JP6828862B2 - A method for producing an adhesive polyaryletherketone resin material and a method for adhering a polyaryletherketone resin material to an adherend. - 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 to an adherend.

Super engineering resins are used in a wide range of applications such as electrical / electronic fields, aerospace fields, automobile industries, medical fields, and general industrial fields. Among these super-engineering resins, the polyaryletherketone resin is expected to be used in various fields because it has excellent chemical and physical properties.

For example, in the field of dental treatment, a technique of using a polyaryletherketone resin material containing this polyaryletherketone resin as a main component as a dental material has been proposed (for example, Patent Document 1). When a polyaryletherketone resin material is used as a dental material, it is necessary to firmly adhere it to an adherend such as a tooth substance or another kind of dental material. Various techniques have been proposed as techniques for adhering such a polyaryletherketone resin material to an adherend (for example, Patent Document 2 and Non-Patent Documents 1 and 2).

Polyaryletherketone resin materials having excellent chemical and physical properties are widely used not only in dental applications but also in various fields. Therefore, regardless of the technical field or application, there is a demand for a technique capable of firmly adhering the polyaryletherketone resin material and the adherend.

When the polyaryletherketone resin material and the adherend are adhered to each other using an adhesive, it is desired to make the adhesive layer thin from the viewpoint of appearance and dimensional stability. For example, in the dental field, when the abutment tooth and the prosthesis made of the dental polyaryl ether ketone resin material are adhered to each other, if the adhesive layer is thick, the suitability of the dental prosthesis is adversely affected and the dental prosthesis is lifted. The amount of cutting and polishing of dental prostheses increases due to occlusal adjustment, which increases the burden on dentists and patients. In another example in the dental field, polyaryl ether ketone resin materials and dentistry When making a dental prosthesis by adhering an adherend such as a filling restoration material or a dental hard resin with an adhesive, if the adhesive layer is thick, it will be visible and the manufactured dentistry Prostheses are inferior in aesthetics.

In the field of dentistry, typical adherends that need to be adhered to a polyaryletherketone resin material are used in the production of composite resins used for filling and repairing dental defects, and for producing prostheses and dentures. Examples thereof include a hard resin, an instantly polymerized resin, and a dental cement used for adhering to yet another member. In most cases, these composite resins, hard resins, immediate polymerization resins, dental cements and the like are composed of a curable composition containing a radically polymerizable monomer and a polymerization initiator. In the case of an adherend outside the field of dentistry, for example, an adhesive material, a coating material, a sealing material, a paint and the like can be mentioned, but when these are also composed of a curable composition containing a radically polymerizable monomer. There are many. Therefore, in the adhesion between the polyaryletherketone resin material and the curable composition containing the radically polymerizable monomer, a technique for adhering the adhesive layer thinly and with high strength is desired.

As an adhesive method between the polyaryletherketone resin material and the adherend, for example, in the field of dentistry, a method of curing an adhesive containing a polymerizable monomer and a photopolymerization initiator by light irradiation is effective. There is a report that. For example, Non-Patent Document 1 describes that a relatively high adhesiveness was obtained by using a hydrophobic dental adhesive. A photocurable adhesive is applied to a polyaryl ether ketone resin material, polymerized and cured by light irradiation, and then an adherend composed of a curable composition containing a radically polymerizable monomer and a polymerization initiator is obtained. High adhesiveness can be obtained by curing while crimping. However, if the photocurable adhesive is irradiated with light before the adherend is crimped, the adhesive is polymerized and cured during the light irradiation to form an indeformable adhesive layer, so that the adhesive is generally used. It is difficult to reduce the thickness of the layer.

Although studies have been conducted to evaluate the adhesiveness of a polyaryletherketone resin material using a dental adhesive (primer) that does not contain a polymerization initiator, high adhesive 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 polyaryletherketone resin material is roughened and cleaned, then the primer is applied, and after holding for 180 seconds, dental resin cement is used as an adherend. The dental resin cement contains a chemical polymerization initiator, and when the dental resin cement is pressure-bonded onto the primer, the primer is started to be cured by the chemical polymerization initiator of the dental resin cement. In this case, since the primer can be deformed for a certain period of time after the dental resin cement is crimped, the thickness of the primer layer becomes thin.

Further, Patent Document 2 describes a conditioning agent containing an adhesive and a high boiling point solvent having bipolarity for a molded product containing a high temperature resistant plastic (including a polyaryletherketone resin material) and a filler. Conditioning techniques have been proposed. Specifically, two conditioning agents consisting of methacrylic silane and dimethyl sulfoxide (DMSO) and methacrylic silane, DMSO and ethanol are shown in Examples. In the adhesion test using the conditioning agent, the contacting surface is infiltrated with the conditioning agent for 2 minutes, the conditioning agent is sprayed with a clean air stream, and then a photocurable dental plastic is pressure-bonded to the adherend surface. , Light is applied to cure the photocurable dental plastic. In this method, since the filler is surface-modified with methacrylic silane to show an adhesive effect, high adhesive strength can be obtained for the molded product containing the filler, but the filler is included. It has no effect on those that do not exist.

Japanese Unexamined Patent Publication No. 2013-144778 Special Table 2010-521257

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

As described above, when the polyaryletherketone resin material and the adherend are adhered, when the adhesive is applied to the polyaryletherketone resin material and then polymerized and cured to adhere the adherend, the adhesive strength is high. It was easy to obtain, but it was difficult to make the adhesive layer thin. On the other hand, in the case of an adhesive that presses the adherend without polymerizing and curing after applying the adhesive to the polyaryletherketone resin material, it is not difficult to thin the adhesive layer, but high adhesive strength cannot be obtained. There was a problem. Therefore, an object of the present invention is to achieve both thinning the thickness of the adhesive layer and obtaining high adhesive strength when adhering the polyaryletherketone resin material to the adherend.

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

As a result of diligent studies to solve the above problems, the inventors conducted a diligent study, and as a result, the polyaryletherketone resin material was irradiated with light and then a polyaryl coated with an adhesive containing a radically polymerizable monomer. The etherketone resin material has high adhesiveness and formation of a thin adhesive layer to an adherend, particularly an adherend composed of a curable composition containing a radically polymerizable monomer and a polymerization initiator. I found that they are compatible. Normally, the adhesive containing the photopolymerization initiator may be irradiated with light, but the polyaryletherketone resin material is not irradiated with light before the adhesive is applied. That is, in the present invention, after light irradiation is performed on a polyaryletherketone resin material that is not normally irradiated with light, an adhesive containing a polymerizable monomer is applied to improve adhesiveness and thin adhesion. It is an invention made by finding that the formation of an agent layer can be compatible with each other.

That is, the present invention is characterized in that the polyaryletherketone resin material is irradiated with light having a maximum peak wavelength of 400 nm to 500 nm , and then an adhesive containing a radically polymerizable monomer is applied. This is a method for producing a polyaryletherketone resin material. The radically polymerizable monomer contained in the adhesive is preferably a radically polymerizable monomer having 40% by mass or more as a polymerizable functional group and having 2 or more (meth) acryloyl groups in the molecule.

The polyaryletherketone resin material in the above-mentioned production method of the present invention is preferably dental.

Another embodiment of the present invention is an adhesion method for adhering an adherend composed of a polyaryl ether ketone resin material and a curable composition containing a radically polymerizable monomer and a polymerization initiator. The polyaryl ether ketone resin material is irradiated with light having a maximum peak wavelength of 400 nm to 500 nm, an adhesive containing a radically polymerizable monomer is applied, and then the polyaryl ether to which the adhesive is applied is applied. This is a method for adhering a polyaryl ether ketone resin material to an adherend, in which an adherend is pressure-bonded onto a ketone resin material to polymerize and cure a curable composition.

Further, the present invention is characterized in that a polyaryletherketone resin material is irradiated with light having a maximum peak wavelength of 400 nm to 500 nm , and then an adhesive containing a radically polymerizable monomer is applied. This is a pretreatment method for an aryletherketone resin material.

When the method according to the present invention is applied, an adhesive polyaryletherketone having high adhesiveness to an adherend, particularly an adherend composed of a curable composition containing a radically polymerizable monomer and a polymerization initiator. A resin material is obtained, and it becomes possible to reduce the thickness of the adhesive layer and increase the adhesive strength between the polyaryletherketone resin material and the adherend. Therefore, for example, in dental applications, when a dental prosthesis made of a polyaryletherketone resin material is attached to an abutment tooth, a treatment having high adhesiveness and high compatibility can be performed, or a polyaryletherketone resin can be used. When a dental prosthesis is made using the material and the dental curable composition, the adhesive layer can be thinned, so that a more aesthetically pleasing dental prosthesis can be made.

Further, if the method according to the present invention is applied, the polyaryletherketone resin material can be sufficiently irradiated with light without considering the curing of the adhesive containing the radically polymerizable monomer. It is easy to set the irradiation conditions and has excellent versatility.

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

Further, if the method according to the present invention is applied, the polyaryletherketone resin material can be sufficiently irradiated with light without considering the curing of the adhesive containing the radically polymerizable monomer. It is easy to set the irradiation conditions and has excellent versatility.

