JP6541185B2 - Adhesive composition for polyaryl ether ketone resin composite material - Google Patents

Description

  The present invention relates to an adhesive composition for polyaryl ether ketone resin composite materials, which has excellent adhesion to polyaryl ether ketone resin composite materials, and is useful as an adhesive and a primer.

  Super engineering resins are used in a wide range of applications, such as the electric and electronic fields, aerospace fields, automotive industry, medical fields, and general industrial fields. Among these super-engineering resins, polyaryl ether ketone resins, in particular, are expected to be used in various fields because of their excellent chemical properties and physical properties.

  For example, in the field of dental treatment, techniques using this polyaryletherketone resin as a dental material have been proposed. When using a polyaryl ether ketone resin material as a dental material, it is effective to contain an inorganic filler such as a silica-based inorganic particle or a titanium dioxide-based particle from the viewpoint of its strength and elastic modulus (for example, Patent Document 1) .

  Such polyaryl ether ketone resin materials having excellent chemical properties and physical properties and further containing an inorganic filler to improve physical properties are used in various fields. It is a possible material.

  When using said polyaryl ether ketone resin complex material, the technique which can adhere | attach this polyaryl ether ketone resin complex material and other-types material more strongly is calculated | required.

  Here, as an example of a composition comprising a resin and silica-based inorganic particles for dental use, a composite resin or a hard resin which is mainly composed of a methacrylate-based monomer, silica-based particles and a polymerization initiator and is used after being polymerized and cured is there. When such composite resin or hard resin is polymerized and cured, and then it is adhered to other dental materials, a method using a silane coupling agent is generally used in many cases, and various products are released from various companies. It is done. In a method using such a silane coupling agent, a primer mainly composed of a silane coupling agent and a volatile solvent is often used.

  Therefore, also in the case of the polyaryl ether ketone resin material, it is to the polyaryl ether ketone resin composite material complexed with the component to which the usual silane coupling agent can react such as metal oxide particles such as silica based inorganic particles and glass fiber. The adhesion is expected to be high with a primer containing a silane coupling agent as described above. However, high adhesion strength can not be obtained with a primer comprising a silane coupling agent and a volatile solvent for a polyaryl ether ketone resin composite material.

  For example, Patent Document 2 discloses adhesion to a polyetheretherketone thermoplastic plastic containing a glass fiber filler using a conditioning agent in which methacrylic silane, which is a silane coupling agent, is dissolved in ethanol, which is a volatile solvent. It is trying, but high adhesion is not obtained. In this patent, high adhesion strength is obtained by using a conditioning agent in which methacryl silane is dissolved in DMSO, which is a high boiling point solvent, but it is difficult to completely remove the high boiling point solvent, and high biological activity is high. It takes time to use as a dental application that requires safety. Although the patent states that the conditioning agent may contain other components such as monofunctional and / or multifunctional (meth) acrylate (polymerizable monomer) based on methacrylate, it is specifically described The composition is not shown.

Further, for example, although there is a report that dental bonding materials are effective as adhesion to polyaryl ether ketone resin materials as described in Non-Patent Document 1, in order to perform more reliable treatment, further improvement in adhesion is achieved. Is desirable. In Non-Patent Document 1, high adhesive strength is obtained using Heliobond (manufactured by Ivocular Vivadent) as a dental bonding agent. For Heliobond, as polymerizable monomers, BisGMA ((1-methylethylidene) bis [4, 1-phenyleneoxy (2-hydroxy-3, 1 -propanediyl)] bismethacrylate), TEGDMA, UDMA (urethanedimethacrylate: 1, 6-dimethacryl-) Although it is described that ethyl-oxy-carbonylamino-2,4,4-trimethylhexane) is blended, it is not described that a coupling agent is blended.

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

DENTAL MATERIALS 26 (2010) 553-559

  As noted above, materials having higher adhesion to polyaryl ether ketone resin composite materials are desired. For polyaryletherketone resin composite materials containing metal oxides such as silica-based inorganic particles, adhesion with a coupling agent is considered to be effective. In order that high adhesive strength can not be obtained with a primer comprising a hydrophobic solvent, for example, a coupling agent having a methacryloyl group as a polymerizable functional group used in ordinary dental materials and a volatile solvent as a main component High adhesion was not obtained with the primer. In addition, technology has also been proposed to obtain high adhesive strength for polyetherketone resin composite materials by using a conditioning agent containing a coupling agent and a high boiling point solvent, but it is easy to remove from the system There is a need for a method for obtaining high adhesion strength in a simple manner and with less anxiety about biosafety, such as using high boiling point solvents. Therefore, it is an object of the present invention to provide a material which has higher adhesion to a polyaryl ether ketone resin composite material, is simple, and has less concern about biological safety.

  In order to solve the above problems, the inventors of the present invention conducted intensive studies, and as a result, a coupling agent having a polymerizable functional group, two or more polymerizable functional groups in the molecule, with respect to the polyaryl ether ketone resin composite material An adhesive composition containing a polymerizable monomer having a group, wherein the polymerizable monomer having two or more polymerizable functional groups in the molecule is 40% by mass or more of the total polymerizable monomers It has been found that high adhesion can be obtained by this, and the present invention has been made.

  That is, the present invention comprises a coupling agent having a polymerizable functional group, a polymerizable monomer having two or more polymerizable functional groups in the molecule, and a polymerizable having two or more polymerizable functional groups in the molecule. The adhesive composition for a polyaryl ether ketone resin composite material, wherein the monomer is 40% by mass or more of the total polymerizable monomers. It is preferable that the compounding quantity of the coupling agent which has a polymerizable functional group is 1-30 mass parts with respect to 100 mass parts of all the polymerizable monomers, and also it is preferable to contain a volatile solvent. The coupling agent having a polymerizable functional group and the polymerizable functional group of the polymerizable monomer having two or more polymerizable functional groups in the molecule are preferably a (meth) acryloyl group.

  According to the present invention, high adhesion can be obtained in adhesion to a polyaryl ether ketone resin composite material. Therefore, for example, in the dental field, it becomes possible to obtain higher adhesion when attaching a dental prosthesis made of a polyaryl ether ketone resin composite material to a tooth using resin cement or the like, or Even when producing a dental prosthesis using an aryl ether ketone resin composite material and a dental material such as a composite resin or a hard resin, it becomes possible to produce a dental prosthesis that is more resistant to breakage, and the present invention The use of the adhesive composition for the polyaryl ether ketone resin composite material of the present invention makes it possible to perform more reliable treatment.

  In addition, it is not necessary to use a high boiling point solvent which is not easy to remove from the system, and there is an advantage such as an adverse effect due to the residual solvent, for example, less fear for biological safety.

  Such an adhesive composition for a polyaryl ether ketone resin composite material of the present invention is extremely useful as an adhesive for a polyaryl ether ketone resin composite material and a primer for a polyaryl ether ketone resin composite material.

  The adhesive composition for a polyaryl ether ketone resin composite material of the present invention comprises (A) a coupling agent having a polymerizable functional group, and (B) a polymerizable unit having two or more polymerizable functional groups in the molecule. It is characterized in that the polymerizable monomer containing a body and having two or more polymerizable functional groups in the (B) molecule is 40% by mass or more of the total polymerizable monomers. The polyaryletherketone resin composite material means a composite material containing a polyaryletherketone resin and a metal oxide.

  The adhesive composition for polyaryl ether ketone resin composite material means an adhesive composition used to bond the polyaryl ether ketone resin composite material to other materials.

  The polymerizable monomer is a compound having a polymerizable functional group, and the coupling agent having a polymerizable functional group is also a polymerizable monomer.

  Hereinafter, details of materials and the like constituting the present embodiment will be described.

(A) Coupling Agent Having a Polymerizable Functional Group The coupling agent is one or more first reactive groups that react with an inorganic compound (in the present invention, a metal oxide), and one or more that react with an organic compound. In the coupling agent having a polymerizable functional group of the present invention, which is a material having a second reactive group, at least one second reactive group that reacts with the organic compound is a polymerizable functional group. By blending a coupling agent into the adhesive composition for a polyaryl ether ketone resin composite material, it is possible to produce a polyaryl ether ketone resin composite material as compared with the case where a coupling agent having a polymerizable functional group is not blended. High adhesion can be obtained.

  As the coupling agent having a polymerizable functional group (A) used in the present invention, known coupling agents can be used without any restriction, and as a general one, one having a structure represented by the following general formula (I) It can be mentioned.

  In the general formula (I), M is a metal element, X is a first reactive functional group, and the first reactive functional group X is a hydroxyl group (OH) or a hydroxyl group directly to the metal element M by hydrolysis ( Y) is a functional group that generates an M-OH structure to which OH is bonded, Y is a second reactive functional group, and the second reactive functional group Y is a functional group having a polymerizable functional group, Z Are other functional groups which do not correspond to X and Y. m and n are each independently an integer of 1 or more, and l is an integer of 0 or 1 or more. m + n + 1 agrees with the valence of the metal element M.

  As the coupling agent, for example, a silane coupling agent in which M in the general formula (I) is silicon, a titanate coupling agent which is titanium, an aluminate coupling agent which is aluminum, a zirconate coupling which is zirconium Although there are agents, silane coupling agents are particularly preferred from the viewpoint of adhesion and handling.

  The first reactive functional group X in the general formula (I) is a hydroxyl group (OH) or a functional group which generates an M-OH structure in which a hydroxyl group (OH) is directly bonded to the metal element M by hydrolysis. Besides, alkoxy group, acryloxy group, halogeno group, amino group and the like can be exemplified. It is surmised that adhesion is obtained by reacting the structure of this M-OH with the metal oxide in the dental polyaryletherketone resin composite material. The first reactive functional group X in the general formula (I) has a small M-OH structure during storage from the viewpoint of its storage stability, and the hydrolysis proceeds by, for example, mixing with an acidic compound immediately before use It is preferable that it is a functional group which produces | generates many M-OH structures which a hydroxyl group (OH) couple | bonds with the metal element M directly, and an alkoxy group, an acryloxy group etc. are mentioned as such a functional group, for example. When a large amount of hydroxyl groups are generated during storage, condensation reaction between the hydroxyl groups occurs to gelate the adhesive composition for polyaryl ether ketone resin composite material, which may prevent storage for a long time. Therefore, X is preferably a functional group such as an alkoxy group or an acryloxy group, and is an alkoxy group having 1 to 5 carbon atoms from the viewpoint of easy handling etc., that is, X is OR (R is 1 to 5 carbon atoms Is more preferable, and in particular, a methoxy group, an ethoxy group or a propoxy group is more preferable.

  The second reactive functional group Y in the general formula (I) is a functional group having a polymerizable functional group, and by this functional group, between the coupling agent and another polymerizable monomer of the adhesive composition The bond is formed, a layer of uniform and strong adhesive composition is formed, and the adhesion is improved. The polymerizable functional group possessed by Y is preferably a radically polymerizable functional group in terms of low biotoxicity and high polymerization activity. Examples of the radically polymerizable functional group include functional groups such as (meth) acryloyl group, vinyl group, styryl group, allyl group and the like, and from the viewpoint of polymerization rate and biosafety, (meth) acryloyl group is particularly preferred. preferable.

  Z in the general formula (I) may be any functional group as long as it does not adversely affect the effects of the present invention as long as the functional group does not fall under X and Y, for example, hydrogen atom, alkyl group, aryl Groups and the like.

