TW201509917A - Novel compound having unsaturated group and composition including said compound - Google Patents

Abstract

The purpose of the present invention is to provide a novel compound capable of improving a metal corrosion-preventing effect of a coating and capable of improving the adhesion between the coating and metal, as a result of being present in the coating. The compound is indicated by formula (1). In the formula (1), ring A is an optionally substituted 5-membered or 6-membered nitrogen-containing aromatic heterocyclic ring, L1 is an (n1+1)-valent linking group, R1 is a hydrogen atom, halogen atom, or a C1-6 alkyl group, n1 is an integer between 1 and 6, Q1 is -O- or -NH-, l1 is 0 or 1, and ring B is an optionally substituted aromatic ring.

Description

Novel compound having an unsaturated group and a composition containing the same

The present invention relates to novel compounds having an unsaturated group and compositions comprising the same.

In order to prevent corrosion of metals and prevent adhesion of dirt, a technique of providing a coating film on the surface of a metal is known.

Patent Document 1 discloses a composition comprising a perfluoropolyether benzotriazole compound and a perfluoropolyether benzotriazole compound, and the perfluoropolyether benzotriazole compound is bonded to a metal substrate to provide resistance. At least one of dirt characteristics and anti-contamination characteristics, easy cleaning characteristics, water repellency, hydrophobicity or oleophobic property.

Patent Document 2 describes a copolymer synthesized from a constituent unit of a monomer such as 1-vinylimidazole to impart a corrosion-control coating film.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2007-523894

[Patent Document 2] Japanese Patent Publication No. 2009-534540

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel compound which can improve the corrosion prevention effect of a metal due to a coating film by being present in a coating film, and can also improve the adhesion of the coating film to metal.

Further, the present invention provides a composition which is excellent in the effect of preventing corrosion of metal and which can form a coating film which is excellent in adhesion to metal and transparency.

The present invention is a compound represented by the formula (1) or (2).

In the formula (1), the ring A is a substituted five or six membered nitrogen-containing aromatic heterocyclic ring, the L ¹ is an n1+1 valent linking group, and the R ¹ is a hydrogen atom, a halogen atom or a C _1-6 alkane. The group, n1 is an integer of 1 to 6, Q ¹ is -O- or -NH-, and l1 is 0 or 1, and ring B is a substituted aromatic ring.

In the formula (2), the ring C is a substituted five or six membered nitrogen-containing aromatic heterocyclic ring, a L ² -based n2+1 valent linking group, an R ² -based hydrogen atom, a halogen atom or a C _1-6 alkane. Base, n2 is an integer from 1 to 6, Q ² is -O- or -NH-, and l2 is 0 or 1.

In the formula (1), the ring A is preferably a five-membered nitrogen-containing aromatic heterocyclic ring containing two or three nitrogen atoms.

Further, in the formula (1), L ^{1 is} preferably represented by the formula (3).

[Chemical 3]-Cm ₁ H2m ₁ +1-n ₁ - (3)

In the formula (3), m1 is an integer from 1 to 20, and n1 is an integer from 1 to 6. However, when m1 is 1, n1 is an integer from 1 to 3, and when m1 is 2, n1 is an integer from 1 to 5.

Further, in the formula (1), the ring B is preferably a hydroxyl group, an amine group, a carboxylic acid group, a nitro group, a halogen group, a thiol group, a cyano group, a decyl group, a sulfonic acid group, a methanesulfonyl group or an alkyl group. Or an aromatic ring substituted with a substituent represented by the formula (4).

In the formula (4), the L ^{3 group} includes a n3+1 valent linking group bonded by -CO-NH-, -CO-O-, -O-CO-NH- or -NH-CO-NH- R ³ is a hydrogen atom, a halogen atom or a C _1-6 alkyl group, and n 3 is an integer of 1 to 6.

Further, in the formula (1), the ring B is preferably a benzene ring.

In the formula (2), the ring C is preferably a five-membered nitrogen-containing aromatic heterocyclic ring containing two or three nitrogen atoms.

Further, in the formula (2), L ^{2 is} preferably represented by the formula (5).

[Chemical 5]-Cm ₂ H2m ₂ +1-n ₂ - (5)

In the formula (5), m2 is an integer of 1 to 20, and n2 is an integer of 1 to 6. However, when m2 is 1, n2 is an integer from 1 to 3, and when m2 is 2, n2 is an integer from 1 to 5.

The present invention is also a composition comprising: a nitrogen-containing aromatic heterocyclic compound containing a polymerizable functional group, a vinylidene fluoride-based resin (B), and a polymer selected from the group consisting of an acrylic monomer and an acrylic polymer. At least one acrylic component (A) in the group.

The present invention is also a composition comprising the above-described nitrogen-containing aromatic heterocyclic compound containing a polymerizable functional group and an optical adhesive.