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

The reason why the adhesiveness of the polyaryletherketone resin material is improved is that the carbonyl group bonded to the two aromatic rings on the surface of the polyaryletherketone resin is activated by light irradiation to generate a radical, and the radical and the adhesion to be applied thereafter are applied. It is presumed that this is because the surface of the polyaryletherketone resin material is modified by the reaction with the radically polymerizable monomer in the agent. By this reaction, the adhesive force at the interface between the adhesive and the polyaryletherketone resin material is dramatically improved. Further, in the adhesive polyaryl ether ketone resin material produced in this way, the radically polymerizable monomer of the entire adhesive is not polymerized and cured to form an adhesive layer having a constant thickness, and the adhesive is not formed. Only the radically polymerizable monomer present near the surface of the polyaryl ether ketone resin material in the material contributes to the reaction based on the radical generation due to the activation of the ketone group, and the radical polymerization in most adhesives. The sex monomer does not polymerize even after coating, and remains as a polymerizable monomer. Moreover, even if the adhesive contains a chemical polymerization initiator, it does not immediately reach a high polymerization rate. Therefore, the adhesive itself exists on the adhesive polyaryletherketone resin material as an easily deformable layer, and an adherend made of a curable composition is laminated and pressure-bonded to the adhesive polyaryletherketone resin material. At the time of laminating and crimping, the adhesive is easily deformed and thinned by the pressure at the time of laminating and crimping. Therefore, when the adherend and the adhesive polyaryletherketone resin material are adhered to each other, the adhesive layer between the adherend and the adhesive polyaryletherketone resin material becomes thin. Since the adherend contains a polymerization initiator, even if the adhesive does not contain the polymerization initiator, the radical polymerization monomer in the adhesive and the radical polymerization in the curable composition The sex monomer is polymerized and the adhesion between the adhesive and the curable composition is also strengthened. As a matter of course, if the adhesive contains a chemical polymerization initiator, the polymerizable property of the adhesive is also improved, so that the adhesive strength is further improved.

<Polyaryletherketone resin material>
The polyaryletherketone resin material that can be used in the present invention contains a blending amount of the polyaryletherketone resin that gives the advantage of using the polyaryletherketone resin such as high strength. , Preferably contains 20% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more of the polyaryletherketone resin.

Such a polyaryletherketone resin material is preferably composed of only the polyaryletherketone resin, but is a material obtained by blending the polyaryletherketone resin with another resin, the polyaryletherketone resin or the polyarylether. A composite material obtained by mixing a blend of a ketone resin and another resin with a filler using a resin matrix (hereinafter, the composite material is also referred to as a polyaryletherketone resin composite material) may be used. Further, trace components such as pigments and stabilizers may be added to these materials.

A polyaryl ether ketone resin is a thermoplastic resin containing at least an aromatic group, an ether group (ether bond) and a ketone group (ketone bond) as its structural unit, and in many cases, an arylene group contains an ether group and a ketone group. It has a linear polymer structure bonded via. Typical examples of the polyaryletherketone resin include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetherketone etherketoneketone (PEKEKK). The aromatic group constituting the structural unit of the polyaryletherketone resin may have a structure having two or more benzene rings, such as a biphenyl structure. In addition, the structural unit of the polyaryletherketone resin may contain a sulfonyl group or other copolymerizable monomer unit.

Other resins that can be blended with the polyaryletherketone resin are not particularly limited as long as they do not significantly deteriorate the physical properties of the polyaryletherketone resin such as rigidity and toughness. Examples thereof include polycarbonate, polyethylene terephthalate, polyphthalamide, polytetrafluoroethylene, and polyphenylene ether. The other resin is preferably less than 50% by mass, more preferably less than 30% by mass, more preferably less than 10% by mass, and even more preferably less than 1% by mass of the total resin.

As the filler that can be blended with the polyaryletherketone resin material, known ones can be used without particular limitation, but an inorganic filler such as amorphous inorganic compound particles is preferable. For example, the material of the filler composed of amorphous inorganic compound particles includes silica glass, borosilicate glass, soda glass, aluminosilicate glass, fluoroaluminosilicate glass, and glass containing heavy metals (for example, barium, strontium, zirconium); Composite inorganic oxides such as silica-zirconia, silica-titania, and silica-alumina; or oxides obtained by adding Group I metal oxides to these composite inorganic oxides; metal inorganic oxides such as silica, alumina, titania, and zirconia. ; And so on.

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

Among these fillers, 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 irradiation is performed, a part of the light that reaches the surface of the polyaryletherketone resin material is scattered by the amorphous inorganic compound particles, so that the polyaryl by light described later is scattered. It is presumed that the activation of the etherketone resin is carried out 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. Is more preferable.

Here, the volume average particle diameter of the filler to be mixed with the polyaryletherketone resin material is measured by using a laser scattering method (LS230 manufactured by Beckman Coulter Co., Ltd. is used as a measuring device and ethanol is used as a dispersion medium). Can be done. At the time of measurement, 0.01 to 1 g of the measurement sample is added to 5 ml of ethanol as a dispersion medium. The liquid in which the sample is suspended is dispersed 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. Cumulative distribution is drawn from the small diameter side for each particle size range (channel) divided based on the particle size distribution measured in this way, and the particle size that becomes a cumulative 50% is the volume average particle size (D50). ).

The blending amount of the amorphous inorganic compound particles in the polyaryletherketone resin composite material is preferably in the range of 10% by mass to 50% by mass from the viewpoint of efficiently scattering light in order to obtain higher adhesiveness. , 20% by mass to 40% by mass is more preferable, and 25% by mass to 35% by mass is further preferable.

The amorphous inorganic compound particles are preferably amorphous silica because they are highly effective in improving the adhesiveness by applying an adhesive to the polyaryletherketone resin material and then irradiating with light. The purity of the amorphous silica particles is preferably 99.5% or more, more preferably 99.9% or more, excluding the amount of water. 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 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 polyaryletherketone 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 device used for performing melt-kneading is not particularly limited, and a known melt-kneading device can be used. For example, a mixer with a heating device, a single-screw melt-kneading device, a twin-screw melt-kneading device, or the like can be used.

<Adhesive>
The adhesive containing a radically polymerizable monomer in the present invention is for adhering an adherend composed of a polyaryletherketone resin material and a curable composition containing a radically polymerizable monomer and a polymerization initiator. In addition, it is applied to the adherend surface of the polyaryletherketone resin material, and is applied after the adherend surface of the polyaryletherketone resin material is irradiated with light. In other words, the adhesive does not polymerize and cure to the point where it cannot be deformed. Therefore, it is easy to thin the adhesive layer when the adherend composed of the curable composition containing the radically polymerizable monomer and the polymerization initiator is contacted and pressure-bonded.

The crimping in the present invention is an adhesion made of a curable composition further containing a radically polymerizable monomer and a polymerization initiator on an adhesive layer applied to an adhesion surface of a polyaryl ether ketone resin material. Placing the body and applying force to the adhesive layer through the uncured adherend, pressing it over the uncured adherend with a hand or machine, comparison of consistency An adherend composed of a curable composition containing a low-target paste-like radically polymerizable monomer and a polymerization initiator is placed on an adhesive, and the adherend is cured before the adherend is cured and does not deform. A solid is placed and pressed against the solid surface, and an adherend composed of a curable composition containing a paste-like radically polymerizable monomer having a relatively low viscosity and a polymerization initiator is applied to the solid surface. This includes contacting and pressing the surface against the adhesive layer. Further, when an adherend composed of a curable composition containing a radically polymerizable monomer and a polymerization initiator is placed on an adhesive and a force is applied to the adhesive layer before curing due to the gravity thereof, the above Although the effect is smaller than that in the case of pressing as in, the effect of the present invention is obtained and is included in the crimping in the present invention.

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

The radically polymerizable monomer contained in the adhesive in the present invention is a compound having a radically polymerizable functional group in the molecule, and known ones can be used without any limitation. Examples of the radically polymerizable functional group include functional groups such as a vinyl group, a styryl group, an allyl group, and a (meth) acryloyl group, and a (meth) acryloyl group is particularly preferable from the viewpoint of polymerization rate and biosafety. .. Examples of preferable radically polymerizable monomers include radically polymerizable monomers having a (meth) acryloyl group shown in (I) to (IV) below.

(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 aspartate , N-methacryloyl-5-aminosalicylic acid, 2-methacryloyloxyethyl hydrogen succinate, 2-methacryloyloxyethyl hydrogenphthalate, 2-methacryloyloxyethyl hydrogenmalate, 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-methacryloyloxy Orthoperic acid, 4-methacryloyloxybenzoic acid, N-methacryloyl-5-aminosalicylic acid, N-methacryloyl-4-aminosalicylic acid, 11-methacryloyloxyundecane-1,1-dicarboxylic acid, 10-methacryloyloxydecane-1,1 −Dicarboxylic acid, 12-methacryloyloxide decane-1,1-dicarboxylic acid, 6-methacryloyloxyhexane-1,1-dicarboxylic acid, 4- (2-methacryloyloxyethyl) trimerite, 4-methacryloyloxyethyl trimerite, 4-Methylloyloxybutyl trimerite, 4-methacryloyloxyhexyl trimerite, 4-methacryloyloxydecyl trimerite, 6-methacryloyloxyethyl naphthalene-1,2,6-tricarboxylic acid anhydride, 6-methacryloyloxyethyl Naphthalene-2,3,6-tricarboxylic acid anhydride, 4-methacryloyloxyethylcarbonylpropionoyl-1,8-naphthalic acid anhydride, 4-methacryloyloxyethylnaphthalene-1,8-to Methacrylates such as recarboxylic acid anhydrides, and acrylates and the like corresponding to these methacrylates.

