JP6529428B2 - Adhesive composition for polyaryl ether ketone resin material - Google Patents

Description

  The present invention relates to an adhesive composition for polyaryl ether ketone resin materials having excellent adhesion to polyaryl ether ketone resin materials.

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

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

  Members comprising polyaryletherketone resins having excellent chemical properties and physical properties are widely used in various fields as well as dental applications. Therefore, regardless of the technical field or application, there is a need for a technique that can more firmly adhere to a member containing a polyaryl ether ketone resin.

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

  For example, Non-Patent Document 1 claims that relatively high adhesion is obtained by using a hydrophobic dental bonding material, and specifically, Heliobond (ivoclar vivadent) is used. It is written that Heliobond contains 1- (methylethylidene) bis [4,1-phenylenoxy (2-hydroxy-3,1-propanedily)] bismethacrylate, TEGDMA and uretanedimethacrylate as polymerizable monomers. There is no disclosure of using a polymerizable monomer having a benzoyl skeleton.

  For example, in Non-Patent Document 2, in addition to relatively high adhesive strength obtained using the dental bonding material Luxatemp Glaze & Bond (DMG), tests using several kinds of dental adhesive compositions were conducted. There is. It is noted that Luxatemp Glaze & Bond contains, as polymerizable monomers, Multifunctional acrylates and methyl methacrylates, and it has a benzoyl skeleton, including other dental adhesive compositions used in the test. It is not disclosed to use the polymerizable monomer which it has.

  As described above, although there is an example of adhesion to a polyaryl ether ketone resin using an adhesive composition containing a polymerizable monomer, there is an example of using a polymerizable monomer having a benzoyl skeleton. It is not disclosed for use.

Unexamined-Japanese-Patent No. 2013-144778

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

  Although studies on adhesion to polyaryl ether ketone resin materials have been conducted including the above-mentioned studies, and techniques for obtaining relatively high adhesion strength have been found, further improvement in adhesion is desired.

Therefore, it is an object of the present invention to provide an adhesive composition capable of obtaining higher adhesion to a polyaryl ether ketone resin material than in the prior art.

  MEANS TO SOLVE THE PROBLEM In order to solve the said subject, as a result of inventors earnestly examining, as a result of using the adhesive composition containing the polymerizable monomer which has a benzoyl skeleton, with respect to polyaryl ether ketone resin material, It discovered that high adhesiveness was obtained, and came to this invention.

  That is, the present invention is an adhesive composition for a polyaryl ether ketone resin material containing a polymerizable monomer having a benzoyl skeleton in the molecule.

  The polymerizable monomer having a benzoyl skeleton in the molecule is preferably one represented by the following general formula (1).

[In the general formula (1), X represents a divalent group, and Ar ¹ and Ar ² each represent an aromatic group having any valence selected from divalent to tetravalent; L ¹ and L ² may be the same or different, and each of L ¹ and L ² has a main chain atom number in the range of 2 to 60, and any valence selected from divalent to tetravalent It represents a hydrocarbon group having a number, each of which may be the same or different, and R ¹ and R ² each represent a hydrogen or a methyl group. In addition, m1, m2, n1 and n2 are each an integer selected from the range of 1 to 3. ]
In addition, it is more preferable that bivalent group X in the said General formula (1) is -O-.

  The adhesive composition for a polyaryl ether ketone resin material more preferably contains 15% by mass to 85% by mass of all polymerizable monomers having a benzoyl skeleton in the molecule. In addition, the adhesive composition for a polyaryl ether ketone resin material further has two or more polymerizable functional groups in the molecule, and does not have a benzoyl skeleton having a viscosity of 100 cP or less measured at 23 ° C. It is preferable to contain a polymerizable monomer, and it is more preferable to contain 40% by mass or more of all polymerizable monomers having a polymerizable monomer having two or more polymerizable functional groups in the molecule.

  According to the present invention, higher adhesion can be obtained in adhesion to polyaryletherketone resin materials as compared to conventional adhesive compositions. Therefore, for example, in the field of dental treatment, when attaching a dental prosthesis made of a polyaryl ether ketone resin material to an abutment tooth, it is more firmly adhered, or a polyaryl ether ketone resin material and a curable composition Can be used to make a dental prosthesis more resistant to breakage when making a dental prosthesis.

  The adhesive composition for polyaryl ether ketone resin material of the present invention is characterized by containing a polymerizable monomer having a benzoyl skeleton. Hereinafter, details of materials and the like constituting the present embodiment will be described.

  The polymerizable monomer having a benzoyl skeleton is a compound having both a benzoyl skeleton and a polymerizable functional group, and such a compound can be used without particular limitation.

  The adhesive composition for a polyaryl ether ketone resin material contains the polymerizable monomer having a benzoyl skeleton, whereby the adhesive composition is used for the polyaryl ether ketone resin material as an adherend. At the same time, a polymerizable monomer having a structure similar to the skeleton of the skeleton of a polyaryletherketone resin having a benzene ring and a carbonyl group adjacent thereto is applied to the adhesion surface of the polyaryletherketone resin material. It becomes. As a result, it is presumed that the interaction between the adherend and the adhesive composition due to stacking of aromatic rings becomes strong, and high adhesiveness can be obtained.

Having a benzoyl skeleton means having a benzoyl group (—C (= O) —C ₆ H ₅ ) structure or having a structure in which a hydrogen atom of the benzoyl group is substituted with another substituent. At this time, the number and position of substituents are not particularly limited, and when the substituents are two or more, these substituents are mutually bonded to form a ring together with the group to which these substituents are respectively bonded It may be done.

  The polymerizable functional group is preferably a radically polymerizable functional group from the viewpoint of low biotoxicity and high polymerization activity, and functional groups such as vinyl group, styryl group, allyl group and (meth) acryloyl group can be mentioned. In particular, (meth) acryloyl group is preferable from the viewpoint of polymerization rate and biological safety.

  It is more preferable that the polymerizable monomer having a benzoyl skeleton has two or more polymerizable functional groups in the molecule. By having two or more polymerizable functional groups in the molecule, the polymer after polymerization of the polymerizable monomer of the adhesive composition can form a network structure, and the strength of the layer of the adhesive composition is increased. Get higher. In particular, when the site having a benzoyl skeleton having a strong interaction with the adherend becomes a part of the strong layer, the effect becomes higher. As a result, it is presumed that higher adhesion can be obtained.

  When the polymerizable monomer having a benzoyl skeleton has two or more polymerizable functional groups in the molecule, it is preferable that a benzoyl skeleton is present in the main chain portion of the functional group connecting the two polymerizable functional groups. When the polymerizable monomer having a benzoyl skeleton has such a structure, the benzoyl skeleton is located in the main chain of the polymer chain formed by curing of the polymerizable monomer of the adhesive composition. And an effect of improving adhesion by the interaction with an adherend by having a benzoyl skeleton, and an effect of improving adhesion by improving the strength of the layer of the adhesive composition by having two or more polymerizable functional groups in the molecule. It is inferred that both of them are likely to be more effectively exhibited.

  As such a polymerizable monomer, for example, the following compounds A1 to A16 group, B1 group, C1 group, D1 group, E1 to E3 group, F1 to F2 group, G1 to G2 group, H1 group, I1 to I2 Polymerizable monomers such as groups, J1, K1 to K2 groups can be mentioned. In addition, compounds described in Japanese Patent No. 3021152 can be exemplified.

  The polymerizable monomer having a benzoyl skeleton preferably has a structure of the general formula (1) shown below.

Here, in the general formula (1), X represents a divalent group, and Ar ¹ and Ar ² each represent an aromatic group having any valence selected from divalent to tetravalent, Each of L ¹ and L ² may be the same or different, and each of L ¹ and L ² has 60 or less of main chain atoms and has any valence selected from divalent to tetravalent It represents a hydrocarbon group which may be the same or different and each of R ¹ and R ² represents a hydrogen atom or a methyl group. M1, m2, n1 and n2 are integers selected from the range of 1 to 3, respectively. The polymerizable monomer represented by the general formula (1) may be an isomer mixture containing two or more kinds of isomers.

Higher adhesiveness can be obtained by using the compound represented by the general formula (1) as the polymerizable monomer having a benzoyl skeleton. This is achieved by using a compound represented by the general formula (1) having a structure (Ar ¹ -X-Ar ² ) containing a highly rigid aromatic group in the central part of the molecule, to form a layer of adhesive composition It is presumed that this is because the strength is high.

In addition, since the compound represented by the general formula (1) has a relatively low viscosity, the polymerizable monomer having a benzoyl skeleton in the adhesive composition is in between the polyaryletherketone resin as the adherend. It is thought that the reason is that they move efficiently to the appropriate position for interaction, and it becomes easy to obtain high interaction. The reason why the compound represented by the general formula (1) exhibits a relatively low viscosity is a structure in which an aromatic group Ar ¹ and an aromatic group Ar ² are bonded to each other via a divalent group X at the molecular center. (Ar ¹ -X-Ar ² ) has a relatively large flexibility in molecular structure and also has low crystallinity compared to biphenyl structures (Ar ¹ -Ar ² ) and the like, which also have large rigidity. And it is guessed that it is by the contribution by the ester bond connected to aromatic group Ar < ¹ >, Ar < ² >.

Next, the polymerizable monomer represented by the general formula (1) will be described in more detail. First, in the general formula (1), Ar ¹ and Ar ² each represent an aromatic group having any valence selected from divalent to tetravalent, and they may be the same or different. good.