  M, n and l in the general formula (I) respectively represent the numbers of functional groups X, Y and Z. Therefore, m + n + 1 agrees with the valence of the metal element M. Since the functional groups X and Y are functional groups essential for obtaining the effects of the present invention, m and n are each independently an integer of 1 or more. On the other hand, l is an integer of 0 or 1 or more, since the functional group Z is not necessarily a functional group that is essential to obtain the effects of the present invention. The first reactive functional group X is the bond strength between the polyaryl ether ketone resin composite material and the adhesive composition for the polyaryl ether ketone resin composite material, and the second reactive functional group Y is the polyaryl Since it is strongly related to the strength of the layer of the adhesive composition for the ether ketone resin composite material, the larger the number of these, the adhesive composition for the polyaryl ether ketone resin composite material and the polyaryl ether ketone resin composite material Interaction with objects becomes stronger and higher adhesion is obtained. Therefore, l is preferably 0 or 1, and more preferably 0. In addition, the strength of the bond between the polyaryletherketone resin composite material and the adhesive composition for the polyaryletherketone resin composite material according to the M-OH structure derived from the first reactive functional group X is particularly adhesion It is particularly preferable that m is 2 or more because it strongly affects the sex. That is, for example, in the case of a silane coupling agent in which the metal element M is silicon having a valence of 4, when m = 3, n = 1, l = 0, or m = 2, n = 2, l = 0. In some cases, it is preferable that m = 2, n = 1, l = 1, and m = 3, n = 1, l = 0, or m = 2, n = 2, l = 0. Is more preferable, and it is particularly preferable that m = 3, n = 1 and l = 0.

  In addition, also when the structure of said general formula (I) is connected by the siloxane bond, and is connected via other functional groups, such as an alkylene group, it can be used.

  As a suitable coupling agent, what is shown to General formula (II) is mentioned.

Here, in the general formula (II), M is a metal element, R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² is any of an alkylene group, an arylene group, an alkylene arylene group and an arylene alkylene group (however, These functional groups may have any functional group as a side chain unless the effects of the present invention are significantly impaired), R ³ is a hydrogen atom or a methyl group, and Z is a hydrogen atom or carbon Represents an alkyl group of 1 to 5; Further, m, n and l each represent the number of functional groups, and m and n are each independently an integer of 1 or more, and l is an integer of 0 or 1 or more. m + n + 1 agrees with the valence of the metal element M. R ¹ is more preferably a methyl group or an ethyl group. R ² is more preferably an alkylene group having 1 to 15 carbon atoms in the main chain, an arylene group having 6 to 20 carbon atoms in the main chain, an alkylene arylene group, or an arylene alkylene group. More preferably, Z is a hydrogen atom or a methyl group. More preferably, l is 0.

  The metal element M in the general formula (II) is preferably silicon as described above, and such a coupling agent can be represented as the following general formula (III).

Here, in the general formula (III), R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² is any of an alkylene group, an arylene group, an alkylene arylene group, and an arylene alkylene group (however, these functional groups) May have any functional group as a side chain unless significantly inhibiting the effects of the present invention), R ³ is a hydrogen atom or a methyl group, Z is a hydrogen atom or an alkyl having 1 to 5 carbon atoms Represents a group. Also, m, n and l each represent the number of functional groups, and m and n are each independently an integer of 1 or more, and l is an integer of 0 or 1 or more. m + n + l = 4. R ¹ is more preferably a methyl group, an ethyl group or a propyl group. R ² is more preferably an alkylene group having 1 to 15 carbon atoms in the main chain, an arylene group having 6 to 20 carbon atoms in the main chain, an alkylene arylene group, or an arylene alkylene group. More preferably, Z is a hydrogen atom or a methyl group. m, n and l are m = 3, n = 1 and l = 0, or m = 2, n = 2 and l = 0, m = 2, n = 1 and l = 1 The case of m = 3, n = 1 and l = 0 is particularly preferable.

  As a coupling agent having a polymerizable functional group which is preferably used, for example, a silane coupling agent is exemplified, and γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyl tritrile Isopropylsilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloyloxypropyltris (methoxyethoxy) silane, γ-methacryloxypropylmethyldiethoxysilane, ω-methacryloyloxydecyltrimethoxysilane, (methacryloxymethyl) methyldimethoxymethane Silane, (methacryloxymethyl) methyldiethoxysilane, methacryloxymethyltrimethoxysilane, O- (methacryloyloxyethyl) -N- (triethoxysilyl) Propyl) carbamate, N- (3-methacryloyl-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 3- (n-methacryloyloxyphenyl) propyltrimethoxysilane, γ-methacryloyloxypropyltriisopropoxysilane, 3 And-(3-methoxy-4-methacryloyloxyphenyl) propyltrimethoxysilane and the like.

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

  Although the compounding quantity of the coupling agent which has a polymerizable functional group is not restrict | limited in particular, The range of 1-30 mass parts with respect to 100 mass parts of all the polymerizable monomers also including the coupling agent which has a polymerizable functional group Is preferable, the range of 2 to 20 parts by mass is more preferable, and the range of 3 to 10 parts by mass is further preferable. When the amount of the coupling agent is too large, a fragile layer formed by dehydration condensation of an excessive coupling agent between M-OH structures is formed in the vicinity of the metal oxide of the adherend, and two or more in the molecule described later The effect obtained by using both the polymerizable monomer having a polymerizable functional group and the coupling agent may be limited. On the other hand, when the amount of the coupling agent is small, there is a possibility that the coupling between the coupling agent and the metal oxide in the polyaryletherketone resin complex sufficient to obtain high adhesion can not be obtained.

(B) A polymerizable monomer having two or more polymerizable functional groups in the molecule The adhesive composition for a polyaryl ether ketone resin composite material of the present invention comprises (B) two or more polymerizable compounds in the molecule. The polymerizable monomer having a functional group is contained, and the polymerizable monomer having two or more polymerizable functional groups in the (B) molecule is contained in 40% by mass or more of all the polymerizable monomers. Using a mixture of a polymerizable monomer having two or more polymerizable functional groups in the (B) molecule contained in 40% by mass or more of the total polymer and a coupling agent having the (A) polymerizable functional group High adhesion can be obtained.

  By blending a polymerizable monomer having two or more polymerizable functional groups in the molecule with 40% by mass or more of the total polymerizable monomers, the strength of the layer of the cured adhesive composition becomes high, and high adhesion is achieved. Sex is obtained.

  When using an adhesive composition in which not more than 40% by mass of the polymerizable monomer having two or more polymerizable functional groups in the molecule is blended, sufficient to obtain high adhesiveness It is difficult to form a layer of uniform and strong adhesive composition. Here, a uniform and strong adhesive composition is obtained by blending 40% by mass or more of all the polymerizable monomers with a polymerizable monomer having two or more polymerizable functional groups in the molecule in the adhesive composition. It is assumed that the layer of (1) is easily formed, and high adhesion can be obtained. A polymerizable monomer having two or more polymerizable functional groups in the molecule by using a polymerizable monomer having two or more polymerizable functional groups in the molecule in 40% by mass or more of the total polymerizable monomers As compared with the case where the body is less than 40% by mass of the total polymerizable monomer, it becomes easy to form a reticulated polymer network after the adhesive composition is cured, and the uniform and strong adhesive composition It is inferred that the layer of

  Known polymerizable monomers having two or more polymerizable functional groups in the molecule can be used without any limitation. The coupling agent having a polymerizable functional group described above (A) also has two or more polymerizable functional groups in the molecule is a coupling agent having a polymerizable functional group (A), and (B) 2.) A polymerizable monomer having two or more polymerizable functional groups in the molecule. The polymerizable functional group is preferably a radically polymerizable functional group from the viewpoint of low biotoxicity and high polymerization activity, and functional groups such as vinyl group, styryl group, allyl group, (meth) acryloyl group and the like can be mentioned. However, (meth) acryloyl group is particularly preferable from the viewpoint of polymerization rate and biological safety.

  As a polymerizable monomer having two or more polymerizable functional groups in the molecule, for example, a radically polymerizable single monomer having two or more (meth) acryloyl groups in the molecule shown in the following (I) to (III) There is a mer.

(I) 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-) Methacryloyloxy tetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxy Liethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytriethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4 -Butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, glycerin dimethacrylate Bis (2-methacryloyloxyethyl) hydrogen phosphate, bis (6- methacryloyl oxyhexyl) hydrogen phosphate and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro- Methacrylates such as 2-hydroxypropyl methacrylate or vinyl monomers having -OH group such as acrylate corresponding to these methacrylates, diisocyanate methylbenzene, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methyl Cyclohexane, isophorone diisocyanate, methylene bis (4-cyclohexene Diaducts obtained from adducts with diisocyanate compounds such as isocyanates); 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethyl, 1,6-bis (methacryloylethyloxycarbonylamino) 2,2, 4-trimethylhexane etc.

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

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

  As the polymerizable monomers having two or more polymerizable functional groups in these molecules, plural kinds of monomers may be used in combination as needed.

  The polymerizable monomer having two or more polymerizable functional groups in these molecules may be used in an amount of 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more based on all the polymerizable monomers. preferable. If the content of the polymerizable monomer having two or more polymerizable functional groups in the molecule is less than 40% by mass, high adhesion is difficult to obtain because the strength of the layer of the adhesive composition is not sufficient.

  It is preferable that a part or all of the polymerizable monomers having two or more polymerizable functional groups in the molecule have two or more polymerizable functional groups in the molecule and a hydrogen bonding functional group. By using a polymerizable monomer having a hydrogen bonding functional group, the strength of the layer of the adhesive composition becomes higher due to hydrogen bonding between the hydrogen bonding functional groups. In addition, the interaction between the polyaryletherketone resin composite material and the layer of the adhesive composition is caused by the interaction between the hydrogen bonding functional group of the polymerizable monomer and the ketone group of the polyaryletherketone resin. It is guessed that it will be higher. In addition, if these hydrogen bonding functional groups have a functional group that generates an M-OH structure in which a coupling agent directly bonds a hydroxyl group (OH) to a metal element M by hydrolysis (hydroxyl group (OH) or hydrolysis), Adhesive composition by interacting with the M-OH moiety or the M-OH moiety generated by hydrolysis to generate a M-OH structure in which a hydroxyl group (OH) is directly bonded to the metal element M by hydrolysis. It is presumed that the strength of the object layer is improved. Furthermore, when the adhesive composition is applied onto the polyaryl ether ketone resin composite material by promoting the uniform mixing of the coupling agent having a polymerizable functional group and the other polymerizable monomer. It is presumed that a layer of uniform adhesive composition is likely to be formed. It is preferable to use a polymerizable monomer having a hydrogen bonding functional group because higher adhesion can be obtained by these actions. It is preferable to use 20 mass% or more of all the polymerizable monomers, and it is more preferable to use 30 mass% or more of the polymerizable monomers having two or more polymerizable functional groups and a hydrogen bonding functional group in the molecule. .

  The hydrogen bond referred to here means a hydrogen atom (donor) which is electrically positively polarized by bonding to an atom (O, N, S, etc.) having high electronegativity, and an electronegative atom having a lone electron pair. It shows that the binding interaction is formed with (Acceptor). The hydrogen bonding functional group in the present invention is a substituent which can function as a donor and an acceptor in the above-mentioned hydrogen bond, and specifically means a hydroxyl group, a thiol group, an amino group, a urethane group, an amide group and the like.

  As the polymerizable monomer having two or more polymerizable functional groups and a hydrogen bonding functional group in such a molecule, known monomers including those exemplified above can be used without particular limitation, and examples thereof include 2 , 2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, glycerol dimethacrylate, bis (2-methacryloyloxyethyl) hydrogen phosphate, bis (6-methacryloyloxyhexyl) hydrogen phosphate and Acrylates corresponding to these methacrylates; methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, etc. or -OH groups such as acrylate corresponding to these methacrylates Obtained from the adduct of a nyl monomer with a diisocyanate compound such as diisocyanate methylbenzene, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate) And the like. Examples thereof include 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethyl, 1,6-bis (methacryloylethyloxycarbonylamino) 2,2,4-trimethylhexane and the like.