(II) Bifunctional radical 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-methacryloyloxytriethoxyphenyl) 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-butane Didiol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, glycerin dimethacrylate, bis (2-methacryloyloxyethyl) hydrogen phosphate, bis (6) -Methacryloxyhexyl) hydrogen phosphate, 2-methacryloyloxyethyl-3'-methacryloyloxy-2'-(3,4-dicarboxybenzoyloxy) propylsuccinate, N, O-dimethacryloyltyrosine and methacrylates thereof Corresponding acrylate; a vinyl monomer having a -OH group such as methacrylate such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate or acrylate corresponding to these methacrylates, and diisocyanate methylbenzene. , 4,4'-Diphenylmethane diisocyanate, Hexame Diaducts obtained from adducts with diisocyanate compounds such as thylene 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 Radical Polymerizable Monomer Trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate and other methacrylates, 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, methylenebis (4-cyclohexylisocyanate), A diaduct obtained from an adduct of a diisocyanate compound such as 4,4-diphenylmethane diisocyanate or trilene-2,4-diisocyanate and glycidol dimethacrylate.

A plurality of types of these radically polymerizable monomers may be used in combination, if necessary. Further, a radically polymerizable monomer other than the above (meth) acrylate-based monomer may be used.

As the radically polymerizable monomer to be blended in the adhesive, the radically polymerizable monomer having two or more radically polymerizable functional groups in the molecule shall be 40% by mass or more of the total radically polymerizable monomer. Is more preferable, 50% by mass or more is more preferable, and 60% by mass or more is further preferable. By using a radically polymerizable monomer having two or more radically polymerizable functional groups in the molecule in an amount of 40% by mass or more of the total radically polymerizable monomer, a uniform and strong adhesive layer can be more easily obtained. Therefore, higher adhesiveness can be obtained.

Further, the radically polymerizable monomer preferably has one or more hydrogen-bonding functional groups in the molecule. An adhesive layer cured on the surface of a polyaryl ether ketone resin material by a radically polymerizable monomer having one or more hydrogen bonding functional groups in the molecule and hydrogen bonding between the hydrogen bonding functional groups. The strength of the radical becomes stronger, and higher adhesiveness can be obtained. The radically 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 30% by mass of the total polymerizable monomer. It is more preferably% or more, and further preferably 50% by mass or more.

In addition, some or all of the polymerizable monomers having one or more hydrogen-bonding functional groups in the molecule may have two or more radically 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 radically polymerizable monomer having two or more radically polymerizable functional groups and one or more hydrogen-binding functional groups in the molecule shall be contained in an amount of 5% by mass or more based on the total radically polymerizable monomers. Is more preferable, 20% by mass or more is more preferable, 30% by mass or more is more preferable, and 50% by mass or more is more preferable.

The hydrogen bond referred to here is a hydrogen atom (donor) that is bonded to an atom having a large electronegativity (O, N, S, etc.) and is electrically positively polarized, and is electrically negative having an isolated electron pair. It shows the binding interaction formed between the atoms (acceptors). The hydrogen-bonding functional group in the present invention is a substituent capable of functioning as a donor and an acceptor in the hydrogen bond, and specifically refers to a hydroxyl group, a thiol group, an amino group, a urethane group, an amide group and the like.

As the radically polymerizable monomer having two or more radically polymerizable functional groups and hydrogen-binding functional groups in the molecule, known ones including those exemplified above can be used without particular limitation, and examples thereof include those exemplified above. , 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, glycerin dimethacrylate, bis (2-methacryloyloxyethyl) hydrogen phosphate, bis (6-methacryloyloxyhexyl) hydrogen Phosphate, 2-methacryloyloxyethyl-3'-methacryloyloxy-2'-(3,4-dicarboxybenzoyloxy) propylsuccinate, N, O-dimethacryloyltyrosine and acrylates corresponding to these methacrylates; 2-hydroxy A vinyl monomer having a -OH group such as a methacrylate such as ethyl methacrylate, 2-hydroxypropyl methacrylate and 3-chloro-2-hydroxypropyl methacrylate or an acrylate corresponding to these methacrylates, and diisocyanate methylbenzene and 4,4'-diphenylmethane. Diaducts obtained from adducts with diisocyanate compounds such as diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate); 1,2-bis (3-methacryloyloxy). Examples thereof include -2-hydroxypropoxy) ethyl and 1,6-bis (methacryloylethyloxycarbonylamino) 2,2,4-trimethylhexane.

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

As the radically polymerizable monomer having two or more radically polymerizable functional groups, hydrogen-binding functional groups and aromatic rings in such a molecule, known ones 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 these methacrylates; methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate or these methacrylates. Examples thereof include diaducts obtained by adding a vinyl monomer having a −OH group such as an acrylate to be added to a diisocyanate compound having an aromatic group such as diisocyanate methylbenzene and 4,4′-diphenylmethane diisocyanate. The radically polymerizable monomer having two or more radically polymerizable functional groups, hydrogen-binding functional groups and aromatic rings in the molecule is preferably used in an amount of 15% by mass or more, preferably 25% by mass or more, of the total radically polymerizable monomers. It is more preferable to use the above. On the other hand, the amount of the radically polymerizable monomer having two or more radically polymerizable functional groups, hydrogen-binding functional groups and aromatic rings in the molecule is preferably 70% by mass or less of the total radically polymerizable monomer. It is more preferably 50% by mass or less. By making the amount of the radically polymerizable monomer having 2 or more radically polymerizable functional groups, hydrogen bonding functional groups and aromatic rings in the molecule 15% by mass or more, the polyaryletherketone resin material and the adhesive layer can be obtained. It is possible to strengthen the interaction of. On the other hand, when a radical polymerizable monomer having two or more radical polymerizable functional groups, a hydrogen bond functional group and an aromatic ring is blended in the molecule in an amount of more than 70% by mass, the hydrogen bond functional groups or the aromatic ring are mixed. Due to the interaction between them, it becomes difficult to handle the radically polymerizable monomer, and it may be difficult to add the radically polymerizable monomer to the adhesive from the viewpoint of workability and the like.

Further, the polyaryletherketone resin material contains a metal oxide such as a metal inorganic oxide, a composite inorganic oxide, or an oxide obtained by adding a group I metal oxide to the composite inorganic oxide as a filler. In the case of a ketone resin composite material, it is also suitable to add a coupling agent having a radically polymerizable functional group as the radically polymerizable monomer.

The coupling agent is a material having a reactive group that chemically bonds with an inorganic compound and a reactive group that chemically bonds with an organic compound. By blending a coupling agent with the adhesive, higher adhesiveness to the polyaryletherketone resin composite material can be obtained. It is presumed that this is because the coupling agent forms a bond with both the metal oxide of the polyaryletherketone resin composite material and the radically polymerizable monomer of the adhesive.

As the coupling agent having a radically polymerizable functional group used in the present invention, known ones can be used without limitation. Examples of the coupling agent include a silane coupling agent, a titanate-based coupling agent, an aluminate-based coupling agent, a zirconeate-based coupling agent, and the like, but the silane coupling agent is particularly preferable from the viewpoint of adhesiveness and handleability. Is.

Examples of the coupling agent having a radically polymerizable functional group that is particularly preferably used include γ-methacryloyloxypropyltrimethoxysilane, for example, a silane coupling agent in which the radically polymerizable functional group is a (meth) acryloyl group. γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyltriisopropylsilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloyloxypropyltris (methoxyethoxy) silane, γ-methacryloxypropylmethyldiethoxysilane, ω -Methacryloxydecyltrimethoxysilane, (methacryloxymethyl) methyldimethoxysilane, (methacryloxymethyl) methyldiethoxysilane, methacrylatemethyltrimethoxysilane, O- (methacryloxyethyl) -N- (triethoxysilylpropyl) Carbamate, N- (3-methacryloyl-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 3- (n-methacryloyloxyphenyl) propyltrimethoxysilane, 3- (3-methoxy-4-methacryloyloxyphenyl) Examples thereof include propyltrimethoxysilane.

The above-mentioned coupling agent having a radically polymerizable functional group may be used alone or in combination of two or more.

The amount of the coupling agent having a radically polymerizable functional group is not particularly limited, but from the viewpoint of adhesiveness, 1 is applied to the total radically polymerizable monomer including the coupling agent having a radically polymerizable functional group. The range of ~ 30% by mass is preferable, the range of 2 to 20% by mass is more preferable, and the range of 3 to 10% by mass is further preferable.

When a coupling agent having a radically polymerizable functional group is blended in the adhesive, the adhesive contains a radically polymerizable monomer having two or more radically polymerizable functional groups in the above-mentioned molecule as a total radical. It is particularly preferable to blend 40% by mass or more with respect to the polymerizable monomer in order to obtain higher adhesiveness.

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

In the present invention, since the adhesive is not irradiated with light, the adhesive may or may not contain a photopolymerization initiator, but the adhesive containing the photopolymerization initiator is lighted. If it hits, it causes gelation and may cause deterioration of storage stability. Therefore, it is preferable not to mix it substantially. Substantially, the amount of the photopolymerization initiator is 0.005 parts by mass or less, more preferably 0.001 parts by mass or less, and not blended with respect to 100 parts by mass of the radically polymerizable monomer. Most preferred.

The thermal polymerization initiator may or may not be contained in the adhesive, but if the adhesive containing the thermal polymerization initiator is heated, it causes gelation and the storage temperature is low. However, since it may cause deterioration of storage stability to a considerable extent, it is more preferable that the mixture is not substantially blended. Substantially, the amount of the photopolymerization initiator is 0.005 parts by mass or less, more preferably 0.001 parts by mass or less, and not blended with respect to 100 parts by mass of the radically polymerizable monomer. Most preferred.