Specific examples of the aromatic groups Ar ¹ and Ar ² include divalent to tetravalent benzenes represented by the following structural formulas Ar-a 1 to Ar-a 3, and bivalents to 4 represented by the following structural formulas Ar-a 4 to Ar-a 6 And naphthalene or divalent to tetravalent anthracene represented by the following structural formulas Ar-a7 to Ar-a9. In these structural formulas, the bond may be provided on any carbon of the benzene ring constituting the aromatic groups Ar ¹ and Ar ² (except for the carbon which forms the bonding portion between the benzene ring and the benzene ring). Can do. For example, in the case of the structural formula Ar-a1 (divalent benzene), two bonds can be provided at any of the ortho position, the meta position, and the para position.

Incidentally, the valence of the aromatic group Ar ¹ is determined according to the number of m1, represented by m1 + 1. Similarly, the valence of the aromatic group Ar ² is determined according to the number of m 2 and is represented by m 2 +1.

Each of the aromatic groups Ar ¹ and Ar ² may have a substituent, in which case the hydrogen of the benzene ring constituting the aromatic groups Ar ¹ and Ar ² is replaced with another substituent. Can. No particular limitation is imposed on the substituent of the aromatic group Ar ¹ and Ar ² as long as it does not contain a reactive group (that is, an acryloyl group or a methacryloyl group) shown at the left side of the general formula (1) at its terminal. And those having a total number (number of atoms) of atoms constituting a substituent in the range of 1 to 60 can be appropriately selected. Specifically, mention may be made of monovalent hydrocarbon group and -COOR ³ having 1 to 20 carbon atoms, -OR ^3, a halogeno group, an amino group, a nitro group, a carboxyl group or the like. R ³ is the same as the monovalent hydrocarbon group having 1 to 20 carbon atoms. In addition, as the monovalent hydrocarbon group having 1 to 20 carbon atoms, a linear or branched hydrocarbon group such as a methyl group or an ethyl group, an alicyclic hydrocarbon group such as a cyclohexyl group, a phenyl group, 1 And heterocyclic groups such as furan.

Ar ¹ and Ar ^{2 each} being a benzene ring, that is, those represented by the structural formulas Ar-a1 to Ar-a3 are more preferable from the viewpoint of adhesion. This is because, in the case of naphthalene and anthracene, the steric hindrance is large compared to the benzene ring, and therefore, the polymerizable monomer having a benzoyl skeleton contained in the adhesive composition and the adherent poly This is because the efficiency of the interaction with the aryl ether ketone resin material is reduced, which may affect the adhesion.

X represents a divalent group, and specifically, the number of atoms in the main chain bridging the aromatic group Ar ¹ and the aromatic group Ar ² as exemplified in the following structural formulas X-1 to X-13. Is a 1 to 3 divalent group.

The number of atoms in the main chain of the divalent group X is more preferably 1. When the number of atoms in the main chain is one, a structure in which the aromatic group Ar ¹ and the aromatic group Ar ² are bonded via one atom is obtained. This is similar to the structure of the polyaryl ether ketone resin, and the polymerizable monomer having a benzoyl skeleton contained in the adhesive composition and the polyaryl ether of the polyaryl ether ketone resin material as the adherend Stacking of aromatic rings between ketone resins can be more efficiently formed, and higher adhesion can be easily obtained. Examples of such divalent group X include X-1 to X-10 among those exemplified in the above structural formula.

  Furthermore, when the number of atoms in the side chain of the divalent group X is large, steric hindrance becomes large, and the polymerizable monomer having a benzoyl skeleton contained in the adhesive composition, and the adherend The efficiency of interaction with certain polyaryl ether ketone resin materials may be reduced, and adhesion may be reduced. Therefore, the number of atoms in the side chain of the divalent group X is preferably 15 or less, more preferably 10 or less, and still more preferably 3 or less. In consideration of this point and the point that the number of atoms in the main chain of the above-mentioned divalent group X is preferably 1, it is preferable that the divalent group X be any one of those exemplified in the above structural formula, X-1 -X-8 and X-10 are preferable, X-1 to X-5 and X-10 are more preferable, and X-1 to X-3 and X-10 are more preferable.

  In addition, it is said that the divalent group X is -O-, the polymerizable monomer having a benzoyl skeleton contained in the adhesive composition, and the polyaryl of polyaryl ether ketone resin material as an adherend. The structure of the ether ketone resin is close to each other, stacking of aromatic rings is more efficiently formed, and higher adhesion is easily obtained, and therefore, it is most preferable. That is, the divalent group X is most preferably X-1.

L ¹ and L ² each represent a hydrocarbon group having any of valence numbers selected from divalent to tetravalent, in which the number of atoms in the main chain is in the range of 2 to 60, and each is identical Or may be different. The number of atoms in the main chain is preferably in the range of 2 to 12, more preferably in the range of 2 to 6, and still more preferably in the range of 2 to 3. By reducing the number of atoms in the main chain, the density of the benzoyl skeleton contained in the polymerizable monomer having a benzoyl skeleton increases, and the interaction between the polyaryl ether ketone resin material and the adhesive composition becomes more It becomes easy to form efficiently, and it becomes easy to obtain higher adhesiveness. Further, by setting the number of atoms of the main chain in the range of 2 to 3, the strength of the layer of the adhesive composition can be easily increased, and high adhesion can be easily obtained.

  The atoms constituting the main chain are basically composed of carbon atoms, and all the atoms may be carbon atoms, but part of carbon atoms constituting the main chain may be replaced by heteroatoms. it can. As this hetero atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom can be mentioned. When the main chain contains an oxygen atom as a hetero atom, an ether bond or an ester bond can be introduced into the main chain. The number of heteroatoms that can be introduced into the main chain is preferably about half or less of the number of atoms in the main chain, and when the number of atoms in the main chain is 2, the number of heteroatoms that can be introduced into the main chain is one. .

In addition, of the atoms constituting the main chain, a substituent may be bonded to at least one atom (usually a carbon atom). Examples of such substituents include an alkyl group having 1 to 3 carbon atoms such as a methyl group, a hydroxyl group, a monovalent hydrocarbon group having a hydroxyl group, halogeno group, -COOR ^4, and -OR ^4. R ⁴ is the same as the alkyl group having 1 to 3 carbon atoms. Further, the monovalent hydrocarbon group having a hydroxyl group preferably has a carbon number in the range of 1 to 3 and more preferably in the range of 1 to 2. Specific examples of the monovalent hydrocarbon group having a hydroxyl _{group, -CH 2 OH, -CH 2 CH} 2 OH, -CH (CH 3) OH and the like.

Specific examples of L ¹ and L ² include the following structural formulas L-b 1 to L-b 14 in the case of n 1 and n 2 = 1 (in the case of L ¹ and L ² being a divalent hydrocarbon group) it can. Of the two bonds shown in these structural formulas, the bond marked * means a bond bonded to the oxygen atom of the ester bond constituting the benzoate structure at the molecular center. Here, in the following structural formulas L-b1 to L-b14, a means an integer selected from the range of 1 to 11, b represents an integer selected from the range of 1 to 19, and c is 0 to 11 represents an integer selected from the range of 11, d represents an integer selected from the range of 0 to 5, e represents an integer selected from the range of 2 to 5, and f is selected from the range of 1 to 6 Represents an integer. In the structural formulas L-b1 to L-b14, the values of a to f are preferably selected in such a range that the number of atoms in the main chain is 12 or less.

On the other hand, in the case of n 1 and n 2 = 2 (L ¹ and L ² are trivalent hydrocarbon groups), in structural formulas L-b 1 to L-b 14, of the carbon atoms constituting the main chain, * The carbon atom at the position farthest from the carbon atom having the attached bond has two bonds. Further, when n1 and n2 = 3 (L1 and L2 each having a tetravalent hydrocarbon group), structural formulas L-b1 to L-b2, L-b6 to L-b8 and L-b10 to L-b14 are used. In the above, among carbon atoms constituting the main chain, a carbon atom at a position farthest from the carbon atom having a bond with an asterisk (*) has three bonds.

In addition, as for the polymerizable monomer of this embodiment shown by General formula (1), it is especially preferable that it is a polymerizable monomer shown by following General formula (2), and General formula (2) is in the general formula (1), m1, m2, n1, n2 = 1, Ar 1, Ar 2 = -C 6 H 4 - shows the structure of a case of a (structural formula Ar-a1).

  As such polymerizable monomers represented by the general formula (2), the above-mentioned compounds E1 to E3 groups, F1 to F2 groups, G1 to G2 groups, H1 groups, I1 to I2 groups, J1 and K1 The polymerizable monomer as described in K2 group is mentioned.

  Further, among the particularly preferable polymerizable monomers represented by the general formula (2), the following general formula (3) is more preferable because the structure is similar to the polyaryl ether ketone resin and the interaction efficiency is high. It is more preferable that it is a polymerizable monomer shown by).

R ¹ , R ² , L ¹ and L ² in the general formula (3) are the same as those in the general formula (1).

  Such polymerizable monomers represented by the general formula (3) include the compounds E1 to E3 groups, F1 to F2 groups, G1 to G2 groups, I1 to I2 groups, and K1 to K2 groups described above. A polymerizable monomer is mentioned.

  The polymerizable monomer having a benzoyl skeleton preferably further has a hydrogen bonding functional group. By having a hydrogen bondable functional group, by using a radically polymerizable monomer having a hydrogen bondable functional group, curing by the hydrogen bond between the hydrogen bondable functional groups on the surface of the polyaryl ether ketone resin material The strength of the layer of the adhesive composition becomes stronger, and higher adhesion can be obtained. The term "hydrogen bond" as used herein refers to an electrically negative hydrogen atom (donor) bonded to an electronegativity large atom (O, N, S, etc.) and having an electrically positive polarity, and an lone electron pair. It shows that the bonding interaction is formed between the two atoms (acceptor). The hydrogen bonding functional group in the present invention is a substituent which can function as a donor and an acceptor in the above-mentioned hydrogen bond, and specifically means a hydroxyl group, a thiol group, an amino group, a urethane group, an amide group and the like.