The nitrogen-containing aromatic heterocyclic compound containing a polymerizable functional group is preferably a compound represented by the formula (14) or the formula (15).

In the formula (14), the ring A is a substituted five or six membered nitrogen-containing aromatic heterocyclic ring, and the R ¹ is a hydrogen atom, a halogen atom or a C _1-6 alkyl group, and the n1 is an integer of 1 to 6, L ^{The 4} series includes a n1+1 valent linking group represented by -CO-NH-, -CO-O-, -O-CO-NH- or -NH-CO-NH-, and the ring B system may be substituted Aromatic ring.

In the formula (15), the ring C is a substituted five or six membered nitrogen-containing aromatic heterocyclic ring, an R ² -based hydrogen atom, a halogen atom or a C _1-6 alkyl group, and the n2 is an integer of 1 to 6, L ^{The 5} series includes a n1+1-valent linking group bonded by -CO-NH-, -CO-O-, -O-CO-NH- or -NH-CO-NH-.

In the formula (14), the ring A is preferably a five-membered nitrogen-containing aromatic heterocyclic ring containing two or three nitrogen atoms.

Further, in the formula (14), L ^{4 is} preferably represented by the formula (16).

In the formula (16), Q ¹ is -O- or -NH-, l1 is 0 or 1, m1 is an integer from 1 to 20, and n1 is an integer from 1 to 6. However, when m1 is 1, n1 is an integer from 1 to 3, and when m1 is 2, n1 is an integer from 1 to 5.

Further, in the formula (14), the ring B is preferably a hydroxyl group, an amine group, a carboxylic acid group, a nitro group, a halogen group, a thiol group, a cyano group, a decyl group, a sulfonic acid group, a methanesulfonyl group or an alkane. An aromatic ring substituted with a substituent or a substituent represented by the formula (17).

In the formula (17), the L ^{6 group} includes a n3+1 valent linking group bonded by -CO-NH-, -CO-O-, -O-CO-NH- or -NH-CO-NH- R ³ is a hydrogen atom, a halogen atom or a C _1-6 alkyl group, and n 3 is an integer of 1 to 6.

Further, in the formula (14), the ring B is preferably a benzene ring.

In the formula (15), the ring C is preferably a five-membered nitrogen-containing aromatic heterocyclic ring containing two or three nitrogen atoms.

Further, in the formula (15), L ^{5 is} preferably represented by the formula (18).

In the formula (18), Q ² is -O- or -NH-, l2 is 0 or 1, m2 is an integer from 1 to 20, and n2 is an integer from 1 to 6. However, when m2 is 1, n2 is an integer from 1 to 3, and when m2 is 2, n2 is an integer from 1 to 5.

The above composition is preferably a nitrogen-containing polymerizable functional group. The content of the aromatic heterocyclic compound is 0.1 to 30% by mass of the composition.

The acrylic component (A) is preferably selected from the group consisting of a (meth) acrylate monomer, a polyfunctional acryl monomer, an unsaturated carboxylic acid monomer, a homopolymer of (meth) acrylate, and a (meth) acrylate. At least one of the group consisting of copolymers.

Further, the acrylic component (A) is more preferably selected from the group consisting of a copolymer of a (meth) acrylate monomer and a polyfunctional (meth) acrylate monomer, a homopolymer of (meth) acrylate, (meth) At least one of the group consisting of a copolymer of an acrylate and an unsaturated carboxylic acid.

The vinylidene fluoride-based resin (B) is preferably vinylidene fluoride and at least one selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, and perfluoro(alkyl vinyl ether). A copolymer of a monomer.

The vinylidene fluoride resin (B) is preferably a copolymer of vinylidene fluoride and tetrafluoroethylene.

The above composition is preferably a paint, more preferably a rust preventive paint.

The present invention is also a coated article characterized by comprising a substrate and a coating film formed on the substrate of the above composition. The above substrate is preferably formed of a metal.

The invention is also a sheet characterized by being formed from the above composition.

The present invention is also a laminated sheet characterized by comprising a release sheet and a sheet formed on the release sheet of the above composition.

The novel compound of the present invention can be added to use a resin as a coating for automobiles. By applying the obtained coating material to a coating film formed of a metal, the effect of preventing corrosion of metal is high and the adhesion to metal is excellent as compared with a coating film not containing the novel compound of the present invention.

The composition of the present invention is a coating film which is excellent in adhesion prevention against metal and which is excellent in adhesion to metal. The obtained coating film is also excellent in transparency.

In the coated article of the present invention, even if it is a metal, it is difficult to corrode the substrate, and the coating film is excellent in adhesion to the substrate, and the transparency of the coating film is high.

The sheet of the present invention has an effect of preventing corrosion of metal and is excellent in adhesion to metal. Moreover, transparency is also excellent.