A chemical polymerization initiator consists of two or more components, and is a polymerization initiator that produces a polymerization active species at around room temperature by mixing all the components immediately before use, and may or may not be contained in the adhesive. Although it is good, it is preferable to contain it from the viewpoint of improving adhesive strength and stability. When a chemical polymerization initiator is contained in an adhesive, it is usually used by storing the adhesive packaging in two or more parts and mixing all the components immediately before use to generate the chemical polymerization initiator activity and applying it. Will be done. In this case, the reaction proceeds slowly from the time of mixing, but it does not immediately lose fluidity and become indeformable. Adhesives containing a chemical polymerization initiator are polymerized very slowly due to the influence of oxygen that inhibits polymerization before crimping the adherend, and oxygen is blocked after crimping the adherend. Polymerization accelerates. Therefore, since the adhesive containing the chemical polymerization initiator becomes indestructible after the adherend is pressure-bonded, a thin adhesive layer can be formed. The amount of the chemical polymerization initiator to be blended is not particularly limited, but if it is too small, it cannot contribute to sufficient polymerization of the adhesive, and if it is too large, the amount of non-polymerized components in the adhesive layer increases, so that the strength of the adhesive layer is increased. It leads to a decrease in. Therefore, the amount of the chemical polymerization initiator is preferably 0.002 parts by mass or more, more preferably 0.02 to 12 parts by mass, and 0.5 parts by mass with respect to 100 parts by mass of the radically polymerizable monomer. Most preferably, it is in the range of ~ 7 parts by mass.

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

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

Examples of the oxidizing agent of 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.

In addition, typical organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, and diarylpers. Oxides and the like can be mentioned.

As the oxidizing agent to be blended in the adhesive of the present invention, an organic peroxide is preferable.

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

Examples of peroxyketals include 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, and 1,1-bis (t-). Butyl peroxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclodecane, 2,2-bis (t-butyl) Examples thereof include peroxy) butane, n-butyl 4,4-bis (t-butyl peroxy) valerate, and 2,2-bis (4,5-di-t-butyl peroxycyclohexyl) propane.

Hydroperoxides include P-methane hydroperoxide, diisopropylbenzene peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydro. Examples thereof include peroxide.

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

Examples of diacyl peroxides include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, and dichloromethane. Oxides, m-toroil benzoyl peroxide, benzoyl peroxide and the like can be mentioned.

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

Peroxyesters include α, α-bis (neodecanoyl peroxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-. Cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivarate, t-butylperoxypivarate, 1 , 1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethyl Peroxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxy Isopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis ( m-Tolu oil peroxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5 bis (benzoylper) Oxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toroil benzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate and the like can be mentioned.

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 may be used alone or in combination of two or more. Among them, hydroperoxides, ketone peroxides, peroxyesters and diacyls may be used. Peroxides are particularly preferable 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 higher from the viewpoint of storage stability of the curable composition as an adhesive or an adherend.

Examples of such organic peroxides include P-methane hydroperoxide, diisopropylbenzene peroxide, 1,1,3,3-tetramethylbutylhydroperoxide, cumenehydroperoxide, t-butylhydroperoxide and the like. 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-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexyl Peroxyesters such as peroxybenzoate, 2,5-dimethyl-2,5 bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, etc. Examples thereof include diacyl peroxides such as octanoyl peroxide, lauroyl peroxide, succinic acid peroxide, m-toroil benzoyl peroxide, and benzoyl peroxide.

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

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

Specific examples of amine compounds 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, and specific examples thereof include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, and the like. Calcium p-toluenesulfinate, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, 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, calcium 2,4,6-triethylbenzenesulfinate, 2, , 4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, Examples thereof include calcium 2,4,6-triisopropylbenzenesulfinate, and sodium p-toluenesulfinate, sodium benzenesulfinate, and sodium 2,4,6-triethylbenzenesulfinate are preferable.

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 the oxime compound include methylethyl ketone oxime, methyl isobutyl ketone oxime, acetophenone oxime, P, P'-dibenzoylquinone oxime and the like.

As the transition metal compound, a transition metal compound having a fourth period can be particularly preferably used. The transition metal compound of the 4th period is a metal compound of groups 3 to 12 of the 4th 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), Zinc (Zn), respectively. Each of the above transition metal elements can have a plurality of valences, but can be blended in the primer or curable composition of the present invention as long as it can act as a reducing agent at a valence that can exist stably. is there. Typical specific examples of such compounds are divanadium tetraoxide (IV), vanadium acetylacetonate (IV) oxide, vanazyl oxalate (IV), vanazyl sulfate (IV), and oxobis (1-phenyl-1). , 3-Butandionate) vanadium (IV), bis (maltlate) oxovanadium (IV) and other + IV-valent vanadium compounds, chromium (II) chloride and other + II-valent chromium compounds, manganese acetate (II), 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 acetate (II), cobalt naphthenate (II), etc. Examples thereof include + II cobalt compounds, + II valent nickel compounds such as nickel naphthenate and nickel (II) chloride, and + I valent copper compounds such as copper (I) chloride and copper (I) bromide.

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

In addition, the adhesive 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, if necessary, as long as the effects of the present invention are not significantly impaired. It may be.

The solvent contained in the adhesive is preferably a volatile solvent. By blending a volatile solvent, the viscosity of the adhesive is lowered, and the radically polymerizable monomer easily penetrates into the fine irregularities on the surface of the polyaryletherketone resin material, or a uniform adhesive layer. It becomes easy to form. In addition, because it is volatile, after the adhesive is applied to the adherend surface of the polyaryletherketone resin material, it is removed from the surface of the polyaryletherketone resin material by an operation such as air blowing, and the adhesiveness due to residual solvent remains. It is possible to suppress the adverse effect on.

Here, the volatile solvent means that the boiling point at 760 mmHg is 100 ° C. or lower, and the vapor pressure at 20 ° C. is 1.0 KPa or more. However, since it is preferable that the volatile solvent volatilizes sufficiently and remains and does not have an adverse effect, 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, if the volatile solvent volatilizes too quickly, it becomes difficult to sufficiently obtain the effect of blending the volatile solvent. Therefore, the vapor pressure of the volatile solvent at 20 ° C. is preferably 60 KPa or less, and more preferably 50 KPa or less. Further, it is more preferable that the boiling point of the volatile solvent at 760 mmHg is 85 ° C. or lower because the lower the boiling point is, the easier it is to remove it from the surface of the polyaryletherketone resin material.

Examples of such preferred volatile solvents 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 in combination of two or more if 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 radically polymerizable monomer. More preferably, it is more preferably 300 parts by mass or more. Further, it is preferably 3000 parts by mass or less, more preferably 2000 parts by mass or less, more preferably 1500 parts by mass or less, and 1000 parts by mass with respect to 100 parts by mass of the total radically polymerizable monomer. More preferably, it is less than or equal to a portion. By using 10 parts by mass or more of the volatile solvent, it is easy for the adhesive to penetrate into the fine irregularities on the surface of the polyaryletherketone resin material, and it is easy to obtain the effect of forming a uniform adhesive layer. Become. By reducing the amount of the volatile solvent to 3000 parts by mass or less, the amount of the radically polymerizable monomer component of the adhesive is reduced, and as a result, the polyaryletherketone when the adhesive is applied to the surface of the polyaryletherketone resin material. The amount of the radically polymerizable monomer present on the surface of the resin material is not insufficient, a uniform and strong adhesive layer is sufficiently formed, and the advantage of blending the volatile solvent can be easily obtained.

The volatile solvent may be used in combination with a low volatility solvent having a vapor pressure of less than 1.0 KPa at 20 ° C. However, if a large amount of a solvent having low volatility is contained, the interaction between the polyaryl ether ketone resin material and the radically polymerizable monomer of the adhesive may be hindered, or the radically polymerizable monomer of the adhesive may be polymerized. There is a risk of inhibiting curing and reducing adhesiveness. Therefore, the solvent having low volatility contained in the adhesive is preferably 40% by mass or less, more preferably 20% by mass or less, and 10% by mass or less, based on the blending amount of the volatile solvent. It is more preferable that there is, and it is most preferable that it is 1% by mass or less.

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

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. When these inorganic fillers are used, those subjected to silane coupling treatment are preferable. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, and vinyl. Triacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyl Dimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane , 11-methacryloyloxyundecyltrimethoxysilane, 11-methacryloyloxyundecylmethyldimethoxysilane and the like.

Examples of organic fillers include polymethylmethacrylate, polymethylmethacrylate-polyethylmethacrylate 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 fillers obtained by mixing the above-mentioned inorganic particles and a polymerizable monomer, polymerizing the mixture, and pulverizing the mixture.

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

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

<Adhesive viscosity>
The viscosity of the adhesive is preferably low. Since the adhesive has a low viscosity, the adhesive easily penetrates into the fine irregularities on the surface of the polyaryletherketone resin material, and it becomes easy to apply the adhesive uniformly to the surface of the polyaryletherketone resin material. , It becomes easier to obtain higher adhesiveness. On the other hand, if the viscosity of the adhesive is too low, the adhesive may be uniformly applied to the adherend surface of the polyaryletherketone resin material, which may have a complicated structure due to reasons such as the adhesive dripping. Things can be difficult. Therefore, the viscosity of the adhesive is preferably in the range of 0.3 cP to 3000 cP, more preferably in the range of 0.4 cP to 500 cP, and more preferably in the range of 0.5 cP to 30 cP at 23 ° C. Is more preferable, and the range of 0.5 cP to 10 cP is most preferable. The viscosity may be measured using a cone plate type viscometer in a thermostatic chamber maintained at 23 ° C. The viscosity of the adhesive containing the chemical polymerization initiator and the radically polymerizable monomer may be measured by adjusting the composition not containing the chemical polymerization initiator.