  In consideration of these conditions, among the polymerizable monomers having a benzoyl skeleton, X is an oxygen atom and is shown in the above-mentioned compounds E1 to E3 as a particularly preferred compound having a hydrogen bonding functional group. And polymerizable monomers can be exemplified.

  The polymerizable monomer having a benzoyl skeleton is preferably used in an amount of 5% by mass or more, preferably 15% by mass or more, and more preferably 25% by mass or more, based on all the polymerizable monomers. It is more preferable to use% or more, and it is further preferable to use 60% by mass or more. When the content of the polymerizable monomer having a benzoyl skeleton is 15% by mass or less, the interaction between the adhesive composition and the polyaryl ether ketone resin material is not sufficiently obtained, and the effect of the present invention is sufficiently obtained. There is a risk that On the other hand, the upper limit of the polymerizable monomer having a benzoyl skeleton is not particularly limited from the viewpoint of adhesiveness, but from the viewpoint of handleability, it is preferably 85% by mass or less of all the polymerizable monomers, 70% It is further preferable that the content is less than or equal to%. When the polymerizable monomer having a benzoyl skeleton is blended in excess of 85% by mass, the interaction between the benzoyl skeleton portions makes it difficult to handle the polymerizable monomer having a benzoyl skeleton, and adhesion is performed from the viewpoint of workability and the like. It may be difficult to formulate in a sex composition.

  In the adhesive composition for polyaryl ether ketone resin material of the present invention, a polymerizable monomer having no benzoyl skeleton other than the polymerizable monomer having a benzoyl skeleton may be blended. The polymerizable functional group of the polymerizable monomer having no benzoyl skeleton is, like the polymerizable functional group of the polymerizable monomer having a benzoyl skeleton, a radical in terms of low biotoxicity and high polymerization activity. The polymerizable functional group is preferable, and functional groups such as vinyl group, styryl group, allyl group and (meth) acryloyl group can be mentioned, and in view of polymerization rate and biological safety, (meth) acryloyl group is particularly preferable.

  Among the polymerizable monomers having no benzoyl skeleton, examples of the polymerizable monomer having a (meth) acryloyl group include the following monofunctional radical polymerizable monomers, bifunctional radical polymerizable monomers, Functional radical polymerizable monomers and tetrafunctional radical polymerizable monomers are exemplified.

(I) Monofunctional radically polymerizable monomer 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-methacryloyl glycine, N-methacryloyl Aspartic acid, N-methacryloyl-5-aminosalicylic acid, 2-methacrylo Roxyethyl hydrogen succinate, 2-methacryloyl oxyethyl hydrogen phthalate, 2-methacryloyl oxyethyl hydrogen malate, 6-methacryloyl oxyethyl naphthalene-1,2,6-tricarboxylic acid, O-methacryloyl tyrosine, N-methacryloyl Tyrosine, N-methacryloyl phenylalanine, 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-methacryloyloxyethyl naphthalene-1,2,6-tricarboxylic acid anhydride, 6-methacryloyloxyethyl naphthalene-2,3,6-tricarboxylic anhydride, 4-methacryloyloxyethyl carbonylpropionoyl-1,8-naphthalic anhydride, 4-methacryloyloxyethyl naphthalene-1,8 -Methacrylates such as tricarboxylic acid anhydrides, and acrylates corresponding to these methacrylates, etc.

(II) Difunctional radically polymerizable monomer 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, 2,2- Bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4-) Methacryloyloxy tetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxy) 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 Salt, 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 these methacrylates Vinyl monomers having -OH groups such as corresponding acrylates, diisocyanate methylbenzene, 4,4'-diphenylmethane diisocyanate, hexamethylethene A diaduct obtained from an adduct with a diisocyanate compound such as diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate); 1,2-bis (3-methacryloyloxy-2-yne; Hydroxypropoxy) ethyl, 1,6-bis (methacryloylethyloxycarbonylamino) 2,2,4-trimethylhexane and the like.

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

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

  The adhesive composition for a polyaryl ether ketone resin material of the present invention has two or more polymerizable functional groups in the molecule among the above-mentioned polymerizable monomers having no benzoyl skeleton, and 23 ° C. It is particularly preferable to blend a polymerizable monomer having a viscosity of 100 cP or less measured in the above. By blending a polymerizable monomer having a viscosity of 100 cP or less, it becomes easy to lower the viscosity of the adhesive composition for polyaryl ether ketone resin material. By lowering the viscosity of the adhesive composition for the polyaryl ether ketone resin material, the adhesive composition can easily penetrate the fine irregularities on the surface of the polyaryl ether ketone resin material, and in particular, the polymerizability of the adhesive composition It becomes easy for the monomer to penetrate into the fine irregularities on the surface of the polyaryl ether ketone resin material, and it is easy to obtain higher adhesion. Moreover, it becomes easy to apply | coat the adhesive composition for polyaryl ether ketone resin material uniformly on the polyaryl ether ketone resin material surface, and it becomes easy to obtain higher adhesiveness.

  The compounding amount of such a polymerizable monomer having two or more polymerizable functional groups in the molecule and having a viscosity of 100 cP or less is 10 parts by mass with respect to 100 parts by mass of all the polymerizable monomers. The range of 70 parts by mass is preferable, and the range of 15 parts by mass to 50 parts by mass is more preferable.

  The viscosity of the polymerizable monomer can be determined by measurement using a cone and plate viscometer in a constant temperature chamber maintained at 23 ° C.

  As such a polymerizable monomer having two or more polymerizable functional groups in the molecule and having a viscosity of 100 cP or less measured at 23 ° C., for example, 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 di Mention may be made of methacrylates, glycerol dimethacrylates and acrylates corresponding to these methacrylates.

  It is preferable to mix | blend the polymerizable monomer which has a 2 or more polymerizable functional group in a molecule | numerator in the adhesive composition for polyaryl ether ketone resin material of this invention. By blending a polymerizable monomer having two or more polymerizable functional groups in the molecule, the strength of the layer of the cured adhesive composition becomes high, and a layer of uniform and strong adhesive composition can be obtained. Since it becomes easy, it is guessed that higher adhesiveness is obtained. Of all polymerizable monomers including a polymerizable monomer having a benzoyl skeleton and a polymerizable monomer having no benzoyl skeleton, a polymerizable unit having two or more polymerizable functional groups in the molecule It is preferable to use 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more of the body. 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 all the polymerizable monomers, a layer of uniform and strong adhesive composition is more easily obtained. Higher adhesion can be obtained.

  Examples of the polymerizable monomer having two or more polymerizable functional groups in the molecule include those represented by general formulas (1) to (3) as those having a benzoyl skeleton, and specifically, the compound A1 Polymerizable monomers such as ~ A16 group, B1 group, C1 group, D1 group, E1 to E3 group, F1 to F2 group, G1 to G2 group, H1 group, I1 to I2 group, J1 and K1 to K2 group And compounds described in Japanese Patent No. 3021152. As a thing which does not have a benzoyl skeleton, (II) bifunctional radically polymerizable monomer shown above, (III) trifunctional radically polymerizable monomer, (IV) tetrafunctional radically polymerizable monomer It can be used.

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

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

  The coupling agent is a compound having at least one or more first reactive groups that react with the inorganic compound and one or more second reactive groups that react with the organic compound. By blending the coupling agent into the adhesive composition for polyaryl ether ketone resin material, higher adhesion to the polyaryl ether ketone resin composite material can be obtained. It is presumed that this is because the coupling agent forms a bond with both the metal oxide of the polyaryl ether ketone resin composite material and the polymerizable monomer of the adhesive composition for the polyaryl ether ketone resin material. .

  As the coupling agent having a polymerizable functional group used in the present invention, known coupling agents can be used without limitation. As the coupling agent, silane coupling agents, titanate coupling agents, aluminate coupling agents, zirconates Although there is a system coupling agent etc., a silane coupling agent is particularly preferable from the viewpoint of adhesion and handleability.

  As a coupling agent having a polymerizable functional group which is particularly preferably used, for example, a silane coupling agent is exemplified as 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) And 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 compounding amount of the coupling agent having a polymerizable functional group is not particularly limited, but from the viewpoint of adhesiveness, 1 to 30 mass based on the total polymerizable monomers including the coupling agent having a polymerizable functional group The range of% is preferable, the range of 2-20 mass% is more preferable, and the range of 3-10 mass% is still more preferable.

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

  Moreover, it is also preferable to mix | blend the polymerizable monomer which has a mercapto group (thiol group) with the adhesive composition for polyaryl ether ketone resin material of this invention, and mix | blends the polymerizable monomer which has a mercapto group By doing this, the effect of improving the adhesion durability can be obtained.

  The polymerizable monomer having a mercapto group is not particularly limited as long as it is a compound having one or more mercapto groups and a polymerizable functional group in the molecule, and in addition to the polymerizable monomer having a free mercapto group A polymerizable monomer capable of producing a mercapto group by tautomerism or a polymerizable monomer capable of producing a mercapto group by stimulation during adhesion operation may be used, and the effect of improving adhesion durability and polyaryl ether ketone resin It is preferable that it is a polymerizable monomer which can produce a mercapto group by tautomerism from a viewpoint of making the storage stability of the adhesive composition for materials make compatible.

  As a polymerizable monomer which can produce a mercapto group by such tautomerism, the compound as shown to A1-A6 of the following general formula is mentioned, for example.