12, 32, 36, 52, 62, 68‧‧‧ Coating film or sheet formed by composition 3

22, 42, 46, 53, 63, 67‧‧‧ Coating film or sheet formed from composition 2

Fig. 1 is a view showing an example of a coating film formed of the composition of the present invention and a laminated structure including the sheet and the laminated sheet of the present invention.

Fig. 2 is a view showing an example of a coating film formed of the composition of the present invention and a laminated structure including the sheet and the laminated sheet of the present invention.

Fig. 3 is a view showing an example of a coating film formed of the composition of the present invention and a laminated structure including the sheet and the laminated sheet of the present invention.

Fig. 4 is a view showing an example of a coating film formed of the composition of the present invention and a laminated structure including the sheet and the laminated sheet of the present invention.

Fig. 5 is a view showing an example of a coating film formed of the composition of the present invention and a laminated structure including the sheet and the laminated sheet of the present invention.

Fig. 6 is a view showing an example of a coating film formed of the composition of the present invention and a laminated structure including the sheet and the laminated sheet of the present invention.

[Best Mode for Carrying Out the Invention]

Hereinafter, the present invention will be specifically described.

[Compound represented by formula (1)]

The present invention is a compound represented by the formula (1).

In the formula (1), the ring A is a substituted five or six membered nitrogen-containing aromatic heterocyclic ring, the L ¹ is an n1+1 valent linking group, and the R ¹ is a hydrogen atom, a halogen atom or a C _1-6 alkane. The group, n1 is an integer of 1 to 6, Q ¹ is -O- or -NH-, and l1 is 0 or 1, and ring B is a substituted aromatic ring.

In formula (1), Preferred . Ring A' can be substituted for a five or six member nitrogen-containing aromatic heterocycle.

In the formula (1), the ring A is preferably a five-membered nitrogen-containing aromatic heterocyclic ring containing two or three nitrogen atoms, more preferably an imidazole ring, a pyrazole ring or a triazole ring. In the formula (1), l1 is preferably 0.

In formula (1), Better . Ring A" is replaceable.

In the formula (1), L ^{1 is} preferably those represented by the formula (3).

[Chemical 16]-Cm ₁ H2m ₁ +1-n ₁ - (3)

In the formula (3), m1 is an integer from 1 to 20, and n1 is an integer from 1 to 6. However, when m1 is 1, n1 is an integer from 1 to 3, and when m1 is 2, n1 is an integer from 1 to 5.

M1 is preferably 1 or 2.

In the formulas (1) and (3), n1 is preferably 1 or 2.

In the formula (1), the ring B may be a hydroxyl group, an amine group, a carboxylic acid group, a nitro group, a halogen group, a thiol group, a cyano group, a decyl group, a sulfonic acid group, a methanesulfonyl group, an alkyl group, or a formula. (4) An aromatic ring substituted with a substituent shown.

In the formula (4), the L ^{3 group} includes a n3+1 valent linking group bonded by -CO-NH-, -CO-O-, -O-CO-NH- or -NH-CO-NH- R ³ is a hydrogen atom, a halogen atom or a C _1-6 alkyl group, and n 3 is an integer of 1 to 6.

In the formula (4), L ^{3 is} preferably those represented by the formula (6).

In the formula (6), Q ³ is -O- or -NH-, m3 is an integer of 1 to 20, and n3 is an integer of 1 to 6. However, when m3 is 1, n3 is an integer from 1 to 3, and when m3 is 2, n3 is an integer from 1 to 5. M3 is preferably 1 or 2.

In the formulas (4) and (6), n3 is preferably 1 or 2.

In the formula (1), the ring B is preferably a benzene ring.

In formula (1), Better Any of them.

In the above formula, Z ¹ is a hydroxyl group, an amine group, a carboxylic acid group, a nitro group, a halogen group, a thiol group, a cyano group, a decyl group, a sulfonic acid group, a methylsulfonyl group, an alkyl group, or a formula (4). Represents a substituent. Z ^{1 is} preferably a hydroxyl group, an amine group or a substituent represented by the formula (4).

[Method for Producing Compound of Formula (1)]

The compound represented by the formula (1) can be produced by reacting a compound represented by the formula (7) with a compound represented by the formula (8).

In the formula (7), the ring A is a substituted five-membered or six-membered nitrogen-containing aromatic heterocyclic ring, and the ring B-based substituted aromatic ring.

In the formula (8), R L ¹¹ lines can be hydroxyl or amine functional groups of the reaction, R ^1, and n1 formula (1) and (3) of lines ¹ and n1 are as defined above. The above amine group may be a nitrogen-containing aromatic heterocyclic secondary amine (-NH-).

