JP6639220B2 - Adhesive composition for polyaryletherketone resin material - Google Patents

Description

  The present invention relates to an adhesive composition for a polyaryletherketone resin material having excellent adhesion durability to a polyaryletherketone resin material.

  Super engineering resins are used in a wide range of applications such as electric / electronics, aerospace, automotive, medical, and general industrial fields. Among these super engineering resins, in particular, polyaryl ether ketone resins 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, a technique using this polyaryletherketone resin as a dental material has been proposed (for example, Patent Document 1). When such a polyaryletherketone resin is used as a dental material, it is necessary to firmly adhere to dental materials and other types of dental materials, and to maintain strong adhesiveness over a long period of time. Several techniques are known as techniques for maintaining a high adhesiveness for a long period of time in bonding a polyaryletherketone resin material to a tooth substance or another type of dental material, that is, exhibiting high adhesive durability. (For example, Non-Patent Documents 1 and 2).

  Non-Patent Document 1 evaluates the adhesiveness to a polyaryletherketone resin material using a commercially available dental bonding material and primer, and Luxatemp Glaze & Bond (DMG) has relatively high adhesive strength and durability. Shows sex. It is disclosed that Luxamp Glaze & Bond contains Multifunction acrylates, methyl methacrylates, catalysts, stabilizers, and additives, but does not mention a polymerizable monomer having a mercapto group. Other dental bonding materials and primers used in this document do not disclose that a polymerizable monomer having a mercapto group is blended.

  Non-Patent Document 2 evaluates the adhesiveness to a polyaryletherketone resin material using Luxatemp Glaze & Bond (DMG) and Monobond Plus (Ivoclar Vivadent), and relatively high adhesive strength and adhesive durability Is shown. In addition, Monobond Plus describes that Ethanol, silane, silane-, phosphoric-, and sulfidemethacrylate are blended, but it is described that a polymerizable monomer having a mercapto group is blended. Absent.

JP 2013-144778 A

DENTAL MATERIALS 28 (2012) 1280-1283 DENTAL MATERIALS 30 (2014) 357-363

  Members containing a polyaryletherketone resin having excellent chemical and physical properties are widely used not only in dental applications but also in various fields. For this reason, regardless of the technical field and application, there is a demand for a technique capable of more firmly adhering to a member containing a polyaryletherketone resin and maintaining a strong adhesive property for a long period of time.

  As described above, a technique capable of obtaining relatively high bonding durability with respect to a polyaryletherketone resin material has been disclosed, but higher bonding durability is required. Particularly in the field of dentistry, in order to use a polyaryletherketone resin material as a dental material in the oral cavity for a long period of time, it is desired to further improve the adhesive durability. Therefore, an object of the present invention is to provide an adhesive composition that can maintain high adhesiveness to a polyaryletherketone resin material for a long time.

The above problem is solved by the present invention described below. That is, the present invention is, polyaryl ether resins, and a polyaryletherketone resin material comprising a metal oxide, the content of these polyaryl ether resin and a metal oxide, the polyaryl ether ketone resin material Expressed in mass% based on the total mass, polyarylether resin: 20 mass% or more, metal oxide : 15 mass% or more and 70 mass% or less, respectively, and the total content of both is 100 mass% or less. , and the the port Leary ether ketone resin material a polyaryletherketone resin material for the adhesive composition to an adherend, can result in a polymerizable monomer or is a mercapto group having a mercapto radical polymerization "(A) a polymerizable monomer having a mercapto group" which is a polymerizable monomer and "(B) which is a polymerizable monomer other than (A) A mixture containing a polymerizable monomer component consisting of a polymerizable monomer having no mercapto group ”and a vanadium compound having a + IV valency and / or a + V valency. A polymerizable monomer having a polymerizable functional group consisting of a mercapto group and a (meth) acryloyl group in the molecule, a polymerizable functional group consisting of a (meth) acryloyl group in the molecule, and a mercapto group due to tautomerism And at least one polymerizable monomer selected from the group consisting of polymerizable monomers having in the molecule a polymerizable functional group comprising a disulfide bond and a (meth) acryloyl group. The polymerizable monomer having a polymerizable functional group consisting of a (meth) acryloyl group in the molecule is used as the component (B), and the content of the component (A) and the content of the component (B) are the same as those of the polymerizable monomer. (A): 0.005% by mass or more and 10% by mass or less, and (B): the balance, expressed in terms of mass% based on the mass of the entire mass component. At least a part of (B) is a polymerizable monomer having two or more polymerizable groups in the molecule, and further includes a polymerizable monomer having two or more polymerizable groups in the molecule based on the above criteria. An adhesive composition for a polyaryletherketone resin material, wherein the content is 40% by mass or more.

  (A) The polymerizable monomer having a mercapto group is preferably a polymerizable monomer capable of generating a mercapto group by tautomerism.

Further, polyaryletherketone resin material for the adhesive compositions of the present invention can be used as a polyaryletherketone resin material for adhesive by incorporating a polymerization initiator comprising an organic peroxide and the polymerization It is also possible to use as a primer without blending an initiator .

  Further, the adhesive composition of the present invention is preferably used for dental use, and the adhesive composition of the present invention and a dental polyaryletherketone resin composite material obtained by blending a metal oxide with a polyaryletherketone resin It is also preferable to provide a dental treatment kit comprising:

  ADVANTAGE OF THE INVENTION According to the adhesive composition for polyaryletherketone resin materials of this invention, high adhesion durability with respect to a polyaryletherketone resin material can be obtained.

  The reason why high adhesive durability can be obtained by using the adhesive composition for a polyaryletherketone resin material of the present invention is not necessarily clear, but the present inventors speculate as follows.

  That is, the polyaryl ether ketone resin has high chemical stability, and when a commonly used adhesive composition such as a dental bonding material is used, the adhesion is performed when the polymerizable monomer of the adhesive composition is a polymer. It is presumed that high adhesiveness can be obtained by forming a uniform and strong layer of the adhesive composition by penetrating and curing fine irregularities on the surface of the aryl ether ketone resin material. Here, since the polyaryl ether ketone resin is a hydrophobic material, when the polyaryl ether ketone resin is held for a long time in a humid environment such as the oral cavity, moisture adheres to the interface between the polyaryl ether ketone resin material and the adhesive composition. It is presumed that the adhesive composition is more likely to be affected, causing the adhesive composition to deteriorate, and the adhesiveness after being held for a long time is greatly reduced. Here, when the adhesive composition containing a polymerizable monomer having a mercapto group is applied to the surface of the polyaryl ether ketone resin material, over time, the mercapto group of the polymerizable monomer having a mercapto group becomes: Reacts with the ketone groups of the polyaryletherketone resin of the polyaryletherketone resin material to form a thioacetal structure. Since the thioacetal structure is a relatively stable bond such as high water resistance and hydrolysis does not easily occur, the bond between the adhesive composition and the polyaryletherketone resin material is stably maintained for a long period of time. Can exist. As a result, it is presumed that high adhesion durability can be obtained.

  The adhesive composition for a polyaryletherketone resin material of the present invention is characterized by containing (A) a polymerizable monomer having a mercapto group.

The adhesive composition for a polyaryletherketone resin material of the present invention can be used, for example, as a primer for a polyaryletherketone resin material or an adhesive for a polyaryletherketone resin material. Here, the primer for polyaryl ether ketone resin material is one use of the adhesive composition for polyaryl ether ketone resin material, and the composition contains a polymerization initiator for polymerizing a polymerizable monomer. It is a material based on a usage form in which a polyaryl ether ketone resin material is bonded to another material without being blended. On the other hand, the adhesive for a polyaryletherketone resin material is one use of the adhesive composition for a polyaryletherketone resin material, in which a polymerization initiator is added to the composition, It is a material based on a usage form in which a polyaryl ether ketone resin material is bonded to another material through polymerization and curing of a monomer.
Hereinafter, the details of the materials and the like constituting the present embodiment will be described.

(A) Polymerizable monomer having a mercapto group The polymerizable monomer having a mercapto group in the present invention is not particularly limited as long as it has at least one polymerizable functional group and a mercapto group in a molecule. Can be used. It is presumed that by having a polymerizable functional group, a layer of a uniform and strong adhesive composition can be formed on the surface to which the polyaryletherketone resin material is applied by polymerizing, and high adhesiveness can be obtained immediately after adhesion. Is done. Furthermore, by having a mercapto group, a bond having high durability is formed with time with the polyaryletherketone resin, and it is possible to maintain high adhesiveness over a long period of time, and obtain high adhesive durability. It is speculated that it can be done.

  The polymerizable functional group is preferably a radical polymerizable functional group in terms of low biotoxicity and high polymerization activity, and examples thereof include functional groups such as a vinyl group, a styryl group, an allyl group, and a (meth) acryloyl group. In particular, a (meth) acryloyl group is preferred from the viewpoint of polymerization rate and biosafety. That is, a (meth) acryloyl group-containing polymerizable monomer having a mercapto group is preferable, and this is preferably a portion other than the (meth) acryloyl group portion of the (B) polymerizable monomer having no mercapto group described below. A monomer having a structure in which a hydrogen atom or a hydroxyl group is substituted with a mercapto group is exemplified.

  Specific examples of the polymerizable monomer having a mercapto group include the following polymerizable monomers having a free mercapto group.

  The polymerizable monomer having a mercapto group may be a polymerizable monomer capable of generating a mercapto group by tautomerism. Examples of the polymerizable monomer capable of generating a mercapto group by such tautomerism include compounds represented by the following general formulas A1 to A6.

In the general formulas A1 to A6, R ¹ is a hydrogen atom or a methyl group, R ² is a divalent saturated hydrocarbon group having 1 to 12 carbon atoms, a —CH ₂ —C ₆ H ₄ —CH ₂ — group, — _{(CH 2) o -Si (CH} 3) 2-O-Si (CH 3) 2 - (CH 2) p - group (. However, o and p are an integer from 1 to 5, respectively), or -CH ₂ CH ₂ OCH ₂ CH ₂ —, and Z is an —OC (＝ O) —, —OCH ₂ —, or —OCH ₂ —C ₆ H ₄ — group (however, any of these groups Z also carbon atoms at the right end binds to an unsaturated carbon in an oxygen atom at the left end is bonded to the group R ^2), Z 'is -OC (= O) -. group (provided that the right edge carbon atoms of not bonded to a saturated carbon, the left end of the oxygen atoms are bonded to the group ^{R 2), -. C 6} H 4 - group, or a bond (wherein group Z ' For bond and refers to the state in which the unsaturated carbon is directly bonded with radical ^{R 2),} Y is -S -., - O-, or -N (R ') - (where, R' is a hydrogen atom, An alkyl group having 1 to 5 carbon atoms).

  Examples of the polymerizable monomer having a functional group capable of generating a mercapto group by tautomerism represented by the general formulas A1 to A6 include the following compounds.

  The mercapto group of the polymerizable monomer having a mercapto group may be generated by some kind of stimulus immediately before using the adhesive composition for a polyaryletherketone resin material. For example, it is known that a disulfide bond is cleaved by reacting with a reducing agent to generate a mercapto group, and for a composition containing a polymerizable monomer having a disulfide bond, a reducing agent is used immediately before use. Is added to obtain a polymerizable monomer having a mercapto group, which can be used as the adhesive composition for a polyaryletherketone resin material of the present invention. When such a mixture of a polymerizable monomer having a disulfide bond and a reducing agent is used, a combination of a polymerizable monomer having a disulfide bond and a reducing agent may be used as long as a mercapto group can be generated. The adhesive composition for a polyaryl ether ketone resin material of the present invention can be used.

  Further, before applying the adhesive composition containing a polymerizable monomer having a disulfide bond, by applying a composition containing a base material capable of cleaving disulfide bonds to the adherend surface, A method in which a polymerizable monomer having a mercapto group is generated when an adhesive composition containing a polymerizable monomer having a disulfide bond is applied can also be used as long as the adhesive property is not significantly adversely affected. Further, after applying an adhesive composition containing a polymerizable monomer having a disulfide bond to an adherend, a composition containing a reducing agent capable of cleaving a disulfide bond (for example, in the case of dental use, a reducing agent is used. It can also be used in the case where a disulfide bond is cut off by pressing a contained dental resin cement) onto the adhesive composition to generate a polymerizable monomer having a mercapto group.