  A part or all of a polymerizable monomer having two or more polymerizable functional groups and a hydrogen bonding functional group in the molecule has two or more polymerizable functional groups and a hydrogen bonding functional group 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 adhesive composition for the polyaryl ether ketone resin composite material and the aromatic ring of the polyaryl ether ketone resin composite material form a stack, It is assumed that the interaction between the polyaryletherketone resin composite material and the layer of the adhesive composition is higher.

  As the polymerizable monomer having two or more polymerizable functional groups, a hydrogen bonding functional group, and an aromatic ring in such a molecule, known monomers including those exemplified above can be used without particular limitation, and examples thereof include Is 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane and an acrylate corresponding to this methacrylate; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2- From the addition of a vinyl monomer having an --OH group such as a methacrylate such as hydroxypropyl methacrylate or an acrylate corresponding to these methacrylates and a diisocyanate compound having an aromatic group such as diisocyanate methylbenzene and 4,4'-diphenylmethane diisocyanate can get Adduct, and the like. 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, and 25% by mass or more of all the polymerizable monomers. Is more 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 of all the polymerizable monomers, and 50% by mass It is more preferable that it is the following. The polyaryletherketone resin composite material and the adhesive composition are obtained by setting the content of the polymerizable monomer having two or more polymerizable functional groups, the hydrogen bonding functional group and the aromatic ring in the molecule to 15% by mass or more. It is possible to strengthen the interaction with the layer. On the other hand, when more than 70% by mass of a polymerizable monomer having two or more polymerizable functional groups, a hydrogen bonding functional group, and an aromatic ring in the molecule is blended, hydrogen bonding functional groups or aromatic rings The interaction may make it difficult to handle the polymerizable monomer, and it may be difficult to add it to the adhesive composition from the viewpoint of workability and the like.

  Furthermore, in addition to a polymerizable monomer having two or more polymerizable functional groups in the molecule, if necessary, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl Methacrylates such as methacrylate, 2-methacryloyloxyethyl dihydrogen phosphate, 6-methacryloyl oxyhexyl dihydrogen phosphate, 10-methacryloyl oxyhexyl dihydrogen phosphate, and polymerizable functional groups such as acrylate corresponding to these methacrylates A polymerizable monomer having only one molecule may be used.

  The compounding amount of the polymerizable monomer having only one of these polymerizable functional groups in the molecule is the amount of the polymerizable agent having two or more polymerizable functional groups in the molecule and the coupling agent having the polymerizable functional group. Although it may determine suitably according to the compounding quantity of a body, 50 mass% or less is preferable among all the polymerizable monomers, and 30 mass% or less is more preferable. When a large amount of polymerizable monomer having only one polymerizable functional group in the molecule is blended, sufficient strength of the layer of the adhesive composition may not be obtained to obtain high adhesiveness.

(C) Volatile solvent It is also preferable to blend a volatile solvent into the adhesive composition for polyaryl ether ketone resin composite material. By blending a volatile solvent, the viscosity of the adhesive composition for a polyaryl ether ketone resin composite material is reduced, and a polymerizable monomer having two or more polymerizable functional groups in the molecule is a polyaryl ether ketone. It becomes easy to penetrate | invade the fine unevenness | corrugation on the surface of resin composite material, or to form the layer of a uniform adhesive composition easily. Further, it is presumed that the mobility of the coupling agent molecule is improved, the reactivity between the metal oxide and the coupling agent molecule is improved, and higher adhesion can be obtained. When a coupling agent is used in which X in the general formula (I) is a functional group that generates an M-OH structure in which a hydroxyl group (OH) is directly bonded to the metal element M by hydrolysis, May be more likely to progress.

  Moreover, since it is volatile, after apply | coating the adhesive composition for polyaryl ether ketone resin composite material to the adhesion surface of polyaryl ether ketone resin composite material, polyaryl ether ketone resin by operation, such as air blow etc. It is removed from the surface of the composite material, and the adverse effect on the adhesion due to the residual solvent can be suppressed.

  Here, the volatile solvent means that the boiling point at 760 mmHg is 100 ° C. or less and the vapor pressure at 20 ° C. is 1.0 KPa or more. However, since it is preferable that the volatile solvent volatilizes sufficiently and does not adversely affect the residue, the vapor pressure at 20 ° C. is more preferably 2.0 KPa or more, further preferably 5.0 KPa or more . On the other hand, when the volatilization of the volatile solvent is too fast, the effect of blending the volatile solvent is not sufficiently obtained. Therefore, the vapor pressure of the volatile solvent at 20 ° C. is preferably 60 KPa or less, more preferably 50 KPa or less. In addition, the boiling point of the volatile solvent at 760 mmHg is more preferably 85 ° C. or less because the lower the boiling point, the easier removal from the surface of the polyaryl ether ketone resin composite material.

  Such preferred volatile solvents include, for example, acetone, methyl ethyl ketone, diethyl ketone, methyl n-propyl ketone, methyl isobutyl ketone, acetonitrile, tetrahydrofuran, diethyl ether, pentane, hexane, toluene, ethyl acetate, methanol, ethanol, 1 -Propanol, isopropanol, water etc. are mentioned. These volatile solvents may be used alone or in combination of two or more if uniform mixing is possible.

  When the application of the adhesive composition for a polyaryl ether ketone resin composite material is an adhesive for a polyaryl ether ketone resin composite material, the blending amount of the volatile solvent is 100 parts by mass of the total polymerizable monomer. The range of 10 parts by mass to 1000 parts by mass is preferable, the range of 10 parts by mass to 500 parts by mass is more preferable, the range of 20 parts by mass to 400 parts by mass is more preferable, and the range of 50 parts by mass to 300 parts by mass is most preferable. When the volatile solvent is less than 10 parts by mass, the degree of decrease in viscosity of the adhesive for the polyaryletherketone resin composite material is small, and the polyaryletherketone is formed on the fine irregularities on the surface of the polyaryletherketone resin composite material. It is difficult for the adhesive for the resin composite material to easily infiltrate or to obtain the effect of forming a uniform adhesive layer. In addition, the effect of improving the reactivity of the coupling agent with the metal oxide of the polyaryl ether ketone resin composite material by improving the mobility of the coupling agent is also hardly obtained. When the volatile solvent is more than 1000 parts by mass, the polymerizable monomer component of the adhesive for the polyaryletherketone resin composite material is reduced, and as a result, the polyaryletherketone resin composite material has a polyarylated surface. When the adhesive for ether ketone resin composite material is applied, the amount of the polymerizable monomer present on the surface of the polyaryl ether ketone resin composite material is insufficient, and the formation of a uniform and strong adhesive layer is insufficient. In some cases, adhesion may be reduced.

  When the application of the adhesive composition for a polyaryl ether ketone resin composite material is a primer for a polyaryl ether ketone resin composite material, the blending amount of the volatile solvent is 10 with respect to 100 parts by mass of all the polymerizable monomers. It is preferably in the range of from 300 parts by mass to 3000 parts by mass, more preferably in the range of from 100 parts by mass to 2000 parts by mass, still more preferably in the range of from 300 parts by mass to 1500 parts by mass, from 500 parts by mass. Most preferably, it is in the range of 1000 parts by mass. In the case of a primer, although it is disadvantageous as compared with an adhesive in forming a layer of a uniform and strong adhesive composition as described later, the decrease in adhesion when using a large amount of solvent is limited. The appropriate amount of solvent is different between the adhesive and the primer. When the amount of the volatile solvent is less than 10 parts by mass, the decrease in viscosity of the primer for the polyaryletherketone resin composite material is small, and the polyaryletherketone resin is formed on the fine irregularities on the surface of the polyaryletherketone resin composite material. It is difficult for the composite material primer to easily penetrate and to obtain an effect of forming a uniform primer layer. In addition, the effect of improving the reactivity of the coupling agent with the metal oxide of the polyaryl ether ketone resin composite material by improving the mobility of the coupling agent is also hardly obtained. When the volatile solvent is more than 3000 parts by mass, the polymerizable monomer component of the primer for the polyaryl ether ketone resin composite material decreases, and as a result, the polyaryl ether ketone on the surface of the polyaryl ether ketone resin composite material When the primer for resin composite material is applied, the amount of the polymerizable monomer present on the surface of the polyaryletherketone resin composite material is insufficient, so that the formation of a uniform and strong primer layer becomes insufficient, and volatility is caused. It becomes difficult to obtain the advantage of blending the solvent.

  The volatile solvent may be used in combination with a less volatile solvent having a boiling point of more than 100 ° C. or a vapor pressure of less than 1.0 KPa at 20 ° C. However, when the solvent having a low volatility is contained in a large amount, the interaction between the polymerizable monomer of the polyaryletherketone resin composite material and the adhesive composition for the polyaryletherketone resin composite material is inhibited. There is a possibility that the adhesion may be lowered by inhibiting the polymerization and curing of the polymerizable monomer of the adhesive composition for a polyaryl ether ketone resin composite material. Therefore, the solvent with low volatility contained in the adhesive composition for polyaryl ether ketone resin composite material is preferably 40% by mass or less with respect to the addition amount of the volatile solvent, and 20% by mass or less. More preferably, the content is 10% by mass or less, and most preferably 1% by mass or less.

(D) Acidic group-containing polymerizable monomer As a coupling agent, X in the general formula (I) is a functional group which forms an M-OH structure in which a hydroxyl group (OH) is directly bonded to the metal element M by hydrolysis. When using a thing, it is also preferable to use (D) acidic group containing polymerizable monomer as a polymerizable monomer. By using the acidic group-containing polymerizable monomer, it is possible to accelerate the hydrolysis reaction of the coupling agent and efficiently generate the M-OH structure. As a result, the reaction between the polyaryl ether ketone resin composite material and the metal oxide proceeds more, and the adhesion is improved.

  However, when the acidic group-containing polymerizable monomer is added to the adhesive composition for a polyaryl ether ketone complex, the acidic group-containing polymerizable monomer and the coupling agent are stored in the same package. Although it is good, from the viewpoint of storage stability, the storage form is divided into at least two packages, and (A) the acidic group-containing polymerizable monomer is blended in a package different from the coupling agent having a polymerizable functional group It is preferable to do. This is because, when the acidic group-containing polymerizable monomer is blended in the same package as the coupling agent having a polymerizable functional group (A), the hydrolysis reaction proceeds during storage, so storage stability The reason is that it is difficult to obtain the advantage of being a functional group that generates an M-OH structure in which a hydroxyl group (OH) is directly bonded to the metal element M due to the hydrolysis that is high.

  As such an acidic group-containing polymerizable monomer, as long as it has at least one polymerizable functional group and at least one acidic group in the molecule, known monomers can be used without particular limitation.

In the present invention, the acidic group means phosphinico group {= P (= O) OH}, phosphono group {-P (= O) (OH) ₂ }, carboxyl group {-C (= O) OH}, sulfo. group _(-SO 3 H) not only the free acid groups with -OH, such as, two are dehydrated condensed acid anhydride structure of the acidic group having an -OH exemplified above (e.g., -C (= O) -O-C (= O)-), or an acid halide group (for example, -C (= O) Cl) in which -OH of the acidic group having -OH exemplified above is substituted with halogen, etc. And a group in which the aqueous solution or aqueous suspension of the polymerizable monomer having the group shows acidity. The acidic group preferably has a pKa of less than 5.

  When the acidic group-containing polymerizable monomer has two or more polymerizable functional groups in the molecule, the compound is a polymerizable monomer having two or more polymerizable functional groups in the molecule and an acidic group. It is also a contained polymerizable monomer.