<Light irradiation method>
In the present invention, after irradiating the adherend surface of the polyaryletherketone resin material with light, an adhesive containing the above-mentioned radically polymerizable monomer is applied to produce an adhesive polyaryletherketone resin material. To do. The atmosphere at the time of light irradiation is not particularly limited and may be performed in the air. Since the radicals generated by light irradiation are captured by oxygen molecules, the effect of obtaining the high adhesiveness of the present invention can be obtained more effectively when light irradiation is performed under oxygen-free conditions. By irradiating the surface of the polyaryletherketone resin material with light, the ketone group of the polyaryletherketone resin material having two aromatic rings existing in the polyaryletherketone resin as substituents is activated, and a radical is generated. To do. The generated radical reacts with the radically polymerizable functional group of the radically polymerizable monomer contained in the adhesive to form a bond between the polyaryletherketone resin material and the adhesive. Next, by pressure-bonding the curable composition containing the radically polymerizable monomer and the start of polymerization from above the adhesive, oxygen is blocked and inhibition of polymerization of the adhesive is suppressed. Further, if the adhesive contains a chemical polymerization initiator, the polymerization is accelerated here. Then, by polymerizing and curing this curable composition, the radically polymerizable functional group of the radically polymerizable monomer of the adhesive reacts with the radically polymerizable functional group of the radically polymerizable monomer of the curable composition. By doing so, a bond is formed between the adhesive and the curable composition. In this way, it is presumed that high adhesiveness can be obtained between the polyaryletherketone resin material and the radically polymerizable curable composition.

Light used for light irradiation for polyaryletherketone resin material surface prior to the application of the present invention, the adhesive is for maximum peak wavelength in the range of 400 nm to 500 nm, in the range of 450nm~500nm Those are particularly preferable. When light having a maximum peak wavelength of 400 nm or less is used, there is a concern that the operator or the like may be adversely affected, or the polyaryletherketone resin material itself may be damaged and its intensity may be reduced. When light having a maximum peak wavelength of 500 nm or more is used, it is difficult to obtain the effect of improving the adhesiveness to the polyaryletherketone resin material.

Here, since the ketone group having two aromatic rings as a substituent has a very small ability to absorb blue light as compared with ultraviolet light, when light having a maximum peak wavelength in the range of 400 nm to 500 nm is used, this In order to obtain the effect of the present invention, it is preferable to give a large amount of light energy. The light energy can be expressed 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 ..

Further, it is more preferable to give a large amount of the above 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.

The light intensity of the light used in the present invention can be measured by using a measuring device capable of measuring the light intensity of light in the range of 400 nm to 500 nm. Examples of such a measuring device include Demetron L. et al. E. D. RADIOMETER (manufactured by Kerr), OPTILUX RADIOMETER (manufactured by Kerr) and the like can be used.

It is more preferable that the adherend surface of the polyaryletherketone resin material in the present invention is roughened. The roughened polyaryletherketone resin material has increased surface irregularities, and higher adhesiveness can be obtained without variation. The roughening treatment may be carried out on the surface to which the adhesive of the polyaryletherketone resin material is to be applied by a simple and safe method before the light irradiation. As a roughening treatment method, it is preferable to sandblast the surface of the polyaryletherketone resin material. Sandblasting can easily and safely roughen the adherend surface of the polyaryletherketone resin material and contribute to the improvement of adhesiveness. The sandblasting treatment may be carried out by a usual method, and generally, alumina particles having a particle size of several μm to several hundred μm are polyaryl at a pressure of several tens of KPa to several MPa using a sandblasting device. It is carried out by spraying on an etherketone resin material. That is, by irradiating the coarsely roughened polyaryletherketone resin material with light and applying an adhesive containing a radically polymerizable monomer, higher adhesiveness can be obtained without variation. It becomes easy.

The effect of irradiating the adherend surface of the polyaryletherketone resin material with light is about 20 minutes, and after irradiating the adherend surface of the polyaryletherketone resin material with light, the radically polymerizable simple molecule is as soon as possible. It is preferable to apply an adhesive containing the weight (a).

<Manufacturing method of adhesive polyaryletherketone resin>
In the adhesive polyaryletherketone resin of the present invention, an adhesive containing a radically polymerizable monomer (a) is applied after irradiating the adherend surface of the polyaryletherketone resin material with light as described above. Obtained by doing. The method of applying the adhesive is not particularly limited, but it is easy to apply the adhesive evenly by soaking it in a dental microbrush or a cotton ball. When the adhesive contains a solvent, it is desirable to dry the solvent from the viewpoint of adhesive strength. The drying method is not particularly limited, but a method of blowing compressed air is convenient.

<Subject>
In the present invention, the adherend to be adhered to the polyaryletherketone resin material comprises a curable composition containing a radically polymerizable monomer and a polymerization initiator.

The adhesive polyaryletherketone resin material obtained by the production method of the present invention has an adherend composed of a curable composition containing a radically polymerizable monomer and a polymerization initiator on its adherend surface. When crimped, high adhesiveness is obtained, and the adhesive layer can be made thin. Therefore, after irradiating the polyaryl ether ketone resin material with light, an adhesive containing a radically polymerizable monomer is applied, and then radical polymerization is carried out on the polyaryl ether ketone resin material to which the adhesive is applied. A polyaryl ether ketone resin material, which comprises crimping an adherend composed of a curable composition containing a sex monomer and a polymerization initiator, and polymerizing and curing the adherend (curable composition). The method of adhering the and the adherend to the adherend is also suitable.

Since the curable composition containing the radically polymerizable monomer and the polymerization initiator has low viscosity at first and can be easily deformed, it is deformed into a desired shape and placed at a desired location. , The function is exhibited by completing the polymerization curing.

The curable composition containing the radically polymerizable monomer and the polymerization initiator can be used without particular limitation as long as it contains the radically polymerizable monomer and the radical polymerization initiator. In the bonding operation to the polyaryletherketone resin material, the pressure is applied to the adherend surface of the polyaryletherketone resin material. By crimping the curable composition containing the radically polymerizable monomer and the polymerization initiator, the thickness of the adhesive layer that has been applied first and has not yet been sufficiently polymerized and cured is reduced, and oxygen is also applied. Suppresses the polymerization inhibition of the adhesive by blocking. At this time, if the adhesive contains a chemical polymerization initiator, the polymerization of the adhesive is accelerated. After that, by completing the polymerization curing of the curable composition, it is presumed that the adhesive is also polymerized and cured to obtain high adhesiveness.

The radically polymerizable monomer contained in the curable composition containing the radically polymerizable monomer and the polymerization initiator is a compound having a radically polymerizable functional group in the molecule, and known ones can be used without any limitation. it can. Examples of the radically polymerizable functional group include functional groups such as a vinyl group, a styryl group, an allyl group, and a (meth) acryloyl group, and a (meth) acryloyl group is particularly preferable from the viewpoint of polymerization rate and biosafety. .. Examples of preferable radically polymerizable monomers include those shown in (I) to (IV) above as examples of radically polymerizable monomers to be blended in an adhesive.

A plurality of types of these radically polymerizable monomers may be used in combination, if necessary. Further, a radically polymerizable monomer other than the above (meth) acrylate-based monomer may be used. The blending amount of these radically polymerizable monomers is preferably in the range of 6 to 60 parts by mass, more preferably in the range of 9 to 55 parts by mass with respect to 100 parts by mass of the curable composition.

As the polymerization initiator contained in the curable composition containing the radically polymerizable monomer and the polymerization initiator, a photopolymerization initiator, a chemical polymerization initiator or a thermal polymerization initiator can be used, and two or more kinds of them can be used. It is also possible to use a combination of polymerization initiators. After the curable composition containing the radically polymerizable monomer and the polymerization initiator is pressure-bonded to the polyaryletherketone resin material, the curable composition can be easily cured. Therefore, photopolymerization is possible. It is preferable to use an initiator and / or a chemical polymerization initiator. The three types of polymerization initiators will be described in more detail below.

As the photopolymerization initiator, known ones can be used without any limitation. Typical photopolymerization initiators include a combination of α-diketones and tertiary amines, a combination of acylphosphine oxide and tertiary amines, a combination of thioxanthones and tertiary amines, and α-aminoacetophenone. Examples thereof include photopolymerization initiators such as a combination of class and tertiary amines, a combination of arylborates and photoacid generators.

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

Examples of the tertiary amine include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p- Dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylanthranic acid methyl ester, N, N-dihydroxyethylaniline, N , N-dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol, p-dimethylaminostylben, 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- Examples thereof include dimethylstearylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2,2'-(n-butylimino) diethanol and the like. These can be used alone or in combination of two or more.

Examples of the acylphosphine oxides include benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5. Examples thereof 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-( Examples thereof include 4-morpholinophenyl) -pentanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -pentanone-1 and the like.

The aryl borate compound is not particularly limited as long as it is a compound having at least one boron-aryl bond in the molecule, and known compounds can be used. Among them, three in one molecule in consideration of storage stability. Alternatively, it is preferable to use an arylborate compound having 4 boron-aryl bonds, and further, an arylborate compound having 4 boron-aryl bonds is more preferable from the viewpoint of ease of handling, synthesis and availability.