  When using a polymerizable monomer having a disulfide bond, the adhering body after mixing a polymerizable monomer having a disulfide bond and a reducing agent capable of cleaving a disulfide bond before use as described above. A method of applying, a method of applying an adhesive composition containing a polymerizable monomer having a disulfide bond to the adherend after applying a composition containing a reducing agent capable of cleaving disulfide bonds to the adherend, A method of applying an adhesive composition containing a polymerizable monomer having a disulfide bond to an adherend surface, and then pressing a composition containing a reducing agent capable of cleaving a disulfide bond from above, or the like is considered. Since a polymerizable monomer having a sufficient amount of a mercapto group is easily obtained to obtain the effects of the present invention, the polymerizable monomer having a disulfide bond and the polymerizable monomer having a disulfide bond may be cleaved. It is preferably applied to the adherend after mixing the reducing agent.

  These polymerizable monomers having a mercapto group can be used alone or in combination of two or more.

  When a polymerizable monomer having a free mercapto group is blended as a polymerizable monomer having a mercapto group, the radical polymerizable functional group which is a radical polymerizable functional group is stored during storage of the adhesive composition for a polyaryletherketone resin material. Particular attention must be paid to storage stability, such as causing an addition reaction to a heavy bond. Focusing on this storage stability viewpoint, the polymerizable monomer having a mercapto group is a polymerizable monomer capable of generating a mercapto group by tautomerism, or by some stimulus immediately before using the adhesive composition. It is preferable that the polymerizable monomer is a polymerizable monomer from which a mercapto group is formed. In addition, when the polymerizable monomer having a mercapto group is a polymerizable monomer in which a mercapto group is generated by some kind of stimulus immediately before using the adhesive composition, the operation becomes complicated and high adhesive durability is required. In some cases, care must be taken in the method of use to produce a polymerizable monomer having sufficient mercapto groups to obtain. Focusing on this operability viewpoint, the polymerizable monomer having a mercapto group is a polymerizable monomer having a free mercapto group, or a polymerizable monomer capable of generating a mercapto group by tautomerism. Is preferred. Considering these points, the polymerizable monomer having a mercapto group is most preferably a polymerizable monomer capable of generating a mercapto group by tautomerism.

The mercapto group of the polymerizable monomer having a mercapto group blended in the adhesive composition for a polyaryletherketone resin material has a ketone group of the polyaryletherketone resin of the polyaryletherketone resin material as the adherend. Since it is presumed to have high adhesion durability due to the reaction, it is preferable that the steric hindrance around the mercapto group of the polymerizable monomer having a mercapto group is small. Here, when the distance between the mercapto group and the polymerizable functional group is short, since the mercapto group is present near the polymer main chain generated by the polymerization reaction of the polymerizable monomer of the adhesive composition, steric hindrance is caused. It may become large, and the reactivity with the ketone group of the polyaryletherketone resin may be reduced. Therefore, it is preferable that a spacer group is present between the polymerizable functional group and the mercapto group. In the general formulas A1 to A6, R ² has 4 or more main chain atoms, that is, carbon atoms. number 4-12 bivalent saturated hydrocarbon _{group, -CH 2 -C 6 H 4 -CH} 2 - _{group, - (CH 2) o -Si} (CH 3) 2 -O-Si (CH 3) 2 - It is preferably a (CH ₂ ) _p -group (where o and p are each an integer of 1 to 5) or a —CH ₂ CH ₂ OCH ₂ CH ₂ — group. Further, the number of atoms in the main chain is 6 or more, that is, a divalent saturated hydrocarbon group having 6 to 12 carbon atoms, a —CH ₂ —C ₆ H ₄ —CH ₂ — group, and — (CH ₂ ) _o −. More preferably, it is a Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ — (CH ₂ ) _p — group (where o and p are each an integer of 1 to 5, and o + p is 3 or more). preferable. Among them, R ² is particularly preferably a divalent saturated hydrocarbon group having 6 to 12 carbon atoms.

  When the polymerizable monomer having a mercapto group is a polymerizable monomer capable of generating a mercapto group by tautomerism, the functional group capable of generating a mercapto group by tautomerism includes a thiouracil group from the viewpoint of adhesion durability. Is more preferable. That is, among the compounds of the general formulas A1 to A6, the compounds of A1 and A2 are more preferable.

  The amount of the polymerizable monomer having a mercapto group is not particularly limited, but is preferably in the range of 0.005% by mass to 10% by mass, and more preferably 0.01% by mass, based on all polymerizable monomers. More preferably, it is in the range of from 5% by mass to 5% by mass, and further preferably in the range of from 0.03% by mass to 1% by mass. If the amount of the polymerizable monomer having a mercapto group is too small, the effect of improving the adhesive durability may not be sufficiently obtained. If the amount of the polymerizable monomer containing a mercapto group is too large, the storage stability of the adhesive composition may be deteriorated. In addition, when the polymerizable functional group of the polymerizable monomer blended in the adhesive composition is a radical polymerizable functional group, the polymerizable monomer of the adhesive composition is polymerized and cured by radical polymerization. Since the mercapto group can act as a chain transfer agent, the efficiency of radical polymerization is reduced, and in particular, the strength of the layer of the adhesive composition applied to the surface of the polyaryletherketone resin material on which the polyaryletherketone resin material is applied is reduced in the initial stage of bonding, and immediately after bonding. There is a possibility that the adhesiveness of the resin may decrease.

(B) Polymerizable monomer having no mercapto group In addition to the polymerizable monomer having a mercapto group, the adhesive composition for a polyaryletherketone resin material of the present invention may be polymerized without a mercapto group. It is preferable to mix a hydrophilic monomer.

  As the polymerizable monomer having no mercapto group, a polymerizable monomer having no polymerizable group and having no mercapto group can be used. Known polymerizable monomers having no polymerizable group and having no mercapto group can be used without any limitation. The polymerizable functional group is preferably a radical polymerizable functional group from the viewpoint of low biotoxicity and high polymerization activity, and examples thereof include functional groups such as a vinyl group, a styryl group, an allyl group, and a (meth) acryloyl group. However, a (meth) acryloyl group is particularly preferred from the viewpoint of polymerization rate and biosafety.

  Examples of the polymerizable monomer having a (meth) acryloyl group include the following monofunctional radical polymerizable monomers, bifunctional radical polymerizable monomers, trifunctional radical polymerizable monomers, and tetrafunctional radical polymerizable monomers. A monomer is exemplified.

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

(II) Bifunctional radical polymerizable monomer 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, 2,2- Bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4- Methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloki Triethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytriethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4 -Butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, glycerin dimethacrylate , Bis (2-methacryloyloxyethyl) hydrogen phosphate, bis (6-methacryloyloxyhexyl) hydrogen phosphate, 2-methacryloyloxyethyl-3′-methacryloyloxy-2 ′-(3,4-dicarboxybenzoyl) Oxy) propyl succinate, N, O-dimethacryloyl tyrosine and acrylates corresponding to these methacrylates; methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, or methacrylates thereof; A vinyl monomer having an -OH group such as a corresponding acrylate, diisocyanate methylbenzene, 4,4'-diphenylmethane diisocyanate, hexamethylene; Diadduct obtained from an adduct with a diisocyanate compound such as diisocyanate, trimethylhexamethylene diisocyanate, diisocyanatemethylcyclohexane, isophorone diisocyanate, and methylenebis (4-cyclohexylisocyanate); 1,2-bis (3-methacryloyloxy-2- (Hydroxypropoxy) ethyl, 1,6-bis (methacryloylethyloxycarbonylamino) 2,2,4-trimethylhexane and the like.

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

(IV) tetrafunctional radical polymerizable monomer pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate and diisocyanatemethylbenzene, diisocyanatemethylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), Diadducts obtained from adducts of diisocyanate compounds such as 4,4-diphenylmethane diisocyanate and tolylene-2,4-diisocyanate with glycidol dimethacrylate.

  The adhesive composition for a polyaryletherketone resin material preferably contains a polymerizable monomer having two or more polymerizable functional groups in a molecule. By blending a polymerizable monomer having two or more polymerizable functional groups in the molecule, the strength of the cured adhesive composition layer is increased, and a uniform and strong adhesive composition layer is obtained. It is presumed that higher adhesiveness can be obtained because it becomes easier. As a result, high adhesiveness is obtained immediately after bonding, and the high initial adhesiveness can be maintained by the action of the polymerizable monomer having a mercapto group, so that high adhesiveness can be obtained even after a long period of time. It will be easier.

  Examples of the polymerizable monomer having two or more polymerizable functional groups in the molecule include (B) a bifunctional radical polymerizable monomer exemplified as a polymerizable monomer having no mercapto group, (B) III) a trifunctional radical polymerizable monomer, (IV) a tetrafunctional radical polymerizable monomer, and (A) a polymerizable monomer having a mercapto group, It is also possible to use a polymerizable monomer having two or more polymerizable functional groups. Therefore, the polymerizable monomer (A) having a mercapto group exemplified in the compound VI group, the compound VII, the compound VIII, and the compound IX is also exemplified as a polymerizable monomer having two or more polymerizable functional groups in a molecule. You can do it.

  These polymerizable monomers having two or more polymerizable functional groups in the molecule may be used in combination of a plurality of types as necessary.

  The polymerizable monomer having two or more polymerizable functional groups in the molecule 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 of all the polymerizable monomers. preferable. By using a polymerizable monomer having two or more polymerizable functional groups in the molecule in an amount of 40% by mass or more of the total polymerizable monomer, a uniform and strong adhesive composition layer can be more easily obtained. , Higher adhesiveness can be obtained.

  It is preferable that some 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 have 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 is further increased by hydrogen bonding between the hydrogen-bonding functional groups. In addition, the interaction between the hydrogen bonding functional group of the polymerizable monomer and the ketone group of the polyaryl ether ketone resin makes the interaction between the polyaryl ether ketone resin material and the layer of the adhesive composition higher. It is presumed that it will be. Therefore, the polymerizable monomer having two or more polymerizable functional groups and a hydrogen bonding functional group in the molecule is preferably used in an amount of 20% by mass or more of all the polymerizable monomers, and more preferably in an amount of 30% by mass or more. More preferred.

  The term “hydrogen bond” as used herein means a hydrogen atom (donor) that is bonded to an atom (O, N, S, etc.) having a high electronegativity and is electrically positively polarized, and an electronegative atom having a lone pair of electrons. (Acceptor). The hydrogen-bonding functional group in the present invention is a substituent capable of functioning as a donor and an acceptor in the above-mentioned hydrogen bonding, and specifically refers to a hydroxyl group, an amino group, a urethane group, an amide group and the like. Further, a mercapto group is also included in the hydrogen bonding functional group in the present invention. Therefore, when (A) the polymerizable monomer having a mercapto group has two or more polymerizable functional groups in the molecule, the polymerizable monomer is (A) a polymerizable monomer having a mercapto group. In addition, it is a polymerizable monomer having two or more polymerizable functional groups in the molecule and having a hydrogen bonding functional group.

  As such a polymerizable monomer having two or more polymerizable functional groups and a hydrogen bonding functional group in a molecule, known ones, including those exemplified above, can be used without any particular limitation. , 2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, glycerin dimethacrylate, bis (2-methacryloyloxyethyl) hydrogen phosphate, bis (6-methacryloyloxyhexyl) hydrogen phosphate, 2-methacryloyloxyethyl-3′-methacryloyloxy-2 ′-(3,4-dicarboxybenzoyloxy) propyl succinate, N, O-dimethacryloyltyrosine and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate , 2-hydroxyp Methacrylate such as pill methacrylate, 3-chloro-2-hydroxypropyl methacrylate or a vinyl monomer having an -OH group such as acrylate corresponding to these methacrylates, diisocyanate methylbenzene, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, Diaducts obtained from adducts with diisocyanate compounds such as trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, and methylene bis (4-cyclohexyl isocyanate); 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) Ethyl, 1,6-bis (methacryloylethyloxycarbonylamino) 2,2,4-trimethyl Acid and the like. Further, the compounds shown in the above-mentioned compound VI group, compound VII, compound VIII and compound IX can also be mentioned as polymerizable monomers having two or more polymerizable functional groups and hydrogen bonding functional groups in the molecule.

  Some or all of the polymerizable monomers having two or more polymerizable functional groups and hydrogen bonding functional groups in the molecule have two or more polymerizable functional groups and hydrogen bonding functional groups in the molecule, and It is more preferred to have an aromatic ring. By having an aromatic ring in the molecule, the aromatic ring of the adhesive composition for the polyaryl ether ketone resin material and the aromatic ring of the polyaryl ether ketone resin material form a stack, and the adhesive composition with the polyaryl ether ketone resin material It is presumed that the interaction of the layers of objects will be higher.