  Specific examples of such acidic group-containing polymerizable monomers include 2- (meth) acryloyloxyethyl dihydrogen phosphate, bis (2- (meth) acryloyl oxyethyl) hydrogen phosphate, 2- (2-) Meta) acryloyloxyethyl phenyl hydrogen phosphate, 10- (meth) acryloyl oxy decyl dihydrogen phosphate, 6- (meth) acryloyl oxy hexyl di hydrogen phosphate, bis (6- (meth) acryloyl oxy hexyl) Polymerizable monomers having a phosphinicoxy group or phosphonooxy group in the molecule, such as hydrogen phosphate, 2- (meth) acryloyloxyethyl 2-bromoethyl hydrogen phosphate, and the like, and acid-free polymers thereof Things and acid halides.

  Also, (meth) acrylic acid, N- (meth) acryloyl glycine, N- (meth) acryloyl aspartic acid, N- (meth) acryloyl-5-aminosalicylic acid, 2- (meth) acryloyl oxyethyl hydrogen succinate, 2- (Meth) acryloyloxyethyl hydrogen phthalate, 2- (Meth) acryloyloxyethyl hydrogen malate, 6- (Meth) acryloyloxyethyl naphthalene-1,2,6-tricarboxylic acid, O- (meth) acryloyl tyrosine N- (meth) acryloyl tyrosine, N- (meth) acryloyl phenylalanine, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-O-aminobenzoic acid, p-vinylbenzoic acid, 2 -(Meth) acryloyloxy rest Intramolecular, such as acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid And polymerizable monomers having one carboxyl group, and acid anhydrides and acid halides thereof.

  Also, 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 10- (meth) acryloyloxydecane-1,1-dicarboxylic acid, 12- (meth) acryloyl oxide decane-1,1-dicarboxylic acid, 6- (Meth) acryloyloxyhexane-1,1-dicarboxylic acid, 2- (meth) acryloyloxyethyl-3′-methacryloyloxy-2 ′-(3,4-dicarboxybenzoyloxy) propyl succinate, 4-bis (2- (meth) acryloyloxyethyl) pyromellitate, N, o-di (meth) acryloyltyrosine, 4- (2- (meth) acryloyloxyethyl) trimellitate, 4- (meth) acryloyloxyethyl trimeryt Tate, 4- (meth) acryloyloxybutyl trimellitate, -(Meth) acryloyloxyhexyl trimellitate, 4- (meth) acryloyloxydecyl trimellitate, 4-acryloyloxybutyl trimellitate, 6- (meth) acryloyloxyethyl naphthalene-1,2,6-tricarboxylic acid Anhydride, 6- (meth) acryloyloxyethyl naphthalene-2,3,6-tricarboxylic acid anhydride, 4- (meth) acryloyloxyethylcarbonylpropionoyl-1,8-naphthalic acid anhydride, 4- (meth) ) Polymerizable monomers having a plurality of carboxyl groups or their acid anhydride groups in the molecule, such as acryloyloxyethyl naphthalene-1,8-tricarboxylic acid anhydride, and acid anhydrides and acid halides thereof It can be mentioned.

  In addition, polymerizable monomers having a phosphono group in the molecule, such as vinylphosphonic acid and p-vinylbenzenephosphonic acid, may be mentioned.

Moreover, the polymerizable monomer which has a sulfo group in molecule | numerators, such as 2- (meth) acrylamido -2- methyl propane sulfonic acid, p-vinylbenzene sulfonic acid, vinyl sulfonic acid, is mentioned.

  In addition to those exemplified above, JP-A-54-11149, JP-A-58-140046, JP-A-59-15468, JP-A-58-173175, JP-A 61-293951, JP-A-7-179401, JP-A-8-208760, JP-A-8-319209, JP-A-10-236912, JP-A-10-245525, etc. Acidic group-containing polymerizable monomers can also be suitably used.

  These acidic group-containing polymerizable monomers may be used alone or in combination of two or more.

  1-40 mass parts is preferable with respect to 100 mass parts of all the polymerizable monomers, and, as for the compounding quantity of an acidic group containing polymerizable monomer, 5-20 mass parts is more preferable. When the amount of the acidic group-containing polymerizable monomer is small, hydrolysis of the coupling agent may be insufficient, and high adhesion may not be obtained. When the amount of the acidic group-containing polymerizable monomer is too large, the water absorbency of the adhesive composition for polyaryl ether ketone resin composite material becomes high. As a result, for example, when used in the oral cavity, excessive absorption of water may cause deterioration of the layer of the adhesive composition, and in particular, long-term adhesion may be reduced.

  In the adhesive composition for a polyaryl ether ketone resin composite material of the present invention, if necessary, a filler, a polymerization inhibitor, a polymerization inhibitor, a dye and the like within a range not significantly inhibiting the effects of the present invention. , Pigments, perfumes, etc. may be contained.

  When a filler is added to the adhesive composition for a polyaryl ether ketone resin composite material of the present invention, if necessary, the filler is not particularly limited and known inorganic fillers, organic fillers, organic-inorganic composite fillers Etc. can be used. By containing the filler, the strength of the adhesive composition which has penetrated into the fine unevenness present on the surface of the polyaryl ether ketone resin composite material is enhanced, and higher adhesion 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. When these inorganic fillers are used, those which have been subjected to silane coupling treatment are preferred. As a silane coupling agent, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyl Triacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacroyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyl Dimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl ether Silane, N- phenyl--γ- aminopropyltrimethoxysilane, 11-methacryloyloxy undecyl trimethoxysilane, 11-methacryloyloxy such acryloyloxy undecyl methyl dimethoxy silane.

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

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

  On the other hand, when the adhesive composition contains a large amount of filler, the viscosity of the adhesive composition tends to increase and the adhesiveness tends to decrease, and the layer of the adhesive composition becomes thick. There is a tendency. Therefore, 20 parts by mass or less is preferable, 100 parts by mass or less is more preferable, 10 parts by mass or less is more preferable, and 5 parts by mass or less is more preferable with respect to 100 parts by mass of the adhesive composition.

  Although the particle size and shape of the filler are not particularly limited, it is preferable that the particle size is small from the viewpoint of forming a uniform layer of the adhesive composition. As a particle diameter of a filler, it is preferable that an average volume particle diameter is 100 micrometers or less, 0.01-10 micrometers is more preferable, and 0.01 micrometers-1 micrometer are still more preferable.

  The adhesive composition for a polyaryl ether ketone resin composite material of the present invention may contain a polymerization initiator and be used as an adhesive for a polyaryl ether ketone resin composite material. It may be used as a primer for aryl ether ketone resin complex material. As described later, since there are advantages in each of the case of using an adhesive and the case of using a primer, they may be appropriately selected according to the application.

  When used as an adhesive for polyaryl ether ketone resin composite materials, a strong and uniform adhesive layer can be easily obtained, as compared to the case where it is used as a primer for polyaryl ether ketone resin composite materials, Higher adhesion can be obtained. From the viewpoint of adhesion, it is preferable to blend a polymerization initiator to form an adhesive for a polyaryl ether ketone resin composite material.

  As the polymerization initiator, a photopolymerization initiator, a chemical polymerization initiator or a thermal polymerization initiator can be used, and two or more kinds of polymerization initiators can be used in combination. In addition, since it can carry out simply when hardening the adhesive agent for polyaryl ether ketone resin composite materials after application to polyaryl ether ketone resin composite materials, photopolymerization initiator and / or chemical polymerization start It is preferred to use an agent. Since polyaryl ether ketone resin is usually an opaque material, it may be difficult to irradiate light to the adhesive, so a chemical polymerization initiator is most preferable. These three types of polymerization initiators will be described in more detail below.

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

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

  As tertiary amines, N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N , N-diethyl-p-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethyl Aminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylanthralic acid methyl ester, N, N-dihydroxyethylaniline, N, N-Dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol p-dimethylaminostilbene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine, tributylamine, tripropylamine Triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate, N, N- Examples include diethylaminoethyl methacrylate, 2,2 '-(n-butylimino) diethanol and the like. These can be used singly or in combination of two or more.

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

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

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

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

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

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

  Representative organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxy dicarbonates, peroxy esters, diaryl peroxides and the like.

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

  As peroxyketals, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-) Butylperoxy) 3,3,5-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 can be mentioned.

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

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

  Examples of diacyl peroxides include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, and succinic acid peroxide. Oxide, m-toluoyl benzoyl peroxide, benzoyl peroxide and the like can be mentioned.

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

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

  Also, t-butyltrimethylsilyl peroxide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and the like can be used as suitable organic peroxides.

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

  A system in which a sulfinic acid such as benzenesulfinic acid or p-toluenesulfinic acid and a salt thereof is further added to an initiator system comprising the organic peroxide and the amine compound, and a barbituric acid such as 5-butyl barbituric acid Even if it is the system which added the initiator, it can be used without any problem.

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

  In addition, chemical polymerization initiators based on aryl borate compounds / acidic compounds can also be used, which utilizes the fact that aryl borate compounds are decomposed by acids to generate radicals.

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

  Examples of aryl borate compounds having three boron-aryl bonds in one molecule include monoalkyltriphenylboron, monoalkyltris (p-chlorophenyl) boron, monoalkyltris (p-fluorophenyl) boron, monoalkyltris (3) 5,5-Bistrifluoromethyl) phenylboron, monoalkyltris [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, monoalkyltris (P-nitrophenyl) boron, monoalkyltris (m-nitrophenyl) boron, monoalkyltris (p-butylphenyl) boron, monoalkyltris (m-butylphenyl) boron, monoalkyltris (p-butyloxyphenyl) ) Boron, monoalkyl tris (m-buty Oxyphenyl) boron, monoalkyltris (p-octyloxyphenyl) boron, monoalkyltris (m-octyloxyphenyl) boron, provided that the alkyl in any compound is n-butyl, n-octyl or n-dodecyl Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutyl ammonium salt, tetramethyl ammonium salt, tetraethyl ammonium salt, tributyl amine salt, triethanolamine salt, methyl pyridinium salt, ethyl pyridinium salt) Examples include butyl pyridinium salts, methyl quinolinium salts, ethyl quinolinium salts or butyl quinolinium salts.

  As an aryl borate compound having 4 boron-aryl bonds in one molecule, tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl) phenyl Boron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis (m-) Nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis (p-octyloxyphenyl) ) Boron, tetrakis (m- Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutyl ammonium salt of butyloxyphenyl) [wherein in any compounds, alkyl represents either n-butyl, n-octyl or n-dodecyl] Tetramethyl ammonium salt, tetraethyl ammonium salt, tributyl amine salt, triethanolamine salt, methyl pyridinium salt, ethyl pyridinium salt, butyl pyridinium salt, methyl quinolinium salt, ethyl quinolinium salt or butyl quinolinium salt, etc. It can be mentioned.

  The various aryl borate compounds exemplified above may be used in combination of two or more.

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

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

  The blending amount of these polymerization initiators is preferably in the range of 0.01 to 10 parts by mass, and more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of all the polymerizable monomers. . When the amount of the polymerization initiator is less than 0.01 parts by mass, curing of the adhesive for polyaryl ether ketone resin composite material is insufficient, and the strength of the adhesive layer tends to be lowered. On the other hand, when the amount of the polymerization initiator exceeds 10 parts by mass, the amount of unreacted polymerization initiator and the residue of the reacted polymerization initiator increase, and the coupling agent of the adhesive and the metal of the polyaryletherketone resin composite material There is a possibility that the interaction with the oxide may be adversely affected, and in particular, it may be a factor to reduce the long-term adhesion.

