JP2016130300A - Primer for polyaryletherketone resin material, adhesive kit, and bonding method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain high adhesive strength to a polyaryletherketone resin material using a primer allowing the thickness of an adhesive layer to be easily thinned.SOLUTION: By a primer (A) for a polyaryletherketone resin material which contains some components of a chemical polymerization initiator (a1), high adhesive strength can be obtained while thinning an adhesive layer. The primer (A) contains a polymerizable monomer (b1), some components of a chemical polymerization initiator (b2), and a polymerization initiator (b3). Some components of the chemical polymerization initiator (b2) can compose an adhesive kit for the polyaryletherketone resin material together with a curable composition (B) capable of forming a chemical polymerization initiator system together with the chemical polymerization initiator (a1).SELECTED DRAWING: None

Description

  The present invention relates to a primer for a polyaryl ether ketone resin material having excellent adhesion to a polyaryl ether ketone resin material, an adhesion kit, and an adhesion method.

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

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

  Members containing polyaryletherketone resins having excellent chemical and physical properties are widely used in various fields as well as dental applications. For this reason, the technique which can adhere | attach more firmly with respect to the member containing polyaryl ether ketone resin regardless of a technical field or a use is calculated | required.

  For example, several techniques have been proposed for bonding to polyaryletherketone resin materials in dental applications.

  For example, Non-Patent Document 1 claims that relatively high adhesiveness was obtained by using a hydrophobic dental bonding material, and specifically, Heliobond (Ivoclar Vivendent) is used. A dental bonding material contains a polymerizable monomer and a polymerization initiator, and high adhesion can be obtained by applying this to an adherend and then curing it by polymerization.

  When adhering a dental polyaryletherketone resin material using a dental bonding material, for example, when adhering an abutment tooth and a prosthesis made of a dental polyaryletherketone resin material, the dental prosthesis is first subjected to dental treatment. Applied to the abutment tooth and dental prosthesis using a dental resin cement (usually composed of a polymerizable monomer, a polymerization initiator and a filler). By bonding the dental bonding material, the dental prosthesis and the abutment tooth are bonded via the dental bonding material and the dental resin cement. However, in this method using a dental bonding material, it is difficult to form a thin bonding material layer. If the bonding material layer is thick, the compatibility of the dental prosthesis will be adversely affected, and the dental prosthesis will be easily lifted, and the amount of cutting and polishing of the dental prosthesis will increase for occlusal preparation. The burden increases. In another example, when a dental prosthesis is produced by laminating a dental filling restorative material or a dental hard resin on a polyaryletherketone resin material, if the bonding material layer is visible, it is aesthetic. Therefore, the bonding material layer is preferably thin.

  On the other hand, when using a primer that does not contain a polymerization initiator in general, rather than a dental bonding material that contains a polymerization initiator and a polymerizable monomer and cures immediately after application to form a film, Since the pressure bonding is performed without curing after the primer application, it is easier to reduce the film thickness as compared with a dental bonding material that is pressure bonded after curing.

  Although examination which evaluated adhesiveness using the dental primer which does not contain a polymerization initiator with respect to a polyaryl ether ketone resin material is performed, high adhesive strength is not acquired. For example, Non-Patent Document 1 uses Clearfil Ceramic Primer (Kuraray Co., Ltd.) and Ecusit Composite Repair (DMG Co., Ltd.), which are commercially available primers for dental prostheses, but the adhesive strength is low. In addition, Clearfil Ceramic Primer indicates that 3-methacryloxypropyl-trimethylsiloxane, 10-methacryloyloxydecycyl-dihydrophosphate, and ethanol are contained in the silane coupling agent. It consists of a monomer and a solvent. It is shown that the Ecusit Composite Repair contains 3-methacryloxypropyl-trimethylsilane and ethanol, which are composed of a silane coupling agent and a solvent.

  Patent Document 2 discloses a conditioning agent containing an adhesive and a high-boiling solvent having a bipolar property for a molded article containing a high-temperature resistant plastic (including a polyaryl ether ketone resin material) and a filler. A conditioning technique has been proposed. Specifically, two types of conditioning agents consisting of methacryl silane and DMSO and methacryl silane, DMSO and ethanol are shown in the examples. However, in these conditioning agents (primers), it is essential to use a high-boiling solvent, and it is difficult to remove completely by air blow, which is usually performed as a work for removing the solvent in dental treatment, and it depends on the residual solvent. There may be concerns about the impact on the surroundings. It is noted that these conditioning agents may contain a polymerization initiator (catalyst), but are not specifically shown. In addition, there is no description on the effect of combining with a dental curable composition such as a dental resin cement having a specific composition, a dental filling restorative material, or a dental hard resin, which will be described later, on adhesiveness.

  Not only in such a dental field, but generally, an adhesion technique that makes it easy to reduce the film thickness of an adhesive layer using a primer that does not contain a polymerization initiator is an aesthetic property of the material obtained after the adhesion operation. And from the viewpoint of dimensional stability.

JP 2013-144778 A Special table 2010-521257

DENTAL MATERIALS 28 (2012) 1280-1283

  As described above, in the case of a bonding material that is bonded to a polyaryletherketone resin material and then pressure-bonded after being applied to the adherend after polymerization and curing, high adhesive strength can be obtained, but the adhesive layer can be made thin. Difficult, for example, during dental treatment, it is difficult to obtain high suitability of the dental prosthesis, or the adhesive layer is visible in the produced dental prosthesis, and the aesthetics may deteriorate. There was a problem in terms of sex and aesthetics. On the other hand, in the case of a primer that is pressure-bonded without being polymerized and cured after being applied to an adherend, there is a problem that high adhesive strength cannot be obtained although it is not difficult to make the adhesive layer thin. Although a technique for obtaining high adhesive strength with a primer that makes it easy to thin the adhesive layer has been proposed, a high boiling point solvent that is not easy to remove from the system must be used. Adhesion with a primer with less concern about biosafety is required. Then, this invention makes it a subject to obtain high adhesive strength with respect to a polyaryl ether ketone resin material using the primer which can make the thickness of an adhesive bond layer thin easily.

  In the present application, the adhesive layer means a layer formed by the composition first applied to the polyaryletherketone resin material, and the primer or polyaryletherketone resin material adhesive kit of the present invention. In the case of, it means a thin film layer obtained by curing the primer.

  In order to solve the above-mentioned problems, the inventors have conducted intensive studies. As a result, an adhesive layer is formed by using a primer containing a partial component of a chemical polymerization initiator for a polyaryletherketone resin material. The inventors have found that high adhesiveness can be obtained while thinning, and have reached the present invention.

  That is, the present invention is (A) a primer characterized in that it contains a partial component of (a1) a chemical polymerization initiator for a polyaryl ether ketone resin material. (A) The primer preferably further contains (a2) a polymerizable monomer. In addition, the partial component of the (a1) chemical polymerization initiator is preferably a fourth-period transition metal compound, and more preferably a + IV valent vanadium compound. In addition, the polymerizable functional group of the (a2) polymerizable monomer is preferably a (meth) acryloyl group. The primer is preferably for dental use.

  According to another invention, (a1) a primer containing (a1) a partial component of a chemical polymerization initiator, (b1) a polymerizable monomer, and (b2) a part of the chemical polymerization initiator. (B3) a polymerization initiator, and (b2) a part of the chemical polymerization initiator may form a chemical polymerization initiator system with the (a1) part of the chemical polymerization initiator (B) curing It is the adhesion kit for polyaryl ether ketone resin materials which consist of an adhesive composition. In this kit, the (A) primer preferably further contains (a2) a polymerizable monomer. In addition, the kit includes (A) a component contained in the primer (a1) chemical polymerization initiator is a transition metal compound in the fourth period, and (B) contained in the curable composition (b2) chemical polymerization initiation It is preferable that a part of the agent is an organic peroxide. (A) It is more preferable that the transition metal compound in the fourth period contained in the primer is a + IV valent vanadium compound.

  According to another invention, (a1) contains a partial component of a chemical polymerization initiator, (A) a primer coating step for imparting a primer to the surface of the polyaryletherketone resin material, and (b1) polymerizability. A monomer, (b2) a partial component of a chemical polymerization initiator, (b3) a polymerization initiator, and (b2) a partial component of the chemical polymerization initiator is a partial component of the (a1) chemical polymerization initiator And (B) a curable composition capable of forming a chemical polymerization initiator system, including a curable composition application step for applying the curable composition from above the primer, and a curable composition curing step for polymerizing and curing the curable composition. This is an adhesion method between a polyaryl ether ketone resin material and a curable composition.

  ADVANTAGE OF THE INVENTION According to this invention, in the adhesion | attachment with respect to a polyaryl ether ketone resin material, high adhesiveness can be obtained, making an adhesive bond layer thin. For this reason, for example, in dental applications, when a dental prosthesis made of a dental polyaryletherketone resin material is attached to an abutment tooth, a high adhesive strength can be obtained and a highly compatible treatment can be performed. When preparing a dental prosthesis using a polyaryletherketone resin material and a dental curable composition, the adhesive layer can be thinned, so that a dental prosthesis with higher aesthetics can be produced. .

  In addition, it is not necessary to use a high boiling point solvent that is not easy to remove from the system, and there is little concern about biosafety.

  The primer of this invention is for adhere | attaching a polyaryl ether ketone resin material and a curable composition, Comprising: (a1) Some chemical polymerization initiator components are contained.

  The primer (A) of the present invention is applied to the polyaryletherketone resin material in the bonding operation to the polyaryletherketone resin material, and is not polymerized and cured before contacting with the curable composition. It is used for By making contact and pressure bonding of the curable composition without polymerizing and curing the primer, the primer layer can be easily thinned.