The compound represented by the formula (7) is preferably a formula The compound shown, more preferably Any of the compounds shown, more preferably Any of the compounds shown, particularly preferred Any of the compounds shown. Ring A' can be substituted for a five or six member nitrogen-containing aromatic heterocycle. Ring A" is substitutable. Z ² is a hydroxyl group, an amine group, a carboxylic acid group, a nitro group, a halogen group, a thiol group, a cyano group, a decyl group, a sulfonic acid group, a methanesulfonyl group or an alkyl group, preferably It is a hydroxyl group or an amine group.

The compound represented by the formula (8) is preferably an isocyanate compound represented by the formula (9).

In the formula (9), m1 m1, n1 and R ¹ are as formula (1) and (3) of, n1 and R ¹ are the same as above lines.

The compound represented by the formula (8) is more preferably a formula Any of the compounds shown.

The compound represented by the formula (7) and the compound represented by the formula (8) are preferably a compound represented by the formula (8) with respect to the compound 1 represented by the formula (7) to be 0.1 to 5 mol. In the manner, two compounds were added to the system to carry out the reaction.

With respect to 1 mol of the compound represented by the formula (7), the compound represented by the formula (8) is sufficient to make the compound represented by the formula (7) and the compound represented by the formula (8) even if it is 0.1 to 1 mol. The compound is reacted.

When Z ² is a hydroxyl group or an amine group, the compound represented by the formula (8) is set to 0.1 to 1 mol per 1 mol of the compound represented by the formula (7), and the preferred reaction formula (7) The ring A of the compound shown and the compound of the formula (8).

When Z ² is a hydroxyl group or an amine group, 2 moles of the compound represented by the formula (7) is added to the system by a compound represented by the formula (8) in a manner more than 1 mole. a compound obtained by reacting a compound represented by the formula (8) with not only the ring A of the compound represented by the formula (7) but also the hydroxyl group or the amine group at the ring B, in the formula (1) Manufacturable Compound. Z ³ is a substituent represented by the formula (4).

The reaction of the compound represented by the formula (7) with the compound represented by the formula (8) can be carried out at 15 to 100 ° C, preferably 15 to 70 ° C. More preferably 20~30 °C. The reaction time is usually from 1 to 10 hours.

The reaction of the compound represented by the formula (7) with the compound represented by the formula (8) can be carried out in the presence of a catalyst. Examples of the catalyst include an organic titanium compound such as tetraethyl titanate or tetrabutyl titanate; an organotin compound such as tin octylate, dibutyltin oxide or dibutyltin dilaurate; and stannous chloride. A halogen such as stannous bromide is stannous or the like. The amount of the catalyst to be used is not particularly limited, and may be appropriately adjusted. For example, it is usually 0.00001 to 3 parts by mass, preferably 0.0001 to 1 part by mass, based on 100 parts by mass of the compound represented by the formula (8). .

The reaction of the compound represented by the formula (7) with the compound represented by the formula (8) can be carried out in a solvent. As the solvent, a solvent which does not inhibit the progress of the reaction may be used, and a conventionally known solvent which is generally used may be used. For example, a ketone solvent such as acetone, methyl isobutyl ketone (MIBK) or methyl ethyl ketone (MEK); an ester solvent such as ethyl acetate or butyl acetate; and HCFC225 (CF ₃ CF ₂ CHCl ₂ / A fluorine-based solvent such as a CClF ₂ CF ₂ CHClF mixture or the like may be used. The alcohol solvent having an OH group is not preferable because it hinders the progress of the reaction. Further, in the system, even if water is present, the reaction proceeds, and it is more preferable that each solvent is dehydrated before use.

[Compound represented by formula (2)]

The compound of the present invention is also a compound represented by the formula (2).

In the formula (2), the ring C is a substituted five or six member nitrogen-containing aromatic heterocyclic ring, L ² is a n2+1 valent linking group, and the R ² is a hydrogen atom, a halogen atom or a C _1-6 alkane. Base, n2 is an integer from 1 to 6, Q ² is -O- or -NH-, and l2 is 0 or 1.

In formula (2), Preferred . The ring C' system may be substituted for a five or six member nitrogen-containing aromatic heterocyclic ring.

In the formula (2), the ring C and the ring C' are preferably a substituted five-membered nitrogen-containing aromatic heterocyclic ring containing two or three nitrogen atoms. L2 is preferably 0.

In formula (2), Better Any of them.

In the formula (2), L ^{2 is} preferably those represented by the formula (5).

[Chem. 36]-Cm ₂ H2m ₂ +1-n ₂ - (5)

In the formula (5), m2 is an integer of 1 to 20, and n2 is an integer of 1 to 6. M2 is preferably 1 or 2. However, when m2 is 1, n2 is an integer from 1 to 3, and when m2 is 2, n2 is an integer from 1 to 5.

In the formulas (2) and (5), n2 is preferably 1 or 2.