  The polymerizable monomer having two or more polymerizable functional groups, hydrogen bonding functional groups, and aromatic rings in the molecule is preferably used in an amount of 15% by mass or more of all the polymerizable monomers, and more preferably 25% by mass or more. Is more preferred. On the other hand, the polymerizable monomer having two or more polymerizable functional groups, hydrogen bonding functional groups, and aromatic rings in the molecule is preferably 70% by mass or less of all polymerizable monomers, and 50% by mass or less. It is more preferred that: By setting the polymerizable monomer having two or more polymerizable functional groups, hydrogen bonding functional groups, and aromatic rings in the molecule to 15% by mass or more, the layer of the polyaryl ether ketone resin material and the adhesive composition can be used. Interaction can be strengthened. On the other hand, when a polymerizable monomer having two or more polymerizable functional groups, a hydrogen-bonding functional group, and an aromatic ring in a molecule exceeds 70% by mass, the hydrogen-bonding functional groups or aromatic rings may be mixed. The interaction makes it difficult to handle the polymerizable monomer, and it may be difficult to mix the polymerizable monomer into the adhesive composition from the viewpoint of workability and the like.

  Known polymerizable monomers having two or more polymerizable functional groups, hydrogen bonding functional groups and aromatic rings in the molecule, including those exemplified above, can be used without particular limitation. Is 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, 2-methacryloyloxyethyl-3′-methacryloyloxy-2 ′-(3,4-dicarboxybenzoyloxy) Propyl succinate, N, O-dimethacryloyl tyrosine and an acrylate corresponding to this methacrylate; a methacrylate such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, or an acrylate corresponding to these methacrylates -OH group such as And vinyl monomers that, diisocyanate methyl benzene, diadduct and the like obtained from the addition of the diisocyanate compound having an aromatic group such as 4,4'-diphenylmethane diisocyanate. Further, the compound represented by the above compound VII can also be mentioned as a polymerizable monomer having two or more polymerizable functional groups, hydrogen bonding functional groups and aromatic rings in the molecule.

  As the polymerizable monomer, an acidic group-containing polymerizable monomer may be blended. By blending the acidic group-containing polymerizable monomer, the mercapto group of the polymerizable monomer having a mercapto group blended in the adhesive composition for a polyaryl ether ketone resin material and the polyaryl ether ketone resin material In some cases, the reaction of the ketone group of the aryl ether ketone resin is further promoted by the acid, and higher adhesion durability may be obtained. The acidic group-containing polymerizable monomer of the present invention does not include (A) a polymerizable monomer having a mercapto group.

  As such an acidic group-containing polymerizable monomer, a known monomer having at least one polymerizable functional group and at least one acidic group in a molecule can be used without any particular limitation.

Note that the acidic group in the present invention includes a phosphinico group {= P (= O) OH}, a phosphono group {-P (= O) (OH) ₂ }, a carboxyl group {-C (= O) OH}, and sulfo group. 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 in which —OH of the acidic group having —OH exemplified above is substituted with halogen (for example, —C (＝ O) Cl). Means a group in which an aqueous solution or suspension of a polymerizable monomer having the group is acidic. 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, It is also a contained polymerizable monomer.

  Specific examples of such an acidic group-containing polymerizable monomer include 2-methacryloyloxyethyl dihydrogen phosphate, bis (2-methacryloyloxyethyl) hydrogen phosphate, and 2-methacryloyloxyethyl phenyl hydrogen phosphate. Fate, 6-methacryloyloxyhexyl dihydrogen phosphate, 10-methacryloyloxydecyl dihydrogen phosphate, bis (6-methacryloyloxyhexyl) hydrogen phosphate, 2-methacryloyloxyethyl 2-bromoethyl hydrogen phosphate Such as a methacrylate having a phosphinicooxy group or a phosphonooxy group in a molecule and an acrylate corresponding to these methacrylates; and Acid anhydrides and acid halides.

  Also, methacrylic acid, N-methacryloylglycine, N-methacryloylaspartic acid, N-methacryloyl-5-aminosalicylic acid, 2-methacryloyloxyethyl hydrogen succinate, 2-methacryloyloxyethyl hydrogen phthalate, 2-methacryloyloxyethyl hydrol Gemmalate, 6-methacryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid, O-methacryloyltyrosine, N-methacryloyltyrosine, N-methacryloylphenylalanine, N-methacryloyl-p-aminobenzoic acid, N-methacryloyl-O- Aminobenzoic acid, 2-methacryloyloxybenzoic acid, 3-methacryloyloxybenzoic acid, 4-methacryloyloxybenzoic acid, N-methacryloyl-5-amino Salicylic acid, such as N- methacryloyl-4-aminosalicylic acid, methacrylate having one carboxyl group in the molecule and the corresponding acrylates to these methacrylates, and their acid anhydrides and acid halides.

  Also, 11-methacryloyloxyundecane-1,1-dicarboxylic acid, 10-methacryloyloxydecane-1,1-dicarboxylic acid, 12-methacryloyloxydecane-1,1-dicarboxylic acid, 6-methacryloyloxyhexane-1,1 -Dicarboxylic acid, 2-methacryloyloxyethyl-3'-methacryloyloxy-2 '-(3,4-dicarboxybenzoyloxy) propyl succinate, N, O-dimethacryloyltyrosine, 4- (2-methacryloyloxyethyl) Trimellitate, 4-methacryloyloxyethyl trimellitate, 4-methacryloyloxybutyl trimellitate, 4-methacryloyloxyhexyl trimellitate, 4-methacryloyloxydecyl trimellitate, 6-methacryloyloxyethyl Naphthalene-1,2,6-tricarboxylic anhydride, 6-methacryloyloxyethylnaphthalene-2,3,6-tricarboxylic anhydride, 4-methacryloyloxyethylcarbonylpropionoyl-1,8-naphthalic anhydride, Methacrylates having a plurality of carboxyl groups or acid anhydride groups in the molecule, such as 4-methacryloyloxyethylnaphthalene-1,8-tricarboxylic anhydride, acrylates corresponding to these methacrylates, and acid anhydrides thereof And acid halides. These acidic group-containing polymerizable monomers may be used alone or in combination of plural kinds.

  The compounding amount of the acidic group-containing polymerizable monomer is preferably 3% by mass or more, more preferably 5% by mass or more, based on all polymerizable monomers. The compounding amount of the acidic group-containing polymerizable monomer is preferably 40% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less, based on all polymerizable monomers. When the amount of the acidic group-containing polymerizable monomer is too small, the mercapto group of the polymerizable monomer having a mercapto group blended in the adhesive composition for a polyaryl ether ketone resin material and the polyaryl of the polyaryl ether ketone resin material The reaction of the ketone group of the ether ketone resin is further promoted by the acid, and it is difficult to obtain the effect of obtaining higher adhesive durability. When the amount of the acidic group-containing polymerizable monomer is too large, the water absorption of the adhesive composition for a polyaryletherketone resin material is increased. As a result, when used in a humid environment such as the oral cavity, the layer of the adhesive composition is likely to be deteriorated due to excessive water absorption, and the adhesive durability may be reduced.

  When the polyaryl ether ketone resin material to be adhered is a polyaryl ether ketone resin composite material containing a metal oxide, a coupling agent having a polymerizable functional group is blended as a polymerizable monomer. It is also preferred.

  A coupling agent is a material that has one or more first reactive groups that react with an inorganic compound and one or more second reactive groups that react with an organic compound. By blending a coupling agent into the adhesive composition for a polyaryletherketone resin material, higher adhesiveness to the polyaryletherketone resin composite material can be obtained. This is presumably because the coupling agent forms a bond with both the metal oxide of the polyaryl ether ketone resin composite material and the polymerizable monomer of the adhesive composition for the polyaryl ether ketone resin material. .

  Known coupling agents having a polymerizable functional group used in the present invention can be used without limitation. Examples of the coupling agent include silane coupling agents, titanate coupling agents, aluminate coupling agents, and zirconates. Although there is a system coupling agent and the like, a silane coupling agent is particularly preferable from the viewpoint of adhesiveness and handleability.

  Particularly preferable examples of the coupling agent having a polymerizable functional group include a silane coupling agent, for example, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyl Triisopropylsilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloyloxypropyltris (methoxyethoxy) silane, γ-methacryloxypropylmethyldiethoxysilane, ω-methacryloyloxydecyltrimethoxysilane, (methacryloxymethyl) methyl Dimethoxysilane, (methacryloxymethyl) methyldiethoxysilane, methacryloxymethyltrimethoxysilane, O- (methacryloyloxyethyl) -N- (triethoxy Rylpropyl) carbamate, N- (3-methacryloyl-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 3- (n-methacryloyloxyphenyl) propyltrimethoxysilane, 3- (3-methoxy-4-methacryloyloxy Phenyl) 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.

  The amount of the coupling agent having a polymerizable functional group is not particularly limited, but from the viewpoint of adhesiveness, 1 to 30% by mass based on all polymerizable monomers including the coupling agent having a polymerizable functional group. % Is preferable, a range of 2 to 20% by mass is more preferable, and a range of 3 to 10% by mass is further preferable.

  When a coupling agent having a polymerizable functional group is blended into the adhesive composition for a polyaryl ether ketone resin material, the adhesive composition for a polyaryl ether ketone resin material contains two or more It is particularly preferable to mix a polymerizable monomer having a polymerizable functional group in an amount of 40% by mass or more based on all polymerizable monomers in order to obtain higher adhesiveness.

  The adhesive composition for a polyaryletherketone resin material of the present invention may be used as an adhesive for a polyaryletherketone resin material by blending a polymerization initiator, or a polyaryletherketone resin without blending a polymerization initiator. It may be used as a primer for materials. As will be described later, there are advantages in each of the case where the adhesive is used and the case where the primer is used.

  When used as an adhesive for a polyaryletherketone resin material, a uniform and strong adhesive layer is easily obtained compared to when used as a primer for a polyaryletherketone resin material. Is easily obtained. From the viewpoint of adhesiveness, it is preferable to mix a polymerization initiator to obtain an adhesive for a polyaryletherketone resin material.

  As the polymerization initiator, a photopolymerization initiator, a chemical polymerization initiator, or a thermal polymerization initiator can be used, and two or more polymerization initiators can be used in combination. In addition, after application to the polyaryletherketone resin material, the photopolymerization initiator and / or the chemical polymerization initiator should be used because it can be easily performed when the adhesive for the polyaryletherketone resin material is cured. Is preferred. Since the polyaryl ether ketone resin is usually an opaque material, it may be difficult to irradiate the adhesive with light, and therefore a chemical polymerization initiator is most preferable. Hereinafter, these three types of polymerization initiators will be described in more detail.

  Known photopolymerization initiators can be used without any limitation. Representative photopolymerization initiators include combinations of α-diketones and tertiary amines, combinations of acylphosphine oxides and tertiary amines, combinations of thioxanthones and tertiary amines, α-aminoacetophenone Initiators, such as combinations of carboxylic acids and tertiary amines, combinations of aryl borates and photoacid generators.

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

  Examples of the tertiary amine include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N , N-diethyl-p-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethyl Aminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylanthranilic acid methyl ester, N, N-dihydroxyethylaniline, N-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 thereof include diethylaminoethyl methacrylate and 2,2 ′-(n-butylimino) diethanol. These can be used alone or in combination of two or more.

  As the acylphosphine oxides, benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5 6-tetramethylbenzoyldiphenylphosphine oxide and the like.

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

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

  The photopolymerization initiators may be used alone or as a mixture of two or more.

  The chemical polymerization initiator is a polymerization initiator which is composed of two or more components and generates a polymerization active species at around room temperature by mixing all components immediately before use. A typical example of such a chemical polymerization initiator is an amine compound / organic peroxide type.

  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 peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxyester, diaryl peroxide and the like.

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

  Examples of peroxyketals include 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, and 1,1-bis (t-hexylperoxy) cyclohexane. 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.

  Examples of the hydroperoxides include P-methane hydroperoxide, diisopropylbenzene peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide. Peroxide and the like.

  Examples of the dialkyl peroxide include α, α-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, and t-butylcumyl. Luper oxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane-3 and the like.