  The reason why high adhesion can be obtained by the primer of the present invention and the adhesion kit for polyaryletherketone resin material using the primer and the curable composition is not clearly understood, but the primer is polymerizable as follows. Although it is slightly different depending on whether the monomer is included or not, it is assumed that it is essentially the same.

  When the primer does not contain a polymerizable monomer, first, the primer is applied to the polyaryl ether ketone resin material, so that a part of the chemical polymerization initiator is present on the surface of the polyaryl ether ketone resin material. Next, when the curable composition is pressure-bonded, the curable composition enters fine irregularities on the surface of the polyaryletherketone resin material. Here, a part of the chemical polymerization initiator contained in the primer is present on the surface of the polyaryletherketone resin material, and this penetrates into the curable composition and starts chemical polymerization in the curable composition. By forming a chemical polymerization initiator system with a part of the agent, the polymerization activity in the vicinity of the interface of the curable composition in contact with the polyaryletherketone resin material is improved. It is assumed that the polymerization rate of the curable composition on the surface of the polyaryletherketone resin material is improved and the strength is increased, so that the interaction between the polyaryletherketone resin material and the curable composition becomes stronger and the adhesiveness is improved. Is done.

  When the primer contains a polymerizable monomer, when the primer is first applied to the polyaryletherketone resin material, the primer penetrates into the fine irregularities on the surface of the polyaryletherketone resin material, Form. Next, when the curable composition is pressure-bonded from after the primer is applied, the primer layer is uncured and is pressed and thinned, and a part of the chemical polymerization initiator contained in the curable composition Penetrates into the primer layer, forms a chemical polymerization initiator system with a part of the chemical polymerization initiator present in the primer layer, and initiates polymerization from the primer. When the primer does not contain some components of the chemical polymerization initiator, the polymerization of the primer layer depends only on the radical species generated in the curable composition, whereas the primer is chemically treated as in the present invention. In the case of containing a partial component of the polymerization initiator, radicals are generated in the primer in addition to the radical species generated in the curable composition, so in the present invention, the primer layer has high polymerizability, The strength of the primer layer is improved. As a result, since the strength of the primer layer on the surface of the polyaryl ether ketone resin material is also improved, the interaction between the polyaryl ether ketone resin material and the primer layer becomes stronger, and high adhesiveness can be obtained. Inferred.

  Details of materials and the like constituting the present embodiment will be described below.

(A) Primer (a1) Partial component of chemical polymerization initiator The (A) primer of this invention contains the partial component of (a1) chemical polymerization initiator. A chemical polymerization initiator is a polymerization initiator which consists of two or more components, and forms a chemical polymerization initiator system when all the components are mixed to generate a polymerization active species near room temperature. In the present invention, (a1) a partial component of the chemical polymerization initiator is blended with the (A) primer, and (a1) the partial component of the chemical polymerization initiator and the chemical polymerization initiator system are configured as a curable composition. By using a curable composition containing a chemical polymerization initiator component, (A) the curable composition can be contacted / compressed without polymerizing and curing the primer, and the curable composition was contacted / compressed. Later, (A) a component of (a1) the chemical polymerization initiator compounded in the primer and the remaining components of the chemical polymerization initiator constituting the chemical polymerization initiator system react with this in the curable composition. Since the chemical polymerization initiator system is formed, the primer layer can be made thin and high adhesive strength can be obtained.

  As the chemical polymerization initiator system, a known one which is composed of two or more components and generates a polymerization active species near room temperature when all the components are mixed can be used without particular limitation. Examples of the chemical polymerization initiator system include a radical polymerizable chemical polymerization initiator system, a cationic polymerizable chemical polymerization initiator system, an anionic polymerizable chemical polymerization initiator system, and the like. The system is preferably a radically polymerizable chemical polymerization initiator system. As such a radical polymerizable chemical polymerization initiator system, a system using a redox reaction composed of an oxidizing agent and a reducing agent is typical.

  In the case of a chemical polymerization initiator system using a redox reaction, any of an oxidizing agent and a reducing agent can be used as a component of (a1) the chemical polymerization initiator to be blended with (A) the primer. When using a primer containing an oxidizing agent, a curable composition containing a reducing agent is used, or when using a primer containing a reducing agent, a curable composition containing an oxidizing agent is used together. You can get an effect.

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

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

  As an oxidizing agent mix | blended with the (A) primer of this invention, an organic peroxide is preferable.

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

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

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

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

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

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

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

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

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

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

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

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

  Specific examples of the amine compound include aromatic amine compounds such as N, N-dimethyl-p-toluidine, N, N-dimethylaniline, and N, N-diethanol-p-toluidine.

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

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

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

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

  Two or more kinds of these oxidizing agents or reducing agents can be used in combination.

  When some components of these chemical polymerization initiators are blended with the (A) primer, it is preferable to blend a reducing agent with the (A) primer. (A) Higher adhesiveness can be obtained by blending a reducing agent with the primer. Although the cause of this is not known in detail, when (A) the primer is applied to the surface of the polyaryletherketone resin material by blending the reducing agent with the primer, (A) the reducing agent in the primer Acts on the resin on the surface of the polyaryl ether ketone resin material, and a part of the carbonyl group is reduced, so that the carbon atom having two arylene groups, a hydroxyl group and a hydrogen atom as a substituent is a polyaryl ether ketone resin material Generated on the surface. Since a radical is easily generated on such a carbon atom having two arylene groups, a hydroxyl group and a hydrogen atom as substituents by hydrogen abstraction, (A) when the primer or the curable composition is polymerized and cured, A bond is formed between the carbon atom adjacent to the hydroxyl group formed on the surface of the polyaryl ether ketone resin material and the radically polymerizable monomer laminated. As a result, it is estimated that the adhesiveness is improved.

  In addition, (A) the reducing agent blended in the primer has high activity as a chemical polymerization initiator and maintains as high fluidity as possible until immediately before the primer layer comes into contact with the curable composition, and storage stability. From the balance of the above, it is preferable to add a transition metal compound of the fourth period, and it is more preferable to use a + IV valent vanadium compound.

  In addition, when using the transition metal compound of the 4th period for the primer, if the amine compound is added to the primer, the effect of improving the adhesive strength is slightly reduced compared to the case where no amine compound is added. It is preferable not to blend. This is presumably because the amine compound is coordinated to the transition metal in the transition metal compound in the fourth period and the activity of the transition metal compound in the fourth period is reduced.

  The primer may be only a partial component of the (a1) chemical polymerization initiator, but a solvent or a polymerizable monomer is preferably blended. By adding a solvent and a polymerizable monomer, the polymerizable monomer necessary for obtaining adhesiveness on the surface of the polyaryletherketone resin material and the polymerizability of the polymerizable monomer are improved. For this reason, it becomes easier to uniformly distribute a part of the component (a1) chemical polymerization initiator, and high adhesiveness is easily obtained. When a component other than the partial component of (a1) chemical polymerization initiator is blended with the primer, the amount of addition of the partial component of (a1) chemical polymerization initiator is not particularly limited, but in the case of an oxidizing agent or a reducing agent, the primer It is preferable that it is the range of 0.001 mass part-10 mass parts with respect to 100 mass parts, It is more preferable that it is the range of 0.004 mass part-1 mass part, 0.008 mass part-0.1 Most preferred is the range of parts by mass. When there are few chemical polymerization initiator components, it is included in the primer (when the polymerizable monomer is included in the primer) and the curable composition applied to the surface of the polyaryletherketone resin material necessary to improve adhesion The effect of improving the polymerizability of the polymerizable monomer is not sufficiently obtained. On the other hand, when a part of the component (a1) chemical polymerization initiator is contained, the storage stability of the primer tends to deteriorate. In addition, a part of the component (a1) chemical polymerization initiator is present at a higher concentration than necessary on the surface of the polyaryl ether ketone resin material. In the present invention, it is estimated that the improvement of the polymerizability of the polymerizable monomer on the surface of the polyaryl ether ketone resin material is most effective in improving the adhesive strength. (A1) Start of chemical polymerization When a component of the agent is present in a concentration higher than necessary, the component of the chemical polymerization initiator contained in the curable composition that penetrates the primer from the curable composition reaches the surface of the polyaryl ether ketone resin material. It reacts with a part of the (a1) chemical polymerization initiator compounded in the primer before the polymerization, and the effect of improving the polymerizability of the polymerizable monomer on the surface of the polyaryl ether ketone resin material becomes limited. There is a case.

(A2) Polymerizable monomer (A) It is preferable that the (a2) polymerizable monomer is further blended with the primer. By adding a polymerizable monomer to the primer, this improves the polymerizable monomer necessary for obtaining adhesion on the surface of the polyaryletherketone resin material and the polymerizability of the polymerizable monomer. (A1) It is easier to evenly distribute some components of the chemical polymerization initiator, and high adhesiveness is easily obtained.

  The polymerizable monomer is a compound having a polymerizable functional group in the molecule, and any known monomer can be used without any limitation. Examples of the polymerizable functional group include a radical polymerizable functional group, a cationic polymerizable functional group, and an anion polymerizable functional group. From the viewpoint of low biotoxicity and high polymerization activity, the radical polymerizable functional group is Preferred are functional groups such as a vinyl group, a styryl group, an allyl group, a (meth) acryloyl group and the like, and a (meth) acryloyl group is particularly preferred from the viewpoint of polymerization rate and biosafety. Examples of preferable radical polymerizable monomers include, for example, radical polymerizable monomers having a (meth) acryloyl group represented by the following (I) to (IV).

(I) Monofunctional radically polymerizable monomers such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, 2-methacryloyloxyethyl dihydrogen phosphate, and the like, and Acrylates corresponding to these methacrylates.