  When used as a primer for a polyaryl ether ketone resin composite material, the thickness of the layer of the adhesive composition is reduced compared to the case of using it as an adhesive for a polyaryl ether ketone resin composite material Things will be easier. By thinning the layer of the adhesive composition, for example in dental applications, a high degree of compatibility is obtained when attaching a dental prosthesis made of polyaryletherketone resin composite material to an abutment tooth, or poly When producing a dental prosthesis using a dental curable composition such as an aryl ether ketone resin composite material and a hard resin, it becomes possible to produce a highly aesthetic dental prosthesis, etc. It becomes easy to provide a material excellent in aesthetics and dimensional stability. From the viewpoint of the thickness of the layer of the adhesive composition, it is preferable to use a primer for a polyaryl ether ketone resin composite material from the viewpoint of aesthetics and dimensional stability without blending a polymerization initiator.

  When a polymerization initiator is not added, a part of components forming a chemical polymerization initiator system (hereinafter also referred to as a part of a chemical polymerization initiator component) in a primer for polyaryl ether ketone resin composite material A curable composition containing a component forming the chemical polymerization initiator system with a part of the chemical polymerization initiator component (for example, in dental use, dental resin cement, dental composite resin, dental It is preferable to use it in combination with a hard resin etc.). That is, a primer for polyaryl ether ketone resin composite material in which a part of the chemical polymerization initiator component is blended is applied to the adherend surface of the polyaryl ether ketone resin composite material, and then chemical polymerization initiation mixed in the primer A curable composition is used over the primer that contains some of the agent components and a chemical initiator component that forms a chemical polymerization initiator system. Thus, in the primer for polyaryl ether ketone resin composite material, in which a part of the chemical polymerization initiator component is not formed, which does not form a chemical polymerization initiator system, the chemical polymerization initiator component of the curable composition causes the chemical reaction. Since the polymerization initiator system is formed, the curability of the primer layer is improved and the adhesion is improved. On the other hand, since the primer does not contain a polymerization initiator such as all components of the chemical polymerization initiator, the primer layer maintains fluidity without polymerization and curing until the curable composition is brought into contact with the primer layer. The primer layer can be made thin by an operation of pressing the curable composition which is usually performed.

  As a partial component of the chemical polymerization initiator component, it is possible to use the component of what was illustrated as a chemical polymerization initiator of the above-mentioned polymerization initiator.

  As a part of the chemical polymerization initiator component, in particular, it is preferable from the viewpoint of improving adhesion to add a compound capable of acting as a reducing agent to the primer for polyaryl ether ketone resin composite material. Although the cause of the improvement in adhesion by this is not known in detail, when this primer is applied to the surface of the polyaryl ether ketone resin composite material by incorporating the reducing agent into the primer, the reducing agent in the primer becomes By acting on the resin on the surface of the polyaryl ether ketone resin composite material and reducing a part of the ketone group, a carbon atom having two arylene groups, a hydroxyl group and a hydrogen atom as a substituent is a polyaryl ether ketone resin It forms on the surface of the composite material. Since a radical is easily generated by hydrogen abstraction on a carbon atom having such two arylene groups, a hydroxyl group and a hydrogen atom as a substituent, polyaryl ether ketone resin composite material when the primer is polymerized and cured. A bond is formed between the carbon atom adjacent to the hydroxyl group generated on the surface and the laminated radical polymerizable monomer. As a result, it is presumed that the adhesion is improved.

  In addition, as a part of the chemical polymerization initiator component, high activity as a chemical polymerization initiator, maintaining the highest possible fluidity until just before the primer layer comes in contact with the curable compound, and storage stability It is preferable to blend the transition metal compound of the 4th cycle into the primer, from the balance of the above. It is more preferable that it is a vanadium compound as a transition metal compound of the 4th period mix | blended with a primer.

  Considering these points, some of the components of the chemical polymerization initiator component to be incorporated into the primer are preferably transition metal compounds of the fourth cycle that can function as a reducing agent, and among the particularly stable vanadium compounds, they have a low oxidation number and reduced Most preferred are vanadium compounds of high performance + IV.

  The viscosity of the adhesive composition for a polyaryl ether ketone resin composite material of the present invention is preferably low. Due to the low viscosity of the adhesive composition for the polyaryl ether ketone resin composite material, the adhesive composition easily penetrates into fine irregularities on the surface of the polyaryl ether ketone resin composite material, and It becomes easy to apply | coat the adhesive composition for polyaryl ether ketone resin composite materials uniformly on the aryl ether ketone resin composite material surface, and it becomes easy to obtain higher adhesiveness. On the other hand, when the viscosity of the adhesive composition for the polyaryl ether ketone resin composite material is too low, the adhesive composition for the polyaryl ether ketone resin composite material has a complicated structure due to the sag or the like. In some cases, it may be difficult to apply the adhesive composition for the polyaryletherketone resin composite material uniformly to the adhesion surface of the polyaryletherketone resin composite material. Therefore, the viscosity of the adhesive composition for a polyaryl ether ketone resin composite material is preferably in the range of 0.3 cP to 3000 cP at 23 ° C., and more preferably in the range of 0.4 cP to 500 cP. The range of 0.5 cP to 30 cP is more preferable, and the range of 0.5 cP to 10 cP is most preferable. The measurement of the viscosity may be performed using a cone-plate viscometer in a temperature-controlled room kept at 23 ° C. The packaging of the adhesive composition for the polyaryl ether ketone resin composite material is divided into two or more, and when the mixture is used immediately before the application to the polyaryl ether ketone resin composite material, 23 ° C. The viscosity may be measured using a cone-plate viscometer immediately after mixing them in a temperature-controlled room kept at.

  The polyaryl ether ketone resin composite material means a composite material in which a polyaryl ether ketone resin and a metal oxide are mixed.

  The polyaryl ether ketone resin composite material which can use the adhesive composition for the polyaryl ether ketone resin composite material of the present invention is a polyaryl of a compounding amount which provides the advantages of the polyaryl ether ketone resin such as high strength. It contains an ether ketone resin, preferably contains 20% by mass or more, more preferably 30% by mass or more, and most preferably 50% by mass or more of a polyaryl ether ketone resin, and a metal oxide It is contained.

  In such a polyaryl ether ketone resin composite material, in addition to a material composed of a composite material in which only a polyaryl ether ketone resin and a metal oxide are mixed, a blend of a polyaryl ether ketone resin and another resin is used. Composite materials mixed with metal oxides used as resin matrix, polyaryletherketone resin or blends of polyaryletherketone resin and other resins are used as resin matrix metal oxides and other fillers Composite materials mixed with each other. In addition, minor components such as pigments and stabilizers may be added to these materials.

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

  Other resins that can be blended with the polyaryl ether ketone resin are not particularly limited as long as they do not significantly deteriorate the physical properties of the polyaryl ether ketone resin such as rigidity and toughness, and examples thereof include polyarylates, Polycarbonate, polyethylene terephthalate, polyphthalamide, polytetrafluoroethylene and polyphenylene ether can be mentioned.

  As a metal oxide, a well-known thing can be utilized without a restriction | limiting especially, Oxides, such as a silica, an alumina, a titania, a zirconia, or complex inorganic oxides, such as a silica- zirconia, a silica-titania, a silica-alumina. Among these, since the reactivity with a silane coupling agent preferable as a coupling agent is high, and high adhesion is easily obtained, silica-based metal oxides such as silica or silica-zirconia, silica-titania, silica-alumina and the like Is preferred, and silica is most preferred. In addition, only one type of these metal oxides may be mix | blended with a polyaryl ether ketone resin composite material, and two or more types may be mix | blended.

  The compounding amount of the metal oxide to the polyaryl ether ketone resin composite material is a polyaryl ether ketone resin because high adhesiveness can be easily obtained by the adhesive composition for a polyaryl ether ketone resin composite material of the present invention. The content is 10% by mass or more of the composite material, preferably 15% by mass or more, and more preferably 25% by mass or more. On the other hand, when a large amount of metal oxide is blended, it becomes difficult to prepare a polyaryl ether ketone resin composite material in which the polyaryl ether ketone resin and the metal oxide are uniformly mixed, and the metal oxide is a polyaryl ether ketone The compounding amount of the metal oxide is a polyaryl ether ketone resin composite material because the resin and the metal oxide are difficult to be separated and it is difficult to obtain the effect of the adhesion improvement by the formation of the bond between the coupling agent and the metal oxide. 70 mass% or less of is preferable, and 50 mass% or less is more preferable.

  The adhesive composition for the polyaryl ether ketone resin material of the present invention is not particularly limited as long as it is used at least for adhesion to the polyaryl ether ketone resin composite material. In addition, when the adhesive composition contains a volatile solvent, natural drying, air blow, etc. before curing the coating layer of the adhesive composition formed on the surface of the polyaryl ether ketone resin composite material The volatile solvent in the coating layer can be removed by In addition, the polyaryl ether ketone resin material used as the to-be-adhered body of the adhesive material of this invention may be called "1st member" hereafter.

  The adhesive composition for a polyaryl ether ketone resin composite material of the present invention is more preferably used for a polyaryl ether ketone resin composite material having a roughened adhesion surface. The roughened poly (aryl ether ketone) resin composite material has higher surface roughness, to which the application of the adhesive composition for poly (aryl ether ketone resin) composite material of the present invention is higher. Adhesiveness can be obtained. The roughening can be carried out in a simple and safe manner before applying the adhesive composition for a polyaryl ether ketone resin composite material of the present invention to the polyaryl ether ketone resin composite material. Roughening treatment may be performed on the adhesion surface of the composite material. As a roughening method, it is preferable to sandblast the surface of the polyaryletherketone resin composite material. Sandblasting is generally performed in a dental laboratory or the like, and can easily and safely roughen the adhesion surface of the polyaryletherketone resin composite material to contribute to the improvement of adhesion. Sandblasting may be carried out by a method which is usually carried out. For example, in the dental field, generally, alumina particles having a particle diameter of several μm to several hundreds of μm are several tens of KPa to several MPa using a sandblasting apparatus. It carries out by injecting on a polyaryl ether ketone resin composite material adhesion side with pressure. That is, when the adhesive composition for polyaryl ether ketone resin composite material of the present invention is applied to the polyaryl ether ketone resin composite material thus roughened, the effect of the present invention is further enhanced. It is possible to demonstrate high. From such a point of view, it can also be used as a kit of the adhesive composition for the polyaryletherketone resin composite material of the present invention and the polyaryletherketone resin composite material having the roughened adhesion surface. It is.

  The adhesion method using the adhesive composition for polyaryl ether ketone resin composite material of the present invention is carried out by applying the adhesive composition of the present invention to the surface of the first member. When the adhesive composition is applied to the surface of the first member, the adhesive composition may be applied to the surface of the first member in the form of a mixture mixed with another composition. Further, the form of applying the adhesive composition to the surface of the first member is not particularly limited. For example, the adhesive composition may be directly applied to the surface of the first member, or other members than the first member. After the adhesive composition is applied to the surface, the adhesive composition can be brought into contact with the surface of the first member by bringing the other member into contact with the first member.