[Method for Producing Compound of Formula (2)]

The compound represented by the formula (2) can give a compound represented by the formula (11), It is produced by reacting with a compound represented by the formula (12).

The ring C system can be substituted for a five or six member nitrogen-containing aromatic heterocyclic ring.

In the formula (12), L ²¹ may be based hydroxyl or amine functional groups of the reaction, R ² and n2 formula (2) and (5) the R ² lines and n2 are as defined above. The above amine group may be a nitrogen-containing aromatic heterocyclic secondary amine (-NH-).

The compound represented by the formula (11) is preferably a formula The compound shown, more preferably Any of the compounds shown. The ring C' system may be substituted for a five or six member nitrogen-containing aromatic heterocyclic ring. Ring C and ring C' are preferably a five-membered nitrogen-containing aromatic heterocyclic ring containing two or three nitrogen atoms.

The compound represented by the formula (12) is preferably an isocyanate compound represented by the formula (13).

In the formula (13), m2, n2 and R ² in formula (2) and (5) of m2, n2 and R ² are the same as described above based.

The compound represented by the formula (12) is more preferably a formula Any of the compounds shown.

The compound represented by the formula (11) and the compound represented by the formula (12) are preferably 1 mol of the compound represented by the formula (11), and the compound represented by the formula (12) is 0.1 to 5 mol. The method is preferably 0.1 to 1 mol, and two compounds are added to the system to carry out the reaction.

The reaction of the compound of the formula (11) with the compound of the formula (12) can be carried out at 15 to 100 ° C, preferably 15 to 70 ° C, more preferably 20 to 30 ° C. The reaction time is usually from 1 to 10 hours.

The reaction of the compound represented by the formula (11) with the compound represented by the formula (12) can be carried out in the presence of a catalyst. Examples of the catalyst include an organic titanium compound such as tetraethyl titanate or tetrabutyl titanate; an organotin compound such as tin octylate, dibutyltin oxide or dibutyltin dilaurate; and stannous chloride. A halogen such as stannous bromide is stannous or the like. The amount of the catalyst to be used is not particularly limited, and may be adjusted as appropriate. For example, it is usually 0.00001 to 3 parts by mass, preferably 0.0001 to 1 part by mass, per 100 parts by mass of the compound represented by the formula (12).

The reaction of the compound represented by the formula (11) with the compound represented by the formula (12) can be carried out in a solvent. As the solvent, a solvent which does not inhibit the progress of the reaction may be used, and a conventionally known solvent which is generally used may be used. For example, a ketone solvent such as acetone, methyl isobutyl ketone (MIBK) or methyl ethyl ketone (MEK); an ester solvent such as ethyl acetate or butyl acetate; and HCFC225 (CF ₃ CF ₂ CHCl ₂ / A fluorine-based solvent such as a CClF ₂ CF ₂ CHClF mixture or the like may be used. The alcohol solvent having an OH group is not preferable because it hinders the progress of the reaction. Further, in the system, even if water is present, the reaction proceeds, and it is more preferable that each solvent is dehydrated before use.

The novel compound of the present invention can be added to use a resin as a coating for automobiles. By applying the obtained coating material to a coating film formed of a metal, the effect of preventing corrosion of the metal is improved as compared with the coating film not containing the novel compound of the present invention, and the adhesion to the metal is also excellent.

Further, the novel compound of the present invention is used by being added to a coating material, and may also be used for a printed substrate, a conductive portion of a multilayer substrate, an electrode of a connector, a silver or copper pattern, a conductive film of silver or a copper mesh, and the like. Conductive part Shift occurs. The term "migration" refers to the adhesion of moisture to the conductive portion of the electronic device, which contacts the conductive portion of the silver or the conductive portion of the copper and applies a voltage between the adjacent conductive portions to cause migration of the metal ions from the anode to the cathode. The phenomenon of metal deposition on the cathode causes an accident of short circuit between the conductive portions due to the condition. In particular, silver or copper is known as a metal that is prone to migration.

The present invention is also a composition comprising a compound represented by the formula (1) or (2), a vinylidene fluoride resin (B), and an acrylic component (A) (hereinafter also referred to as "the composition of the present invention" Object 1").

Further, in the case of the composition 2 of the present invention to be described later, the compound represented by the formula (14) or the formula (15) is substituted with the compound represented by the formula (1) or (2), and the present invention can be applied. Composition 1.

Since the composition 1 of the present invention contains the above novel compound, it can form a coating film or sheet which is excellent in adhesion prevention with metal and which is excellent in adhesion to metal. The obtained coating film or sheet is excellent in transparency and insulation. Further, various conductive portions may be prevented from occurring in the printed circuit board, the conductive portion of the multilayer substrate, the electrode of the connector, the silver or copper pattern, the conductive film of silver or copper mesh, and the like.