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

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

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

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

  (A) The polymerizable monomer (a2) blended in the primer contains 50% by mass or more of a polymerizable monomer having two or more polymerizable functional groups in the molecule based on the total polymerizable monomer. It is preferable that it contains 70% by mass or more. By having two or more polymerizable functional groups in the molecule, the polymer can form a network structure, the strength of the primer layer cured on the surface of the polyaryletherketone resin material is higher, and higher adhesion Will be obtained.

  Moreover, it is more preferable that the (a2) polymerizable monomer blended in the (A) primer has a hydrogen bonding functional group. By using a polymerizable monomer having a hydrogen bonding functional group, the hydrogen bond between the hydrogen bonding functional groups increases the strength of the primer layer cured on the surface of the polyaryl ether ketone resin material. High adhesiveness can be obtained. The polymerizable monomer having a hydrogen bonding functional group is preferably contained in an amount of 30% by mass or more, more preferably 50% by mass or more, based on the total polymerizable monomers. The hydrogen bond referred to here is an electrically negative hydrogen atom (donor) that is bonded to an atom (O, N, S, etc.) having a high electronegativity and is electrically positively polarized and has a lone electron pair. This indicates a bonding interaction formed with a simple atom (acceptor). The hydrogen-bonding functional group in the present invention is a substituent that can function as a donor and acceptor in the hydrogen bond, and specifically includes a hydroxyl group, a thiol group, an amino group, a urethane group, an amide group, and the like.

  A part or all of the polymerizable monomers having two or more polymerizable functional groups and hydrogen bonding functional groups in the molecule have two or more polymerizable functional groups and hydrogen bonding functional groups in the molecule; and It is more preferable to have an aromatic ring. By having an aromatic ring in the molecule, the aromatic ring of the polymerizable monomer of the primer and the aromatic ring of the polyaryl ether ketone resin form a stack, and the interaction between the polyaryl ether ketone resin material and the adhesive layer is more It will be expensive. Since higher adhesiveness can be obtained by these actions, it is preferable to use a polymerizable monomer having an aromatic ring. The polymerizable monomer having two or more polymerizable functional groups, a hydrogen bonding functional group and an aromatic ring in the molecule is preferably used in an amount of 15% by mass or more, more preferably 25% by mass or more of the polymerizable monomer. Further preferred. On the other hand, the polymerizable monomer having two or more polymerizable functional groups, a hydrogen bonding functional group and an aromatic ring in the molecule is preferably 70% by mass or less, and 50% by mass or less of the polymerizable monomer. More preferably. By making the polymerizable monomer having two or more polymerizable functional groups, hydrogen bondable functional groups and aromatic rings in the molecule 20% by weight or more, the interaction between the polyaryletherketone resin material and the adhesive layer can be increased. It becomes possible to make it strong. On the other hand, when more than 70% by mass of a polymerizable monomer having two or more polymerizable functional groups, hydrogen bonding functional groups, and aromatic rings in the molecule, polyaryls are present due to excessive aromatic rings. The balance of the interaction between the aromatic ring of the ether ketone resin and the aromatic ring of the polymerizable monomer is lost.

  Moreover, it is a case where a radical polymerizable monomer is used as the polymerizable monomer, and (a1) a part of the chemical polymerization initiator contained in the primer is a radical polymerizable chemical polymerization initiator-based reducing agent. In the case of a transition metal compound having a fourth period, it is also preferable that the radical polymerizable monomer contains an acidic group-containing radical polymerizable monomer. In this case, the total amount of the radical polymerizable monomer may be an acidic group-containing radical polymerizable monomer, and a part thereof may be an acidic group-containing radical polymerizable monomer. By using an acidic group-containing radical polymerizable monomer, the inside of the primer becomes acidic, and the reaction between the transition metal compound and the organic peroxide in the fourth period is activated.

  Examples of the acidic group-containing radical polymerizable monomer include 2-methacryloyloxyethyl dihydrogen phosphate, 6-methacryloyloxyhexyl dihydrogen phosphate, 10-methacryloyloxydecyl dihydrogen phosphate, bis (2 -Methacryloyloxyethyl) hydrogen phosphate, bis (6-methacryloyloxyhexyl) hydrogen phosphate, (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloyl aspartic acid, N- (meta ) Acryloyl-5-aminosalicylic acid, 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 10- (meth) acryloyloxydecane-1,1-dicarboxylic acid, 12- (meth) acrylic Ileoxide decane-1,1-dicarboxylic acid, 4- (meth) acryloyloxybutyl trimellitate, 4- (meth) acryloyloxyhexyl trimellitate, 4- (meth) acryloyloxydecyl trimellitate, 2- ( And (meth) acrylamido-2-methylpropanesulfonic acid.

  The viscosity of the (a2) polymerizable monomer blended in the primer is preferably low. This is because the viscosity of the polymerizable monomer compounded in the primer is low, and it is easy for some components of the chemical polymerization initiator (b2) contained in the curable composition to diffuse after penetrating into the primer. Thus, the curability of the primer is improved and high adhesiveness is easily obtained. Therefore, the viscosity of the polymerizable monomer (a2) blended in the primer is preferably 1500 cP or less, more preferably 500 cP or less, and further preferably 100 cP or less at 23 ° C. Viscosity may be measured using a cone plate viscometer in a temperature-controlled room maintained at 23 ° C. after mixing all the components of the polymerizable monomer blended in the primer until uniform.

  The addition amount of these (a2) polymerizable monomers is preferably in the range of 1000% by mass to 5000000% by mass with respect to a partial component of the (a1) chemical polymerization initiator, and preferably 2000% by mass to 300000% by mass. The range is more preferable, and the range of 5000% to 150,000% by mass is most preferable. As described above, when the amount of the polymerizable monomer (a2) is excessive with respect to a part of the component (a1) chemical polymerization initiator, it is difficult to obtain the effect of improving the polymerization property, and the effect of improving the adhesiveness is limited. It will be something like that. On the other hand, when the amount of the polymerizable monomer (a2) is too small relative to a part of the component (a1) chemical polymerization initiator, the storage stability may be lowered, for example, the polymerization proceeds during storage.

  By blending the solvent into the primer as described above, it becomes easy to evenly dispose a part of the (a1) chemical polymerization initiator compound blended in the primer on the surface of the polyaryletherketone resin material. Since it becomes easy to improve property, it is also preferable to contain a solvent.

  The solvent may be removed from the surface of the polyaryletherketone resin material by an operation such as air blow after a part of the component (a1) chemical polymerization initiator is uniformly disposed on the surface of the polyaryletherketone resin material. Since it is preferable, it is preferable that it is a volatile solvent. Here, the volatile solvent means that the boiling point at 760 mmHg is 100 ° C. or lower and the vapor pressure at 20 ° C. is 1.0 KPa or higher. However, since it is preferable that the volatile solvent is sufficiently volatilized and remains in the adhesive layer without adverse effects, the vapor pressure at 20 ° C. is more preferably 2.0 KPa or more, and 5.0 KPa or more. More preferred. On the other hand, when the volatilization of the volatile solvent is too fast, it is difficult to obtain an effect of uniformly arranging a part of the component (a1) chemical polymerization initiator on the surface of the polyaryl ether ketone resin material. Therefore, the vapor pressure at 20 ° C. of the volatile solvent is preferably 60 KPa or less, and more preferably 50 KPa or less. Further, since the lower boiling point is easier to remove from the surface of the polyaryletherketone resin material, the boiling point at 760 mmHg of the volatile solvent is more preferably 80 ° C. or lower.

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

  Further, 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. In that case, if a large amount of a low-volatility solvent is contained, the polyaryl ether There is a possibility that the adhesion may be lowered by inhibiting the interaction between the ketone resin composite material and the polymerizable monomer of the primer or by inhibiting the polymerization and hardening of the polymerizable monomer of the primer. In addition, the use of a high-boiling solvent that is not easy to remove from the system may increase anxiety about biosafety. Therefore, the low volatility solvent contained in the primer is preferably 40% by mass or less, more preferably 20% by mass or less, and more preferably 10% by mass or less with respect to the addition amount of the volatile solvent. More preferably, it is most preferably 1% by mass or less.

  When the primer contains a polymerizable monomer, an increase in the amount of the solvent added to the polymerizable monomer is advantageous for forming a thin adhesive layer. The effect of improving adhesiveness due to inclusion is reduced. Therefore, the addition amount of the solvent is preferably in the range of 10 parts by weight to 3000 parts by weight, more preferably in the range of 100 parts by weight to 2000 parts by weight, with respect to 100 parts by weight of the polymerizable monomer. The range of 300 to 1500 parts by mass is more preferable, and the range of 500 to 1000 parts by mass is most preferable.

  When the primer does not contain a polymerizable monomer, the solvent is preferably in the range of 90 parts by mass to 99.999 parts by mass with respect to 100 parts by mass of the primer, and in the range of 99 parts by mass to 99.996 parts by mass. More preferably, the range is 99.9 parts by mass to 99.992 parts by mass.

  The primer of the present invention may contain a filler as necessary. As the filler, known inorganic fillers, organic fillers, organic-inorganic composite fillers and the like can be used without particular limitation. By containing the filler, the strength of the primer entering the fine irregularities present on the surface of the polyaryletherketone resin material is increased, and higher adhesiveness is easily obtained.

  Examples of the inorganic filler include quartz, silica, silica-alumina, silica-titania, silica-zirconia, lanthanum glass, barium glass, strontium glass, fluoroaluminosilicate glass, and the like. In addition, when using these inorganic fillers, those subjected to silane coupling treatment are preferable. As the silane coupling agent, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyl Triacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyl Dimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylate Silane, N- phenyl--γ- aminopropyltrimethoxysilane, 11-methacryloyloxy undecyl trimethoxysilane, 11-methacryloyloxy such acryloyloxy undecyl methyl dimethoxy silane.