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

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

  Examples of peroxyesters include α, α-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1- Cyclohexyl-1-methylethyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, 1 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-hexylperoxyisopropylmonocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5 , 5-Trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, t-butylperoxyisopropylmonocarbonate, t-butylperoxy Oxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate , T-butyl peroxybenzoate, bis ( - butylperoxy) isophthalate.

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

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

  A system obtained by further adding a sulfinic acid such as benzenesulfinic acid or p-toluenesulfinic acid or a salt thereof to an initiator system comprising the organic peroxide and the amine compound; a barbituric acid system such as 5-butyl barbituric acid Even a system containing an initiator can be used without any problem.

  Further, a transition metal compound / organic peroxide-based chemical polymerization initiator may also be used. Specific examples of the transition metal compound include, for example, vanadium dioxide (IV), vanadium 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), vanadium trioxide (V), sodium metavanadate (V), and ammonium (V) metavanadate; scandium iodide ( Scandium compounds such as III), titanium compounds such as titanium (IV) chloride and titanium (IV) tetraisopropoxide, chromium compounds such as chromium (II) chloride, chromium (III) chloride, chromate and chromate, acetic acid Manganese compounds such as manganese (II) and manganese (II) naphthenate; Iron compounds such as iron (II) chloride, iron (II) chloride, iron (III) acetate and iron (III) chloride; cobalt compounds such as cobalt (II) acetate and cobalt (II) naphthenate; nickel (II) chloride Copper compounds such as copper chloride (I), copper (I) bromide, copper (II) chloride, and copper (II) acetate; and zinc compounds such as zinc chloride (II) and zinc acetate (II). Is exemplified. Among these transition metal compounds, it is preferable to use a vanadium compound having a + IV valency and / or a + V valency because high adhesiveness is easily obtained. Examples of the organic peroxide include those exemplified above.

  Further, an aryl borate compound / acidic compound-based chemical polymerization initiator utilizing the fact that an aryl borate compound is decomposed by an acid to generate a radical can also be used.

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

  As aryl borate compounds having three boron-aryl bonds in one molecule, monoalkyltriphenylboron, monoalkyltris (p-chlorophenyl) boron, monoalkyltris (p-fluorophenyl) boron, monoalkyltris (3 , 5-Bistrifluoromethyl) 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-butyl) Oxyphenyl) boron, monoalkyltris (p-octyloxyphenyl) boron, monoalkyltris (m-octyloxyphenyl) boron (however, in any compound, alkyl is n-butyl, n-octyl or n-dodecyl) Any of the following): sodium, lithium, potassium, magnesium, tetrabutylammonium, tetramethylammonium, tetraethylammonium, tributylamine, triethanolamine, methylpyridinium, ethylpyridinium, Examples thereof include a butylpyridinium salt, a methylquinolinium salt, an ethylquinolinium salt, and a butylquinolinium salt.

  As aryl borate compounds having four boron-aryl bonds in one molecule, tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl) phenyl Boron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis (m- Nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis (p-octyloxyphenyl) ) Boron, tetrakis (m- Sodium, lithium, potassium, magnesium, tetrabutylammonium salts of octyloxyphenyl) boron (wherein alkyl in any compound represents n-butyl, n-octyl or n-dodecyl) , Tetramethylammonium salt, tetraethylammonium salt, tributylamine salt, triethanolamine salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt or butylquinolinium salt, etc. 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-described aryl borate compound / acidic compound-based polymerization initiator. The organic peroxide and the transition metal compound are as described above.

  Examples of the thermal polymerization initiator include, 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. And barbituric acids such as 5-butyl barbituric acid and 1-benzyl-5-phenyl barbituric acid; and sulfinic acid salts such as sodium benzenesulfinate and sodium p-toluenesulfinate.

  The compounding amount of these polymerization initiators is preferably in the range of 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, based on 100 parts by mass of all the polymerizable monomers. . If the amount of the polymerization initiator is less than 0.01 part by mass, the curing of the adhesive for the polyaryletherketone resin material becomes insufficient, the strength of the adhesive layer decreases, and high adhesiveness tends to be hardly obtained. On the other hand, when the polymerization initiator exceeds 10 parts by mass, the amount of the unreacted polymerization initiator or the residue of the reacted polymerization initiator increases, and the mercapto group of the polymerizable monomer having a mercapto group of the adhesive, It may adversely affect the interaction of the polyaryletherketone resin material with the ketone groups of the polyaryletherketone resin, which may be a factor in lowering the adhesive durability.

  When used as a primer for a polyaryletherketone resin material, it is easier to make the thickness of the adhesive composition layer thinner than when used as an adhesive for a polyaryletherketone resin material. Become. By thinning the layer of the adhesive composition, for example, in dental applications, a high compatibility can be obtained when mounting a dental prosthesis made of a polyaryletherketone resin material to an abutment, or a polyarylether When producing a dental prosthesis using a dental curable composition such as a ketone resin material and a hard resin, it is possible to produce a high-aesthetic dental prosthesis or the like. It becomes easy to provide a material with excellent stability. From the viewpoint of the thickness of the layer of the adhesive composition, it is preferable to use a primer for a polyaryletherketone resin material without blending a polymerization initiator.

  When the polymerization initiator is not blended, a part of the components forming the chemical polymerization initiator system (hereinafter, also referred to as a part of the chemical polymerization initiator component) is blended into the primer for the polyaryl ether ketone resin material. A curable composition containing a part of this chemical polymerization initiator component and a component forming a chemical polymerization initiator system (for example, in dental applications, dental resin cement, dental composite resin, dental hard resin, etc.) ) Is preferably used in combination. That is, a primer for a polyaryletherketone resin material containing a part of the chemical polymerization initiator component is applied to the surface to which the polyaryletherketone resin material is applied, and then one of the chemical polymerization initiator components contained in the primer is applied. A curable composition containing a chemical polymerization initiator component forming a chemical polymerization initiator system with a part component is used from above the primer. As a result, in the primer for the polyaryletherketone resin material, which does not form the chemical polymerization initiator system and includes a part of the chemical polymerization initiator component, the chemical polymerization is started by the chemical polymerization initiator component of the curable composition. Since the agent system is formed, the curability of the primer layer is improved, and the adhesiveness is improved. On the other hand, since the chemical polymerization initiator system is not formed by the primer alone, the primer layer maintains fluidity until immediately before using the curable composition, and the advantage that the thickness of the layer of the adhesive composition can be reduced is impaired. Not.

  As a part of the chemical polymerization initiator component, the components exemplified as the chemical polymerization initiator of the above-mentioned polymerization initiator can be used.

  As a part of the chemical polymerization initiator component, it is particularly preferable to mix a component capable of acting as a reducing agent in the primer for the polyaryletherketone resin material from the viewpoint of improving the adhesiveness. Although the cause of the improvement in adhesiveness is not known in detail, by adding a reducing agent to the primer, when the primer is applied to the surface of the polyaryletherketone resin material, the reducing agent in the primer is converted to a polyaryletherketone resin. By acting on the resin on the surface of the ether ketone resin material and reducing a part of the ketone groups, carbon atoms having two arylene groups, a hydroxyl group and a hydrogen atom as substituents are added to the surface of the polyaryl ether ketone resin material. Generate. Since radicals are easily generated by hydrogen abstraction on such a carbon atom having two arylene groups, a hydroxyl group, and a hydrogen atom as substituents, when the primer is polymerized and cured, the surface of the polyaryl ether ketone resin material is A bond is formed between the carbon atom adjacent to the generated hydroxyl group and the laminated radical polymerizable monomer. As a result, it is presumed that the adhesiveness is improved.

  Also, as a part of the chemical polymerization initiator component, the high activity as a chemical polymerization initiator and the fact that the primer layer maintains the highest possible fluidity immediately before contact with the curable composition and has storage stability From the viewpoint of the balance of the properties and the like, it is preferable to mix the transition metal compound of the fourth period with the primer. It is more preferable that the transition metal compound of the fourth cycle to be blended in the primer is a vanadium compound.

  In view of these points, a part of the chemical polymerization initiator component blended in the primer is preferably a transition metal compound of the fourth period, which can act as a reducing agent, and is particularly low in the oxidation number among the stable vanadium compounds and has a low oxidation number. Most preferred are + IV valent vanadium compounds.

  The amount of the chemical polymerization initiator component is 0.002 to 10 parts by mass, based on 100 parts by mass of all the polymerizable monomers, particularly from the balance between the adhesion immediately after adhesion and the storage stability of the primer. Is more preferably in the range of 0.007 to 2 parts by mass, and most preferably in the range of 0.01 to 1 part by mass.

  In addition, the adhesive composition for a polyaryletherketone resin material of the present invention may further include a solvent, a filler, a polymerization inhibitor, a polymerization inhibitor, and a dye, if necessary, as long as the effects of the present invention are not significantly impaired. , Pigments, perfumes and the like.

  It is also preferable to add a volatile solvent to the adhesive composition for a polyaryletherketone resin material. By adding a volatile solvent, the viscosity of the adhesive composition for a polyaryl ether ketone resin material is reduced, and the polymerizable monomer having two or more polymerizable functional groups in the molecule is a polyaryl ether ketone resin material. It is easy to penetrate into fine irregularities on the surface of the film, or to form a uniform layer of the adhesive composition. In addition, since it is volatile, after the adhesive composition for a polyaryl ether ketone resin material is applied to the surface to which the polyaryl ether ketone resin material is applied, the surface of the polyaryl ether ketone resin material is removed by an operation such as air blowing. It can be removed and the adverse effect on 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 remains without adverse effects, the vapor pressure at 20 ° C. is more preferably 2.0 KPa or more, even more preferably 5.0 KPa or more. . On the other hand, if the volatilization of the volatile solvent is too fast, it is difficult to sufficiently obtain the effect of blending the volatile solvent. Therefore, the vapor pressure of the volatile solvent at 20 ° C. is preferably 60 KPa or less, and more preferably 50 KPa or less. Since the lower the boiling point, the easier it is to remove from the surface of the dental polyaryletherketone resin material, the boiling point of the volatile solvent at 760 mmHg is more preferably 85 ° C. or lower.

  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 and the like. These volatile solvents may be used alone or, if they can be uniformly mixed, a plurality of them may be mixed.

  When the application of the adhesive composition for a polyaryletherketone resin material is an adhesive for a polyaryletherketone resin material, the amount of the volatile solvent is from 10 parts by mass to 100 parts by mass of the total polymerizable monomer. The range is preferably 1000 parts by mass, more preferably 10 parts by mass to 500 parts by mass, still more preferably 20 parts by mass to 400 parts by mass, and most preferably 50 parts by mass to 300 parts by mass. When the amount of the volatile solvent is less than 10 parts by mass, the degree of decrease in the viscosity of the adhesive for the polyaryletherketone resin material is small, and the adhesion of the polyaryletherketone resin material to fine irregularities on the surface of the polyaryletherketone resin material is small. It is difficult to obtain an effect that the material easily penetrates or that a uniform adhesive layer is formed. When the amount of the volatile solvent is more than 1000 parts by mass, the amount of the polymerizable monomer component of the adhesive for the polyaryl ether ketone resin material decreases, and as a result, the surface of the polyaryl ether ketone resin material has When the adhesive is applied, the amount of the polymerizable monomer present on the surface of the dental polyaryletherketone resin material is insufficient, and the formation of a uniform and strong adhesive layer is insufficient, and the adhesiveness is reduced. In some cases.

  When the application of the adhesive composition for a polyaryletherketone resin material is a primer for a polyaryletherketone resin material, the amount of the volatile solvent is from 10 parts by mass to 3000 parts by mass based on 100 parts by mass of the total polymerizable monomer. The range is preferably from 100 parts by mass to 2,000 parts by mass, more preferably from 300 parts by mass to 1500 parts by mass, even more preferably from 500 parts by mass to 1,000 parts by mass. Most preferably, it is within the range. In the case of a primer, it is disadvantageous in forming a layer of a uniform and strong adhesive composition as compared with an adhesive, but the decrease in adhesiveness when a large amount of a solvent is used is limited. Therefore, the appropriate amount of solvent differs between the case of the adhesive and the case of the primer. When the amount of the volatile solvent is less than 10 parts by mass, the degree of decrease in the viscosity of the primer for the polyaryl ether ketone resin material is small, and the primer for the polyaryl ether ketone resin material has fine irregularities on the surface of the polyaryl ether ketone resin material. It is difficult to obtain the effect of easily penetrating or forming a uniform primer layer. When the amount of the volatile solvent is more than 3000 parts by mass, the amount of the polymerizable monomer component of the primer for the polyaryl ether ketone resin material decreases, and as a result, the primer for the polyaryl ether ketone resin material is formed on the surface of the polyaryl ether ketone resin material. Insufficient amount of polymerizable monomer present on the surface of the polyaryl ether ketone resin material when applied, the formation of a uniform and strong primer layer becomes insufficient, and the advantage of adding a volatile solvent is obtained. It becomes difficult.

