to 7 having different light energy. Examples 2-7 all showed high bond strength compared to Example 1 which is less than 15000 mJ / cm ² . Examples 3 to 7 having a light energy of 30000 mJ / cm ² or more all exhibited high adhesive strength as compared with Examples 1 and 2 having a light energy of less than 30000 mJ / cm ² . Examples 4-7 whose light energy is 45000 mJ / cm < ² > or more all showed high adhesive strength compared with Examples 1-3 which are less than 45000 mJ / cm < ² >.

Using the same primer and irradiating light with the same light energy, when comparing Examples 4 to 7 in which the light intensity at the time of light irradiation and the light irradiation time are different, the light intensity is 400 mW / cm ² or more. Examples 4, 5, and 7 all showed high bond strength compared to Example 6 which is less than 400 mW / cm ² . Examples 4 and 7 having a light intensity of 800 mW / cm ² or more all exhibited high adhesive strength as compared with Examples 5 and 6 having a light intensity of less than 800 mW / cm ² .

  When the same primer was used, and the surface treatment was performed with the same light intensity and the same light irradiation time, but when comparing Examples 4 and 8 using different dental visible light irradiators, the LED irradiator and the halogen type were compared. Similar tensile bond strength was obtained with both irradiators.

  When light irradiation was performed under the same conditions, but comparing Examples 1, 9, and 10 in which the composition of the primer applied to the polyaryl ether ketone resin material surface was different, among the radical polymerizable monomers contained in the primer, In Examples 1 and 9 in which 40% by mass or more is a radical polymerizable monomer having two or more radical polymerizable functional groups in the molecule, 2 in the molecule among the radical polymerizable monomers contained in the primer. Compared with Example 10 in which the radical polymerizable monomer having the above radical polymerizable functional group was less than 40% by mass, the adhesive strength was high.

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

  Comparing Examples 11 and 12 and Comparative Example 5 using the same primer composition, the polyaryletherketone resin material was irradiated with light after being applied with a primer, and the adhesive polyaryletherketone resin material of the present invention In Examples 11 and 12 where the tensile adhesion strength was evaluated, the adhesive polyaryletherketone resin of the present invention was not irradiated with light after the primer was applied to the polyaryletherketone resin material. Compared with the comparative example 5 which evaluated tensile adhesive strength with respect to the polyaryl ether ketone resin material which is not material, all showed high adhesive strength.

The same primer was used and the same light irradiator was used, but the light energy was 45000 mJ / cm ² or more when comparing Examples 11 and 12 having different light energies because the light intensity and light irradiation time were different. Example 11 showed a higher bond strength compared to Example 12, which is less than 45000 mJ / cm ² .

  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.

  When the same primer composition was used and light irradiation was performed under the same conditions, the compositions of the polyaryletherketone resin materials were different, and Example 3 and Example 11 and Example 4 and Example 12 were compared. Examples 3 and 4 in which amorphous silica, which is an amorphous inorganic compound particle, are blended in a polyaryl ether ketone resin material are examples 11 and 12 in which amorphous inorganic compound particles are not blended, respectively. In comparison, it showed high adhesive strength.

Claims (7)

  A method for producing an adhesive polyaryletherketone resin material, comprising: applying a primer containing a radical polymerizable monomer to a 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.   The radically polymerizable monomer of the primer, wherein 40% by mass or more is a radically polymerizable monomer having two or more (meth) acryloyl groups in the molecule as a polymerizable functional group. A method for producing an adhesive polyaryletherketone resin material. The adhesive polyaryletherketone resin material according to any one of claims 1 to 3, wherein the polyaryletherketone resin material contains an amorphous inorganic compound having an average volume particle size of 0.7 µm to 2.0 µm. Manufacturing method.   The production method according to claim 1, wherein the adhesive polyaryletherketone resin material is dental.   A pretreatment method for a polyaryletherketone resin material, which comprises applying a primer containing a radical polymerizable monomer to a polyaryletherketone resin material and then irradiating with light.   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 radically polymerizable. After applying a primer containing a monomer, light irradiation is performed, and then the adherend is pressure-bonded onto the polyaryletherketone resin material coated with the primer, and the adherend is polymerized and cured. And a method for bonding the polyaryletherketone resin material and the adherend.