The composition 1 of the present invention can form a coating film having excellent corrosion preventing effect, transparency, and metal adhesion, and is particularly suitable as a rust preventive coating for protecting a metal surface.

Examples of the metal include copper, silver, aluminum, iron, SUS, nickel, molybdenum, chromium, zinc, and various other steel sheets. In particular, copper or silver is preferred because it exhibits excellent metal adhesion and rust resistance. It is especially good for copper. according to Thus, the composition of the present invention is more suitable as a coating composition for rust prevention of copper or silver. Copper is not only a copper plate, but also a copper-plated copper substrate, and may be a laminated copper foil on a substrate. Silver is not only a silver plate, but also a person who deposits silver on a substrate, and may be a laminated silver foil on a substrate.

The composition 1 of the present invention can also be used for a printed substrate, a conductive portion of a multilayer substrate, an electrode of a connector, a silver or copper pattern, a conductive film of silver or copper mesh, a metal fine particle such as silver or copper, or a metal nanoparticle. A conductive film composed of a rice noodle or the like, various conductive portions suppress migration, and is also suitable as a coating composition for suppressing migration.

The present invention is also a coated article comprising a substrate and a coating film formed on the substrate of the composition 1 described above.

The present invention is also a composition comprising: a nitrogen-containing aromatic heterocyclic compound containing a polymerizable functional group, a vinylidene fluoride-based resin (B), and a component selected from the group consisting of an acrylic monomer and an acrylic polymer. At least one of the acrylic components (A) (hereinafter also referred to as "the composition 2 of the present invention").

The composition 2 of the present invention can form a coating film or sheet which is excellent in adhesion prevention against metal and which is excellent in adhesion to metal. The obtained coating film or sheet is excellent in transparency and insulation.

Further, the coating film or sheet obtained from the composition 2 of the present invention may be various conductive materials for the printed substrate, the conductive portion of the multilayer substrate, the electrode of the connector, the silver or copper pattern, the conductive film of silver or copper mesh, and the like. The Ministry inhibits migration from occurring.

The term "migration" refers to the attachment of moisture to the conductive portion of an electronic device. When a voltage is applied to the conductive portion of the silver or the conductive portion of the copper and a voltage is applied between the adjacent conductive portions, the metal ions from the anode to the cathode are caused to migrate, so that the metal is precipitated at the cathode, and the short circuit between the conductive portions occurs due to the condition. Accident. In particular, silver or copper is known as a metal that is prone to migration.

The nitrogen-containing aromatic heterocyclic compound containing a polymerizable functional group is, for example, a compound represented by the formula (20) described later or a part of the compound represented by the formula (24) is substituted with an organic group containing a polymerizable functional group. By.

In the nitrogen-containing aromatic heterocyclic compound containing a polymerizable functional group, examples of the polymerizable functional group include a carbon-carbon double bond, a vinyl group, a vinyloxy group, an allyl group, a (meth) acrylonitrile group, and a Malay. Sulfhydryl, styryl, cinnamyl and the like. The polymerizable functional group is preferably a carbon-carbon double bond.

The nitrogen-containing aromatic heterocyclic compound containing a polymerizable functional group is preferably a compound represented by the formula (14) or the formula (15).

[Compound represented by formula (14)]

In the formula (14), the ring A is a substituted five or six membered nitrogen-containing aromatic heterocyclic ring, and the R ¹ is a hydrogen atom, a halogen atom or a C _1-6 alkyl group, and the n1 is an integer of 1 to 6, L ^{The 4} series includes a n1+1 valent linking group represented by -CO-NH-, -CO-O-, -O-CO-NH- or -NH-CO-NH-, and the ring B system may be substituted Aromatic ring.

In formula (14), Preferred . Ring A' can be substituted for a five or six member nitrogen-containing aromatic heterocycle.

In the formula (14), the ring A is preferably a five-membered nitrogen-containing aromatic heterocyclic ring containing two or three nitrogen atoms, more preferably an imidazole ring, a pyrazole ring or a triazole ring.

In formula (14), Better . Ring A" is replaceable.

In the formula (14), L ^{4 is} preferably those represented by the formula (16).

In the formula (16), Q ¹ is -O- or -NH-, l1 is 0 or 1, m1 is an integer from 1 to 20, and n1 is an integer from 1 to 6. However, when m1 is 1, n1 is an integer from 1 to 3, and when m1 is 2, n1 is an integer from 1 to 5. M1 is preferably 1 or 2. L1 is preferably 0.

In the formulas (14) and (16), n1 is preferably 1 or 2.

In the formula (14), the ring B may be via a hydroxyl group, an amine group, a carboxylic acid group, a nitro group, a halogen group, a thiol group, a cyano group, a decyl group, a sulfonic acid group, a methanesulfonyl group, an alkyl group, Or an aromatic ring substituted with a substituent represented by the formula (17).