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

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

  On the other hand, if the primer contains a large amount of filler, the viscosity of the primer tends to increase and the adhesiveness tends to decrease, and the adhesive layer tends to become thicker. Therefore, the amount of the filler added to the primer is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less with respect to 100 parts by mass of the primer.

  The particle size and shape of the filler are not particularly limited, but are preferably small from the viewpoint of forming a uniform adhesive layer. The particle size of the filler is preferably an average volume particle size of 100 μm or less, more preferably 0.01 to 10 μm, and still more preferably 0.01 μm to 1 μm.

  In addition, the primer may contain other components such as a polymerization inhibitor, a polymerization inhibitor, a dye, a pigment, and a fragrance as long as the effects of the present invention are not significantly impaired.

  The primer may or may not contain a polymerization initiator other than a chemical polymerization initiator, such as a thermal polymerization initiator and a photopolymerization initiator, in addition to (a1) a partial component of the chemical polymerization initiator. More preferred. When the polymerization initiator is included, care must be taken so that the primer is not unintentionally polymerized and fluidity is not lost after the primer is applied and before the curable composition is pressure-bonded. Even when the fluidity is maintained, it is somewhat difficult to make the adhesive layer thin if the primer is partially polymerized and cured due to unintended polymerization. Therefore, when the polymerization initiator is blended in the primer, it becomes necessary to pay attention to the above points due to unintended polymerization by the polymerization initiator, so that the operation during use becomes complicated. In some cases.

  The viscosity of the primer is preferably low. Due to the low viscosity of the primer, the primer easily penetrates into fine irregularities on the surface of the polyaryletherketone resin material, and (a1) the chemical polymerization initiator is uniformly distributed on the polyaryletherketone resin material surface. It becomes easy to apply some components, and higher adhesiveness is easily obtained. On the other hand, when the viscosity of the primer is too low, it is difficult to uniformly apply the primer to the adherend surface of the polyaryletherketone resin material, which may have a complicated structure due to causes such as dripping of the primer It may become. Therefore, the viscosity of the primer is preferably in the range of 0.3 cP to 3000 cP at 23 ° C., more preferably in the range of 0.4 cP to 500 cP, and in the range of 0.5 cP to 30 cP. More preferably, the range of 0.5 cP to 10 cP is most preferable. The viscosity may be measured using a cone plate viscometer in a thermostatic chamber maintained at 23 ° C.

  As described above, the primer (A) in the present invention is applied to the polyaryletherketone resin material in the bonding operation to the polyaryletherketone resin material, and before contacting with the curable composition. It is used without being polymerized and cured. By pressing the curable composition without polymerizing and curing the primer, the primer layer can be easily thinned.

  It should be noted that the primer is not polymerized and cured (i) when no polymerizable monomer is blended in the primer, (ii) the primer contains a part of the component (a1) chemical polymerization initiator and starts chemical polymerization When the agent system is not formed, or (iii) the primer contains a polymerizable monomer and (a1) all components that form the chemical polymerization initiator system as a part of the chemical polymerization initiator, but is curable It means any case where the primer can be easily deformed when the composition is pressure-bonded to the primer. The primer can be easily deformed when the curable composition of (iii) is pressure-bonded to the primer, and in order to use this composition as a primer, after the treatment according to the method of using the primer is performed For example, when the primer is divided into a plurality of packages, the viscosity after standing for 10 minutes at 23 ° C. and atmospheric pressure after performing a predetermined operation such as mixing or volatilizing a volatile solvent by air blow It is also preferably 100000 cP or less at 23 ° C., more preferably 50000 cP or less, further preferably 10,000 cP or less, and most preferably 5000 cP or less. The viscosity may be measured using a cone plate viscometer after performing a predetermined treatment such as mixing or air blowing in a thermostatic chamber maintained at 23 ° C.

  In addition, (i) When a polymerizable monomer is not blended in the primer, (ii) When the primer contains a partial component of (a1) chemical polymerization initiator and does not form a chemical polymerization initiator system Or (iii) a primer containing a polymerizable monomer and (a1) all components that form a chemical polymerization initiator system as a partial component of the chemical polymerization initiator, but the curable composition is pressure-bonded to the primer In the case where the primer can be easily deformed, (iii) a polymerizable monomer and (a1) all components that form a chemical polymerization initiator system as a partial component of the chemical polymerization initiator. When the primer is easily deformable when it is pressure-bonded to the primer, but there is a concern about storage stability, or when mixing and using two or more components Special attention should be paid to (I) When a polymerizable monomer is not blended in the primer, or (ii) (a1) a part of the chemical polymerization initiator in the primer. Preferred is the case of containing the components and not forming a chemical polymerization initiator system. In addition, since it is preferable from the viewpoint of adhesiveness to mix a polymerizable monomer with a primer as described above, (ii) a primer that can contain a polymerizable monomer (a1) a chemical polymerization initiator More preferably, it contains some components and does not form a chemical polymerization initiator system. That is, the primer does not contain all the components of the chemical polymerization initiator system as a partial component of the (a1) chemical polymerization initiator, but lacks a part of the components that form the chemical polymerization initiator system. Most preferably, no agent system is formed.

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

  Adhesion to the polyaryletherketone resin material by the primer of the present invention is mainly caused by the penetration of the polymerizable monomer of the primer or the curable composition into the fine irregularities on the surface of the polyaryletherketone resin material. It is estimated that high adhesiveness can be obtained. By blending this primer with a part of the chemical polymerization initiator (a1), the polymerizability of the polymerizable monomer that has penetrated into the fine irregularities on the surface of the polyaryletherketone resin material is improved, and the part is cured. By increasing the strength of the product, it is presumed that the interaction between the polyaryl ether ketone resin material and the curable composition becomes stronger and the adhesiveness is improved.

  The primer (A) of the present invention contains (b1) a polymerizable monomer, (b2) a component of a chemical polymerization initiator, (b3) a polymerization initiator, and (b2) a part of the chemical polymerization initiator. The component may be used for bonding in combination with the (a1) partial component of the chemical polymerization initiator and (B) a curable composition capable of forming a chemical polymerization initiator system, or an adhesion kit for polyaryl ether ketone resin materials It can be done.

  The polyaryletherketone resin material adhesion kit of the present invention is for bonding a polyaryletherketone resin material and a curable composition.

  Hereinafter, (B) the curable composition in the adhesive kit for polyaryletherketone resin material of the present invention used with (A) primer will be described.

(B) Curable composition The (B) curable composition in the adhesion kit for polyaryletherketone resin material and the adhesion method of the present invention is the same as the curable composition used with the primer of the present invention described above. .

  The curable composition is low in viscosity at first and can be easily deformed, so it can be deformed into a desired shape and placed in a desired location, and then its function can be demonstrated by polymerization and curing. It is.

  The curable composition in the present invention is one in which a primer is applied to a polyaryletherketone resin material in a bonding operation to the polyaryletherketone resin material, and then the primer is pressure-bonded from above without being polymerized and cured. . By applying pressure to the present curable composition without polymerizing and curing the primer, the primer layer that has been previously applied and not yet polymerized and cured is thinned, and then blended into the present curable composition. (B2) A part of the chemical polymerization initiator penetrates into the primer to improve the polymerizability of the primer layer and increase its strength, so that the interaction between the polyaryletherketone resin material and the curable composition is further improved. It is presumed that it becomes stronger and the adhesiveness is improved.

  In this curable composition, (b1) a polymerizable monomer and (b2) a partial component of a chemical polymerization initiator and (b3) a polymerization initiator are blended. Details of materials and the like constituting the present embodiment will be described below.

(B1) Polymerizable monomer The polymerizable monomer is a compound having a polymerizable functional group in the molecule, and any known polymerizable monomer used in a conventional curable composition can be used without any limitation. it can. The polymerizable functional group is preferably a radical polymerizable functional group from the viewpoint of low biotoxicity and high polymerization activity, and examples thereof include vinyl groups, styryl groups, allyl groups, and the like. In view of safety, a (meth) acryloyl group is particularly preferable. Examples of preferred polymerizable monomers include those listed as polymerizable monomers that can be suitably blended in the primer.

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

  When a polymerizable monomer is blended in the primer, the polymerizable monomer of the curable composition is preferably compatible with the polymerizable monomer of the primer. By being compatible, (b2) part of the chemical polymerization initiator compounded in the curable composition can easily penetrate into the primer, improving the curability of the polymerizable monomer of the primer, It becomes easy to obtain higher adhesiveness. The compatibility of the polymerizable monomer of the curable composition with the polymerizable monomer of the primer means that all components of the polymerizable monomer blended in the curable composition and the primer are blended. It is possible to judge by confirming that all components of the polymerizable monomer are sufficiently stirred and mixed at a ratio of 1: 1, and then left to stand for 10 minutes to confirm that they are uniform.

  In addition, when the (a1) chemical polymerization initiator included in the primer is partly a transition metal compound in the fourth period and the primer does not contain an acidic compound such as an acidic group-containing polymerizable monomer, the curability is increased. It is preferable to mix an acidic group-containing polymerizable monomer as the polymerizable monomer of the composition. As described above, the reaction between the transition metal compound and the organic peroxide in the fourth period is activated by acidifying the primer, but this effect is an acidic group-containing polymerization as a polymerizable monomer of the curable composition. It can also be obtained when a functional monomer is added. In this case, the acidic group-containing polymerizable monomer is preferably used in an amount of 10 parts by mass or more, more preferably 20 parts by mass or more based on 100 parts by mass of the total polymerizable monomer of the curable composition. . However, if a large amount of the acidic group-containing polymerizable monomer is blended, the aesthetic properties of the curable composition can be lowered. Therefore, the acidic group-containing polymerizable monomer is a total polymerizable monomer of the curable composition. The amount is preferably 50 parts by mass or less, more preferably 30 parts by mass or less with respect to 100 parts by mass.