In the general formulas A1 to A6, R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent C 1-12 saturated hydrocarbon group, 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 (where o and p are each an integer of 1 to 5), or -CH 2 ₂ CH ₂ OCH ₂ CH ₂ -group, Z is -OC (= O)-group, -OCH ₂ -group, or -OCH ₂ -C ₆ H ₄ -group (provided that any of these groups Z The carbon atom at the right end is bonded to unsaturated carbon and the oxygen atom at the left end is bonded to the group R ² ), and Z ′ is —OC ((O) — group (however, the carbon atom at the right end is 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, It is a C1-C5 alkyl group).

  As a polymerizable monomer which has a functional group which can produce a mercapto group by the tautomerism shown to these general formula A1-A6, the compound Z1-Z3 group shown next is mentioned.

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

  Although the compounding quantity of the polymerizable monomer which has a mercapto group is not specifically limited, It is preferable that it is the range of 0.005 mass%-10 mass% with respect to all the polymerizable monomers, and 0.01 mass%. The range of 5 to 5% by mass is more preferable, and the range of 0.03% to 1% by mass is even more preferable. If the content of the polymerizable monomer having a mercapto group is too small, the effect of improving the adhesion durability may not be sufficiently obtained. When the blending 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, when the polymerizable monomer of the adhesive composition is polymerized and cured by radical polymerization Since the mercapto group can function 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 adhesion surface of the polyaryletherketone resin material decreases in the initial stage of adhesion. There is also a possibility that the adhesion of

  The adhesive composition for a polyaryl ether ketone resin material of the present invention may be blended with a polymerization initiator to be used as an adhesive for a polyaryl ether ketone resin material, or a polyaryl ether ketone resin without blending a polymerization initiator. It may be used as a material primer. As described later, since there are advantages in each of the case of using an adhesive and the case of using a primer, they may be appropriately selected according to the application.

  When used as an adhesive for polyaryl ether ketone resin materials, a uniform and strong adhesive layer can be easily obtained as compared with the case where it is used as a primer for polyaryl ether ketone resin materials, and higher adhesion can be obtained. Is easier to obtain. From the viewpoint of adhesion, it is preferable to blend a polymerization initiator to form an adhesive for a polyaryl ether ketone 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 kinds of polymerization initiators can be used in combination. In addition, since it can carry out simply when hardening the adhesive agent for polyaryl ether ketone resin materials after application to polyaryl ether ketone resin materials, using a photopolymerization initiator and / or a chemical polymerization initiator Is preferred. Since polyaryl ether ketone resin is usually an opaque material, it may be difficult to irradiate light to the adhesive, so a chemical polymerization initiator is most preferable. These three types of polymerization initiators will be described in more detail below.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The blending amount of these polymerization initiators is preferably in the range of 0.01 to 10 parts by mass, and more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of all the polymerizable monomers. . When the amount of the polymerization initiator is less than 0.01 parts by mass, the curing of the adhesive for polyaryletherketone resin material is insufficient, the strength of the adhesive layer is lowered, and high adhesiveness tends to be difficult to be obtained. On the other hand, when the amount of the polymerization initiator exceeds 10 parts by mass, the residual amount of the unreacted polymerization initiator or the reacted polymerization initiator may be large, which may be a factor to reduce the long-term adhesion.

  When used as a primer for polyaryl ether ketone resin materials, it is easier to make the thickness of the layer of adhesive composition thinner than when used as an adhesive for polyaryl ether ketone resin materials Become. By thinning the layer of adhesive composition, for example in dental applications, a high degree of compatibility is obtained when attaching a dental prosthesis made of a dental polyaryletherketone resin material to an abutment tooth, When producing a dental prosthesis using a dental polyaryl ether ketone resin material and a dental curable composition such as a hard resin, it is possible to produce a highly aesthetic dental prosthesis. From the viewpoint of the thickness of the layer of the adhesive composition, it is preferable to use a primer for polyaryl ether ketone resin material without blending a polymerization initiator.

  When a polymerization initiator is not added, a part of components forming the chemical polymerization initiator system (hereinafter, also referred to as a part of chemical polymerization initiator components) is added to the primer for polyaryl ether ketone resin material And a curable composition containing a component forming a chemical polymerization initiator system with a part of the chemical polymerization initiator component (for example, in dental use, dental resin cement, dental composite resin, dental hard resin, etc. Is preferably used in combination with That is, a primer for polyaryl ether ketone resin material containing a part of the chemical polymerization initiator component is applied to the adherend surface of the polyaryl ether ketone resin material, and then one of the chemical polymerization initiator components mixed in the primer A curable composition comprising a component part and a chemical polymerization initiator component forming a chemical polymerization initiator system is used over the primer. Thus, in the primer for polyaryl ether ketone resin material, in which a part of the chemical polymerization initiator component is not formed, which does not form the chemical polymerization initiator system, the chemical polymerization initiator is initiated 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 adhesion is improved. On the other hand, since the primer alone does not form a chemical polymerization initiator system with the primer alone, the primer layer maintains fluidity until just before using the curable composition, and the advantage that the thickness of the layer of the adhesive composition can be reduced is impaired I can not.

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

  As a part of the chemical polymerization initiator component, it is particularly preferable from the viewpoint of improving adhesion to incorporate a compound capable of acting as a reducing agent into the primer for polyaryl ether ketone resin material. Although the cause of the improvement in adhesion by this is not known in detail, when this primer is applied to the surface of the polyaryl ether ketone resin material by incorporating a reducing agent into the primer, the reducing agent in the primer is polyaryl. By acting on the resin on the surface of the ether ketone resin material and reducing a part of the ketone group, a carbon atom having two arylene groups, a hydroxyl group and a hydrogen atom as a substituent on the surface of the polyaryl ether ketone resin material Generate Since a radical is easily generated by hydrogen abstraction on such a carbon atom having two arylene groups, a hydroxyl group and a hydrogen atom as a substituent, the polyaryl ether ketone resin material surface is formed when the primer is polymerized and cured. 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 adhesion is improved.

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

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

  The compounding amount of a part of the chemical polymerization initiator component is in the range of 0.002 to 10 parts by mass with respect to 100 parts by mass of all the polymerizable monomers, from the balance of adhesion and storage stability of the primer. Is more preferably 0.007 to 2 parts by mass, and most preferably 0.01 to 1 parts by mass.

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

  It is also preferred to incorporate a volatile solvent into the adhesive composition for polyaryl ether ketone resin materials. By blending a volatile solvent, the viscosity of the adhesive composition for polyaryl ether ketone resin material is reduced, and it becomes easy to form a layer of a uniform adhesive composition. In addition, since the adhesive composition for the polyaryletherketone resin material is applied to the adherend surface of the polyaryletherketone resin material due to its volatility, it is possible from the surface of the polyaryletherketone resin material by an operation such as air blow. It is removed, and the adverse effect on the adhesion due to the residual solvent can be suppressed.

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

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

  When the application of the adhesive composition for a polyaryl ether ketone resin material is an adhesive for a polyaryl ether ketone resin material, the blending amount of the volatile solvent is 10 parts by mass with respect to 100 parts by mass of all the polymerizable monomers. The range of 1000 parts by mass is preferable, the range of 10 parts by mass to 500 parts by mass is more preferable, the range of 20 parts by mass to 400 parts by mass is more preferable, and the range of 50 parts by mass to 300 parts by mass is most preferable. When the amount of the volatile solvent is less than 10 parts by mass, the decrease in viscosity of the adhesive for the polyaryletherketone resin material is small, and the fine irregularities on the surface of the polyaryletherketone resin material adhere to the polyaryletherketone resin material. It is difficult to obtain the effect of easily infiltrating the material and forming a uniform adhesive layer. When the volatile solvent is more than 1000 parts by mass, the polymerizable monomer component of the adhesive for the polyaryl ether ketone resin material decreases, and as a result, the polyaryl ether ketone resin material surface is used for the polyaryl ether ketone resin material When the adhesive is applied, the amount of the polymerizable monomer present on the surface of the polyaryl ether ketone resin material is insufficient, so that the formation of the uniform and strong adhesive layer becomes insufficient and the adhesiveness is lowered. is there.

  When the application of the adhesive composition for a polyaryl ether ketone resin material is a primer for a polyaryl ether ketone resin material, the blending amount of the volatile solvent is 10 parts by mass to 3000 parts by mass with respect to 100 parts by mass of all the polymerizable monomers. It is preferably in the range of parts by mass, more preferably in the range of 100 parts by mass to 2000 parts by mass, still more preferably in the range of 300 parts by mass to 1500 parts by mass, and preferably 500 parts by mass to 1000 parts by mass It is most preferable that it is a range. In the case of a primer, it is disadvantageous compared with an adhesive in forming a layer of a uniform and strong adhesive composition, but the decrease in adhesion when using a large amount of solvent is limited. Therefore, the appropriate amount of solvent is different between the adhesive and the primer. When the amount of the volatile solvent is less than 10 parts by mass, the decrease in viscosity of the primer for the polyaryl ether ketone resin material is small, and the fine irregularities on the surface of the polyaryl ether ketone resin material have the primer for the polyaryl ether ketone resin material. It is difficult to obtain the effect of easily invading or forming a uniform primer layer. When the volatile solvent is more than 3000 parts by mass, the polymerizable monomer component of the primer for polyaryl ether ketone resin material decreases, and as a result, the primer for polyaryl ether ketone resin material on the surface of polyaryl ether ketone resin material The amount of the polymerizable monomer present on the surface of the polyaryl ether ketone resin material is insufficient when applying the resin, so that the formation of a uniform and strong primer layer becomes insufficient, and the advantage of compounding a volatile solvent is obtained. It becomes difficult.

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

  You may mix | blend a metal oxide as a filler with the adhesive composition for polyaryl ether ketone resin material of this invention.

  Examples of the metal oxide include oxides such as silica, alumina, titania and zirconia, and complex inorganic oxides such as silica-zirconia, silica-titania and silica-alumina.