  In addition, when the polymerizable monomer to be added to the adhesive composition for a polyaryl ether ketone resin composite material is a radical polymerizable monomer, a polyaryl ether ketone resin in which an adhesion surface is reacted with a reducing agent It is also suitable to use for composite materials. By reducing the surface of the polyaryl ether ketone resin composite material with a reducing agent, the ketone group of the polyaryl ether ketone resin is reduced, and the surface of the adherend has two arylene groups, a hydroxyl group and a hydrogen atom as substituents. Carbon atoms will be present. Since this carbon atom is a structure which easily generates a radical, when the adhesive composition cures by radical polymerization, a bond is formed between the polymerizable monomer and the polyaryletherketone resin. This leads to a further improvement in adhesion. In this case, the reducing agent is preferably a hydride reducing agent from the viewpoint of its reaction efficiency, and particularly preferably sodium borohydride from the viewpoint of ease of handling and the like. As a method of reacting the polyaryl ether ketone resin composite material and the reducing agent, for example, a mass of the polyaryl ether ketone resin composite material is put into a solution in which the reducing agent is dissolved and heated, or the reducing agent is dissolved. There is a method in which the solution is applied to the adhesion surface of the polyaryl ether ketone resin composite material and then heated in an oven or the like. The reaction temperature (heating temperature) in that case is preferably 60 ° C. to 180 ° C., and more preferably 90 ° C. to 150 ° C. from the viewpoint of reaction efficiency, workability and the like. The solvent for dissolving the reducing agent may be one which can dissolve the reducing agent in an amount necessary for the reaction and which does not deactivate the reducing agent or does not inhibit the function of the reducing agent, for example, dimethyl Sulfoxide, 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 decreases and the effect of improving the adhesiveness is hardly obtained, and if the concentration is too high or the reducing agent is not completely dissolved, polyaryletherketone resin composite Since there is a risk that the reducing agent or the reaction residue of the reducing agent may precipitate on the surface of the body material to reduce the reactivity, the range of 0.1 mol / l to 30 mol / l while the reducing agent is completely dissolved. Preferably, the range of 0.5 mol / l to 5 mol / l is more preferable.

  In the adhesion method using the adhesive composition for polyaryl ether ketone resin composite material of the present invention, an adhesive application step of applying the adhesive composition of the present invention to the surface of the first member, and as necessary Curing the adhesive composition. In the adhesive application step, the adhesive composition may be applied to the surface of the first member in the form of a mixture mixed with other compositions, and in the curing step, the adhesive composition may be combined with other compositions. It may be cured in the form of a mixed mixture. Further, the form of applying the adhesive composition to the surface of the first member is not particularly limited. For example, the adhesive composition may be directly applied to the surface of the first member, or other members than the first member. After the adhesive composition is applied to the surface, the adhesive composition can be brought into contact with the surface of the first member by bringing the other member into contact with the first member.

  If the first member is a member in the vicinity of the adherend which comes into contact with the adhesive composition for polyaryl ether ketone resin composite material of the present invention at the time of adhesion, the first member is composed of polyaryl ether ketone resin composite material It may be a similar member. Further, the bonding target of the adhesive composition for polyaryl ether ketone resin composite material of the present invention may be only the first member, or may be the first member and the second member.

  When the object to be bonded is made of only the first member, for example, one end and the other end of the ring-shaped first member provided with the joint can be bonded using the adhesive composition of the present embodiment. Moreover, you may adhere | attach in the form filled with the adhesive composition of this embodiment to the recessed part of the 1st member in which recessed parts, such as a hole and a groove | channel, were provided. In this case, the recess is embedded and the layer of the adhesive composition filled in the recess is adhered to the inner wall surface of the recess of the first member. It is also possible to produce a structure covered with the adhesive composition of the present invention by applying the adhesive composition of the present invention to the surface of the first member.

  Moreover, when an adhesion | attachment target object consists of two members, a 1st member and a 2nd member, a 1st member and a 2nd member are adhere | attached using the adhesive composition of this embodiment. Here, the second member is not particularly limited as long as it is a member capable of adhering to the adhesive composition of the present embodiment. For example, a member which forms a solid before starting the bonding operation (hereinafter referred to as “solid second” It may be referred to as “a component”, and it is in the form of a paste or liquid before the start of the bonding operation, and hardens during the bonding operation, and solidifies after completion of the bonding operation. Component (hereinafter may be referred to as "curable second member").

  The solid second member may be a polyaryl ether ketone resin composite material similarly to the first member, and a member which does not contain the polyaryl ether ketone resin composite material at all in the vicinity of the adherend surface (first member May be a different member).

  The curable second member may function as an adhesive. In this case, the cured product of the adhesive composition for a polyaryl ether ketone resin composite material of the present invention and the cured product of a curable second member can be firmly bonded. In addition to this, the curable second member can also be used for adhesion to other solid members (hereinafter sometimes referred to as "third member"). For example, if the curable second member has a property of firmly adhering to the surface of the third member, the adhesive composition for the polyaryl ether ketone resin composite material of the present invention on the first member side The first member and the third member can be firmly bonded by applying the second member before curing and bonding to the third member side. The third member can be used without particular limitation as long as it is a known solid member, but normally, a member in the vicinity of the adhesion surface uses a member (a member different from the first member) which is not a polyaryletherketone resin composite material Is preferred. The details of the first member, the second member and the third member will be described later.

  The specific adhesion procedure can be appropriately determined according to the composition of the adhesion target and the adhesive composition for polyaryl ether ketone resin composite material.

  When the adhesive composition for a polyaryl ether ketone resin composite material is an adhesive for a polyaryl ether ketone resin composite material containing all components of a polymerization initiator, adhesion is carried out according to the following procedure. be able to.

  When only the first member is used as the bonding object, for example, after the adhesive is applied to the surface of the first member, the adhesive may be cured. When a thermal polymerization initiator or a photopolymerization initiator is used as the polymerization initiator, the adhesive can be cured by heating or light irradiation after coating. When a chemical polymerization initiator is used as the polymerization initiator, an adhesive mixed with all components of the chemical polymerization initiator may be applied to the surface of the first member immediately before application. In this case, the adhesive can be cured as time passes after application.

  In the case where the first member and the solid second member are used as the bonding object, for example, after applying the adhesive to the surface of at least one of the first member or the solid second member, the first member and the solid The second member may be brought into contact via the coating layer of the adhesive, and then the adhesive may be cured.

  In the case of using the first member and the curable second member as the bonding object, for example, after the adhesive is applied to the surface of the first member, the curable second member is further applied, and the adhesive and the curable second member are applied. The curing process may be carried out in one step of simultaneously curing the component, or after the coating and curing of the adhesive are sequentially performed, the two step curing of sequentially coating and curing the curable second member Processing may be performed. The timing of the curing treatment, the number of times, and the curing method (heat curing, light curing, chemical curing) can be appropriately selected according to the kind of the polymerization initiator blended in the adhesive and the curable second member.

  When the third member is further used, for example, after an adhesive is applied to the surface of the first member and a curable second member is applied to the surface of the third member, the adhesive for the first member is applied. The second surface and the surface of the third member to which the curable second member is applied may be brought into contact with each other, and then the adhesive and the curable second member may be cured. In this case, before the first member and the third member are brought into contact with each other, any one member of the adhesive and the curable second member is first cured and the first member and the third member are brought into contact with each other. The other member can also be cured.

  Further, after applying an adhesive and a curable second member to the surface of the first member in this order, the third member is brought into contact with the surface to which the adhesive of the first member and the curable second member are applied, Thereafter, the adhesive and the curable second member may be cured. In this case, after the adhesive is applied to the surface of the first member and cured, the curable second member is further applied, and the surface of the first member on which the curable second member is applied and the third member The curable second member may be cured after the contact. Alternatively, after the curable second member and the adhesive are applied in this order on the surface of the third member, the first member is brought into contact with the surface of the third member on which the curable second member and the adhesive are applied, Thereafter, the curable second member and the adhesive may be cured. In this case, after the curable second member is applied and cured on the surface of the third member, an adhesive is further applied, and the surface of the third member on which the adhesive is applied is brought into contact with the first member After that, the adhesive may be cured. In addition, the member which applies an adhesive material and a curable 2nd member, the timing, and the timing which hardens these members can be selected suitably.

  When the adhesive composition for a polyaryl ether ketone resin composite material is a primer for a polyaryl ether ketone resin composite material not containing all the components of a polymerization initiator, adhesion is carried out according to the following procedure. Can.

  In the case of using the first member and the curable second member as the bonding object, for example, after applying the primer to the surface of the first member, the curable second member is further applied, and then the curable second member is cured You should do it. The timing of the curing treatment and the curing method (heat curing, light curing, chemical curing) can be appropriately selected according to the type of the polymerization initiator to be blended in the curable second member.

  When the third member is further used, for example, after a primer is applied to the surface of the first member and a curable second member is applied to the surface of the third member, the surface of the first member on which the primer is applied The surface on which the three-member curable second member is applied may be brought into contact, and thereafter, the curable second member may be cured.

  In addition, after the primer and the curable second member are applied in this order to the surface of the first member, the third member is brought into contact with the surface of the first member on which the primer and the curable second member are applied. The curable second member may be cured. Alternatively, after the curable second member and the primer are applied in this order on the surface of the third member, the surface of the third member on which the curable second member and the primer are applied is brought into contact with the first member, The curable second member may be cured. In addition, the member which apply | coats a primer or curable 2nd member, the timing, and the timing which hardens a curable 2nd member can be selected suitably.

  The solid second member to which the adhesive composition of the present invention can be applied is not particularly limited as long as it is a member made of a known solid material, and the material composition and the structure of the member, the first member and the solid second member May be the same or different. When the solid second member is a member including a polyaryl ether ketone resin composite material as in the first member, the adhesive composition of the present embodiment is the same as in the case of bonding to the first member. It is possible to adhere to the solid second member with high adhesion. The material constituting the solid second member is, for example, a) various resins such as polyaryl ether ketone resin, materials mainly composed of organic substances other than resin (pulp materials etc.), metals, used in the first member Materials that can be artificially produced or purified such as inorganic compounds, b) composite materials using two or more of the materials shown in a), or c) non-artificial materials such as teeth and bones It may be a biomaterial or the like.

  Moreover, a curable 2nd member contains at least a polymerization initiator and a polymerizable monomer. As each component which comprises a curable 2nd member, the material which can be used with the adhesive composition for polyaryl ether ketone resin composite materials of this invention can be combined suitably, and can be utilized. However, the composition of the curable second member is usually selected to be different from the adhesive composition for the polyaryletherketone resin composite material of the present invention actually used for adhesion. In addition, since the curable second member contains a polymerizable monomer, the curable second member and the adhesive composition of the present invention are firmly adhered. When the third member is further used, the polymerizable monomer contained in the curable second member may also interact with the surface of the third member to bond the curable second member to the third member. it can. Preferably, the composition of the curable second member is selected to have a high affinity to the material constituting the adhered portion of the third member.

  The third member is not particularly limited as long as it is a member made of a known solid material, and the same member as the solid second member can be used. However, as the third member, in general, it is preferable to use a member in which the deposition part constituting material does not contain the polyaryl ether ketone resin composite material.

  The adhesive composition for polyaryl ether ketone resin composite material of the present invention can be used in any application. In addition, as the bonding object, at least a first member according to the application is used, and further, if necessary, a) solid second member, b) curable second member, or c) curable second A member and a third member are used. However, the adhesive composition for polyaryl ether ketone resin composite materials of the present invention is preferably used in the dental field.

  In dental applications, particularly high adhesion is required because adhesion is required in the particularly severe environment of the oral cavity, and it is easy to meet the requirements by using the adhesive composition of the present invention. It becomes. In addition, adhesive compositions used in dental applications are often designed with special consideration for their affinity to dentin. The properties required of a suitable adhesive composition are not the same, as the dentin and the polyaryl ether ketone resin composite material are largely different in properties such as surface properties. Therefore, there is a need for adhesive compositions that can provide high adhesion, particularly when using polyaryletherketone resin composite materials for dental applications.

  Also, in dental applications, it is necessary to be able to preserve the adhesive composition without causing deterioration over a long period of time (excellent storage stability), since the adhesive composition is usually used in extremely small amounts for each dental treatment. Be From this point, the storage form is divided into at least two packages when compounding the (A) coupling agent having a polymerizable functional group and the (D) acidic group-containing polymerizable monomer in the adhesive composition (A) Blending the (D) acidic group-containing polymerizable monomer in a package different from the coupling agent having the polymerizable functional group (A) is particularly preferable as an adhesive composition used for dental use is there.