As arylborate compounds having three boron-aryl bonds in one molecule, monoalkyltriphenylboron, monoalkyltris (p-chlorophenyl) boron, monoalkyltris (p-fluorophenyl) boron, monoalkyltris (3) , 5-Bistryfluoromethyl) phenylboron, monoalkyltris [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, monoalkyltris (P-Nitrophenyl) boron, monoalkyltris (m-nitrophenyl) boron, monoalkyltris (p-butylphenyl) boron, monoalkyltris (m-butylphenyl) boron, monoalkyltris (p-butyloxyphenyl) ) Boron, monoalkyltris (m-butyloxyphenyl) boron, monoalkyltris (p-octyloxyphenyl) boron, monoalkyltris (m-octyloxyphenyl) boron (However, in any compound, alkyl is n- (Indicating either butyl, n-octyl or n-dodecyl), sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, tributylamine salt, triethanolamine Examples thereof include salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts and the like.

Tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, and tetrakis (3,5-bistrifluoromethyl) phenyl are examples of arylborate compounds having four boron-aryl bonds in one molecule. Boron, Tetrax [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] Boron, Tetrax (p-nitrophenyl) Boron, Tetrax (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 [However, in any compound, alkyl indicates either n-butyl, n-octyl or n-dodecyl], 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 or Butyl quinolinium salt and the like can be mentioned.

The photoacid generator used in the present invention produces Bronsted acid or Lewis acid by light irradiation, and even if a sensitizer is required, it decomposes under visible light irradiation to generate an acid. Known ones can be used without any restrictions.

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

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

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

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

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

Examples of peroxyketals include 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, and 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) Examples thereof include peroxy) butane, n-butyl 4,4-bis (t-butyl peroxy) valerate, and 2,2-bis (4,5-di-t-butyl peroxycyclohexyl) propane.

Hydroperoxides include P-methane hydroperoxide, diisopropylbenzene peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydro. Examples thereof include peroxide.

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

Examples of diacyl peroxides include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, and dichloromethane. Examples thereof include oxides, m-toroil benzoyl peroxides, and benzoyl peroxides.

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

Peroxyesters include α, α-bis (neodecanoyl peroxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-. Cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivarate, t-butylperoxypivarate, 1 , 1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethyl Peroxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxy Isopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis ( m-Tolu oil peroxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5 bis (benzoylper) Oxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toroil benzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate and the like can be mentioned.

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 may be used alone or in combination of two or more. Among them, hydroperoxides, ketone peroxides, peroxyesters and diacyls may be used. Peroxides are particularly preferable 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 higher from the viewpoint of storage stability of the curable composition.

A system in which sulfinic acid such as benzenesulfinic acid, p-toluenesulfinic acid and a salt thereof is further added to an initiator system composed of the organic peroxide and the amine compound, and a barbituric acid system such as 5-butylbarbituric acid. It can be used without any problem even if it contains an initiator.

In addition, a transition metal compound / organic peroxide-based chemical polymerization initiator can also be mentioned. Specific examples of the transition metal compound include divanadium tetraoxide (IV), vanadium acetylacetate (IV) oxide, vanadil oxalate (IV), vanadil sulfate (IV), and oxobis (1-phenyl-1, 1, 3-Butandionate) vanadium (IV), bis (maltlate) oxovanadium (IV), vanadium homooxide (V), sodium metavanadate (V), ammon metavanadate (V) and other vanadium compounds, scandium iodide ( Scandium compounds such as III), titanium compounds such as titanium (IV) chloride and tetraisopropoxide of titanium (IV) tetraisopropoxide, chromium compounds such as chromium (II) chloride, chromium (III) chloride, chromium acid and chromate, acetic acid. Manganese compounds such as manganese (II) and manganese naphthenate (II), iron compounds such as iron (II) acetate, iron (II) chloride, iron (III) acetate and iron (III) chloride, cobalt (II) acetate, Cobalt compounds such as cobalt naphthenate (II), nickel compounds such as nickel chloride (II), copper compounds such as copper (I) chloride, copper (I) bromide, copper (II) chloride, and copper (II) acetate, Zinc compounds such as zinc chloride (II) and zinc acetate (II) are exemplified. Among these transition metal compounds, it is preferable to use a vanadium compound having a + IV value and / or a + V value because high adhesiveness can be easily obtained.

It is also possible to use an arylborate compound / acidic compound-based polymerization initiator that utilizes the fact that the arylborate compound is decomposed by an acid to generate radicals.

As the aryl borate compound, a compound that can be used as a photopolymerization initiator can be used. Further, two or more kinds of aryl borate compounds may be used in combination.

The acidic compound is used as a proton source and is a component used to react with the above-mentioned arylborate compound to produce arylborane.

Such acidic compounds include inorganic acids and organic acids generally known as blended acids, and polymerizable groups together with acidic groups, and are themselves polymerizable acidic group-containing polymerizable singles. Polymers are used.

In such acidic compounds, hydrochloric acid, sulfuric acid, nitrate, phosphoric acid and the like are typical examples of inorganic acids, and acetic acid, propionic acid, maleic acid, fumaric acid, phthalic acid and benzoic acid are typical organic acids. , Trichloroacetic acid, trifluoroacetic acid, citric acid and carboxylic acids such as trimellitic acid; sulfonic acids such as p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid; methylphosphonic acid, phenylphosphonic acid, dimethyl Phosphonic acids, phosphoric acids such as diphenylphosphinic acid; and the like are typical. In addition to phenols and thiols, solid acids such as acidic ion exchange resins and acidic alumina can also be used as the acidic compounds in the present invention.

Further, the acidic group-containing polymerizable monomer is a compound having at least one acidic group and at least one polymerizable unsaturated group in one molecule, and it is polymerized by itself, and the acidic component is eluted by polymerization curing. In the present invention, it is most preferably used as an acidic compound because there is no risk of such factors.

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

Examples of the thermal polymerization initiator include peroxides of benzoyl peroxide, p-chlorobenzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxydicarbonate, diisopropylperoxydicarbonate and the like. Azo, azo compounds such as azobisisobutyronitrile, tributylborane, partial oxides of tributylborane, sodium tetraphenylborate, sodium tetrakis (p-fluorophenyl) borate, boron such as triethanolamine tetraphenylborate. Examples thereof include compounds, barbituric acids such as 5-butylbarbituric 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, and 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 0.01 parts by mass or more, the curable composition containing the radically polymerizable monomer and the polymerization initiator is sufficiently cured even immediately after curing, and the physical properties are not deteriorated. Further, when the polymerization initiator is 10 parts by mass or less, the operability of the curable composition is good.

The curable composition may also contain other components such as a filler, a solvent, a polymerization inhibitor, a polymerization inhibitor, a dye, a pigment, and a fragrance, if necessary.

For example, the curable composition using a filler suppresses the polymerization shrinkage of the curable composition, improves the operability of the curable composition, or improves the mechanical properties of the cured product. Can be done. In particular, regarding the polymerization shrinkage rate, for example, when a large amount of curable composition is used, the polymerization shrinkage of the curable composition becomes large, and the polymerization shrinkage stress generated by the polymerization shrinkage causes the curable composition and the polyaryl ether. There is a risk that some peeling may occur between the adhesive applied to the surface of the ketone resin material or between the curable composition and the adhesive applied to the surface, making it difficult to obtain high adhesiveness. is there.

As the filler, a known inorganic filler or an organic-inorganic composite filler 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. Further, as a cation-eluting inorganic filler, silicate glass, fluoroaluminosilicate glass and the like can be used as needed. These inorganic fillers may be used alone or in admixture of two or more.

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

The particle size of these fillers is 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 intended 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 refractive indexes may be used in combination.

It is preferable that the inorganic filler is treated with a surface treatment agent typified by a silane coupling agent. In this case, the affinity between the inorganic filler and the radically 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. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, and 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 radically polymerizable monomer and the mechanical physical characteristics of the cured product, depending on the purpose of use, but in general, it is generally determined. It is preferably in the range of 50 to 1500 parts by mass, and more preferably in the range of 70 to 1000 parts by mass with respect to 100 parts by mass of the radically polymerizable monomer.

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

Further, the adhesive polyaryletherketone resin materials obtained by the production method of the present invention can be adhered to each other through a curable composition containing a radically polymerizable monomer and a polymerization initiator, or the production of the present invention can be performed. It is also possible to bond the adhesive polyaryletherketone resin material obtained by the method to the third member.

When the adhesive polyaryletherketone resin materials obtained by the production method of the present invention are bonded to each other through a curable composition containing a radically polymerizable monomer and a polymerization initiator, for example, holes, grooves, etc. The curability in the form of filling the recesses of the adhesive polyaryletherketone resin material obtained by the production method of the present invention provided with recesses with a curable composition containing a radically polymerizable monomer and a polymerization initiator. The composition may be adhered to a polyaryletherketone resin material. In this case, the recess is embedded and the curable composition filled in the recess is adhered to the inner wall surface of the recess of the adhesive polyaryletherketone resin material obtained by the production method of the present invention.

Further, for example, when the curable composition containing the radically polymerizable monomer as an adherend and the polymerization initiator has a property of firmly adhering to the surface of another member (third member). By bringing the third member into contact with the adherend and polymerizing and curing the adherend, the adhesive polyaryletherketone resin material of the present invention and the third member can be firmly adhered to each other. The third member can be used without particular limitation as long as it is a known solid member.