(B2) Partial Component of Chemical Polymerization Initiator As described above, the chemical polymerization initiator is a polymerization initiator that is composed of two or more components and generates polymerization active species near room temperature when all the components are mixed. The partial component of the chemical polymerization initiator contained in the curable composition is capable of forming a chemical polymerization initiator system with the partial component of (a1) the chemical polymerization initiator contained in the (A) primer ( B) Part of the chemical polymerization initiator (b2) of the curable composition and part of the (a1) chemical polymerization initiator of the (A) primer can be combined to act as a chemical polymerization initiator. is there. (B) A component of (b2) chemical polymerization initiator contained in the curable composition penetrates the primer layer after pressure-bonding the curable composition to form a chemical polymerization initiator system inside the primer layer. Thus, radical species are generated to improve the polymerizability of the primer layer, and high adhesiveness can be obtained.

  The specific explanation of the chemical polymerization initiator is as described above, and the chemical polymerization initiator system is composed of two or more components, and a known one that generates a polymerization active species near room temperature when all the components are mixed. Can be used without any particular restrictions.

  When the chemical polymerization initiator using the redox reaction is blended separately into the (A) primer and the (B) curable composition, it is higher by blending the reducing agent into the (A) primer as described above. Since adhesiveness is obtained, it is preferable that (A) a reducing agent is blended with the primer and (B) an oxidizing agent is blended with the curable composition.

  It is preferable that the addition amount of the partial component of this (b2) chemical polymerization initiator is the range of 0.001 mass part-10 mass parts with respect to 100 mass parts of curable compositions, 0.05 mass part- The range of 5 parts by mass is more preferable, and the range of 0.01 parts by mass to 1 part by mass is most preferable. (B2) When there are few partial components of the chemical polymerization initiator, the effect of improving the polymerizability of the polymerizable monomer on the surface of the polyaryletherketone resin material sufficient to improve the adhesion cannot be obtained, and is high Adhesion is difficult to obtain. On the other hand, when a part of the component (b2) chemical polymerization initiator is contained in a large amount, the storage stability of the curable composition tends to deteriorate.

(B3) Polymerization initiator The curable composition improves the polymerizability of the polymerizable monomer blended in the primer together with a part of the (a1) chemical polymerization initiator contained in the (A) primer. Or (b2) for improving the polymerizability of the polymerizable monomer of the curable composition in the vicinity of the adhesion surface of the polyaryletherketone resin material when no polymerizable monomer is blended in the primer. In addition to a partial component of the chemical polymerization initiator, (b3) a polymerization initiator for mainly polymerizing and curing the curable composition is contained. (B3) The polyaryletherketone resin material is polymerized and cured together with the primer when the primer contains a polymerizable monomer while the curable composition is polymerized by containing a polymerization initiator. And the curable composition can be bonded.

  As the polymerization initiator, a photopolymerization initiator, a chemical polymerization initiator, or a thermal polymerization initiator can be used, and two or more polymerization initiators can be used in combination. In addition, since the hardening of a curable composition can be performed simply, it is preferable to use a photoinitiator and / or a chemical polymerization initiator. Hereinafter, these three kinds of polymerization initiators will be described in more detail.

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

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

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

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

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

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

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

  As described above, the chemical polymerization initiator is a polymerization initiator that is composed of two or more components and generates polymerization active species near room temperature when all the components are mixed. Any known initiator can be used without any limitation. Specifically, it is exemplified as (a) a partial component of the chemical polymerization initiator blended with the primer (A) and (b2) a partial component of the chemical polymerization initiator blended with (B) the curable composition. To do.

  In addition, the component of the chemical polymerization initiator as the polymerization initiator (b3) for curing the curable composition, (A) the primer contains (a1) a partial component of the chemical polymerization initiator and the chemical polymerization initiator It can also be used as a component of the (b2) chemical polymerization initiator that forms the system.

  In other words, when (B3) a curable composition is blended with a chemical polymerization initiator (b3) as a polymerization initiator, a part of the chemical polymerization initiator (b2) is used as a component of the chemical polymerization initiator system. The chemical polymerization initiator contained may be (b3) a polymerization initiator, and the same substance may act as (b2) a partial component of the chemical polymerization initiator and (b3) a polymerization initiator.

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

  The blending amount of these polymerization initiators is preferably in the range of 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the polymerizable monomer. When the amount of the polymerization initiator is less than 0.01 parts by mass, the curing of the curable composition becomes insufficient particularly immediately after curing, and there is a great possibility that the properties of the curable composition such as strength will be adversely affected. Even when the polymerization initiator exceeds 10 parts by mass, there is a high possibility of adversely affecting the properties of the curable composition such as operation grace time and storage stability.

  In addition, when the component of the chemical polymerization initiator as the polymerization initiator (b3) for curing the curable composition is used as a partial component of the chemical polymerization initiator (b2), most of the component is cured. When it is consumed as a chemical polymerization initiator for polymerizing and curing the adhesive composition, some components of the chemical polymerization initiator for penetrating into the primer and contributing to the improvement of the curability of the primer layer are insufficient. In such a case, the blending amount of a part of the component (b2) chemical polymerization initiator is 1 to 8 parts by mass per 100 parts by mass of the polymerizable monomer, and other chemicals are used. The component of the polymerization initiator is preferably in the range of 0.01 to 5 parts by mass. Furthermore, the blending amount of the partial component of (b2) chemical polymerization initiator is preferably 100% by mass or more, more preferably 150% by mass or more with respect to the other components of the chemical polymerization initiator. .

  In the present invention, when a polymerizable monomer is blended in (A) the primer, polymerization of this polymerizable monomer is carried out by (A) a part of (a1) chemical polymerization initiator blended in the primer. In addition to the generation of radicals due to the reaction of a component of component (B) and (b2) a chemical polymerization initiator blended with the curable composition, (B) radical species generated when the curable composition is cured It can also be done by moving to the primer layer. For this reason, it is preferable that the curable composition has high polymerizability, and it is particularly preferable that the polymerizability in the initial stage of polymerization is high.

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

  For example, it is also preferable to blend a filler for the purpose of improving the strength of the curable composition. As the filler, known inorganic fillers, organic fillers, and organic-inorganic composite fillers are used without any limitation.

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

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

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

  The particle size of these fillers is not particularly limited. For example, when the curable composition is a dental curable composition used in a dental application, a filler having an average particle diameter of 0.01 μm to 100 μm, which is generally used as a dental material, depends on the purpose. Can be used as appropriate. However, when the particle size of the filler is large, the filler bites into the primer layer before curing, and a uniform primer layer cannot be formed, and the effect of blending the polymerizable monomer into the primer is sufficiently obtained. In some cases, the particle size of the filler blended in the curable composition is preferably 20 μm or less, and more preferably 10 μm or less.

  Moreover, when the particle size of a filler is as large as 10 micrometers or more, it is especially preferable that the shape of a filler is spherical. When the shape of the filler is irregular, the filler tends to bite into the primer layer before curing compared to the spherical case, and the effect of blending the polymerizable monomer into the primer is sufficient. It is likely to be a cause that cannot be obtained. Here, the spherical shape does not necessarily need to be a true sphere, and may be a substantially spherical shape. In general, a photograph of an inorganic filler is taken with a scanning electron microscope, 100 particles randomly observed in the unit field of view are selected at random, and the particle diameter in the direction perpendicular to the maximum particle diameter is set to the maximum diameter. The average degree of uniformity divided by may be 0.6 or more, more preferably 0.8 or more.

  Further, the refractive index of the filler is not particularly limited, and may be appropriately set according to the purpose. A plurality of fillers having different particle size ranges and different refractive indexes may be used in combination.

  The blending amount of these fillers is often determined appropriately in consideration of the viscosity when mixed with the polymerizable monomer and the mechanical properties of the cured product, depending on the purpose of use. In the method, particularly when the particle size of the filler is as large as 10 μm or more, if the filler is too much, the filler is likely to bite into the primer layer before curing, and the primer has a polymerizable single amount. Since the effect of blending the body is likely to be insufficient, the amount is preferably 600 parts by mass or less and more preferably 300 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

  The packaging form of the curable composition can be appropriately determined on the condition that the storage stability is not impaired. When all components of the chemical polymerization initiator are blended in the curable composition, each component is included in the same packaging. When they coexist, polymerization starts during storage. Therefore, at the time of storage, it is preferable to divide into at least two packages so that all these components do not coexist in one package. For example, when a chemical polymerization initiator is combined with an organic peroxide / amine compound combination, the paste containing the organic peroxide and the paste containing the amine compound may be packaged separately and mixed immediately before use. Is possible.

  The polyaryl ether ketone resin material that can be used in the present invention contains a polyaryl ether ketone resin in a blending amount that provides advantages such as high strength, and preferably 20% by mass of the polyaryl ketone resin. More preferably, the content is 30% by mass or more, and most preferably 50% by mass or more. Such a polyaryl ether ketone resin material includes, in addition to a material composed only of a polyaryl ether ketone resin, a material obtained by blending another resin with a polyaryl ether ketone resin, a polyaryl ether ketone resin, or a polyaryl ether ketone resin. A composite material obtained by blending with other fillers using a blend of other resins as a resin matrix. Moreover, you may add trace components, such as a pigment and a stabilizer, to these materials.