  As a dental polyaryletherketone resin composite material (a dental first member) that can be used as a dental member, at least a portion in the vicinity of the adherend surface or the entire dental first member can be a polyaryletherketone resin and a metal. A denture, an artificial tooth, a denture base, a dental implant, a crown restorative material, an abutment construction material and the like made of a polyaryletherketone resin composite material containing an oxide and the like can be mentioned. Moreover, as a hardenable 2nd member (hardenable 2nd member) which can be used as a dental member, a dental composite resin, a dental hard resin, a dental cement, a dental bonding material, a dental immediate polymerization Resin etc. are mentioned. Furthermore, as the third member, dental members such as dentures made of natural teeth, metal materials, ceramic materials, resin materials, etc., artificial teeth, denture bases, dental implants, crown restorative materials, abutment construction materials, etc. Etc.

  As an example of the method of use of the present invention, a dental hard resin is used as the second member, and a dental polyaryletherketone resin composite material and a dental hard resin are used for the polyaryletherketone resin composite material of the present invention The process of laminating these materials using the adhesive composition to make a dental prosthesis is included. Specifically, for example, the adhesive composition for a polyaryl ether ketone resin composite material of the present invention is applied to the surface of a dental polyaryl ether ketone resin composite material molded into a desired shape, and thereafter, from there on The hard resin can be laminated and cured to make a desired dental prosthesis.

  As another example, a dental cement is used as the second member, and the adhesive composition for a polyaryl ether ketone resin composite material of the present invention is used to make a polyaryl ether ketone resin composite material The step of attaching the prosthesis to the tooth defect may be mentioned. Specifically, for example, the adhesive composition for polyaryl ether ketone resin composite material of the present invention is applied to the adhesion surface of the prosthesis made of polyaryl ether ketone resin composite material prepared in advance, and from above Dental cement can be applied and worn on the teeth.

  Dental parts are required to have mechanical strength that can withstand pressure applied repeatedly during meshing and water resistance to saliva as properties that can withstand use in the oral cavity, but they have excellent mechanical strength and chemical durability. It is extremely easy to sufficiently meet these needs with a dental first member made of a polyaryl ether ketone resin composite material having the following.

  From the viewpoint of color tone and physical properties, as a dental material, particularly a polyaryl ether ketone resin used as a dental restorative material, an ether group and a ketone group constituting the main chain are arranged in the order of ether ether ether ketone It is preferable to use a polyetheretherketone having a repeating unit, or a polyetherketoneketone having a repeating unit arranged in the order of ether, ketone and ketone.

EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The abbreviations and titles shown in the examples are as follows.
[Coupling agent]
<Silane coupling agent>
MPS: γ-methacryloyloxypropyl trimethoxysilane MDS: ω-methacryloyloxydecyl trimethoxysilane MBS: 3- (3-methoxy-4-methacryloyloxyphenyl) propyltrimethoxysilane [radically polymerizable monomer]
<A polymerizable monomer having two or more polymerizable functional groups in the molecule and containing no acidic group>
-BisGMA: 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane-3G: triethylene glycol dimethacrylate-UDMA: 1, 6-bis (methacryloylethyloxycarbonylamino) 2, 2,4-trimethylhexane <acidic group-containing polymerizable monomer having two or more polymerizable functional groups in the molecule>
PM2: bis (2-methacryloyloxyethyl) hydrogen phosphate <a polymerizable monomer having only one polymerizable functional group in the molecule and having no acid group>
HEMA: 2-hydroxyethyl methacrylate <acidic group-containing polymerizable monomer having only one polymerizable functional group in the molecule>
-PM 1: 2-methacryloyloxyethyl dihydrogen phosphate-MDP: 10-methacryloyl oxydecyl dihydrogen phosphate [polymerization initiator]
<Organic peroxide>
・ TMBPO: 1,1,3,3-tetramethylbutyl hydroperoxide <+ Vanadium compound of IV>
· BMOV: bis (maltolate) oxovanadium (IV)

  Tables 1 and 2 show the composition of each adhesive composition, and Table 3 shows the composition of each primer composition.

  As a polyaryl ether ketone resin composite material, spherical silica (average particles) surface-treated with a polyetheretherketone resin (manufactured by Daicel Evonik Co., Ltd .: VESTAKEEP M2G), and γ-methacryloyloxypropyltrimethoxysilane as a metal oxide What mixed the diameter of 1.0 micrometer so that a metal oxide might be 30 mass parts with respect to 70 mass parts of polyetheretherketone resin was used. The mixing method is as follows. First, a predetermined amount of a polyetheretherketone resin and a metal oxide are measured, and this is charged into a kneading lab plastometer (made by Toyo Seiki Co., Ltd.), and melt kneading is performed for 5 minutes under the conditions of a test temperature of 370 ° C. and a rotational speed of 100 rpm. The melt-kneaded product was recovered.

  Each test method is as follows.

(Tensile bond strength measurement)
The above polyaryl ether ketone resin composite material was formed into a plate having a thickness of about 2 mm by injection molding to obtain an adherend. The adherend surface of this adherend was polished with # 800 water-resistant abrasive paper and sandblasted (Alumina particles with a particle size of about 50 μm were sprayed for 10 seconds at a pressure of about 0.2 MPa using a sandblasting apparatus) It was coarsened. Then, it was immersed in water and exposed to ultrasonic waves for 5 minutes, and subsequently, it was immersed in acetone and washed by ultrasonic waves for 5 minutes. Subsequently, a double-sided tape having a hole of 3 mm in diameter was attached to the surface to be adhered.
Then, the adhesive composition (the storage form is divided into two or more packages after mixing all components) was applied to this hole, and after standing for 10 seconds, it was dried by spraying compressed air for about 10 seconds. A dental cement material (Bistite II, manufactured by Tokuyama Dental Co., Ltd.) was applied thereon, and a stainless steel attachment was pressure-welded thereon, to produce an adhesion test piece. The above-mentioned adhesion test piece is held at 37 ° C. for 24 hours, and then pulled using a tensile tester (Autograph, manufactured by Shimadzu Corporation) at a crosshead speed of 2 mm / min to obtain a polyaryl ether ketone resin composite The tensile bond strength between the material and the adhesive composition for polyaryletherketone resin composite material was measured. The tensile bond strength of the polyaryl ether ketone resin composite material and the adhesive composition for the polyaryl ether ketone resin composite material was measured by measuring each of four test pieces for each example or each comparative example. , The mean value and the standard deviation (SD) were determined.

(Adhesive layer thickness)
The above polyaryl ether ketone resin composite material was formed into a plate having a thickness of about 2 mm by injection molding to obtain an adherend. The adherend surface of this adherend was polished with # 800 water-resistant abrasive paper and sandblasted (Alumina particles with a particle size of about 50 μm were sprayed for 10 seconds at a pressure of about 0.2 MPa using a sandblasting apparatus) It was coarsened. Then, it was immersed in water and exposed to ultrasonic waves for 5 minutes, and subsequently, it was immersed in acetone and washed by ultrasonic waves for 5 minutes. Thereafter, the adhesive composition was applied to the surface of the adherend, allowed to stand for 10 seconds, and then compressed air was sprayed for about 10 seconds for drying. Thereafter, a dental cement material (Bistite II, manufactured by Tokuyama Dental Co., Ltd.) is applied on the adhesive composition, and further, a hard dental resin (manufactured by Tokuyama Dental Co., Ltd .: Pearl Esthetic) is cured thereon to produce an attachment. The test piece was produced by press-contacting. After holding the above-mentioned test piece at 37 ° C. for 24 hours, it was cut perpendicularly to the deposition surface using a diamond cutter to expose the cross section of the bonding site. After the bonded portion was polished with # 3000 water-resistant abrasive paper, the thickness of the layer of the adhesive composition was measured as the thickness of the adhesive layer with a laser microscope (manufactured by Keyence Corporation).

Example 1
(A) 0.1 g of MPS as a coupling agent component having a polymerizable functional group, and 2.94 g of bisGMA as a polymerizable monomer component having (2) or more polymerizable functional groups in the (B) molecule 1.96 g, 0.05 g of TMBPO as a polymerization initiator component, and 10 g of acetone as a volatile solvent component (C) were mixed with stirring to obtain a solution A.
(B) As a polymerizable monomer component having two or more polymerizable functional groups in the molecule, 2.04 g of bisGMA, 1.36 g of 3G, (D) as a polymerizable monomer component containing an acidic group 0.8 g of PM1, (B) a polymerizable monomer component having two or more polymerizable functional groups in the molecule and (D) 0.8 g of PM2 as an acidic group-containing polymerizable monomer component, a polymerization initiator A mixture of 0.05 g of BMOV as a component and 10 g of acetone as a volatile solvent component (C) was mixed with stirring to obtain a solution B.
Immediately before use, solutions A and B were collected in equal amounts and mixed to obtain an adhesive for a polyaryl ether ketone resin composite material, and used quickly in the test. Table 1 shows the composition of the adhesive for the polyaryl ether ketone resin composite material and the compositions of the solutions A and B before mixing.
Using the adhesive for the polyaryl ether ketone resin composite material, the tensile bond strength and the adhesive layer thickness of the polyaryl ether ketone resin composite material were measured. The results are shown in Table 4.

<Examples 2 and 3>
An adhesive for a polyaryl ether ketone resin composite material was prepared according to Example 1 except that the composition was changed to the composition shown in Table 1, and the tensile bond strength and the adhesive layer thickness to the polyaryl ether ketone resin composite material were prepared. Was measured. The results are shown in Tables 4 and 6.

<Examples 4 to 13, Comparative Examples 1 to 3>
An adhesive for polyaryl ether ketone resin composite material was prepared according to Example 1 except that the composition was changed to the composition shown in Tables 1 and 2, and the tensile bond strength to the polyaryl ether ketone resin composite material was measured. did. The results are shown in Table 4.

Example 14
0.4 g of MPS as a coupling agent component having a polymerizable functional group (A), 2.76 g of bisGMA as a polymerizable monomer component having two or more polymerizable functional groups in the (B) molecule, 3G1. 84 g of (C) 25 g of acetone as a volatile solvent were mixed with stirring to obtain a solution A.
(B) 2.04 g of bisGMA, 1.36 g of 3G as a polymerizable monomer component having two or more polymerizable functional groups in the molecule, and (PM) PM1 as an acidic group-containing polymerizable monomer component (D) 0.8 g, (B) 0.8 g of PM2 as a polymerizable monomer component having two or more polymerizable functional groups in the (B) molecule and (D) an acidic group-containing polymerizable monomer component, (C) volatility 25 g of acetone as a solvent component was mixed with stirring to obtain a solution B.
Liquid A and B were collected and mixed in the same amount immediately before use to obtain a primer for polyaryl ether ketone resin composite material and used for the test. Table 3 shows the composition of the primer for the polyaryl ether ketone resin composite material and the compositions of the solutions A and B before mixing.
The primer for the polyaryl ether ketone resin composite material was used to measure the tensile bond strength and the adhesive layer thickness of the polyaryl ether ketone resin composite material. The results are shown in Tables 5 and 6.

Example 15
A primer for polyaryl ether ketone resin composite material was prepared according to Example 1 except that the composition was changed to the composition shown in Table 3, and the tensile bond strength and the adhesive layer thickness to the polyaryl ether ketone resin composite material were It was measured. The results are shown in Tables 5 and 6.