  The volatile solvent may be used in combination with a low-volatile solvent having a vapor pressure of less than 1.0 KPa at 20 ° C. However, when a large amount of a solvent having low volatility is contained, the interaction between the polyaryletherketone resin material and the polymerizable monomer of the adhesive composition for a polyaryletherketone resin material is inhibited, There is a possibility that the polymerizable monomer of the adhesive composition for a ketone resin material may be inhibited from polymerizing and curing, thereby deteriorating the adhesiveness. Therefore, the solvent having low volatility contained in the adhesive composition for a polyaryletherketone resin material is preferably 40% by mass or less, and more preferably 20% by mass or less based on the amount of the volatile solvent. Is more preferably 10% by mass or less, and most preferably 1% by mass or less.

  It is also preferable to mix a metal oxide as a filler in the adhesive composition for a polyaryl ether ketone resin material of the present invention. The reaction between the mercapto group of the polymerizable monomer having a mercapto group blended in the adhesive composition and the ketone group of the polyaryletherketone resin of the polyaryletherketone resin material is further promoted by the acid, and the higher adhesive durability May be obtained.

  Examples of the metal oxide include oxides such as silica, alumina, titania, and zirconia, and composite inorganic oxides such as silica-zirconia, silica-titania, and silica-alumina. Among them, in particular, silica-based metal oxides such as silica or silica-zirconia, silica-titania, and silica-alumina, which have high reactivity with a silane coupling agent which is preferable as a coupling agent, and easily obtain high adhesiveness. Is preferred, and silica is most preferred. These metal oxides may be used alone or in combination of two or more in the polyaryletherketone resin composite material.

  These metal oxides may be surface-treated with a coupling agent such as a silane coupling agent as long as the surface acid sites remain, but are preferably used without surface treatment.

  In addition, a filler other than the above-mentioned metal oxide may be blended as needed. When a filler is compounded, known inorganic fillers, organic fillers, organic-inorganic composite fillers and the like can be used without any particular limitation, including the above-mentioned metal oxide. It is speculated that the inclusion of the filler increases the strength of the layer of the adhesive composition that has penetrated into fine irregularities present on the surface of the polyaryletherketone resin material, and also has the effect of making it easier to obtain higher adhesiveness. Is done.

  Examples of the inorganic filler include lanthanum glass, barium glass, strontium glass, fluoroaluminosilicate glass, and the like, in addition to the above metal oxides.

  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. Examples include particles made of an organic polymer such as a copolymer.

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

  On the other hand, when the adhesive composition contains a large amount of filler, in addition to the tendency that the viscosity of the adhesive composition increases and the adhesiveness decreases, the layer of the adhesive composition becomes thicker There is a tendency. Therefore, the blending amount of the filler in the adhesive composition is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less based on 100 parts by mass of the adhesive composition.

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

  The viscosity of the adhesive composition for a polyaryletherketone resin material of the present invention is preferably low. The low viscosity of the adhesive composition for a polyaryl ether ketone resin material makes it easier for the primer to penetrate into fine irregularities on the surface of the polyaryl ether ketone resin material, and also allows the primer to uniformly spread on the surface of the polyaryl ether ketone resin material. It becomes easy to apply the adhesive composition for a polyaryletherketone resin material to the composition, and higher adhesiveness is easily obtained. On the other hand, when the viscosity of the adhesive composition for a polyaryletherketone resin material is too low, the polyaryletherketone resin material may have a complicated structure due to dripping or the like. In some cases, it may be difficult to uniformly apply the adhesive composition for a polyaryl ether ketone resin material to the surface to which the ether ketone resin material is adhered. Therefore, the viscosity of the adhesive composition for a polyaryletherketone resin material at 23 ° C. is preferably in the range of 0.3 cP to 3000 cP, more preferably in the range of 0.4 cP to 500 cP. The range is more preferably from 0.5 cP to 30 cP, and most preferably from 0.5 cP to 10 cP. The viscosity may be measured using a cone-plate viscometer in a constant temperature room maintained at 23 ° C. When the packaging of the adhesive composition for a polyaryletherketone resin material is divided into two or more, and these are mixed and used immediately before being applied to the polyaryletherketone resin material, the temperature is kept at 23 ° C. Immediately after mixing them indoors, the viscosity may be measured using a cone-plate viscometer.

  The method for producing the adhesive composition for a polyaryletherketone resin material of the present invention is not particularly limited, and may be in accordance with a known method for producing an adhesive composition. Generally, all components to be blended may be weighed and mixed well until uniform.

  The polyaryl ether ketone resin material that can be used for the adhesive composition for a polyaryl ether ketone resin material of the present invention is a polyaryl ether ketone resin having a compounding amount that provides the advantages of the polyaryl ether ketone resin such as high strength. It preferably contains 20% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more of a polyaryletherketone resin.

  Such a polyaryletherketone resin material is, in addition to a material consisting of only a polyaryletherketone resin, a material obtained by blending another resin with a polyaryletherketone resin, a polyaryletherketone resin or a polyaryletherketone resin. It is a composite material or the like in which a mixture of other resins is used as a resin matrix and mixed with a filler. Further, a trace component such as a pigment and a stabilizer may be added to these materials.

  The polyaryl ether ketone resin is a thermoplastic resin containing at least an aromatic group, an ether group (ether bond) and a ketone group (ketone bond) as its structural unit. In many cases, the arylene group has an ether group and a ketone group. It has a linear polymer structure bonded through Representative examples of the polyaryletherketone resin include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetherketoneetherketoneketone (PEKEKK). 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. The structural unit of the polyaryletherketone resin may contain a sulfonyl group or another copolymerizable monomer unit.

  Other resins that can be blended with the polyaryletherketone resin are not particularly limited as long as they do not significantly deteriorate the physical properties of the polyaryletherketone resin such as rigidity and toughness, for example, polyarylate, Examples include polycarbonate, polyethylene terephthalate, polyphthalamide, polytetrafluoroethylene, and polyphenylene ether. When the polyaryl ether ketone resin is blended with another resin, the content of the polyaryl ether ketone resin is preferably 50% by mass or more, more preferably 70% by mass or more, and preferably 90% by mass or more of the whole resin. More preferably, it is more preferably 99% by mass or more.

  As the filler that can be blended with the polyarylketone resin material, known fillers can be used without any particular limitation, but inorganic fillers are preferred. For example, as a material of the filler, silica glass, borosilicate glass, soda glass, aluminosilicate glass, and fluoroaluminosilicate glass, glass containing heavy metals (for example, barium, strontium, and zirconium); Ceramics such as crystallized glass, crystallized glass on which crystals such as diopside and leucite are precipitated; composite inorganic oxides such as silica-zirconia, silica-titania, silica-alumina; or composite oxides thereof And an inorganic oxide such as silica, alumina, titania, and zirconia.

  It is particularly preferable that the polyaryletherketone resin material used as the adherend of the adhesive composition of the present invention is a polyaryletherketone resin composite material obtained by blending a metal oxide as a filler. By using a polyaryl ether ketone resin material as an adherend as a polyaryl ether ketone resin composite material containing a metal oxide, higher adhesion durability can be easily obtained. This is because, by mixing the metal oxide, when the adhesive composition for a polyaryletherketone resin material is applied to the surface to be adhered, the vicinity of the surface to be adhered becomes acidic due to the surface acid points of the metal oxide, As a result, the reaction between the mercapto group of the polymerizable monomer having a mercapto group blended in the adhesive composition for a polyaryletherketone resin material and the ketone group of the polyaryletherketone resin of the polyaryletherketone resin material occurs. It is presumed that it is further promoted by acid. By blending the metal oxide with the polyaryl ether ketone resin material as the adherend, the mercapto group of the polymerizable monomer having a mercapto group blended in the adhesive composition for the polyaryl ether ketone resin material is particularly useful. Since an acid is easily generated in the vicinity of the adhered surface where the reaction of the ketone group of the polyaryl ether ketone resin of the polyaryl ether ketone resin material occurs, the acidic group-containing polymerizable monomer is added to the adhesive composition described above. It is presumed that the reaction proceeds more easily as compared with the method of mixing and the method of mixing the metal oxide with the adhesive composition.

  Examples of the metal oxide include oxides such as silica, alumina, titania, and zirconia, and composite inorganic oxides such as silica-zirconia, silica-titania, and silica-alumina. From the viewpoint of physical properties as a polyaryletherketone resin composite material, and from the viewpoint of easily obtaining an adhesion durability improving effect when the above-described adhesive composition for a polyaryletherketone resin material of the present invention is used, The metal oxide to be blended is preferably silica or a silica-based metal oxide which is a composite oxide of silica and another metal, and silica or silica-titania, and silica-based zirconia are particularly preferable. Most preferred.

  The amount of the metal oxide to be added to the polyaryl ether ketone resin material is such that the adhesive composition for a polyaryl ether ketone resin material of the present invention can easily obtain high adhesion durability, and therefore the polyaryl ether ketone resin composite material Is preferably blended in an amount of 15% by mass or more, more preferably 25% by mass or more. On the other hand, the amount of the filler including the metal oxide is preferably 70% by mass or less, and more preferably 50% by mass or less, from the viewpoint of the physical properties of the polyaryletherketone resin material.

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

  The bonding method is not particularly limited as long as the adhesive composition for a polyaryletherketone resin material of the present invention is used at least for bonding to a polyaryletherketone resin material. When a volatile solvent is contained in the adhesive composition, before the coating film layer of the adhesive composition formed on the surface of the polyaryletherketone resin material is cured, the adhesive is applied by air drying or air blowing. The volatile solvent in the film layer can be removed. In addition, the polyaryletherketone resin material which becomes the adherend of the adhesive of the present invention may be hereinafter referred to as a “first member”.

  The adhesive composition for a polyaryl ether ketone resin material of the present invention is more preferably used for a polyaryl ether ketone resin material whose surface is roughened. The roughened polyaryletherketone resin material has increased surface irregularities, and higher adhesiveness can be obtained by applying the adhesive composition of the present invention thereto. Roughening is a technique that can be easily and safely performed before applying the adhesive composition of the present invention to the polyaryletherketone resin material, and is performed on the surface to which the polyaryletherketone resin material is applied. What is necessary is just to perform a process. As a roughening treatment method, it is preferable to sandblast the surface of the polyaryletherketone resin material. Sandblasting is generally performed in dental laboratories and the like, and can easily and safely roughen the adhered surface of the polyaryletherketone resin material, thereby contributing to an improvement in adhesiveness. The sand blasting treatment may be carried out by a commonly used method, for example, in the dental field, generally, alumina particles having a particle size of several μm to several hundred μm are converted to several tens of KPa to several MPa using a sand blasting device. This is carried out by spraying the polyaryl ether ketone resin material-coated surface with pressure. That is, when the adhesive composition of the present invention is applied to the polyaryletherketone resin material thus roughened, the effect of the present invention can be more enhanced. From such a viewpoint, it can be used as a kit comprising the adhesive composition for a polyaryletherketone resin material of the present invention and a polyaryletherketone resin material having a roughened adherend surface.

  The bonding method using the adhesive composition for a polyaryletherketone resin material of the present invention is performed 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 a state of being mixed with another composition. The form in which the adhesive composition is applied 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 may be applied to a member other than the first member. After applying the adhesive composition to the surface, the adhesive composition can be brought into contact with the surface of the first member by bringing another member into contact with the first member.

  The bonding method using the adhesive composition for a polyaryletherketone resin material of the present invention includes an adhesive applying step of applying the adhesive composition of the present invention to the surface of the first member, and optionally an adhesive composition. And a curing step of curing the object. In the adhesive application step, the adhesive composition may be applied to the surface of the first member in a state of a mixture mixed with another composition, and in the curing step, the adhesive composition is combined with the other composition. It may be cured in the state of a mixed mixture. The form in which the adhesive composition is applied 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 may be applied to a member other than the first member. After applying the adhesive composition to the surface, the adhesive composition can be brought into contact with the surface of the first member by bringing another member into contact with the first member.