  In addition, if necessary, fillers other than the above metal oxides may be blended. When the filler is blended, the filler may be any known inorganic filler, organic filler, organic-inorganic composite filler, etc. without particular limitation, including the metal oxides. It is speculated that the inclusion of the filler enhances the strength of the layer of the adhesive composition which has penetrated into the fine irregularities present on the surface of the polyaryl ether ketone resin material, and has the effect of being able to easily obtain higher adhesion. Be done.

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

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

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

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

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

  The viscosity of the adhesive composition for polyaryl ether ketone resin material of the present invention is preferably low. The low viscosity of the adhesive composition for the polyaryl ether ketone resin material makes it easy for the adhesive composition to penetrate into fine irregularities on the surface of the polyaryl ether ketone resin material, and the polyaryl ether ketone resin material It becomes easy to apply | coat the adhesive composition for polyarylether ketone resin material uniformly on the surface, and it becomes easy to obtain higher adhesiveness. On the other hand, when the viscosity of the adhesive composition for polyaryl ether ketone resin material is too low, polyaryl which may have a complicated structure due to the adhesive composition for polyaryl ether ketone resin material dripping etc. It may be difficult to apply the adhesive composition for polyaryl ether ketone resin material uniformly to the adherend surface of the ether ketone resin material. Therefore, the viscosity of the adhesive composition for a polyaryl ether ketone resin material is preferably in the range of 0.3 cP to 3000 cP at 23 ° C., more preferably in the range of 0.4 cP to 500 cP, 0 More preferably, it is in the range of 0.5 cP to 30 cP, and most preferably in the range of 0.5 cP to 10 cP. The measurement of the viscosity may be performed using a cone-plate viscometer in a temperature-controlled room kept at 23 ° C. In addition, the packaging of the adhesive composition for polyaryl ether ketone resin material is divided into two or more, and when mixing and using these immediately before apply | coating to polyaryl ether ketone resin material, the thermostat kept at 23 degreeC The viscosity may be measured using a cone-plate viscometer immediately after mixing them in a room.

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

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

  Moreover, it is more preferable to use the adhesive composition for polyaryl ether ketone resin material of this invention with respect to the polyaryl ether ketone resin material in which the adhesion surface was roughened. The polyaryletherketone resin material having a roughened adhesion surface has higher surface roughness, so that by applying the adhesive of the present invention to this adhesion surface, higher adhesion can be obtained. Can do. The surface roughening treatment may be carried out before applying the adhesive composition of the present invention to the polyaryletherketone resin material. The roughening method is not particularly limited, and any known roughening method can be used, but sandblasting is preferable from the viewpoint of simplicity and safety. Sandblasting can be generally carried out by spraying alumina particles having a particle diameter of several μm to several hundreds of μm onto the adherend surface of the first member at a pressure of several tens KPa to several MPa using a sandblasting apparatus. .

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

  The first member may be any member as long as the portion in the vicinity of the adherend which comes into contact with the adhesive composition for polyaryl ether ketone resin material of the present invention upon adhesion is made of polyaryl ether ketone resin material. It may be. Moreover, the adhesion target of the adhesive composition for polyaryl ether ketone 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 made of only the first member, for example, one end and the other end of the ring-shaped first member provided with the joint can be bonded using the adhesive composition of the present embodiment. Moreover, you may adhere | attach in the form filled with the adhesive composition of this embodiment to the recessed part of the 1st member in which recessed parts, such as a hole and a groove | channel, were provided. In this case, the recess is embedded and the layer of the adhesive composition filled in the recess is adhered to the inner wall surface of the recess of the first member. It is also possible to produce a structure covered with the adhesive composition of the present invention by applying the adhesive composition of the present invention to the surface of the first member.

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

  The solid second member may be a polyaryl ether ketone resin material like the first member, and a member which does not contain any polyaryl ether ketone resin in the vicinity of the adherend surface (a member different from the first member) It may be

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

  The specific adhesion procedure can be suitably determined according to the composition of the adhesion target and the adhesive composition for the polyaryletherketone resin material.

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

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

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

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

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

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

  When the adhesive composition for a polyaryl ether ketone resin material is a primer for a polyaryl ether ketone resin material which does not contain all components of a polymerization initiator, adhesion can be performed by the following procedure.

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

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

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

  Incidentally, as described above, the adhesive composition for a polyaryl ether ketone resin material of the present invention is an adhesive for a polyaryl ether ketone resin material by blending all components of a polymerization initiator and polymerizing and curing them at the time of use. It can also be used, or it can be used as a primer for polyaryl ether ketone resin material without blending all components of the polymerization initiator. Here, when the adhesive composition of the present invention is compared with an adhesive composition which does not use a polymerizable monomer having a benzoyl skeleton and is not the one of the present invention, the case of using as a primer is used as an adhesive It has a great influence on adhesion strength compared to. Therefore, since the effect of the present invention is greater, it is preferable to use as a primer for polyaryl ether ketone resin material. This is because, in the case of a primer, the strength of the layer of the adhesive composition is often lower than that of the adhesive because no polymerization initiator is added, and the polyaryletherketone resin material as the adherend is Interaction is weak. Therefore, it is presumed that the degree of the interaction between the polymerizable monomer having a benzoyl skeleton and the polyaryl ether ketone resin material contributes to adhesion is large.

  The polyaryl ether ketone resin material which can use the adhesive composition for a polyaryl ether ketone resin material of the present invention preferably contains 20 mass% or more of polyaryl ether ketone resin, and contains 30 mass% or more The content is more preferably 50% by mass or more. When the polyaryl ether ketone resin material contains 20% by mass or more of the polyaryl ether ketone resin, the polymerizable monomer having a benzoyl skeleton and the polyaryl ether ketone contained in the adhesive composition for the polyaryl ether ketone resin material As the interaction with the resin can be made larger, it becomes easy to obtain higher adhesion. In addition to this, the strength of the polyaryl ether ketone resin material can be further enhanced.

  Such polyaryl ether ketone resin material may be composed only of polyaryl ether ketone resin, but a material obtained by blending polyaryl ether ketone resin with other resin, polyaryl ether ketone resin or polyaryl ether ketone resin And other resins are used as a resin matrix as a composite material mixed with a filler (hereinafter, the composite material is also referred to as a polyaryl ether ketone resin composite material). In addition, minor components such as pigments and stabilizers may be added to these materials.

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

  Other resins that can be blended with the polyaryl ether ketone resin are not particularly limited, but resins that do not significantly deteriorate the physical properties of the polyaryl ether ketone resin such as rigidity and toughness Preferable examples include polyarylate resin, polycarbonate resin, polyethylene terephthalate resin, polyphthalamide resin, polytetrafluoroethylene resin, polyphenylene ether resin and the like. When a polyaryl ether ketone resin and another resin are blended, the polyaryl ether ketone resin is preferably 50% by mass or more of the total resin, more preferably 70% by mass or more, and 90% by mass or more. Is more preferably 99% by mass or more.

  As a filler which can be blended with the polyaryl ketone resin material which can be used for the adhesive composition for polyaryl ether ketone resin material of the present invention, known ones can be used without any particular limitation, but an inorganic filler is preferable. For example, as the material of the filler, silica glass, borosilicate glass, soda glass, aluminosilicate glass, fluoroaluminosilicate glass, glass containing heavy metals (for example, barium, strontium, zirconium); Glass ceramics such as crystallized glass, crystallized glass in which crystals such as diopside and leucite are precipitated; complex inorganic oxides such as silica-zirconia, silica-titania, silica-alumina, or complex oxides thereof Oxides to which a Group I metal oxide is added; metal inorganic oxides such as silica, alumina, titania and zirconia; and the like.

  Moreover, it is preferable that an inorganic filler is contained 15 mass% or more in a polyaryl ether ketone resin composite material, and it is preferable that 25 mass% or more is contained. Moreover, it is preferable that it is 70 mass% or less, and, as for the compounding ratio of the inorganic filler in polyaryl ether ketone resin composite material, it is more preferable that it is 50 mass% or less.

  Such polyaryl ether ketone resin composite materials include: a) a composite material in which only a polyaryl ether ketone resin and an inorganic filler are mixed; b) a resin matrix comprising a mixture of a polyaryl ether ketone resin and another resin And composite materials in which minor components such as pigments and stabilizers are further added to the composite materials shown in c) a) or b).

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

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

The third member is not particularly limited as long as it is a member made of a known solid material, and the same member as the solid second member can be used. However, as the third member, in general, it is preferable to use a member in which the deposition part constituting material does not contain the polyaryl ether ketone resin.
Bonding in the dental field
The adhesive composition for polyaryl ether ketone resin material of the present invention can be used in any application. In addition, as the bonding object, at least a first member according to the application is used, and further, if necessary, a) solid second member, b) curable second member, or c) curable second A member and a third member are used. However, it is preferable that the adhesive composition for a polyaryl ether ketone resin material of the present invention be used in the dental field.

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

  A dental polyaryletherketone resin material (first dental member) that can be used as a dental component includes a denture, an artificial tooth, a denture base, and a dental prosthesis partially or entirely produced using a polyaryletherketone resin. Implants, crown restorative materials, abutment construction materials, etc. Moreover, as a hardenable 2nd member (hardenable 2nd member) which can be used as a dental member, a dental composite resin, a dental hard resin, a dental cement, a dental bonding material, a dental immediate polymerization Resin etc. are mentioned. Furthermore, as the third member, dental members such as dentures made of natural teeth, metal materials, ceramic materials, resin materials, etc., artificial teeth, denture bases, dental implants, crown restorative materials, abutment construction materials, etc. Etc.

  As an example of the method of use of the present invention, a dental hard resin is used as the second member, and a dental polyaryletherketone resin material and a dental hard resin are used by using the polyaryletherketone resin material of the present invention The process of laminating the material of (1) and producing a dental prosthesis is mentioned. 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. Can be hardened to make the desired dental prosthesis.