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

  Other resins that can be blended with the polyaryl ketone resin are not particularly limited as long as they do not significantly deteriorate the properties of the polyaryl ether ketone resin such as rigidity and toughness. For example, polyarylate, polycarbonate , Polyethylene terephthalate, polyphthalamide, polytetrafluoroethylene, and polyphenylene ether.

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

  The bonding method using the primer of the present invention is not particularly limited, but (A) a primer coating step for imparting a primer to the surface of the polyaryletherketone resin material, (b1) a polymerizable monomer, (b2) chemical polymerization initiation (B3) a part of the chemical polymerization initiator, and (b2) a part of the chemical polymerization initiator forms a chemical polymerization initiator system with the part of the (a1) chemical polymerization initiator. It is preferable to use (B) the curable composition provision process which provides the curable composition from the top of a primer, and the curable composition hardening process which polymerizes and hardens a curable composition at least. When the primer contains a volatile solvent, after applying the primer to the surface of the polyaryletherketone resin material, before applying the curable composition, the primer coating layer is naturally dried or air blown, etc. Volatile solvents can be removed. In addition, the polyaryl ether ketone resin material used as the adherend of the adhesive of the present invention may be hereinafter referred to as “first member”.

  In the primer application step, the adhesive composition may be applied to the surface of the first member in a mixed state with another composition. In the curable composition curing step, the curable composition is another composition. You may make it harden | cure in the state of the mixture mixed with.

  The form in particular which gives a primer to the surface of a 1st member is not restrict | limited, For example, what is necessary is just to apply | coat a primer using a brush etc.

  The primer of the present invention is more preferably used for a polyaryletherketone resin material having a roughened coating surface. Since the surface roughness of the polyaryletherketone resin material having a roughened adherence surface increases, applying the primer of the present invention to the adherend surface can provide higher adhesion. I can do it. The roughening treatment of the adherend surface may be performed before applying the primer of the present invention to the polyaryl ether ketone resin material. The roughening treatment method is not particularly limited, and a known roughening treatment method can be used. From the viewpoint of simplicity and safety, sandblasting is preferable. The sandblasting treatment can be generally performed by injecting alumina particles having a particle size of several μm to several hundreds of μm onto the adherend surface of the first member at a pressure of several tens of KPa to several MPa using a sandblasting device. .

  The first member may be any member as long as the portion in the vicinity of the adherend that comes into contact with the primer of the present invention at the time of bonding is made of a polyaryl ether ketone resin material.

  By using the primer of the present invention, it is possible to bond the first member and the curable composition, and the adhesive polyaryletherketone resin material of the present invention can be bonded to each other via the curable composition. It is also possible to bond the adhesive polyaryletherketone resin material of the present invention and the third member.

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

  Further, for example, when the curable composition has a property of firmly bonding to the surface of another member (third member), the polyaryletherketone resin material and the third member are firmly bonded. be able to. The third member can be used without particular limitation as long as it is a known solid member, but it is usually preferable to use a member in which the vicinity of the adherend surface is not a polyaryl ether ketone resin material.

  The primer of the present invention contains (b1) a polymerizable monomer, (b2) a partial component of a chemical polymerization initiator, (b3) a polymerization initiator, and (b2) one of the chemical polymerization initiators. The partial component can be combined with (B) a curable composition capable of forming a chemical polymerization initiator system with a part of the chemical polymerization initiator (a1) to form an adhesive kit for polyaryl ether ketone resin material. .

  Also, a kit comprising the (A) primer of the present invention and a polyaryletherketone resin material having a roughened coating surface, the (A) primer of the present invention, (B) a curable composition, and an adhesion A kit comprising a polyaryletherketone resin material having a roughened surface may be used.

  Further, when (A) the primer contains a radical polymerizable monomer and (B) the polymerizable monomer of the curable composition is a radical polymerizable monomer, the surface to be adhered is reacted with a reducing agent. It is also suitable for use with a polyaryl ether ketone resin material. By reducing the surface of the polyaryletherketone resin material with a reducing agent, the carbonyl group of the polyaryletherketone resin is reduced, and carbon atoms having two arylene groups, hydroxyl groups and hydrogen atoms as substituents on the adherend surface. Comes to exist. Since this carbon atom has a structure that easily generates radicals, when the primer (a curable composition if the primer does not contain a radical polymerizable monomer) is cured by radical polymerization, the carbon atom is contained in the primer or the curable composition. A bond is formed between the radical polymerizable monomer and the polyaryletherketone resin. This further improves the adhesion. In this case, the reducing agent is preferably a hydride reducing agent from the viewpoint of reaction efficiency, and sodium borohydride is most preferable from the viewpoint of easy handling.

  As a method of reacting the polyaryl ether ketone resin material and the reducing agent, for example, a mass of the polyaryl ether ketone resin is put into a solution in which the reducing agent is dissolved and heated, or a solution in which the reducing agent is dissolved is polyaryl. There is a method in which an ether ketone resin material is applied to a surface to be coated and then heated in an oven or the like. In this case, the reaction temperature (heating temperature) is preferably 60 ° C. to 180 ° C., more preferably 90 ° C. to 150 ° C. from the viewpoint of reaction efficiency and workability. As the solvent for dissolving the reducing agent, a solvent that can dissolve the reducing agent in an amount necessary for the reaction and that does not deactivate the reducing agent or inhibit the function of the reducing agent may be used. Sulphoxide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone and the like are preferable, and dimethyl sulfoxide is particularly preferable. If the concentration of the reducing agent in the reducing agent solution is too low, the reaction efficiency is lowered and it is difficult to obtain the effect of improving the adhesion. If the reducing agent is too high or the reducing agent is not completely dissolved, the polyaryl ether ketone resin material Since the reducing agent and the reaction residue of the reducing agent may be deposited on the surface of the metal, the reactivity may be reduced, so that the reducing agent is completely dissolved, and the range of 0.1 mol / l to 30 mol / l is preferable, The range of 0.5 mol / l to 5 mol / l is more preferable.

  The primer of the present invention can be used for any application, but is preferably used in a dental application.

  In the dental field, there is a great demand for highly aesthetic members, and the advantage of thinning the adhesive layer is particularly great. In addition, dental adhesive compositions that are usually used in dental applications are often designed with particular consideration for the affinity with the tooth substance. The properties required for an appropriate adhesive composition are not the same because the properties of the tooth and the polyaryletherketone resin material, including their surface properties, differ greatly. Therefore, when using a polyaryl ether ketone resin material especially for a dental use, the adhesive composition and adhesion | attachment method from which high adhesiveness is acquired are calculated | required.

  When the primer of the present invention is used for dental use, the polyaryl ether ketone resin material for which the polyaryl ether ketone resin material that can be used for the primer of the present invention is used for dental use is the polyaryl ether ketone resin of the present invention. Examples thereof include dentures, artificial teeth, denture bases, dental implants, crown restoration materials, and abutment building materials, which are partially or wholly made using materials.

  As a polyaryl ether ketone resin used as a dental material, particularly a dental restorative material, from the viewpoint of color tone and physical properties, ether groups and ketone groups constituting the main chain are repeated in the order of ether, ether, and ketone. It is preferable to use polyether ether ketone having units, or polyether ketone ketone having repeating units arranged in the order of ether, ketone, and ketone.

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

  In the present invention, when a polymerizable monomer is blended in (A) the primer, polymerization of this polymerizable monomer is carried out by (A) a part of (a1) chemical polymerization initiator blended in the primer. In addition to the generation of radicals by the chemical polymerization initiator system formed by the components and (b2) a part of the chemical polymerization initiator compounded in the (B) curable composition, (B) the curable composition is polymerized and cured. It can also be performed by the radical species generated during the transfer to the primer layer. Therefore, it is preferable that the polymerizability of the curable composition is higher because the polymerizability of the primer is further improved and high adhesiveness is easily obtained.

  In the case where the curable composition is cured with a chemical polymerization initiator, such as dental resin cement, it can be considered that the initial polymerizability is higher when the curing time described in JIST6611; 2009 is shorter. Therefore, from the viewpoint of adhesion, when the curable composition used in combination with the primer of the present invention is cured with a chemical polymerization initiator, the operation time measured by the method described in JIST6611; 2009 is 5 minutes or less. It is preferable that the time is 3 minutes 30 seconds or less.

  In the case where the curable composition is cured with a photopolymerization initiator, such as a dental hard resin, it can be considered that the initial polymerizability is higher when the ambient light stability described in JIST6517; 2011 is shorter. Therefore, from the viewpoint of adhesiveness, when the curable composition used in combination with the primer of the present invention is cured with a photopolymerization initiator, the environmental light stability measured according to the method described in JIST6517; 2011 is 120 seconds or less. It is preferable that it is 90 seconds or less. In addition, from the viewpoint of operability of the curable composition, it is preferable that the ambient light stability is 60 seconds or more, particularly when used in dental applications. Note that the environmental light stability measured according to the method described in JIST6517; 2011 is, specifically, about 30 mg of the curable composition in a dark room and placed on the upper surface of the slide glass, and the illuminance is 8000 ±. By irradiating the curable composition with light using a 1000 lx dental technician irradiation light source, and then immediately placing a second slide glass on the curable composition after the light irradiation and applying a shearing force. When the curable composition is pressed into a thin layer, when there is no obvious difference in the presence or absence of cracks or voids compared to the curable composition that was subjected to the same operation without light irradiation, It means the maximum light irradiation time.