In the formula (17), the L ^{6 group} includes a n3+1 valent linking group bonded by -CO-NH-, -CO-O-, -O-CO-NH- or -NH-CO-NH- R ³ is a hydrogen atom, a halogen atom or a C _1-6 alkyl group, and n 3 is an integer of 1 to 6.

In the formula (17), L ^{6 is} preferably those represented by the formula (19).

In the formula (19), Q ³ is -O- or -NH-, m3 is an integer from 1 to 20, and n3 is an integer from 1 to 6. M3 is preferably 1 or 2.

In the formulas (17) and (19), n3 is preferably 1 or 2.

In the formula (14), the ring B is preferably a benzene ring.

In formula (14), Better Any of them.

In the above formula, Z ¹ is a hydroxyl group, an amine group, a carboxylic acid group, a nitro group, a halogen group, a thiol group, a cyano group, a decyl group, a sulfonic acid group, a methylsulfonyl group, an alkyl group, or a formula (17). Represents a substituent. Z ^{1 is} preferably a hydroxyl group, an amine group or a substituent represented by the formula (17).

[Method for Producing Compound of Formula (14)]

The compound represented by the formula (14) can be produced by reacting a compound represented by the formula (20) with a compound represented by the formula (21).

In the formula (20), the ring A is a substituted five-membered or six-membered nitrogen-containing aromatic heterocyclic ring, and the ring B-based substituted aromatic ring.

R of formula (21), L ⁴¹ may be based hydroxyl or amine functional groups of the reaction, as R ^1, and n1 of formula (14) and (16) of lines ¹ and n1 are as defined above. The above amine group may be a nitrogen-containing aromatic heterocyclic secondary amine (-NH-).

The compound represented by formula (20) is preferably a formula The compound shown, more preferably Any of the compounds shown, more preferably Any of the compounds shown, particularly preferred Any of the compounds shown. Ring A' can be substituted for a five or six member nitrogen-containing aromatic heterocycle. Ring A" is substitutable. Z ² is a hydroxyl group, an amine group, a carboxylic acid group, a nitro group, a halogen group, a thiol group, a cyano group, a decyl group, a sulfonic acid group, a methanesulfonyl group or an alkyl group, preferably It is a hydroxyl group or an amine group.

The compound represented by the formula (21) is preferably an isocyanate compound represented by the formula (22).

Formula (22), m1, n1 and R ¹ are as formula (14) and (16) of m1, n1 and R ¹ are the same as above lines.

The compound represented by the formula (21) is more preferably a formula Any of the compounds shown.

The compound represented by the formula (20) and the compound represented by the formula (21) are preferably 1 to 5 moles per mole of the compound represented by the formula (20). In the manner of the ear, two compounds are added to the system to carry out the reaction.

With respect to 1 mol of the compound represented by the formula (20), the compound represented by the formula (21) is a compound represented by the formula (21) and a compound represented by the formula (21) even if it is 0.1 to 1 mol. The reaction system is sufficient.

When Z ² is a hydroxyl group or an amine group, the compound represented by the formula (21) is set to 0.1 to 1 mol per 1 mol of the compound represented by the formula (20), and the preferred reaction formula (20) a ring A of the compound shown and a compound of the formula (21).

When Z ² is a hydroxyl group or an amine group, 2 moles of the compound of the formula (20) is added to the system by a compound represented by the formula (21) in a manner more than 1 mole. a compound obtained by reacting a compound represented by the formula (21) with not only the ring A of the compound represented by the formula (20) but also the hydroxyl group or the amine group at the ring B, in the formula (14) Manufacturable Compound. Z ³ is a substituent represented by the formula (17).

The reaction of the compound of the formula (20) with the compound of the formula (21) can be carried out at 15 to 100 ° C, preferably 15 to 70 ° C, more preferably 20 to 30 ° C. The reaction time is usually from 1 to 10 hours.

a compound represented by formula (20) and a compound represented by formula (21) The reaction of the compound can be carried out in the presence of a catalyst. Examples of the catalyst include an organic titanium compound such as tetraethyl titanate or tetrabutyl titanate; an organotin compound such as tin octylate, dibutyltin oxide or dibutyltin dilaurate; and stannous chloride. A halogen such as stannous bromide is stannous or the like. The amount of the catalyst to be used is not particularly limited, and may be appropriately adjusted. For example, it is usually 0.00001 to 3 parts by mass, preferably 0.0001 to 1 part by mass, per 100 parts by mass of the compound represented by the formula (21). degree.