When the adherend is adhered to the polyaryletherketone resin material by the method of adhering the polyaryletherketone resin material of the present invention to the adherend, a curable composition containing a radically polymerizable monomer and a polymerization initiator is contained. The adherend made of is polymerized and cured to become a cured product.

A laminate can be produced by the above-mentioned bonding method of the present invention. After irradiating the polyaryletherketone resin material with light, an adhesive containing the radically polymerizable monomer (a) is applied, and the polyaryletherketone resin material coated with the adhesive is radically polymerizable. When an adherend composed of a curable composition containing a monomer and a polymerization initiator is pressure-bonded, the adherend is polymer-cured, and the polyaryletherketone resin material and the adherend are adhered, the polyarylether It can be a laminate having an adhesive (cured adhesive) layer and an adherend (cured adherend) on a ketone resin material. Further, when the polyaryletherketone resin material and the third member are bonded using the bonding method of the present invention, an adhesive (cured adhesive) layer and an adherend (cured) are formed on the polyaryletherketone resin material. It can be an adherend) or a laminated body having a third member.

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

In the field of dentistry, there is a great demand for shortening treatment time and highly aesthetic members, and the advantage of thinning the adhesive layer is particularly great. In addition, in dental applications, blue light is often used instead of ultraviolet light in consideration of safety to the living body, and dental laboratories are equipped with the corresponding equipment, so the maximum peak wavelength It is preferably used in the field of dentistry because it can be widely implemented by using existing equipment by using light having a wavelength of 400 nm to 500 nm.

As a dental polyaryletherketone resin material using the adhesive polyaryletherketone resin material obtained by the production method of the present invention for dental use, the adhesive polyaryletherketone resin obtained by the production method of the present invention is used. Examples include dentures, artificial teeth, denture bases, dental implants, crown restoration materials, abutment construction materials, etc., which are partially or wholly prepared using.

As a curable composition containing a radically polymerizable monomer and a polymerization initiator that can be used as a dental member, a dental curable composition can be used. The dental curable composition is a curable composition used for dental treatment, and since it has low viscosity at first and can be easily deformed, it is deformed into a desired shape and installed at a desired location. After that, it exerts its function 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, dentures 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. Examples include members.

As an example of the method of using the adhesive dental polyaryletherketone resin material obtained by the production method of the present invention, a dental hard resin is used as a dental curable composition, and the dental polyaryletherketone resin material is used. And dental hard resin are laminated to prepare a dental prosthesis. Specifically, for example, an adhesive poly by irradiating a desired surface of a dental polyaryletherketone resin material molded into a desired shape with light and applying an adhesive containing a radically polymerizable monomer. Obtain an aryletherketone resin material. After that, a hard resin is laminated on the resin, adjusted to a desired shape, and then cured to prepare a desired dental prosthesis. Since the dental prosthesis has high adhesiveness, it is easy to make it hard to break, and since the adhesive layer can be thinned, it is easy to make a dental prosthesis with high aesthetics.

Another example is a step of using dental cement as a dental curable composition and attaching a prosthesis made of a polyaryletherketone resin material to a tooth defect. Specifically, for example, an adhesive poly by irradiating the adherend surface of a prosthesis made of a polyaryletherketone resin material prepared in advance with light and applying an adhesive containing a radically polymerizable monomer to the adherend surface. Obtain an aryletherketone resin material. Dental cement can be applied to the adherend surface to attach the dental polyaryletherketone resinous prosthesis to the teeth. At that time, since it is possible to make the adhesive layer thin while obtaining high adhesiveness, the compatibility of the prosthesis made of the dental polyaryletherketone resin material obtained by the production method of the present invention is high. It becomes easy to make it.

As a polyaryletherketone resin used as a dental material, particularly a dental restoration material, the ether group and the ketone group constituting the main chain are arranged in the order of ether ether ketone from the viewpoint of color tone and physical properties. However, it is preferable to use a polyetheretherketone having a repeating unit, or a polyetherketone ketone having a repeating unit arranged in the order of ether, ketone, and ketone.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. The abbreviations and titles shown in the examples are as follows.

[Radical polymerizable monomer]
<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 in
-PM1: 2-methacryloyloxyhexyl dihydrogen phosphate-HEMA: 2-hydroxyethyl methacrylate [chemical polymerization initiator]
-BPO: Benzoyl peroxide-DMBE: p-dimethylaminobenzoic acid ethyl ester [photopolymerization initiator]
-CQ: camphorquinone-DMBE: p-dimethylaminobenzoic acid ethyl ester [adhesive containing radically polymerizable monomer]
As the adhesive containing the radically polymerizable monomer, the adhesive having the composition shown in Table 1 was used.

(Adhesive preparation)
The adhesive containing the radically polymerizable monomer was prepared by mixing the radically polymerizable monomer, the solvent and the polymerization initiator shown in Table 1 and stirring until all the components became uniform. The adhesives (B4, B5, B6) containing the chemical polymerization initiator were packaged in two (A and B) and mixed immediately before to prepare the final adhesive (TOTAL). .. A and B indicate the composition of each sachet, and TOTAL indicates the composition after mixing.

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

[Polyaryletherketone resin material]
As the polyaryletherketone resin material, the following two types of polyaryletherketone resin materials C1 and C2 were used.

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

Polyaryletherketone resin material C2: VESTAKEEP M2G (manufactured by Daicel Evonik), which is a polyaryletherketone resin, was used.

(Measurement of tensile adhesive strength between polyaryletherketone resin material and cured product of curable composition)
The polyaryletherketone resin material was molded into a plate shape of 2 mm × 13 mm × 13 mm by injection molding. After polishing the adherend surface of 13 mm × 13 mm with # 800 water-resistant abrasive paper, it is roughened by sandblasting (alumina particles with a particle size of about 50 μm were sprayed at a pressure of about 0.2 MPa for 10 seconds using a sandblasting device). Elephantization was performed. Then, it was washed by immersing it in water and exposing it to ultrasonic waves for 5 minutes, and then immersing it in acetone and exposing it to ultrasonic waves for 5 minutes. Next, a 0.2 μm-thick double-sided tape having a hole with a diameter of 3 mm was attached to the adherend surface.

After that, the holes were irradiated with light and an adhesive containing a radically polymerizable monomer was applied and dried. The order of light irradiation, application of the adhesive containing the radically polymerizable monomer, and drying is as shown in Tables 2 and 3. Light irradiation was performed on the above-mentioned holes using a dental visible light irradiator under the conditions shown in Tables 2 and 3. To apply and dry the adhesive containing the radically polymerizable monomer, apply the adhesive containing the radically polymerizable monomer, allow it to stand for 10 seconds after application, and then blow compressed air for about 10 seconds to dry it. I went by doing. In this way, 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 radically polymerizable monomer and a polymerization initiator as an adherend, is applied to the adherend surface portion (hole portion of the double-sided tape). An adhesion test piece was prepared by applying the coating and pressing a cylindrical stainless steel attachment having a diameter of 8 mm and a height of 2 mm onto the coating. After holding the above-mentioned adhesion test piece at 37 ° C. for 24 hours, it is pulled at a cross head speed of 2 mm / min using a tensile tester (Autograph, manufactured by Shimadzu Corporation) to produce it by the manufacturing method of the present invention. The tensile adhesive strength of the dental cement material, which is a curable composition containing the adhesive polyaryletherketone resin material, the radically polymerizable monomer, and the polymerization initiator, was measured. The tensile adhesive strength was measured for each of the five test pieces in each Example or Comparative Example, and the average value and standard deviation (SD) were determined.

As a dental visible light irradiator, L1 is referred to as L1. E. Demetron II (LED irradiator manufactured by Kerr) and Optilux500 (halogen irradiator manufactured by Kerr) were used as L2. Both of these light irradiators have a maximum peak wavelength of light to be irradiated between 450 nm and 500 nm. The light intensity is determined by Demetron L. et al. E. D. A light intensity of 400 nm to 500 nm was measured using RADIOMETER (manufactured by Kerr). The distance between the tip of the light guide and the irradiation surface was changed to obtain a desired light intensity, which was used in the test.

(Measurement of adhesive layer thickness)
The polyaryletherketone resin material was molded into a plate shape of 2 mm × 13 mm × 13 mm by injection molding. The adherend surface of this polyaryletherketone resin material was polished with # 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 device. ) Was used for roughening. Then, it was washed by immersing it in water and exposing it to ultrasonic waves for 5 minutes, and then immersing it in acetone and exposing it to ultrasonic waves for 5 minutes.

Then, the adherend surface of the polyaryletherketone resin material was irradiated with light and an adhesive containing a radically polymerizable monomer was applied and dried. The order of light irradiation, application of the adhesive containing the radically polymerizable monomer, and drying is as shown in Tables 2 and 3. Light irradiation was performed using a dental visible light irradiator under the conditions shown in Tables 2 and 3. To apply and dry the adhesive containing the radically polymerizable monomer, apply the adhesive containing the radically polymerizable monomer, allow it to stand for 10 seconds, and then blow compressed air for about 10 seconds to dry it. Was done by. Then, a dental cement material (manufactured by Tokuyama Dental Co., Ltd .: Bistite II), which is a curable composition containing a radically polymerizable monomer and a polymerization initiator as an adherend, is applied on the adherend surface, and further. A test piece was prepared by pressing a cylindrical attachment having a diameter of 8 mm and a height of 2 mm, which was prepared by curing a hard dental resin (manufactured by Tokuyama Dental Co., Ltd .: Pearl Esthe). 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 bonded portion. After polishing this adhesive portion with # 3000 water-resistant abrasive paper, the thickness of the adhesive layer was measured with a laser microscope (manufactured by KEYENCE).