  In the adhesive kit of the present invention, as one of the preferred embodiments in the dental field, the dental curable composition is a dental resin cement, and (A) the primer and (B) the dental curable composition of the present adhesive kit. A composition, and a form in which a dental prosthesis made of a dental polyaryletherketone resin material is attached to a dental defect by using a pretreatment material for a tooth surface treatment material or other material as necessary There is. In that case, high adhesiveness is necessary for mounting the dental prosthesis. Also, a thin adhesive layer is necessary to enhance the suitability of the dental prosthesis. In the adhesive kit of the present invention, as another preferred embodiment in the dental field, (B) the dental curable composition is a dental filling restorative material or a dental hard resin, and the (A A dental prosthesis in which a dental polyaryletherketone resin material and a dental filling restorative material or a dental hard resin are laminated using a primer, (B) a dental curable composition, and a dental polyaryletherketone resin material The form which produces a thing is mentioned. In this embodiment, for example, in order to improve aesthetics, a dental prosthesis in which a dental polyaryletherketone resin material is laminated with a dental filling / restoration material, a dental hard resin, etc., is used, and has high strength and high aesthetics Can be a prosthesis. At that time, high adhesiveness is necessary in order to make full use of the high strength and high aesthetic properties of the prepared dental prosthesis. Moreover, it can become a thing with higher aesthetics by making an adhesive bond layer thin.

  As an example, when the dental curable composition is a dental resin cement, for example, a dental prosthesis made of a polyaryletherketone resin material by the adhesive kit for dental polyaryletherketone resin material of the present invention is used as a dentin. It can be glued to etc. As an example, when the dental curable composition is a dental bonding material, for example, a dental polyaryl is obtained by bonding a general dental filling restorative material or a dental hard resin and a dental polyaryletherketone resin material. It is possible to produce a dental prosthesis in which an ether ketone resin material is laminated with a dental filling / restoring material or a dental hard resin. As an example, when the dental curable composition is a dental filling / restoration material or a dental hard resin, for example, a dental polyaryletherketone resin material and a dental filling / restoration material or a dental hard resin can be laminated only with this kit. In addition to general dental filling restoration materials and dental hard resins, it is laminated with dental polyaryletherketone resin materials and dental filling restoration materials and dental hard resins in combination with general dental filling restoration materials and dental hard resins. It is also possible to produce a dental prosthesis.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not restrict | limited to these Examples. The abbreviations and titles shown in the examples are as follows.
[Chemical polymerization initiator]
<Organic peroxide>
-BPO: Benzoyl peroxide-TMBPO: 1,1,3,3-tetramethylbutyl hydroperoxide <tertiary amine>
DEPT: N, N-diethanol-p-toluidine <+ IV-valent vanadium compound>
BMOV: Bis (maltolate) oxovanadium (IV)
<Sulfinic acid compound>
TEBS: 2,4,6-triethylbenzenesulfinate sodium [radical polymerizable monomer]
BisGMA: 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane 3G: triethylene glycol dimethacrylate UDMA: 1,6-bis (methacryloylethyloxycarbonylamino) 2, 2,4-trimethylhexane, D-2.6E: 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane, PM1: 2-methacryloyloxyethyl dihydrogen phosphate, PM2: bis (2-methacryloyloxyethyl) ) Hydrogen phosphate / HEMA: 2-hydroxyethyl methacrylate [photoinitiator]
CQ: camphorquinone DMBE: p-dimethylaminobenzoic acid ethyl ester [filler]
F1: Spherical silica-zirconia (average particle size 0.4 μm) surface-treated with γ-methacryloyloxypropyltrimethoxysilane F2: Spherical silica-zirconia (average particle size 0.07 μm) γ-methacryloyloxypropyl Surface treatment with trimethoxysilane ・ F3: Surface treatment of amorphous silica-zirconia (average particle size 3 μm) with γ-methacryloyloxypropyltrimethoxysilane

  As the adherend, VESTAKEEEP MC4420 (manufactured by Daicel Evonik), which is a polyether ether ketone resin material, was used.

  Each test method is as follows.

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

Thereafter, a primer was applied to the hole, allowed to stand for 10 seconds, and then dried by blowing compressed air for about 10 seconds. When a bonding material is used in place of the primer (B1), the bonding material is applied to this hole, left for 10 seconds, dried by blowing compressed air for about 10 seconds, and then a dental irradiator (TOXOH) The bonding material was irradiated with light for 10 seconds at Powerlight, manufactured by Tokuyama Dental Co., Ltd .; light output density 700 mW / cm ² ), and cured.

  When the curable composition is cured by chemical polymerization (R1, R2), apply the curable composition on the applied primer, and then press the stainless steel attachment onto the curable composition. Produced. Further, when neither a primer nor a bonding material was used, the following operation was performed without performing the operation after applying the primer or the bonding material.

When the curable composition is cured by photopolymerization (R3, R4), fix a paraffin hook having a hole with a thickness of 0.5 mm and a diameter of 8 mm so as to be concentric with the hole of the double-sided tape. A simulated cavity was formed. The simulated cavity was filled with a curable composition, allowed to stand for 10 seconds, pressed with a polyester sheet, and then pressed with a dental irradiator (Tokuso Power Light, manufactured by Tokuyama Dental Corp .; light output density 700 mW / cm ² ). The dental curable composition was irradiated with light for 2 seconds to be cured. A dental resin cement (Bistite II, manufactured by Tokuyama Dental Co., Ltd.) was applied thereon, and a stainless steel attachment was further pressed onto it to prepare an adhesion test piece.

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

(Adhesive layer thickness)
The polyaryl ether ketone resin material was molded into a plate having a thickness of about 2 mm by injection molding to obtain an adherend. After the adherend surface of this adherend was polished with a # 800 water-resistant abrasive paper, sandblasting (alumina particles having a particle size of about 50 μm were sprayed at a pressure of about 0.2 MPa for 10 seconds using a sandblasting apparatus). Roughening was performed. Thereafter, the substrate was immersed in water and exposed to ultrasonic waves for 5 minutes, and then washed by being immersed in acetone and exposed to ultrasonic waves for 5 minutes. Thereafter, a primer was applied to the adherend surface, allowed to stand for 10 seconds, and then dried by blowing compressed air for about 10 seconds. When a bonding material is used in place of the primer (B1), the bonding material is applied to this hole, left for 10 seconds, dried by blowing compressed air for about 10 seconds, and then a dental irradiator (TOXOH) Power bonding, manufactured by Tokuyama Dental Co., Ltd .; light output density 700 mW / cm 2) was applied to the bonding material for 10 seconds to be cured. Thereafter, a dental cement material (Bistite II, manufactured by Tokuyama Dental Co.) is applied onto the primer or bonding material, and further, a dental hard resin (manufactured by Tokuyama Dental Co., Ltd .: Pearl Este) is further cured thereon. The test piece was produced by pressing. After holding the above-mentioned test piece at 37 ° C. for 24 hours, it was cut perpendicularly to the adherend surface using a diamond cutter to expose the cross section of the adhesion site. After this adhesion site was polished with # 3000 water-resistant abrasive paper, the thickness of the primer layer or bonding material layer was measured as the adhesive layer thickness with a laser microscope (manufactured by Keyence Corporation).

<Example 1>
(A1) 0.001 g of BMOV as a partial component of the chemical polymerization initiator and 10 g of ethanol as a solvent component were mixed with stirring to prepare a primer P1. The primer composition is shown in Table 1. (B1) 4 g of D-2.6E as a polymerizable monomer component, 1 g of bisGMA, 3 g of 3G, 1 g of PM1, and 1 g of PM2, (b3) One component of a chemical polymerization initiator as a polymerization initiator As a paste, 0.3 g of DEPT was added, and 17.5 g of F1 and 12.5 g of F3 were further added and mixed as filler components. Immediately before use, 1 g of the paste was taken, and 8.7 mg of BPO was added and mixed as a component of (b2) a part of the chemical polymerization initiator and (b3) the remaining component of the polymerization initiator to obtain a curable composition R1 And quickly used for testing. Table 3 shows the composition of the curable composition. Using the primer P1 and the curable composition R1, the tensile adhesion strength to the polyaryletherketone resin material and the thickness of the primer layer were measured. The results are shown in Table 4.

<Example 2>
(A2) 3 g of bisGMA as a polymerizable monomer component and 2 g of 3G are mixed, (a1) 0.005 g of BMOV is added as at least one component of a chemical polymerization initiator, and 5 g of ethanol is stirred and mixed as a solvent component Primer P2 was prepared. The primer composition is shown in Table 1. Using the primer P2 and the curable composition R1 prepared in Example 1, the tensile adhesion strength and the thickness of the primer layer with respect to the polyaryl ether ketone resin material were measured. The results are shown in Table 4.

<Examples 3 to 12, Comparative Example 1>
Primers P3 to P13 were prepared according to Example 2 except that the composition was changed to the composition shown in Table 1. Using the primers P3 to P13 and the curable composition R1 produced in Example 1, the tensile adhesive strength and the thickness of the primer layer for the polyaryletherketone resin material were measured. The results are shown in Table 4. In Example 5, (B) DEPT contained in the curable composition corresponds to (b2) a partial component and (b3) polymerization initiator of the chemical polymerization initiator, and BPO (b2) chemical polymerization. It differs from the other examples in that it does not correspond to a partial component of the initiator, but only corresponds to (b3) a polymerization initiator.

<Example 13>
A curable composition R2 was prepared in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 3. Using the primer P4 produced in Example 4 and the curable composition R2, the tensile adhesion strength and the thickness of the primer layer with respect to the polyaryl ether ketone resin material were measured. The results are shown in Table 4.