  As another example, a prosthesis made of polyaryl ether ketone resin material using dental cement as the second member and using the adhesive composition for poly aryl ether ketone resin material of the present invention, The process of mounting | wearing a tooth defect part is mentioned. Specifically, for example, the polyaryl ether ketone resin material of the present invention is applied to the adhesion surface of a prosthesis made of a polyaryl ether ketone resin material prepared in advance, and dental cement is applied from above to apply to teeth. It can be worn.

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

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

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The abbreviations and titles shown in the examples are as follows.

[Polymerizable monomer]
<Polymerizable monomer having a benzoyl skeleton>
Polymerizable monomers M1 to M10 having the structures shown below were used.
M1

・ M2

The present polymerizable monomer was obtained using the method described in Example 2 of Japanese Patent No. 3021152.
M3

The present polymerizable monomer was obtained according to the synthesis method of M3 described below.
・ M4

The present polymerizable monomer was obtained according to the synthesis procedure of M4 described below.
M5

The present polymerizable monomer was obtained according to the synthesis method of M5 described below.
・ M6

The present polymerizable monomer was obtained according to the synthesis procedure of M6 described below.
・ M7

The present polymerizable monomer was obtained according to the synthesis method of M7 described below.
・ M8

The present polymerizable monomer was obtained according to the synthesis procedure of M8 described below.

  The present polymerizable monomer is obtained as a mixture of the following compounds (a), (b) and (c), and the ratio is 65: 30: 5 in molar ratio. Moreover, said g and h are average values of the mixture of compound (a), (b), (c). The repeating number g and h of the unit structure also means an average value in the polymerizable monomer M9 described below, and in each molecule, the values of g and h can be integer values of 0 or more. . That is, the polymerizable monomer M9 described below is also a mixture of two or more types of polymerizable monomers having different combinations of integer values (g, h).

M9

The present polymerizable monomer was obtained according to the synthesis procedure of M9 described below.
・ M10

The present polymerizable monomer was obtained according to the synthesis procedure of M10 described below.

<Polymerizable monomer having no benzoyl skeleton>
<A polymerizable monomer having two or more polymerizable functional groups in the molecule>
-BisGMA: 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane-3G: triethylene glycol dimethacrylate <A polymerizable monomer having only one polymerizable functional group in the molecule Mer>
-MMA: methyl methacrylate In addition, among the above-mentioned polymerizable monomers having no benzoyl skeleton, only 3G has two or more polymerizable functional groups in the molecule and is measured at 23 ° C. It corresponds to the polymerizable monomer which does not have a benzoyl skeleton whose viscosity is 100 cP or less.

[Photoinitiator]
CQ: camphorquinone DMBE: p-dimethylaminobenzoic acid ethyl ester Table 1 shows the composition of the primer for the polyaryl ether ketone resin material, and Table 2 shows the composition of the adhesive for the polyaryl ether ketone resin material.

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

  Each test method is as follows.

(Tensile bond strength measurement)
The above polyaryl ether ketone resin material was formed into a plate having a thickness of about 2 mm by injection molding to obtain an adherend. The adherend surface of this adherend was polished with # 800 water-resistant abrasive paper and sandblasted (Alumina particles with a particle size of about 50 μm were sprayed for 10 seconds at a pressure of about 0.2 MPa using a sandblasting apparatus) It was coarsened. Then, it was immersed in water and exposed to ultrasonic waves for 5 minutes, and subsequently, it was immersed in acetone and washed by ultrasonic waves for 5 minutes. Subsequently, a double-sided tape having a hole of 3 mm in diameter was attached to the surface to be adhered.
Thereafter, the adhesive composition was applied to the holes, allowed to stand for 10 seconds, and dried by blowing compressed air for about 10 seconds. Then, when the adhesive composition is an adhesive, light is applied to the adhesive applied for 10 seconds with a dental irradiator (Tokso Power Light, manufactured by Tokuyama Dental Co., Ltd .; light output density 700 mW / cm ² ) It was irradiated and cured. A dental cement material (Bistite II, manufactured by Tokuyama Dental Co., Ltd.) was applied thereon, and a stainless steel attachment was pressure-welded thereon, to produce an adhesion test piece. After holding the above adhesion test piece at 37 ° C for 24 hours, it is pulled at a crosshead speed of 2 mm / min using a tension tester (Autograph, manufactured by Shimadzu Corporation), and a polyaryl ether ketone resin material and The tensile bond strength with the adhesive composition for polyaryl ether ketone resin material was measured. The tensile bond strength of the polyaryl ether ketone resin material and the adhesive composition for the polyaryl ether ketone resin material was measured for each of the five test pieces for each example or each comparative example, and the average value Standard deviation (SD) was determined.

(Synthesis of polymerizable monomer)
About the thing applicable to the polymerizable monomer shown by General formula (1) among the polymerizable monomers which have benzoyl frame | skeleton, it synthesize | combined by the following procedures.

<Synthesis of Acid Chloride (A)>
A first mixed solution of 25.3 g (0.096 mol) of 4,4'-diphenyletherdicarboxylic acid, 0.85 g (0.012 mol) of dimethylformamide and 80 ml of toluene was prepared. A second mixture consisting of 58.4 g (0.46 mol) of thionyl chloride and 20 ml of toluene was slowly added dropwise at room temperature to the first mixture under stirring. After completion of the dropwise addition, the liquid obtained was heated to 95 ° C. and refluxed for 3 hours. Then, by cooling the yellow transparent liquid obtained after heating and refluxing, there is a case where it is called 4,4'-diphenyletherdicarboxylic acid chloride (hereinafter referred to as "acid chloride (A)") having the molecular structure shown below. To obtain a toluene solution of Further, the toluene solution is subjected to rotary evaporation to remove toluene, thionyl chloride and hydrogen chloride at 40 ° C. to obtain 26.9 g (0.091 mol, 95% yield) of a solid of 4,4′-diphenyletherdicarboxylic acid chloride. The

<Composition of M5>
By adding 120 ml of methylene chloride to 15.3 g (0.052 mol) of the acid chloride (A), a dispersion containing the acid chloride (A) was obtained. A mixed solution of 16.9 g (0.13 mol) of 2-hydroxyethyl methacrylate, 7.7 g (0.13 mol) of triethylamine, 0.16 g (0.0013 mol) of 4-dimethylaminopyridine, 0.002 g of BHT and 10 ml of methylene chloride Were gradually added dropwise to the dispersion of the above acid chloride (A) at -78.degree. C. using a dropping funnel, and the mixture was further stirred for 5 hours. Water was added to the liquid obtained after dropping and stirring, and the solvent was removed using a rotary evaporator. The residue obtained after solvent removal was dissolved in 100 ml of toluene, washed with 0.5 N hydrochloric acid solution, washed with saturated brine, dried over magnesium sulfate and filtered. The obtained filtrate was concentrated by a rotary evaporator, and the concentrate was further dried under vacuum to obtain M5 (yield 19.0 g, 76%, HPLC purity 97%). The data of the obtained ¹ H NMR spectrum of M5 were as follows.
¹ H NMR δ 1.93 (s, 6 H), 4.58 (t, 4 H), 4.63 (t, 4 H), 5.59 (s, 2 H), 6. 14 (s, 2 H), 7. 06 (d, 4 H), 7.96 (d, 4 H).

<Composition of M3>
After dissolving 48.4 g (0.2 mol) of 4,4-diformyl diphenyl sulfide synthesized by the synthesis method described in JP-A-2005-154379 in 200 ml of t-butanol and 50 ml of water, phosphoric acid The reaction solution was prepared by adding 50 ml of an aqueous solution of sodium hydrogen and 140 g (2 mol) of 2-methyl-2-butene and further adding 36 g (0.4 mol) of sodium chlorite. Next, the reaction solution was stirred for 5 hours, and then the reaction solution was acidified using 1N hydrochloric acid solution to precipitate a solid. Subsequently, the reaction solution in which the solid precipitated was suctioned and filtered, and then the precipitated solid was washed with water. The solid (compound) obtained after washing was vacuum dried to obtain 4,4′-dicarboxydiphenyl sulfide (yield 45.5 g, 83%).

  Next, the acid chloride (A) was used except that 26.4 g (0.096 mol) of 4,4'-dicarboxydiphenyl sulfide was used instead of 25.3 g (0.096 mol) of 4,4'-diphenyl ether dicarboxylic acid. In the same manner as in the synthesis method of 2), 28.4 g (0.091 mol) of 4,4'-diphenyl sulfide dicarboxylic acid chloride was synthesized.

Subsequently, M3 (yield) was obtained in the same manner as the method of synthesizing M5 except that 16.1 g (0.052 mol) of 4,4'-diphenyl sulfide dicarboxylic acid chloride was used instead of 15.3 g of acid chloride (A). 18.9 g (yield 73%, HPLC purity 91%) was obtained. In addition, the data of the obtained ¹ H NMR spectrum of M3 were as follows.
¹ H NMR δ 1.93 (s, 6 H), 4.52 (t, 4 H), 4.63 (t, 4 H), 5.58 (s, 2 H), 6.11 (s, 2 H), 7. 30 (d, 4 H), 7.81 (d, 4 H).

<Composition of M4>
After dissolving 44.8 g (0.2 mol) of 4,4'-diformyldiphenylmethane synthesized by the synthesis method described in JP-A-2005-154379 in 200 ml of t-butanol and 50 ml of water, A reaction solution was obtained by adding 50 ml of an aqueous solution of sodium hydrogen acid and 140 g (2 mol) of 2-methyl-2-butene and further adding 36 g (0.4 mol) of sodium chlorite. Next, the reaction solution was stirred for 5 hours, and then the reaction solution was acidified using 1N hydrochloric acid solution to precipitate a solid. Subsequently, the reaction solution in which the solid precipitated was suctioned and filtered, and then the precipitated solid was washed with water. The obtained solid (compound) was vacuum-dried to obtain 39.8 g (yield 83%) of 4,4'-dicarboxydiphenylmethane.