  The first member may be any member as long as the portion near the adherend that comes into contact with the adhesive composition for a polyaryletherketone resin material of the present invention at the time of bonding is made of a polyaryletherketone resin material. There may be. The bonding target of the adhesive composition for a polyaryletherketone resin 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 composed of only the first member, for example, one end and the other end of the ring-shaped first member provided with the abutment can be bonded using the adhesive composition of the present embodiment. Alternatively, the adhesive composition of the present embodiment may be adhered to a concave portion of the first member provided with a concave portion such as a hole or a groove. In this case, the recess is embedded and the layer of the adhesive composition filled in the recess is bonded to the inner wall surface of the recess of the first member. Further, by applying the adhesive composition of the present invention to the surface of the first member, it is possible to produce a structure covered with the adhesive composition of the present invention.

  When the object to be bonded is composed of two members, the first member and the second member, the first member and the second member are bonded using the adhesive composition of the present embodiment. Here, the second member is not particularly limited as long as it is a member that can be bonded to the adhesive composition of the present embodiment. For example, a member that is solid before the bonding operation is started (hereinafter, referred to as “solid second May be referred to as “members”), and forms a paste or a liquid before the start of the bonding operation, and is cured during the bonding operation to form a solid after the bonding operation is completed. (Hereinafter, may be referred to as “curable second member”).

  The solid second member may be a polyaryletherketone resin material like the first member, and a member that does not include the polyaryletherketone resin material in the vicinity of the adhered surface (a member different from the first member). ).

  The curable second member may function as an adhesive. In this case, the cured product of the adhesive composition for a polyaryletherketone resin material of the present invention and the cured product of the curable second member can be firmly bonded. In addition to this, the curable second member can be used for bonding to another solid member (hereinafter, may be referred to as “third member”). For example, if the curable second member is a member having the property of firmly adhering to the surface of the third member, the first member side is provided with the adhesive composition for a polyaryletherketone resin material of the present invention on the first member side. Then, the first member and the third member can be firmly bonded to each other by applying the curable second member before curing to the third member side and performing bonding. The third member can be used without any particular limitation as long as it is a known solid member. Usually, however, a member (a member different from the first member) in which a portion near the surface to be adhered is not a polyaryletherketone resin material is used. preferable. The details of the first member, the second member, and the third member will be described later.

  A specific bonding procedure can be appropriately determined according to the composition of the bonding object or the adhesive composition for a polyaryletherketone resin material.

  When the adhesive composition for a polyaryletherketone resin material is an adhesive for a polyaryletherketone resin material containing all components of the polymerization initiator, the adhesion can be performed in the following procedure.

  When only the first member is used as the bonding target, for example, the adhesive may be applied to the surface of the first member, and then 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 application. When a chemical polymerization initiator is used as the polymerization initiator, an adhesive mixed so that all components of the chemical polymerization initiator are blended may be applied to the surface of the first member immediately before application. In this case, the adhesive can be cured as time elapses after the application.

  When the first member and the solid second member are used as the object to be bonded, for example, after applying an adhesive to the surface of at least one of the first member and the solid second member, the first member and the solid The second member may be brought into contact with the adhesive through a coating layer of the adhesive, and then the adhesive may be cured.

  When the first member and the curable second member are used as the bonding target, for example, after applying the adhesive to the surface of the first member, the curable second member is further applied, and the adhesive and the curable second member are applied. A one-step curing process for simultaneously curing the member may be performed, or a two-step curing in which the application and curing of the curable second member are sequentially performed after the application and curing of the adhesive are sequentially performed. Processing may be performed. The timing of the curing treatment, the number of curing treatments, and the curing method (thermal curing, light curing, chemical curing) can be appropriately selected according to the type of the polymerization initiator mixed in the adhesive and the curable second member.

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

  Further, after applying the adhesive and the curable second member to the surface of the first member in this order, the adhesive and the curable second member of the first member are brought into contact with the coated surface and the third member, Thereafter, the adhesive and the curable second member may be cured. In this case, after the adhesive is applied and cured on the surface of the first member, the curable second member is further applied, and the surface and the third member of the first member on which the curable second member is applied are further applied. After the contact, the curable second member may be cured. Alternatively, after applying the curable second member and the adhesive on the surface of the third member in this order, the curable second member of the third member and the surface to which the adhesive has been applied are brought into contact with the first member, 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. The members and timing for applying the adhesive and the curable second member, and the timing for curing these members can be appropriately selected.

  When the adhesive composition for a polyaryletherketone resin material is a primer for a polyaryletherketone resin material that does not contain all the components of the polymerization initiator, the adhesion can be performed in the following procedure.

  When the first member and the curable second member are used as the bonding target, for example, after applying a primer to the surface of the first member, the curable second member is further applied, and then the curable second member is cured. It should be done. The timing of the curing treatment and the curing method (thermal curing, light curing, chemical curing) can be appropriately selected according to the type of the polymerization initiator to be mixed with the curable second member.

  When the third member is further used, for example, 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 three members may be brought into contact with the surface to which the curable second member has been applied, and then the curable second member may be cured.

  Further, after applying the primer and the curable second member on the surface of the first member in this order, the primer and the curable second member of the first member are brought into contact with the surface to which the second member is applied, and then, The curable second member may be cured. Alternatively, after applying the curable second member and the primer on the surface of the third member in this order, the curable second member of the third member and the surface to which the primer has been applied are brought into contact with the first member, and then The curable second member may be cured. In addition, a member and timing for applying the primer and the curable second member, and a timing for curing the curable second member can be appropriately selected.

  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 are the first member and the solid second member. May be the same or different. When the solid second member is made of a member containing a polyaryletherketone resin material in the same manner as the first member, the adhesive composition of the present embodiment has a solid state as in the case of being adhered to the first member. It is also possible to adhere with high adhesiveness to the second member. Examples of the material constituting the solid second member include: a) various resins such as polyaryletherketone resin, a material mainly containing an organic substance other than the resin (such as pulp material), a metal, and a first member. B) a composite material using two or more of the materials shown in a), or c) a non-artificial material such as a tooth or bone. It may be a biomaterial or the like.

  The curable second member contains at least a polymerization initiator and a polymerizable monomer. As each component constituting the curable second member, a material that can be used in the adhesive composition for a polyaryletherketone resin material of the present invention can be appropriately combined and used. However, the composition of the curable second member is usually selected from a composition different from the adhesive composition for a polyaryletherketone resin material of the present invention actually used for adhesion. Since the curable second member contains a polymerizable monomer, the curable second member and the adhesive composition of the present invention are firmly bonded. When the third member is further used, the polymerizable monomer contained in the curable second member also interacts with the surface of the third member to bond the curable second member and the third member. it can. It is preferable that the composition of the curable second member is selected to have a high affinity with the constituent material 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, it is usually preferable to use a member in which the constituent material does not include a polyaryletherketone resin material.

  The adhesive composition for a polyaryletherketone resin material of the present invention can be used for any purpose. Further, at least a first member according to the intended use is used as the object to be bonded. Further, if necessary, a) a solid second member, b) a curable second member, or c) a curable second member. A member and a third member are used. However, the adhesive composition for a polyaryletherketone resin material of the present invention is preferably used in the dental field.

  In dental applications, in particular, high adhesiveness and adhesive durability are required in view of the necessity of bonding in a particularly moist and severe environment such as the oral cavity, and by using the adhesive composition of the present invention, It is particularly easy to respond to requests.

  Further, in dental applications, since the adhesive composition is usually used in a very small amount for each dental treatment, it is required that the adhesive composition can be stored for a long time without deterioration (excellent storage stability). Can be Further, it is desired that the bonding operation be completed quickly from the viewpoint of reducing the burden on the patient. In this respect, the polymerizable monomer having a mercapto group (A) is a polymerizable monomer capable of forming a mercapto group by tautomerism, which is a particularly preferable form as an adhesive composition used for dental applications. .

  As a dental polyaryletherketone resin material (dental first member) that can be used as a dental member, at least a portion near an adhered surface or the entire dental first member is made of a polyaryletherketone resin material. Dentures, artificial teeth, denture bases, dental implants, crown restoration materials, abutment building materials, and the like. The curable second member (dental curable second member) that can be used as a dental member includes a dental composite resin, a dental hard resin, a dental cement, a dental bonding material, and a dental immediate polymerization. Resins. Further, as the third member, dental members such as dentures, artificial teeth, denture bases, dental implants, crown restoration materials, abutment building materials made of natural teeth, metal materials, ceramic materials, resin materials, etc. And the like.

  When the adhesive composition for a polyaryl ether ketone resin material of the present invention is used for dental use, a dental polyaryl ether ketone resin material and a dental resin such as a tooth material or a dental cement or a dental hard resin are used. It can be used as a material for bonding materials used in dental treatments including materials.

  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 polyaryl ether ketone resin material and a dental hard resin are bonded to the polyaryl ether ketone resin material adhesive composition of the present invention. To laminate these materials to produce a dental prosthesis. Specifically, for example, the adhesive composition for a polyaryletherketone resin material of the present invention is applied to the surface of a dental polyaryletherketone resin material molded into a desired shape, and then a hard resin is laminated thereon. It can be cured to produce the desired dental prosthesis.

  As another example, using a dental cement as the second member, using the adhesive composition for a polyaryletherketone resin material of the present invention, a prosthesis made of a polyaryletherketone resin material, The step of attaching to a tooth defect part is mentioned. Specifically, for example, the adhesive composition for a polyaryl ether ketone resin material of the present invention is applied to the surface of a prosthesis made of a polyaryl ether ketone resin material prepared in advance, and a dental cement is applied thereon. It can be applied and attached to teeth.

  Dental materials are required to have sufficient mechanical strength to withstand repeated pressure during meshing and water resistance to saliva as properties that can withstand use in the oral cavity, but excellent mechanical strength and chemical durability It is extremely easy for the first dental member made of a polyaryletherketone resin material having the following to sufficiently meet these needs.

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

  In addition, when used as a dental application, by blending a metal oxide with the polyaryletherketone resin, favorable physical properties and color tone that are preferable when used as a dental application can be easily provided. In addition, when the metal oxide is blended with the polyaryl ether ketone resin material as described above, high adhesive durability can be obtained when the adhesive composition for a polyaryl ether ketone resin material of the present invention is used. It is preferable from the viewpoint of easiness. Therefore, especially in dental applications, the adhesive composition for a polyaryletherketone resin material of the present invention is combined with a polyaryletherketone resin composite material obtained by blending a metal oxide with the polyaryletherketone resin material. It is preferred to use.

  Therefore, in order to utilize the adhesive composition for a polyaryletherketone resin material of the present invention for dental treatment, the dental composition comprising the adhesive composition for a dental polyaryletherketone resin material of the present invention and a metal oxide is used. As a dental treatment kit for a polyaryletherketone resin composite material for dental use. Specifically, a dental treatment kit including a primer for a dental polyaryl ether ketone resin material and a polyaryl ether ketone resin composite material containing a metal oxide, or a dental polyaryl ether ketone resin material It can be used as a dental treatment kit including an adhesive and a polyaryletherketone resin composite material containing a metal oxide.

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

[Radical polymerizable monomer]
<Polymerizable monomer having a mercapto group>
MTU-6, MMT-11, VTD, and 5VS shown below were used.

<Polymerizable monomer having no mercapto group>
<Polymerizable monomer having two or more polymerizable functional groups in the molecule>
BisGMA: 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane3G: triethylene glycol dimethacrylate <polymerizable monomer having only one polymerizable functional group in the molecule MER>
-MDP: 10-methacryloyloxydecyl dihydrogen phosphate-HEMA: 2-hydroxyethyl methacrylate-MMA: methyl methacrylate

[Polymerization initiator]
<Organic peroxide>
TMBPO: 1,1,3,3-tetramethylbutyl hydroperoxide <+ IV-valent vanadium compound>
BMOV: bis (maltolate) oxovanadium (IV)

Table 1 shows the composition of the adhesive composition for each polyaryletherketone resin material.
As the polyaryl ether ketone resin material of the adherend, three types of C1, C2 and C3 shown below were used.