<Example 14>
(B1) 3 g of bisGMA as a polymerizable monomer component, 2 g of 3G are mixed, (b2) 0.2 g of TMBPO is added as a partial component of a chemical polymerization initiator, and (b3) light as a polymerization initiator 0.05 g of CQ and 0.05 g of DMBE were added as a polymerization initiator component, 18 g of F1 and 12 of F2 were further added and mixed as a filler component, and paste was obtained to obtain a curable composition R3. Table 3 shows the composition of the curable composition. Using the primer P4 produced in Example 4 and the curable composition R3, the tensile adhesive strength and the thickness of the primer layer with respect to the polyaryl ether ketone resin material were measured. The results are shown in Table 4.

<Example 15>
Using the primer P4 produced in Example 4 and vis-tite II (manufactured by Tokuyama Dental Co., Ltd.), which is a commercially available dental resin cement, as the curable composition, the tensile adhesive strength and the primer layer for the polyaryl ether ketone resin material The thickness of was measured. The results are shown in Table 4. In addition, bistitite II contains BPO which is an organic peroxide as a chemical polymerization initiator component.

<Example 16>
(B1) 3 g of bisGMA as a polymerizable monomer component, 2 g of 3G are mixed, (b3) 0.05 g of CQ and 0.05 g of DMBE are added as a photopolymerization initiator component which is a polymerization initiator, As a filler component, 18 g of F1 and 12 of F2 were added and mixed, and pasted to obtain a curable composition R4. Table 3 shows the composition of the curable composition. Using the primer P4 produced in Example 4 and the curable composition, the tensile bond strength and the thickness of the primer layer with respect to the polyaryl ether ketone resin material were measured. The results are shown in Table 4.

<Comparative example 2>
3 g of bisGMA as a polymerizable monomer component, 2 g of 3G are mixed, 0.05 g of CQ and 0.05 g of DMBE are added as a photopolymerization initiator component, and 4.9 g of ethanol is stirred and mixed as a solvent component. Bonding material B1 was produced. Using the bonding material B1 and the curable composition R1 produced in Example 1, the tensile adhesion strength to the polyaryl ether ketone resin material and the thickness of the bonding material layer were measured. The results are shown in Table 4.

<Comparative Example 3>
R1 prepared in Example 1 was used as the curable composition, and the tensile adhesion strength to the polyaryletherketone resin material was measured without using a primer and a bonding material. Since the primer layer / bonding material layer does not exist, the thickness is not measured. The results are shown in Table 4.

(Evaluation results)
Table 4 shows the measurement results of the tensile adhesive strength between the polyether ether ketone resin material of each example and each comparative example, the primer, and the curable composition.

  Examples 1-16 which used the primer of this invention showed high adhesive strength, though it was all the thickness of the adhesive bond layer thin compared with the comparative example. On the other hand, (A) Primer does not contain (a1) a partial component of the chemical polymerization initiator (no chemical polymerization initiator component) in Comparative Example 1, although the adhesive layer is thin. High bond strength could not be obtained. Further, in Comparative Example 2 in which the bonding material was cured before the curable composition was pressure-bonded using the bonding material instead of the primer, a high adhesive strength was obtained, but the adhesive layer was thick. It was. Further, in Comparative Example 3 using only the curable composition without using a primer, the thickness of the adhesive layer is thin because there is no primer layer, but high adhesion strength cannot be obtained. It was. In this study, the adhesive layer having a thickness of less than 1 μm means that the primer layer is very thin and measurement is difficult.

  Examples 1, 4, 8, and 9 using the same curable composition use the same solvent as the primer, and (a1) + IV-valent vanadium that is all the same as a partial component of the chemical polymerization initiator BMOV which is a compound is used, and the blending amounts thereof are the same, but Examples 4, 8, and 9 containing a polymerizable monomer are different from those of Example 1 containing no polymerizable monomer. In comparison, the adhesive strength was high. Furthermore, Examples 8 and 9 containing acidic group-containing polymerizable monomers (PM1, PM2) as the polymerizable monomer of the primer showed higher adhesive strength than Example 4 not containing them.

  Examples 4, 10, 11, and 12 using the same curable composition use the same polymerizable monomer and solvent for the primer, and (a1) are all the same as a partial component of the chemical polymerization initiator. BMOV, which is a + IV valent vanadium compound, is used, but the amount added to the primer is different. When these are compared, Examples 4 and 11 in which the addition amount of some components of the chemical polymerization initiator is in the range of 0.008 to 0.1 parts by mass with respect to 100 parts by mass of the primer are chemical polymerization initiators. As compared with Example 10 in which the addition amount of the partial component was 0.008 parts by mass or less with respect to 100 parts by mass of the primer and Example 12 was 0.1 parts by mass or more, high adhesive strength was exhibited.

  In Examples 2 to 4 using the same curable composition, BMOV, which is a + IV valent vanadium compound, is used as a primer as a component of (a1) chemical polymerization initiator. The addition amount of some components of the (a1) chemical polymerization initiator to the monomer is the same, and the same polymerizable monomer and solvent are used, but the ratio of the polymerizable monomer and the solvent is different. . When these were compared, the adhesive strength was almost the same, but Example 2 with a large amount of the polymerizable monomer was thicker in adhesive layer than Examples 3 and 4.

  (B2) In Examples 4 to 7 using the same curable composition containing the organic peroxide BPO and the tertiary amine DEPT as a partial component of the chemical polymerization initiator, the same amount of polymerizability was used for the primer. The monomer and solvent differ only in the type of some components of the (a1) chemical polymerization initiator. When these were compared, Example 4 in which the + IV vanadium compound BMOV, which is a transition metal compound in the fourth period, was blended as a partial component of the (a1) chemical polymerization initiator was blended with BPO, which is an organic peroxide. Compared to Example 5, Example 6 containing DEPT, which is a tertiary amine, and Example 7 containing TEBS, which is a sulfinic acid compound, the adhesive strength was higher.

  (A1) The same primer containing the + IV vanadium compound BMOV is used as a partial component of the chemical polymerization initiator, and (b2) the organic peroxide BPO is included as a partial component of the chemical polymerization initiator, but the composition When Examples 4, 13, and 14 using different curable compositions are compared, Example 4 in which PM1 and PM2 which are acidic group-containing polymerizable monomers are included in the curable composition is not included in this example. Compared with Examples 13 and 14, the adhesive strength was high. This is because the reaction between the organic peroxide and the transition metal compound in the fourth period such as the + IV vanadium compound is activated by the acid, the curability of the primer layer is improved, and higher adhesion can be obtained. Although the effect is smaller than when the acidic group-containing polymerizable monomer is blended with the primer, it shows that the primer is effective even when the acidic group-containing polymerizable monomer is blended with the curable composition.

  Moreover, as shown in Example 15, high adhesive strength was obtained also when the primer of this invention and the commercially available curable composition were used.

  Example 16 using the primer of the present invention and (b2) a curable composition not containing a part of the chemical polymerization initiator included the primer of the present invention and (b2) a part of the chemical polymerization initiator. Although it is somewhat inferior in adhesive strength compared with Examples 1-15 using the curable composition containing, it shows high adhesive strength compared with Comparative Example 1 using a primer that is not of the present invention. It was.

  Since the primer of the present invention can be used in combination with the curable composition containing (b2) a partial component of the chemical polymerization initiator, higher primer strength can be obtained. Therefore, the primer of the present invention and (b1) polymerizable An adhesion kit comprising a monomer, (b2) a partial component of a chemical polymerization initiator, and (b3) a curable composition containing a polymerization initiator is an adhesion kit for a polyaryl ether ketone resin material. Useful as.

Claims (11)

(A) Primer containing a partial component of (a1) chemical polymerization initiator for polyaryl ether ketone resin material. The (A) primer according to claim 1, further comprising (a2) a polymerizable monomer. The primer (A) according to claim 1 or 2, wherein (a1) at least a part of the chemical polymerization initiator is a transition metal compound having a fourth period. (A1) The primer (A) according to claim 3, wherein at least a part of the chemical polymerization initiator is a + IV vanadium compound. The (A) primer according to any one of claims 2 to 4, wherein the polymerizable functional group of the polymerizable monomer is a (meth) acryloyl group. The primer (A) according to any one of claims 1 to 5, which is used for a dental polyaryletherketone resin material. (A) primer according to any one of claims 1 to 6,
(B1) a polymerizable monomer, (b2) a partial component of a chemical polymerization initiator, (b3) a polymerization initiator, and (b2) a partial component of the chemical polymerization initiator is the component (a1) (B) a curable composition capable of forming a chemical polymerization initiator system with a partial component of the polymerization initiator,
An adhesion kit for polyaryletherketone resin material. The adhesive kit for polyaryl ether ketone resin material according to claim 7, wherein (A) the primer further contains (a2) a polymerizable monomer. (A) The partial component of (a1) chemical polymerization initiator contained in the primer is a transition metal compound in the fourth period,
(B) contained in the curable composition, (b2) (A) contained in the primer (a1) a chemical polymerization initiator component that forms a chemical polymerization initiator system with a part of the chemical polymerization initiator component is organic peroxidation The adhesive kit for polyaryletherketone resin materials according to claim 7 or 8, which is a product. The adhesive kit for polyaryletherketone resin material according to claim 9, wherein (A1) the partial component of the (a1) chemical polymerization initiator contained in the primer is a + IV valent vanadium compound. A primer application step for applying the primer (A) according to any one of claims 1 to 6 to the surface of the polyaryletherketone resin material; (b1) a polymerizable monomer; and (b2) a chemical polymerization initiator. Part of component (b3) contains a polymerization initiator, and part of component (b2) chemical polymerization initiator can form a chemical polymerization initiator system with part of component (a1) chemical polymerization initiator. (B) A polyaryletherketone resin material and a curable composition comprising a curable composition applying step for applying the curable composition from above the primer and a curable composition curing step for polymerizing and curing the curable composition. Bonding method with.