  Next, the acid chloride (A) was used except that 23.0 g (0.096 mol) of 4,4'-dicarboxydiphenylmethane was used instead of 25.3 g (0.096 mol) of 4,4'-diphenylether dicarboxylic acid. 25.2 g (0.091 mol) of 4,4'-diphenylmethanedicarboxylic acid chloride were synthesized in the same manner as in the synthesis method of

Subsequently, M4 (yield 18%) was obtained in the same manner as the method of synthesizing M5 except that 14.4 g (0.052 mol) of 4,4'-diphenylmethanedicarboxylic acid chloride was used instead of 15.3 g of acid chloride (A). .7 g, yield 75%, HPLC purity 94%) were obtained. In addition, the data of the obtained ¹ H NMR spectrum of M 4 were as follows.
¹ H NMR δ 1.93 (s, 6 H), 3.85 (s, 2 H), 4.52 to 4.63 (m, 8 H), 5.58 (s, 2 H), 6.12 (s, 2 H) ], 7.15 (d, 4H), 7.86 (d, 4H).
<Composition of M6>
M6 (yield 19.9 g, yield) in the same manner as the synthesis method of M5 except that 18.7 g (0.13 mol) of 2-hydroxypropyl methacrylate was used instead of 16.9 g of 2-hydroxyethyl methacrylate 75%, HPLC purity 97%) were synthesized. In addition, the data of the obtained ¹ H NMR spectrum of M6 were as follows.
¹ H NMR δ 1.40 (d, 6 H), 1.93 (s, 6 H), 4.61 (d, 4 H), 4.74 (t, 2 H), 5.56 (s, 2 H), 6. 13 (s, 2 H), 7.01 (d, 4 H), 7. 92 (d, 4 H).
<Composition of M7>
-Process 1-
8.6 g (0.1 mol) of methacrylic acid, 18.0 g (0.2 mol) of 1,4-butanediol, 0.86 g (0.005 mol) of p-toluenesulfonic acid, and 0.1 g of BHT as a polymerization inhibitor The mixture was placed in a glass container, heated to 85 ° C. and stirred. Next, the reaction system in the heated and stirred state was depressurized, and stirring was continued for 5 hours while removing water from the reaction system. Thereafter, the obtained liquid was cooled, purified using silica gel column chromatography, and concentrated to obtain 6.7 g (yield 42%) of 4-hydroxybutyl methacrylate.
-Process 2-
Next, while stirring a solution of 3.0 g (0.01 mol) of acid chloride (A), 70 ml of methylene chloride and 0.001 g of di-tertbutylmethylphenol in another glass container, the solution is stirred. A solution of 3.5 g (0.022 mol) of the above 4-hydroxybutyl methacrylate, 2.0 g (0.02 mol) of triethylamine, 0.025 g (0.0002 mol) of 4-dimethylaminopyridine in 10 ml of methylene chloride It dripped slowly over 1 hour. After completion of the dropwise addition, the solution obtained was stirred at room temperature for 1 hour, water was added, and the solvent was removed using a rotary evaporator. The residue obtained after solvent removal was dissolved in 100 ml of toluene, washed with 0.5 N hydrochloric acid solution, washed with saturated brine, dried over magnesium sulfate and filtered. The obtained filtrate was again concentrated by a rotary evaporator, and the concentrate was further dried under vacuum to obtain M7 (yield 4.1 g, yield 76%, HPLC purity 97%). The data of the obtained ¹ H NMR spectrum of M7 were as follows.
¹ H NMR δ 1.52-1.63 (m, 8 H), 1.93 (s, 6 H), 4.14 (t, 4 H), 4.27 (t, 4 H), 5.59 (s, 2 H) 6.13 (s, 2 H), 7.05 (d, 4 H), 7. 93 (d, 4 H).

<Composition of M8>
12.9 g (0.05 mol) of 4,4'-diphenyletherdicarboxylic acid, 0.02 g (0.00009 mol) of benzyltriethylammonium chloride, 0.02 g of BHT, 12.8 g of glycidyl methacrylate (0.09 mol) 0.00009 mol), 20 g of dimethylformamide was added and reacted at 100 ° C. for 4 hours. To the liquid obtained by the reaction, 40 ml of ethyl acetate was added to make a homogeneous solution. Next, this solution was transferred to a separatory funnel, washed three times with 40 ml of 10 wt% aqueous potassium carbonate solution, and further three times with distilled water, and then the ethyl acetate layer was recovered. Thereafter, magnesium sulfate was added to the collected ethyl acetate layer to remove water contained in the ethyl acetate layer. Subsequently, magnesium sulfate was filtered off from the ethyl acetate layer, and the filtrate was concentrated by a rotary evaporator to obtain a concentrate. The concentrate was further dried under vacuum to give M8 (yield 22.8 g, 84% yield, HPLC purity 95%). In addition, the data of the obtained ¹ H NMR spectrum of M8 were as follows.
¹ H NMR δ 1.93 (s, 6 H), 3.90 (d, 0.8 H), 4.30 to 4.70 (m, 9.2 H), 5.59 (s, 2 H), 6.16 (S, 2 H), 7.07 (d, 4 H), 8.07 (d, 4 H).

<Composition of M9>
After dissolving 5-hexen-1-ol (30.1 g, 0.3 mol) in 100 ml of methylene chloride, 33.4 g (0.33 mol) of triethylamine and 1.8 g (0.015 mol) of N, N-dimethylaminopyridine The added solution was adjusted, and the solution was further cooled on ice. Next, a methylene chloride solution in which 31.4 g (0.3 mol) of methacrylic acid chloride was dissolved in methylene chloride (50 ml) was added dropwise to the ice-cooled solution. After completion of the dropwise addition, the solution obtained was stirred at room temperature for 3 hours, 100 ml of distilled water was added, and the mixture was extracted three times with methylene chloride. The solvent was removed from the methylene chloride layer obtained by extraction using a rotary evaporator to obtain a residue. Furthermore, the obtained residue was dissolved in 100 ml toluene. The obtained toluene solution was washed three times with 0.5 N hydrochloric acid solution, then three times with saturated brine solution, and dried over magnesium sulfate solution. After drying, the magnesium sulfate solution was filtered off, the filtrate was concentrated by a rotary evaporator, and the concentrate was further dried under vacuum to obtain 46.4 g (yield 92%) of 5-hexen-1-yl methacrylate.

  After dissolving 45.4 g (0.27 mol) of the obtained 5-hexen-1-yl methacrylate in 100 ml of methylene chloride, 196 g (equivalent to 0.675 mol) of a 60% by mass metachloroperbenzoic acid / water mixture is added, and the solution is stirred at room temperature. Stir for 10 hours. After stirring, the by-product metachlorobenzoic acid was filtered off, and the filtrate was subjected to reduction treatment with 150 ml of a 15% by mass aqueous sodium sulfite solution. The methylene chloride layer separated from the filtrate after reduction treatment was washed twice with a 5% by mass aqueous potassium carbonate solution, dried over magnesium sulfate, and concentrated by a rotary evaporator to obtain a concentrate. Then, the concentrate was further dried under vacuum to obtain 44.8 g (yield 90%) of 5,6-epoxyhexan-1-yl methacrylate.

23.0 g (0.125 mol) of the obtained 5,6-epoxyhexan-1-yl methacrylate, 12.9 g (0.05 mol) of 4,4'-diphenyletherdicarboxylic acid, 0.045 g of benzyltriethyl ammonium chloride A mixture of (0.2 mmol) and 0.03 g of p-methoxyphenol was stirred at 90 ° C. for 4 hours. The mixture after heating and stirring was allowed to cool to room temperature, 50 ml of water was added, and the mixture was extracted with methylene chloride. The obtained methylene chloride layer was dried over magnesium sulfate and concentrated by a rotary evaporator to obtain a concentrate. Furthermore, the concentrate was dried under vacuum to obtain M9 (yield 29.0 g, 0.046 mol, 93% yield, HPLC purity 95%). In addition, the data of the obtained ¹ H NMR spectrum of M9 were as follows.
¹ H NMR δ 1.29 (t, 4 H), 1.44 (m, 4 H), 1.57 (t, 4 H), 1.93 (s, 6 H), 3.85 (d, 1.9 H), 4.15 to 4.70 (m, 8.1 H), 5.59 (s, 2 H), 6.16 (s, 2 H), 7.05 (d, 4 H), 7.95 (d, 4 H) .

<Composition of M10>
A solution obtained by dissolving 50.0 g (0.8 mol) of ethylene glycol, 40.5 g (0.4 mol) of triethylamine, 0.49 g (4 mol) of N, N-dimethylaminopyridine in 100 ml of methylene chloride while stirring It cooled to 0 degreeC. Next, to this solution, a solution of 44.8 g (0.2 mol) of acid chloride (A) dissolved in methylene chloride (200 ml) was slowly dropped over 2 hours. The solution obtained after the addition was stirred for a further 1 hour, then water was added and the solvent was removed using a rotary evaporator. The residue obtained after solvent removal was dissolved in 100 ml of toluene, washed with 0.5 N hydrochloric acid solution, washed with saturated brine, dried over magnesium sulfate and filtered. The obtained filtrate was again concentrated by a rotary evaporator, and the concentrate was purified by silica gel column chromatography to obtain 41.6 g (yield 60%) of 4,4'-bis (2-hydroxyethoxycarbonyl) diphenyl ether .