  As the adherend C1, spherical silica (average particle size: 1.0 μm) having been surface-treated with a polyetheretherketone resin (VESTAKEEP M2G, manufactured by Daicel Evonik) and γ-methacryloyloxypropyltrimethoxysilane as a metal oxide. ) Was used so that the metal oxide was mixed in an amount of 30 parts by mass with respect to 70 parts by mass of the polyether ether ketone resin. The mixing method is as follows. First, a predetermined amount of a polyether ether ketone resin and a metal oxide are weighed, and they are put into a kneading lab plast mill (manufactured by Toyo Seiki Co., Ltd.) and melt-kneaded at a test temperature of 370 ° C. and a rotation speed of 100 rpm for 5 minutes. After that, the melt-kneaded product was recovered.

  As the adherend C2, spherical silica surface-treated with polyetheretherketone resin (manufactured by Daicel Evonik: VESTAKEEEP M2G) and γ-methacryloyloxypropyltrimethoxysilane as a metal oxide (average particle size: 1.0 μm) ) Was used so that the metal oxide was mixed with 85 parts by mass of the polyether ether ketone resin so that the metal oxide was 15 parts by mass. The mixing method is as follows. First, a predetermined amount of a polyether ether ketone resin and a metal oxide are weighed, and they are put into a kneading lab plast mill (manufactured by Toyo Seiki Co., Ltd.) and melt-kneaded at a test temperature of 370 ° C. and a rotation speed of 100 rpm for 5 minutes. After that, the melt-kneaded product was recovered.

  As the adherend C3, a polyaryletherketone resin (manufactured by Daicel Evonik Co., Ltd .: STEEPEEP M2G) was used.

  Each test method is as follows.

(Initial tensile bond strength measurement)
The polyaryl ether ketone resin material was molded into a plate having a thickness of about 2 mm by injection molding to obtain an adherend. After the adherend surface of the adherend is polished with # 800 water-resistant abrasive paper, it is sandblasted (alumina particles having a particle diameter of about 50 μm are sprayed at a pressure of about 0.2 MPa for 10 seconds using a sandblasting device). Roughening was performed. Thereafter, the substrate was immersed in water and exposed to ultrasonic waves for 5 minutes, and then immersed in acetone and exposed to ultrasonic waves for 5 minutes to perform cleaning. Next, a double-sided tape having a hole with a diameter of 3 mm was attached to the surface to be adhered.
Thereafter, the adhesive composition was applied to the holes, allowed to stand for 10 seconds, and then dried by blowing 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 further pressed thereon to prepare an adhesive test piece. After holding the above-mentioned adhesion test piece at 37 ° C. for 24 hours, it was pulled at a crosshead speed of 2 mm / min using a tensile tester (Autograph, manufactured by Shimadzu Corporation) to obtain a polyaryletherketone resin material. The tensile adhesive strength with the adhesive composition for a polyaryletherketone resin material was measured. The measurement of the tensile adhesive strength between the polyaryletherketone resin material and the adhesive composition for the polyaryletherketone resin material was carried out for each of the examples or comparative examples, for each of five test pieces, and for the average value. The standard deviation (SD) was determined.

(Durable tensile bond strength measurement)
The polyaryl ether ketone resin material was molded into a plate having a thickness of about 2 mm by injection molding to obtain an adherend. After the adherend surface of the adherend is polished with # 800 water-resistant abrasive paper, it is sandblasted (alumina particles having a particle diameter of about 50 μm are sprayed at a pressure of about 0.2 MPa for 10 seconds using a sandblasting device). Roughening was performed. Thereafter, the substrate was immersed in water and exposed to ultrasonic waves for 5 minutes, and then immersed in acetone and exposed to ultrasonic waves for 5 minutes to perform cleaning. Next, a double-sided tape having a hole with a diameter of 3 mm was attached to the surface to be adhered.
Thereafter, the adhesive composition was applied to the holes, allowed to stand for 10 seconds, and then dried by blowing 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 further pressed thereon to prepare an adhesive test piece. After holding the above-mentioned adhesive test piece at 37 ° C. for 24 hours, put it in a thermal shock tester, immerse it in a 4 ° C. water tank for 1 minute, transfer it to a 60 ° C. water tank, immerse it for 1 minute and return it to the 4 ° C. water tank again Was repeated 3000 times. Thereafter, a tensile tester (Autograph, manufactured by Shimadzu Corporation) was used to pull at a crosshead speed of 2 mm / min to pull the polyaryletherketone resin material and the adhesive composition for the polyaryletherketone resin material. The durable adhesive strength was measured. The measurement of the tensile durability adhesive strength between the polyaryletherketone resin material and the adhesive composition for the polyaryletherketone resin material was measured for each of the five test pieces for each example or each comparative example, and the average value was obtained. And standard deviation (SD) were determined.

  Further, the average value of the obtained durable tensile bond strength was obtained from the average value of the initial tensile bond strength when a test was performed using the same adhesive composition for a polyaryl ether ketone resin material as follows. The adhesion durability was determined according to the formula.

(Adhesive layer thickness)
The polyaryl ether ketone resin material was molded into a plate having a thickness of about 2 mm by injection molding to obtain an adherend. After the adherend surface of the adherend is polished with # 800 water-resistant abrasive paper, it is sandblasted (alumina particles having a particle diameter of about 50 μm are sprayed at a pressure of about 0.2 MPa for 10 seconds using a sandblasting device). Roughening was performed. Thereafter, the substrate was immersed in water and exposed to ultrasonic waves for 5 minutes, and then immersed in acetone and exposed to ultrasonic waves for 5 minutes to perform cleaning. Thereafter, the adhesive composition was applied to the surface of the adherend, allowed to stand for 10 seconds, and then dried by blowing compressed air for about 10 seconds. By applying a dental cement material (Bistite II, manufactured by Tokuyama Dental Co., Ltd.) on top of it, and then hardening a dental hard resin (manufactured by Tokuyama Dental Co., Ltd .: Pearl Esthe), pressing the attachment made by pressing, Test pieces were prepared. After holding the above-mentioned test piece at 37 ° C. for 24 hours, it was cut perpendicularly to the surface to be adhered using a diamond cutter to expose the cross section of the bonding site. After this 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 using a laser microscope (manufactured by Keyence Corporation).

<Example 1>
(A) 0.01 g of MTU-6 as a polymerizable monomer component having a mercapto group, 4.995 g of bisGMA as a polymerizable monomer component having two or more polymerizable functional groups in the molecule, and 4 G of 3G 0.995 g, 0.1 g of TMBPO as a chemical polymerization initiator component as a polymerization initiator component, and 20 g of acetone as a solvent component were stirred and mixed to obtain a composition A. (A) 0.01 g of MTU-6 as a polymerizable monomer component having a mercapto group, 4.995 g of bisGMA as a polymerizable monomer component having two or more polymerizable functional groups in the molecule, and 4 G of 3G 0.995 g, 0.1 g of BMOV as a chemical polymerization initiator component as a polymerization initiator component, and 20 g of acetone as a solvent component were stirred and mixed to obtain a composition B. An equal amount of the composition A and the composition B were mixed to obtain an adhesive composition B1 for a polyaryletherketone resin material, which was an adhesive for a polyaryletherketone resin material, and was quickly used for the test. Table 1 shows the composition of the adhesive composition for a polyaryletherketone resin material. Using the adhesive composition B1, the initial tensile bond strength, the durable tensile bond strength, and the adhesive layer thickness of the polyaryletherketone resin material C1 were measured. In addition, adhesion durability was calculated. Table 2 shows the results.

<Example 2>
(A) 0.01 g of MMT-11 as a polymerizable monomer component having a mercapto group, 4.995 g of bisGMA as a polymerizable monomer component having two or more polymerizable functional groups in a molecule, and 4 of 3G 0.995 g, 0.1 g of TMBPO as a chemical polymerization initiator component as a polymerization initiator component, and 20 g of acetone as a solvent component were stirred and mixed to obtain a composition A. (A) 0.01 g of MMT-11 as a polymerizable monomer component having a mercapto group, 4.995 g of bisGMA as a polymerizable monomer component having two or more polymerizable functional groups in a molecule, and 4 of 3G 0.995 g, 0.1 g of BMOV as a chemical polymerization initiator component as a polymerization initiator component, and 20 g of acetone as a solvent component were stirred and mixed to obtain a composition B. An equal amount of the composition A and the composition B were mixed to obtain an adhesive composition B2 for a polyaryletherketone resin material, which was an adhesive for a polyaryletherketone resin material, and was quickly used for the test. Table 1 shows the composition of the adhesive composition for a polyaryletherketone resin material. Using the adhesive composition B2, the initial tensile bond strength and the durable tensile bond strength to the polyaryletherketone resin material C1 were measured. In addition, adhesion durability was calculated. Table 2 shows the results.

<Examples 3 to 8, Example 12, Comparative Example 1>
Except for changing to the composition shown in Table 1, according to Example 2, adhesives B3 to B8, B12, and B13 for polyaryletherketone resin material, which are adhesives for polyaryletherketone resin material, were prepared. Using the adhesive composition, the initial tensile bond strength and the durable tensile bond strength to the polyaryletherketone resin material C1 were measured. In addition, adhesion durability was calculated. Table 2 shows the results.

<Example 9>
(A) 0.01 g of MTU-6 as a polymerizable monomer component having a mercapto group, 4.495 g of bisGMA as a polymerizable monomer component having two or more polymerizable functional groups in the molecule, 4G of 3G .495 g, 1 g of MDP as an acidic group-containing polymerizable monomer component having only one polymerizable functional group in a molecule, 0.1 g of TMBPO as a chemical polymerization initiator component as a polymerization initiator component, and a solvent component As a result, a composition A obtained by stirring and mixing 20 g of acetone was obtained. (A) 0.01 g of MTU-6 as a polymerizable monomer component having a mercapto group, 4.495 g of bisGMA as a polymerizable monomer component having two or more polymerizable functional groups in the molecule, 4G of 3G .495 g, 1 g of MDP as an acidic group-containing polymerizable monomer component having only one polymerizable functional group in a molecule, 0.1 g of BMOV as a chemical polymerization initiator component as a polymerization initiator component, and a solvent component As a result, a composition B obtained by stirring and mixing 20 g of acetone was obtained. An equal amount of the composition A and the composition B were mixed to obtain an adhesive composition B9 for a polyaryletherketone resin material, which was an adhesive for a polyaryletherketone resin material, and quickly used in the test. Table 1 shows the composition of the adhesive composition for a polyaryletherketone resin material. Using the adhesive composition B9, the initial tensile bond strength, the durable tensile bond strength, and the adhesive layer thickness of the polyaryletherketone resin material C1 were measured. In addition, adhesion durability was calculated. Table 2 shows the results.

<Example 10>
(A) 0.01 g of MTU-6 as a polymerizable monomer component having a mercapto group, 3.745 g of bisGMA as a polymerizable monomer component having two or more polymerizable functional groups in a molecule, and 3G of 3G .745 g, 1 g of MDP as an acidic group-containing polymerizable monomer component having only one polymerizable functional group in the molecule, and as a polymerizable monomer component having only one polymerizable functional group in the molecule. A composition A was obtained by stirring and mixing 1.5 g of HEMA, 0.1 g of TMBPO as a chemical polymerization initiator component as a polymerization initiator component, and 20 g of acetone as a solvent component. (A) 0.01 g of MTU-6 as a polymerizable monomer component having a mercapto group, 3.745 g of bisGMA as a polymerizable monomer component having two or more polymerizable functional groups in a molecule, and 3G of 3G .745 g, 1 g of MDP as an acidic group-containing polymerizable monomer component having only one polymerizable functional group in the molecule, and as a polymerizable monomer component having only one polymerizable functional group in the molecule. A composition B was obtained by stirring and mixing 1.5 g of HEMA, 0.1 g of BMOV as a chemical polymerization initiator component as a polymerization initiator component, and 20 g of acetone as a solvent component. An equal amount of the composition A and the composition B were mixed to obtain an adhesive composition B10 for a polyaryletherketone resin material, which was an adhesive for a polyaryletherketone resin material, and was quickly used for the test. Table 1 shows the composition of the adhesive composition for a polyaryletherketone resin material. Using the adhesive composition B10, the initial tensile bond strength and the durable tensile bond strength to the polyaryletherketone resin material C1 were measured. In addition, adhesion durability was calculated. Table 2 shows the results.