Example 16
0.4 g of MPS as a coupling agent component having a polymerizable functional group (A), 27.6 g of bisGMA as a polymerizable monomer component having two or more polymerizable functional groups in the (B) molecule, 3G1. 84 g of (C) 25 g of acetone as a volatile solvent were mixed with stirring to obtain a solution A.
(B) As a polymerizable monomer component having two or more polymerizable functional groups in the molecule, 2.04 g of bisGMA, 1.36 g of 3G, 0.001 g of BMOV as a polymerization initiator component, (D) acidity 0.8 g of PM1 as a polymerizable monomer component containing a group, (B) a polymerizable monomer component having two or more polymerizable functional groups in the molecule and (D) an acidic group-containing polymerizable monomer 0.8 g of PM2 as a component and 25 g of acetone as a volatile solvent component (C) were mixed with stirring to obtain a solution B.
Liquid A and B were collected and mixed in the same amount immediately before use to obtain a primer for polyaryl ether ketone resin composite material and used for the test. Table 3 shows the composition of the primer for the polyaryl ether ketone resin composite material and the compositions of the solutions A and B before mixing. Although BMOV is added to this system as a part of the polymerization initiator component, this alone does not work as a polymerization initiator and a polymerization reaction does not occur, so this composition is a polyaryl ether ketone resin complex It is used as a primer for materials.
The primer for the polyaryl ether ketone resin composite material was used to measure the tensile bond strength to the polyaryl ether ketone resin composite material. The results are shown in Table 5.

<Comparative Examples 4 to 6>
A primer for polyaryl ether ketone resin composite material was prepared according to Example 1 except that the composition was changed to the composition shown in Table 3, and the tensile bond strength to the polyaryl ether ketone resin composite material was measured. The results are shown in Table 5.

(Evaluation results)
Table 4 shows the measurement results of the tensile bond strength of the polyetheretherketone resin materials of Examples 1 to 13 and Comparative Examples 1 to 3 using the adhesive for the polyaryletherketone resin composite material. Table 5 shows the measurement results of the tensile bond strengths of the polyaryl ether ketone resin composite materials of Examples 14 to 16 and Comparative Examples 4 to 6 using the primer for the polyaryl ether ketone resin composite material. Table 6 shows the measurement results of the adhesive layer thickness when using the adhesive for the polyaryl ether ketone resin composite material of Example 2 and 3 and the primer for the polyaryl ether ketone resin composite material of Example 14 and 15 Show.

  In Examples 1 to 13 using the adhesive for a polyaryl ether ketone resin composite material of the present invention, Comparative Example 1 which does not contain a coupling agent, and polymerization having two or more polymerizable functional groups in the molecule All showed high adhesive strength as compared with the case of using the non-inventive adhesive of Comparative Examples 2 and 3 in which the monomer is less than 40% by mass of the total polymerizable monomer.

  For the adhesive for polyaryl ether ketone resin composite material, the same amount of volatile solvent and polymerization initiator are blended, and the same kind of coupling agent and polymerizable monomer are used, but the blending amount is different When Examples 1-5 are compared, the polymerizable monomer which has a 2 or more polymerizable functional group in a molecule | numerator is 60 mass% or more of all the polymerizable monomers, and the compounding quantity of a coupling agent is a total polymerization. In Examples 2 to 4 in the range of 2 to 20 parts by mass with respect to 10 parts by mass of the hydrophobic monomer, the compounding amount of the coupling agent is less than 2 parts by mass with respect to 100 parts by mass of all the polymerizable monomers In comparison with Example 1 which is Example 1 and Example 5 which exceeds 20 mass parts, high adhesive strength was shown. In Examples 2 and 3 in which the compounding amount of the coupling agent is in the range of 3 to 10 parts by mass with respect to 10 parts by mass of the total polymerizable monomers, the compounding amount of the coupling agent is the total polymerizable unit amount It showed high adhesive strength as compared with Example 4 exceeding 10 parts by mass with respect to 100 parts by mass of the body.

  The adhesive agent for the polyaryl ether ketone resin composite material is prepared by blending the same amount of the coupling agent, the volatile solvent and the polymerization initiator, and comparing Examples 5 and 6 having different polymerizable monomer compositions. Example 5 in which the polymerizable monomer having two or more polymerizable functional groups is 60% by mass or more of the total polymerizable monomers is a polymerizable monomer having two or more polymerizable functional groups in the molecule. It showed high adhesion strength as compared with Example 6 whose dimer is less than 60% by mass of the total polymerizable monomer.

  The adhesive agent for the polyaryl ether ketone resin composite material is prepared by blending the same amount of the coupling agent, the polymerizable monomer, and the polymerization initiator and comparing Examples 5 and 7 in which the presence or absence of the volatile solvent is different, Example 5 containing a volatile solvent showed higher adhesion strength as compared to Example 7 containing no volatile solvent.

  The adhesive agent for the polyaryl ether ketone resin composite material is compounded with the same amount of the coupling agent, the volatile solvent, and the polymerization initiator, and compared with 5, 8 having different polymerizable monomer compositions. Example 5 which mix | blended the polymerizable monomer showed high adhesive strength compared with Example 8 which does not mix | blend an acidic group containing polymerizable monomer. In Example 8 in which the acidic group-containing polymerizable monomer is not contained, it is presumed that the hydrolysis of the coupling agent did not proceed sufficiently and the effect of blending the coupling agent was not sufficiently obtained.

  The adhesive agent for the polyaryl ether ketone resin composite material contains the same amount of the coupling agent, the volatile solvent, and the polymerization initiator, and the comparison of 2, 10, 11 having different polymerizable monomer compositions gives a molecule Example 2 in which 20% by mass or more of all polymerizable monomers were blended with polymerizable monomers (bisGMA, UDMA, PM2) having two or more polymerizable functional groups in the inside and having a hydrogen bonding functional group , 10 have at least 20% by mass of all polymerizable monomers (bisGMA, UDMA, PM2) having at least two polymerizable functional groups in the molecule and having a hydrogen bonding functional group It showed high adhesive strength as compared with Example 11 which is not blended. Furthermore, the compounding amount of the polymerizable monomer having two or more polymerizable functional groups, a hydrogen bonding functional group and an aromatic ring in the molecule is 15% by mass to 70% by mass of all the polymerizable monomers. Example 2 has high adhesion strength as compared with Examples 10 and 11 in which a polymerizable monomer having two or more polymerizable functional groups, a hydrogen bonding functional group and an aromatic ring in the molecule is not blended. Indicated.

  An adhesive for a polyaryl ether ketone resin composite material comprising the same amount of a coupling agent, a polymerizable monomer, a volatile solvent and a polymerization initiator, and containing an acidic group in the composition of the polymerizable monomer Comparing Examples 4 and 9, in which only the type of polymerizable monomer is different, shows the same adhesive strength regardless of the type of the acidic group-containing polymerizable monomer.

  An adhesive for a polyaryl ether ketone resin composite material was prepared by blending the same amount of the coupling agent, the polymerizable monomer, the volatile solvent, and the polymerization initiator, and the only difference was the type of the coupling agent. Comparison of 12 and 13 showed the same adhesive strength regardless of the type of coupling agent.

  In Examples 14 to 16 using the primer for the polyaryl ether ketone resin composite material of the present invention, Comparative Example 4 containing no coupling agent, a polymerizable single having two or more polymerizable functional groups in the molecule All showed high adhesion strength as compared with the case of using the non-inventive primer of Comparative Examples 5 and 6 in which the dimer is less than 40% by mass of the total polymerizable monomer.

  About the primer for polyaryl ether ketone resin composite material, the coupling agent, the volatile solvent, the polymerization initiator, and the polymerizable monomer of the same same amount are blended, and the polymerization start as a partial component of the chemical polymerization initiator component Comparing Examples 14 and 16 in which the presence or absence of the compounding of BMOV which is an agent component is different, Example 16 in which BMOV is compounded shows higher adhesion strength as compared with Example 14 in which BMOV is not compounded. Bistite II, which is a dental cement material used in this test, contains BPO, which is a peroxide, as a polymerization initiator component as a partial component of a chemical polymerization initiator component, and is a polyaryl ether ketone resin complex When a primer is applied to the adhesion surface of the material and Bistite II is applied thereon, BPO in the dental cement penetrates into the primer and chemical polymerization is initiated by the reaction between BMOV and BPO in the primer. Since it acts as an agent and the polymerizability of the polymerizable monomer of the primer is improved, it is presumed that the adhesive strength is improved.

  Comparison of Examples 1 to 13, which are adhesives for polyaryl ether ketone resin composite materials, and Examples 14 to 16, which are primers for poly aryl ether ketone resin composite materials, the combination of a polymerization initiator and a volatile solvent When the composition other than the amount was the same, the adhesive for the polyaryl ether ketone resin composite material showed higher adhesive strength, and from the viewpoint of adhesive strength, the adhesive was a preferable result. On the other hand, in Examples 2 and 3 which are adhesives for polyaryl ether ketone resin composite materials, and in Examples 14 and 15 which are primers for polyaryl ether ketone resin composite materials, the adhesive layer (the adhesive composition Layers) When the thicknesses were compared, the adhesive layer was thinner in Examples 14 and 15, and the primer was a preferable result from the viewpoint of the adhesive layer thickness. In the present examination, the adhesive layer having a thickness of less than 1 μm means that the adhesive layer was very thin and measurement was difficult.

Claims (11)

(A) a composition containing a coupling agent and a heavy polymerizable monomer having a polymerizable functional group, more than 40% by weight of the total polymerizable monomer contained in the composition is, (B ) A polyaryletherketone resin composite material comprising a composition which is a polymerizable monomer having two or more polymerizable functional groups in the molecule and which is a composite material in which a polyaryletherketone resin and a metal oxide are mixed It has adhesiveness against, polyaryl ether ketone resin composite material for the adhesive composition. (A) The coupling agent having a polymerizable functional group is represented by the following general formula (I)

(In the general formula (I), M is a metal element, X is a hydroxyl group (OH) or a functional group forming a M-OH structure in which a hydroxyl group (OH) is directly bonded to the metal element M by hydrolysis, Y is a polymerizable functional group Z is a functional group having a group, and Z is any other functional group not corresponding to X and Y. m and n are each independently an integer of 1 or more, l is an integer of 0 or 1 or more, and m + n + 1 is a metal element Match the valence of M.)
The adhesive composition for a polyaryl ether ketone resin composite material according to claim 1, which has the structure shown in 1.   The polyaryl ether according to claim 1 or 2, wherein the compounding amount of the coupling agent having the polymerizable functional group (A) is in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the total polymerizable monomer. Adhesive composition for ketone resin composite materials. (C) The polyaryl ether according to any one of claims 1 to 3, which contains a volatile solvent having a boiling point of 100 ° C. or less at 760 mmHg and a vapor pressure of 1.0 KPa or more at 20 ° C. Adhesive composition for ketone resin composite materials.   The coupling agent having a polymerizable functional group and the polymerizable functional group of a polymerizable monomer having two or more polymerizable functional groups in the molecule are (meth) acryloyl groups. Adhesive composition for polyaryl ether ketone resin composite materials as described above.   (A) The coupling agent having a polymerizable functional group is a functional group in which X in general formula (I) is hydrolyzed to form an M-OH structure in which a hydroxyl group (OH) is directly bonded to the metal element M, and The adhesive composition for a polyaryl ether ketone resin composite material according to any one of claims 2 to 4, which comprises (D) an acidic group-containing polymerizable monomer. The adhesive composition for polyaryl ether ketone resin composite material according to any one of claims 1 to 6, which is for dental use. A primer for polyaryl ether ketone resin composite material comprising the adhesive composition for poly aryl ether ketone resin composite material according to any one of claims 1 to 7.   The adhesive composition for polyaryl ether ketone resin composite material according to any one of claims 1 to 7, which contains a polymerization initiator.   An adhesive for a polyaryl ether ketone resin composite material comprising the adhesive composition for a polyaryl ether ketone resin composite material according to claim 9.   The storage form is divided into at least two packages, and (A) a coupling agent having a polymerizable functional group and (D) an acidic group-containing radically polymerizable monomer are mixed in separate packages. The adhesive composition for polyaryl ether ketone resin composite materials as described in 6.