In a solution obtained by dissolving 34.6 g (0.1 mol) of the obtained 4,4'-bis (2-hydroxyethoxycarbonyl) diphenyl ether and 3.2 g (5 mmol) of dibutyltin dilaurate in 100 ml of anhydrous dimethylformamide Further, 31.0 g (0.2 mol) of 2-methacryloyloxyethyl isocyanate was added, and the mixture was stirred at room temperature for 3 hours. To the solution after stirring, 100 ml of methylene chloride was added, and the solution was washed three times with distilled water using a separatory funnel, and the methylene chloride layer was dried using magnesium sulfate. After drying, the magnesium sulfate was filtered off, the filtrate was concentrated on a rotary evaporator and the concentrate was further dried in vacuo to give M10 (yield 63.7 g, 97%, HPLC purity 94%). In addition, the data of the obtained ¹ H NMR spectrum of M10 were as follows.
¹ H NMR δ 1.93 (s, 6 H), 3.30 (t, 4 H), 4.40-4.56 (m, 12 H), 5. 60 (s, 2 H), 6.17 (s, 2 H) ), 7.06 (d, 4 H), 7.98 (d, 4 H), 8.03 (s, 2 H).

Example 1
5 g of M1, 5 g of 3G as a polymerizable monomer component and 20 g of acetone as a solvent component are added and stirred to obtain a primer for polyaryl ether ketone resin material which is an adhesive composition for poly aryl ether ketone resin material The The composition of the adhesive composition for polyaryl ether ketone resin material is shown in Table 1. With respect to the adhesive composition for the polyaryl ether ketone resin material, the tensile bond strength to the polyaryl ether ketone resin material was measured. The results are shown in Table 3.

Examples 2 to 15 / Comparative Examples 1 and 2
For polyaryletherketone resin material which is an adhesive composition for polyaryletherketone resin material according to Example 1 except that the adhesive composition for polyaryletherketone resin material is changed to the composition shown in Table 1. A primer was made and the adhesive composition was used to determine the tensile bond strength to the polyaryletherketone resin material. The results are shown in Table 3.

Example 16
5 g of M8 as a polymerizable monomer component, 5 g of 3 G, 0.2 g of CQ as a polymerization initiator component, 0.2 g of DMBE, and 20 g of acetone as a solvent component are stirred and added to polyaryl ether ketone resin material An adhesive for a polyaryl ether ketone resin material, which is an adhesive composition for use in the present invention, was obtained. The composition of the adhesive composition for polyaryl ether ketone resin material is shown in Table 2. With respect to the adhesive composition for the polyaryl ether ketone resin material, the tensile bond strength to the polyaryl ether ketone resin material was measured. The results are shown in Table 4.

Examples 17, 18 and Comparative Example 3
For polyaryletherketone resin material which is an adhesive composition for polyaryletherketone resin material according to Example 16 except that the adhesive composition for polyaryletherketone resin material is changed to the composition shown in Table 2. An adhesive was made and the adhesive composition was used to determine the tensile bond strength to the polyaryletherketone resin material. The results are shown in Table 4.

(Evaluation results)
Table 3 shows the results of measurement of the tensile bond strength for the polyetheretherketone resin material of the primer of each example and each comparative example, and Table 4 shows the results of the measurement of the tensile bond strength for the polyetheretherketone resin material of the adhesive. Show.

  As to the evaluation results, when comparing Examples 1 to 15 using the primer for polyaryl ether ketone resin material and Comparative Examples 1 and 2, all Examples 1 to 15 in which the polymerizable monomer having a benzoyl skeleton is blended are Compared with Comparative Examples 1 and 2 in which the polymerizable monomer having a benzoyl skeleton was not blended, high tensile adhesive strength was exhibited.

  The following can be said by comparing Examples 1 to 10 using the same amount of the polymerizable monomer having benzoyl skeleton, the polymerizable monomer having no benzoyl skeleton, and the solvent.

  Examples 8 to 10, in which the polymerizable monomer having a benzoyl skeleton incorporated has a hydrogen bonding functional group, are compared with Examples 1 to 7 having no hydrogen bonding functional group, It showed high adhesive strength.

  Examples 3 to 10, in which the polymerizable monomer having a benzoyl skeleton compounded corresponds to the general formula (1), have high tensile adhesion strength compared to the examples 1 and 2 not corresponding to the general formula (1) Indicated.

  Examples 5 to 10, in which a polymerizable monomer in which X is an oxygen atom in the general formula (1), have high adhesion strength as compared with Examples 3 and 4 in which X is not an oxygen atom. The

  When using the same amount of solvent and using the polymerizable monomer having the same kind of benzoyl skeleton but using different composition of the polymerizable monomer, the followings are compared: Can be said. Examples 8 and 11 to 14 in which the compounding amount of the polymerizable monomer having a benzoyl skeleton is 15% by mass or more of all the polymerizable monomers are less than 15% by mass in comparison with Example 14. It showed high adhesive strength. Examples 8, 11 and 12 in which the compounding amount of the polymerizable monomer having a benzoyl skeleton is 25% by mass or more of all the polymerizable monomers are less than 25% by mass in comparison with Examples 13 and 14. And showed high adhesion strength. Examples 8 and 11 in which the compounding amount of the polymerizable monomer having a benzoyl skeleton is 40% by mass or more of all the polymerizable monomers are less than 40% by mass in comparison with Examples 12 to 14 It showed high adhesive strength. Example 11 in which the compounding amount of the polymerizable monomer having a benzoyl skeleton is 60% by mass or more of all the polymerizable monomers is less than 60% by mass in comparison with Examples 8 and 12 to 14 It showed high adhesive strength.

The polymerizable monomer and solvent having the same amount of benzoyl skeleton are used, and the polymerizable monomer having the same amount of benzoyl skeleton is used, but the polymerizability having no benzoyl skeleton is used. The following can be said by comparing Examples 12 and 15 having different monomer compositions. First, Example 12 in which a polymerizable monomer having two or more polymerizable functional groups in the molecule and having a benzoyl skeleton having a viscosity of 100 cP or less measured at 23 ° C. and having no benzoyl skeleton was High adhesion compared to Example 15 in which no polymerizable monomer having two or more polymerizable functional groups and having a viscosity of 100 cP or less measured at 23 ° C. and having no benzoyl skeleton is compounded It showed strength. In addition, Example 12 in which the polymerizable monomer having two or more polymerizable functional groups in the molecule is 40% by mass or more among the polymerizable monomers is compared with Example 15 in which the content is less than 40% by mass. In addition, when Examples 16 to 18 and Comparative Example 3 in which an adhesive for a polyaryl ether ketone resin material was used were compared, Example 16 in which a polymerizable monomer having a benzoyl skeleton was blended was used. All of the samples of the comparative examples 3 to 18 which did not contain a polymerizable monomer having a benzoyl skeleton exhibited high tensile adhesive strength.

  Moreover, Examples 1 to 15 used as a primer for polyaryl ether ketone resin material without blending a polymerization initiator as an adhesive composition for polyaryl ether ketone resin material are polymerizable monomers having a benzoyl skeleton. The adhesive strength improvement of 400% or more was seen from Comparative Examples 1 and 2 in which the primer was not blended. On the other hand, Examples 16 to 18 in which a polymerization initiator was blended and used as an adhesive for a polyaryl ether ketone resin material are adhesives from which a polymerizable monomer having a benzoyl skeleton is not blended, from Comparative Example 3 An improvement of 10 to 20% in adhesive strength was observed. From this point, it is shown that the effect of blending the polymerizable monomer having a benzoyl skeleton in the primer is large.

Claims (9)

  An adhesive composition for a polyaryl ether ketone resin material, comprising a polymerizable monomer having a benzoyl skeleton in the molecule. The adhesive composition for a polyaryletherketone resin material according to claim 1, wherein the polymerizable monomer having a benzoyl skeleton in the molecule is represented by the following general formula (1).

[In the general formula (1), X represents a divalent group, and Ar ¹ and Ar ² each represent an aromatic group having any valence selected from divalent to tetravalent; L ¹ and L ² may be the same or different, and each of L ¹ and L ² has a main chain atom number in the range of 2 to 60, and any valence selected from divalent to tetravalent It represents a hydrocarbon group having a number, each of which may be the same or different, and R ¹ and R ² each represent a hydrogen or a methyl group. In addition, m1, m2, n1 and n2 are each an integer selected from the range of 1 to 3. ]   The adhesive composition for a polyaryl ether ketone resin material according to claim 2, wherein the divalent group X in the general formula (1) is -O-.   The poly according to any one of claims 1 to 3, wherein the compounding amount of the polymerizable monomer having a benzoyl skeleton in the molecule is in the range of 15% by mass to 85% by mass of all the polymerizable monomers. Adhesive composition for aryl ether ketone resin material.   The adhesive composition for polyaryl ether ketone resin material according to any one of claims 1 to 4, wherein the polymerizable monomer having a benzoyl skeleton in the molecule has a hydrogen bonding functional group. .   The polymer according to any one of claims 1 to 5, further comprising a polymerizable monomer having two or more polymerizable functional groups in the molecule and having a benzoyl skeleton having a viscosity of 100 cP or less measured at 23 ° C. An adhesive composition for a polyaryl ether ketone resin material according to one aspect.   The polyaryl ether ketone as described in any one of Claims 1-6 whose polymerizable monomer which has a 2 or more polymerizable functional group in a molecule | numerator is 40 mass% or more of all the polymerizable monomers. Adhesive composition for resin materials.   The primer for polyaryl ether ketone resin material which consists of an adhesive composition as described in any one of Claims 1-7.   The adhesive composition for polyaryl ether ketone resin material according to any one of claims 1 to 7, which is for dental use.