<Example 11>
An adhesive B11 for a polyaryletherketone resin material, which is an adhesive for a polyaryletherketone resin material, was prepared according to Example 10, except that the composition was changed to the composition shown in Table 1, and the adhesive composition was used. Then, the initial tensile bond strength and the durable tensile bond strength to the polyaryletherketone resin material C1 were measured. In addition, adhesion durability was calculated. Table 2 shows the results.

<Examples 13 and 14>
According to Example 1, using the adhesive composition B1 for a polyaryletherketone resin material, the initial tensile adhesive strength and the durable tensile adhesive strength to the polyaryletherketone resin materials C2 and C3 were measured. In addition, adhesion durability was calculated. Table 2 shows the results.

<Example 15>
(A) 0.01 g of MTU-6 as a polymerizable monomer component having a mercapto group, 4.995 g of bisGMA as a polymerizable monomer component having two or more polymerizable functional groups in the molecule, and 4 G of 3G 0.995 g, 0.002 g of BMOV as a partial component of the chemical polymerization initiator, and 50 g of acetone as a solvent component were stirred and mixed, and the adhesive composition for a polyaryl ether ketone resin material as a primer for the polyaryl ether ketone resin material was used. P1 was obtained. Table 1 shows the composition of the adhesive composition for a polyaryletherketone resin material. In this system, BMOV is added as a part of the polymerization initiator component. However, since this alone does not work as a polymerization initiator and does not cause a polymerization reaction, the present composition is used for a polyaryletherketone resin material. Used as a primer.
Using the adhesive composition P1, the initial tensile bond strength, the durable tensile bond strength, and the adhesive layer thickness of the polyaryletherketone resin material C1 were measured. In addition, adhesion durability was calculated. Table 2 shows the results.

<Example 16>
(A) 0.01 g of MTU-6 as a polymerizable monomer component having a mercapto group, 4.995 g of bisGMA as a polymerizable monomer component having two or more polymerizable functional groups in the molecule, and 4 G of 3G 0.995 g, 1 g of MDP as an acidic group-containing polymerizable monomer component having only one polymerizable functional group in a molecule, 0.002 g of BMOV as a partial component of a chemical polymerization initiator, and acetone as a solvent component. 50 g of the mixture was stirred and mixed to obtain an adhesive composition P2 for a polyaryletherketone resin material, which was a primer for the polyaryletherketone resin material. Table 1 shows the composition of the adhesive composition for a polyaryletherketone resin material. In this system, BMOV is added as a part of the polymerization initiator component. However, since this alone does not work as a polymerization initiator and does not cause a polymerization reaction, the present composition is used for a polyaryletherketone resin material. Used as a primer.
Using the adhesive composition P2, the initial tensile bond strength, the durable tensile bond strength, and the adhesive layer thickness of the polyaryletherketone resin material C1 were measured. In addition, adhesion durability was calculated. Table 2 shows the results.

<Comparative Example 2>
Except for changing to the composition shown in Table 1, according to Example 15, an adhesive composition P3 for a polyaryletherketone resin material, which is a primer for a polyaryletherketone resin material, was prepared. Using this, the initial tensile bond strength and the durable tensile bond strength to the dental polyaryletherketone resin material C1 were measured. In addition, adhesion durability was calculated. Table 2 shows the results.

  Examples 1 to 14 using the adhesive for a polyaryletherketone resin material of the present invention were Comparative Examples 1 using an adhesive not containing a polymerizable monomer having a mercapto group and not of the present invention. All showed higher adhesive durability than that of.

  For the adhesive for polyaryletherketone resin material, the same amount of polymerization initiator and solvent are blended, and the same polymerizable monomer having the same mercapto group and the same polymerizable monomer are used. When Examples 1 and 5 to 8 were different from each other, the adhesive durability showed almost the same value, but there was a difference in the initial tensile adhesive strength, and the amount of the polymerizable monomer having a mercapto group was changed. However, Examples 1 to 5 to 7, which are in the range of 0.03% by mass to 1% by mass, with respect to all the polymerizable monomers, have a slightly higher initial tension as compared with Example 8 exceeding 1% by mass. The bond strength was indicated.

  For the adhesive for polyaryletherketone resin material, the same amount of polymerizable monomer, polymerization initiator and solvent are blended, and the same amount of polymerizable monomer having mercapto group is blended. When Examples 1 to 4 are different from each other, the polymerizable monomers having a mercapto group compounded in these adhesives are all polymerizable monomers capable of generating a mercapto group by tautomerism. Example 1, in which the functional group capable of generating a mercapto group due to variability is a thiouracil group, exhibited slightly higher adhesion durability than Examples 2 to 4, which are other functional groups. In Examples 1 and 2 in which the polymerizable functional group of the polymerizable monomer having a mercapto group was a (meth) acryloyl group, the initial tensile adhesive strength was slightly higher than in Examples 3 and 4 in which the polymerizable monomer was a vinyl group. Showed.

  Examples 1, 9 to 12 in which the same amount of a polymerizable monomer having the same amount of a mercapto group, a polymerization initiator, and a solvent are blended and the composition of the polymerizable monomer is different for the adhesive for polyaryletherketone resin material. In comparison, Examples 9 and 10 in which the acidic group-containing polymerizable monomer was blended exhibited slightly higher adhesion than Examples 1, 11, and 12 in which the acidic group-containing polymerizable monomer was not blended. It showed durability. Examples 1, 9, 10, and 12 in which a polymerizable monomer having two or more polymerizable functional groups in the molecule was mixed in an amount of 40% by mass or more of all the polymerizable monomers were 40% by mass. It showed a higher initial tensile adhesive strength and a higher durable tensile adhesive strength as compared with Example 11 which was less than. Further, the polymerizable monomer having two or more polymerizable functional groups and a hydrogen bonding functional group in the molecule accounts for 20% by mass or more of all polymerizable monomers, and two or more in the molecule. Examples 1, 9, and 10 in which the polymerizable monomer having a polymerizable functional group, a hydrogen bonding functional group, and an aromatic ring are in a range of 15% by mass to 70% by mass of all the polymerizable monomers. The polymerizable monomer having two or more polymerizable functional groups and a hydrogen bonding functional group in the molecule is less than 20% by mass of all the polymerizable monomers, and has two or more polymerizable functional groups in the molecule. The polymerizable monomer having a functional group, a hydrogen bonding functional group, and an aromatic ring has a slightly higher initial adhesive strength as compared with Example 12 in which the total amount of the polymerizable monomer is less than 15% by mass. Was.

  Examples 15 and 16 using the primer for a polyaryletherketone resin material of the present invention were compared with Comparative Example 2 using a primer not containing the polymerizable monomer having a mercapto group and not of the present invention. All showed high adhesive durability.

  For the primer for the polyaryletherketone resin material, the same amount of a polymerizable monomer having the same amount of a mercapto group, a polymerization initiator, and a solvent were blended, and Examples 15 and 16 in which the composition of the polymerizable monomer was different were compared. Example 16 in which the acidic group-containing polymerizable monomer was blended exhibited slightly higher adhesion durability than Example 15 in which the acidic group-containing polymerizable monomer was not blended.

  When the same adhesive composition for polyaryl ether ketone resin material was used and the compositions of the polyaryl ether ketone resin materials to be adhered were different from those in Examples 1, 13 and 14, it was found that the polyaryl ether ketone resin had a metal In Examples 1 and 13 in which a polyaryl ether ketone resin material containing silica as an oxide was used as an adherend, a polyaryl ether ketone resin material comprising only a polyaryl ether ketone resin and containing no metal oxide was used. Showed higher adhesion durability than Example 14 in which was used as an adherend. In Example 1 in which a polyaryl ether ketone resin composite material containing 25% by mass or more of a metal oxide was used as an adherend, the polyaryl ether ketone resin containing less than 25% by mass of a metal oxide was used. The adhesive durability was higher than that of Example 13 in which the composite material was used as an adherend.

  A comparison of Examples 1 and 15 in which the same adherend was tested using the same polymerizable monomer and an adhesive for a polyaryletherketone resin material and a primer showed that the adhesive durability was high. Showed equivalent values. On the other hand, the initial tensile adhesive strength was higher in Example 1, and the thickness of the adhesive layer was smaller in Example 15. Similarly, a test was performed on the same adherend using an adhesive for a polyaryletherketone resin material and a primer using the same polymerizable monomer, and Examples 9 and 16 were tested. In comparison, the adhesive durability was equivalent, the initial tensile adhesive strength was higher in Example 9, and the thickness of the adhesive layer was lower in Example 16. In the present study, the case where the thickness of the adhesive layer is less than 1 μm means that the adhesive layer was extremely thin and measurement was difficult. That is, in the case of the same polymerizable monomer composition, the adhesive and the primer had the same adhesive durability. The initial adhesive strength was higher for the adhesive, and the adhesive had a more favorable result than the primer from the viewpoint of adhesiveness. The thickness of the adhesive layer was smaller in the case of the primer, and from the viewpoint of the thickness of the adhesive layer, the primer was more preferable than the adhesive.

Claims (3)

Polyaryl ether resin, and a polyaryletherketone resin material comprising a metal oxide, the content of these polyaryl ether resin and a metal oxide, a reference the polyaryletherketone resin material total mass expressed in mass% of, respectively, polyaryl ether resin: 20 wt% or more, the metal oxide: 15 mass% or more, 70 wt% or less, the total content of both is not more than 100 mass%, Po Leary ether An adhesive composition for a polyaryl ether ketone resin material having a ketone resin material as an adherend,
“(A) a polymerizable monomer having a mercapto group”, which is a polymerizable monomer having a mercapto group or a polymerizable monomer capable of generating a mercapto group, and a polymerizable monomer other than (A) A mixture containing a polymerizable monomer component consisting of “(B) a polymerizable monomer having no mercapto group” and a + IV-valent and / or + V-valent vanadium compound,
In the mixture,
As (A), a polymerizable monomer having a polymerizable functional group consisting of a mercapto group and a (meth) acryloyl group in the molecule, a polymerizable functional group consisting of a (meth) acryloyl group in the molecule, and At least one type of polymerization selected from the group consisting of a polymerizable monomer capable of generating a mercapto group due to variability, and a polymerizable monomer having a polymerizable functional group comprising a disulfide bond and a (meth) acryloyl group in the molecule; Using a functional monomer,
As the (B), a polymerizable monomer having a polymerizable functional group consisting of a (meth) acryloyl group in a molecule is used,
The contents of (A) and (B) are represented by mass% based on the mass of the entire polymerizable monomer component, and (A) is 0.005 mass% or more and 10 mass%, respectively. The following, and (B): residual,
At least a part of (A) and / or (B) is a polymerizable monomer having two or more polymerizable groups in a molecule, and further has two or more polymerizable groups in the molecule based on the above criteria. The content of the polymerizable monomer having is 40% by mass or more,
An adhesive composition for a polyaryl ether ketone resin material, comprising: (A) the polymerizable monomer having a mercapto group is at least one compound selected from the compounds having the structures represented by the following A1 to A6, and a polymerizable monomer capable of generating a mercapto group by tautomerism; The adhesive composition for a polyaryletherketone resin material according to claim 1, which is a body.

｛In the general formulas A1 to A6, R ¹ is a hydrogen atom or a methyl group, R ² is a divalent saturated hydrocarbon group having 1 to 12 carbon atoms, a —CH ₂ —C ₆ H ₄ —CH ₂ — group, A — (CH ₂ ) _o —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ — (CH ₂ ) _p — group (where o and p are each an integer of 1 to 5), or — A CH ₂ CH ₂ OCH ₂ CH ₂ — group, and Z is a —OC (＝ O) — group, an —OCH ₂ — group, or a —OCH ₂ —C ₆ H ₄ — group (however, any of these groups also carbon atoms at the right end binds to an unsaturated carbon in Z, an oxygen atom at the left end is bonded to the group R ^2), Z 'is -OC (= O) -. group (provided that the right edge carbon atoms The carbon atom is bonded to an unsaturated carbon, and the leftmost oxygen atom is bonded to the group R ² ), a —C ₆ H ₄ — group, or a bond (here, the group Z 'is a case of a bond refers to a state in which the unsaturated carbon is directly bonded with radical ^{R 2),} Y is -S -., - O-, or -N (R') - (where, R 'is A hydrogen atom and an alkyl group having 1 to 5 carbon atoms). ｝   The adhesive for a polyaryletherketone resin material, comprising the adhesive composition for a polyaryletherketone resin material according to claim 1 or 2, wherein the mixture further contains a polymerization initiator containing an organic peroxide.