<Example 1>
5 g of bisGMA as a radically polymerizable monomer component having two or more radically polymerizable functional groups in the molecule, 5 g of 3G as a solvent component, 50 g of acetone as a solvent component, and the radically polymerizable monomer is stirred and mixed until uniform. Adhesive B1 containing the above was obtained. Table 1 shows the composition and viscosity of the adhesive. A double-sided tape having a hole with a diameter of 3 mm was attached to the surface of the polyaryletherketone resin material C1 to form a dental visible light irradiator L1. E. Using Demetrin II (LED irradiator manufactured by Kerr) under the condition that the light intensity of the light irradiation surface is 800 mW / cm ² by adjusting the distance between the tip of the light guide and the light irradiation surface, light irradiation is performed for 10 seconds. Next, the adhesive B1 containing the radically polymerizable monomer described above was applied to this surface, and compressed air was applied to remove the solvent. Using the adhesive polyaryletherketone resin material thus obtained, the tensile adhesive strength of the polyaryletherketone resin material and the curable composition containing the radically polymerizable monomer and the polymerization initiator is measured. The thickness of the adhesive layer was measured. The conditions and measurement results are shown in Table 2.

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

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

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

<Examples 20 to 26>
Polyaryletherketone resin material and radically polymerizable monomer are polymerized according to Examples 1, 3, 8, 12, 15, 16 and 19, respectively, except that the polyaryletherketone resin material is changed to C2. The tensile adhesive strength with the curable composition containing the initiator and the thickness of the adhesive layer were measured. The conditions and measurement results are shown in Table 3.

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

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

From the study results (Table 2) using C1 as the polyaryletherketone resin material, the following can be said.

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

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

In Example 19 and Comparative Example 4, an adhesive containing a photopolymerization initiator was used, and all the conditions were the same except for the order of application and drying of the adhesive and light irradiation. In Example 19, the adhesive is applied and dried after light irradiation, and the adhesive layer is thin. On the other hand, in Comparative Example 4, the adhesive is applied and dried before light irradiation, and the adhesive layer is thick. From these results, it can be confirmed that the thickness of the adhesive layer can be reduced by applying and drying the adhesive after light irradiation. This is because the adhesive is light-irradiated by applying and drying the adhesive before the light irradiation, and the adhesive containing the photopolymerization initiator is polymerized and cured, and cannot be deformed. It is thought that this is because it has become. The adhesive strength did not change significantly due to the difference in the order of application and drying of the adhesive and light irradiation.

Comparing Examples 1 to 8 in which the same adhesive and the same light irradiator are used and their light intensity and light irradiation time are different, Examples 2 to 8 having a light energy of 15,000 mJ / cm ² or more are 15,000 mJ. It can be confirmed that the adhesive strength is higher than that of Example 1, which is less than / cm ² . Further, it can be confirmed that Examples 3 to 8 having a light energy of 30,000 mJ / cm ² or more show higher adhesive strength than Examples 1 and 2 having a light energy of less than 30,000 mJ / cm ² . Further, it can be confirmed that Examples 4 to 8 having a light energy of 45,000 mJ / cm ² or more show higher adhesive strength than Examples 1 to 3 having a light energy of less than 45,000 mJ / cm ² .

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

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

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

Comparing Examples 1, 12, 13, and 14 in which adhesives containing different amounts of chemical polymerization initiators and the same light irradiator were used and light irradiation was performed under the same light irradiation conditions, the chemical polymerization initiators were found. From Example 1 using an adhesive that does not contain it, it can be confirmed that Examples 12, 13 and 14 using an adhesive containing 0.002 parts by mass or more of the chemical polymerization initiator show high adhesive strength. Further, Example 12 in which the content of the chemical polymerization initiator is in the range of 0.5 to 7% by mass has higher adhesive strength than Examples 13 and 14 in which the content is less than 0.5 parts by mass or larger than 7 parts by mass. It was confirmed that it shows the above.

Comparing Examples 1, 16, 17, and 18 in which adhesives containing different amounts of photopolymerization initiators and the same light irradiator were used and light irradiation was performed under the same light irradiation conditions, the photopolymerization initiators It was confirmed that the adhesive strength was about the same regardless of the content. Even if an adhesive containing a photopolymerization initiator was used, it is considered that there was almost no effect on the adhesive strength because the adhesive was not irradiated with light.

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

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

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

In Example 26 and Comparative Example 8, the conditions are the same except for the order of application and drying of the adhesive and light irradiation. In Example 26, the adhesive is applied and dried after light irradiation, and the adhesive layer is thin. On the other hand, in Comparative Example 8, the adhesive is applied and dried before light irradiation, and the adhesive layer is thick. From these results, it can be confirmed that the thickness of the adhesive layer can be reduced by applying and drying the adhesive after light irradiation. This is because the adhesive is light-irradiated by applying and drying the adhesive before the light irradiation, and the adhesive containing the photopolymerization initiator is polymerized and cured, and cannot be deformed. It is thought that this is because it has become. It should be noted that the adhesive strength did not change significantly due to the difference in the order of application and drying of the adhesive and light irradiation.

Comparing Examples 20 to 22 in which the same adhesive and the same light irradiator are used and their light intensity and light irradiation time are different, Examples 21 and 22 having a light energy of 45,000 mJ / cm ² or more have 45,000 mJ. It can be confirmed that the adhesive strength is higher than that of Example 20 which is less than / cm ² .

Comparing Examples 20 and 23 in which adhesives with and without a chemical polymerization initiator were used and light irradiation was performed under the same light irradiation conditions using the same light irradiator, adhesives containing no chemical polymerization initiator were obtained. From Example 20 used, it can be confirmed that Example 23 using an adhesive containing 0.002 parts by mass or more of the chemical polymerization initiator exhibits high adhesive strength.

Comparing Examples 20 and 25 in which the adhesives having different photopolymerization initiators and the same light irradiator were used and the light irradiation was performed under the same light irradiation conditions, regardless of the presence or absence of the photopolymerization initiator. , It was confirmed that the adhesive strength was about the same. Even if an adhesive containing a photopolymerization initiator was used, it is considered that there was almost no effect on the adhesive strength because the adhesive was not irradiated with light.

The following can be said by comparing the study results using C1 as the polyaryletherketone resin material (Table 2) and the study results using C2 as the polyaryletherketone resin material (Table 3).

Examples 1 and 20, Example 4 and Example 21, and Example 8 and Example 22 in which different polyaryl ether ketone resin materials were irradiated with light under the same conditions using the same adhesive. Comparing Example 12 and Example 23, Example 15 and Example 24, Example 16 and Example 25, and Example 19 and Example 26, respectively, the polyaryl ether ketone resin material contains amorphous inorganic compound particles. Examples 1, 4, 8, 12, 15, 16 and 19 in which the amorphous silica is blended are Examples 20, 21, 22 and 23 in which the amorphous inorganic compound particles are not blended, respectively. It was confirmed that the adhesive strength was slightly higher than that of 24, 25 and 26.

Claims (9)

After the maximum peak wavelength in the polyaryletherketone resin material is irradiated with light is 400 nm to 500 nm, adhesion polyaryl ether, which comprises applying an adhesive containing a radical polymerizable monomer (a) a A method for producing a ketone resin material. Among the radical polymerizable monomers of the adhesive, the adhesive of claim 1 is a radical polymerizable monomer having two or more (meth) acryloyl groups in more than 40% by weight in the molecule as a polymerizable functional group A method for producing a sex-polyaryl ether ketone resin material. The method for producing an adhesive polyaryletherketone resin material according to claim 1 or 2 , wherein the adhesive contains a chemical polymerization initiator (b). The method for producing an adhesive polyaryletherketone resin material according to any one of claims 1 to 3 , wherein the adhesive polyaryletherketone resin material is for dentistry. After the maximum peak wavelength in the polyaryletherketone resin material is irradiated with light is 400 nm to 500 nm, polyaryletherketone resin, which comprises applying an adhesive containing a radical polymerizable monomer (a) a Material pretreatment method. The method for pretreating a polyaryletherketone resin material according to claim 5 , wherein the adhesive further contains a chemical polymerization initiator (b). An adhesive method for adhering a polyaryl ether ketone resin material and an adherend composed of a curable composition containing a radically polymerizable monomer and a polymerization initiator, wherein the polyaryl ether ketone resin material has a maximum peak wavelength. After irradiating with light having a temperature of 400 nm to 500 nm, an adhesive containing the radically polymerizable monomer (a) is applied, and the adherend is formed on the polyaryl ether ketone resin material to which the adhesive is applied. A method for adhering a polyaryl ether ketone resin material to an adherend, which comprises crimping and polymerizing and curing the adherend. The method for adhering a polyaryletherketone resin material to an adherend according to claim 7 , wherein the adhesive further contains a chemical polymerization initiator (b). After the maximum peak wavelength in the polyaryletherketone resin material is irradiated with light is 400 nm to 500 nm, an adhesive is applied containing radically polymerizable monomer and (a), the adhesive is applied polyaryl A method for producing a laminate, which comprises crimping an adherend composed of a curable composition containing a radically polymerizable monomer and a polymerization initiator onto an etherketone resin material to polymerize and cure the adherend. ..