The reaction of the compound represented by the formula (20) with the compound represented by the formula (21) can be carried out in a solvent. As the solvent, a solvent which does not inhibit the progress of the reaction may be used, and a conventionally known solvent which is generally used may be used. For example, a ketone solvent such as acetone, methyl isobutyl ketone (MIBK) or methyl ethyl ketone (MEK); an ester solvent such as ethyl acetate or butyl acetate; and HCFC225 (CF ₃ CF ₂ CHCl ₂ / A fluorine-based solvent such as a CClF ₂ CF ₂ CHClF mixture or the like may be used. The alcohol solvent having an OH group is not preferable because it hinders the progress of the reaction. Further, in the system, even if water is present, the reaction proceeds, and it is more preferable that each solvent is dehydrated before use.

[Compound represented by formula (15)]

In the formula (15), the ring C is a substituted five or six membered nitrogen-containing aromatic heterocyclic ring, an R ² -based hydrogen atom, a halogen atom or a C _1-6 alkyl group, and the n2 is an integer of 1 to 6, L ^{The 5} series includes a n1+1-valent linking group bonded by -CO-NH-, -CO-O-, -O-CO-NH- or -NH-CO-NH-.

In formula (15), Preferred . The ring C' system may be substituted for a five or six member nitrogen-containing aromatic heterocyclic ring.

In the formula (15), the ring C and the ring C' are preferably a substituted five-membered nitrogen-containing aromatic heterocyclic ring containing two or three nitrogen atoms.

In formula (15), Better Any of them.

In the formula (15), L ^{5 is} preferably those represented by the formula (18).

In the formula (18), Q ² is -O- or -NH-, l2 is 0 or 1, m2 is an integer from 1 to 20, and n2 is an integer from 1 to 6. However, when m2 is 1, n2 is an integer from 1 to 3, and when m2 is 2, n2 is an integer from 1 to 5.

In the formulas (15) and (18), n2 is preferably 1 or 2.

[Method for Producing Compound of Formula (15)]

The compound represented by the formula (15) can be produced by reacting a compound represented by the formula (24) with a compound represented by the formula (25).

The ring C system can be substituted for a five or six member nitrogen-containing aromatic heterocyclic ring.

In the formula (25), L ⁵¹ is a functional group reactive with a hydroxyl group or an amine group, and R ² and n ^{2 are} the same as the above-mentioned R ² and n ² groups of the formulae (15) and (18). The above amine group may be a nitrogen-containing aromatic heterocyclic secondary amine (-NH-).

The compound represented by the formula (24) is preferably a formula The compound shown, more preferably Any of the compounds shown. The ring C' system may be substituted for a five or six member nitrogen-containing aromatic heterocyclic ring. Ring C and ring C' are preferably a five-membered nitrogen-containing aromatic heterocyclic ring containing two or three nitrogen atoms.

The compound represented by the formula (25) is preferably an isocyanate compound represented by the formula (26).

In the formula (26), m2 m2, n2 and R ² in formula (15) and (18) of, n2 and R ² lines above.

The compound represented by the formula (25) is more preferably a formula Any of the compounds shown.

The compound represented by the formula (24) and the compound represented by the formula (25) are preferably 1 mol of the compound of the formula (25) with respect to 1 mol of the compound represented by the formula (24). The method is preferably 0.1 to 1 mol, and two compounds are added to the system to carry out the reaction.

The reaction of the compound of the formula (24) with the compound of the formula (25) can be carried out at 15 to 100 ° C, preferably 15 to 70 ° C, more preferably 20 to 30 ° C. The reaction time is usually from 1 to 10 hours.

The reaction of the compound represented by the formula (24) with the compound represented by the formula (25) can be carried out in the presence of a catalyst. Examples of the catalyst include an organic titanium compound such as tetraethyl titanate or tetrabutyl titanate; an organotin compound such as tin octylate, dibutyltin oxide or dibutyltin dilaurate; and stannous chloride. A halogen such as stannous bromide is stannous or the like. The amount of the catalyst to be used is not particularly limited, and may be appropriately adjusted. For example, it is usually 0.00001 to 3 parts by mass, preferably 0.0001 to 1 part by mass, per 100 parts by mass of the compound represented by the formula (25). degree.

The reaction of the compound represented by the formula (24) with the compound represented by the formula (25) can be carried out in a solvent. As the solvent, a solvent which does not inhibit the progress of the reaction may be used, and a conventionally known solvent which is generally used may be used. For example, a ketone solvent such as acetone, methyl isobutyl ketone (MIBK) or methyl ethyl ketone (MEK); an ester solvent such as ethyl acetate or butyl acetate; and HCFC225 (CF ₃ CF ₂ CHCl ₂ / A fluorine-based solvent such as a CClF ₂ CF ₂ CHClF mixture or the like may be used. The alcohol solvent having an OH group is not preferable because it hinders the progress of the reaction. Further, in the system, even if water is present, the reaction proceeds, and it is more preferable that each solvent is dehydrated before use.

In the composition 2 of the present invention, a coating film having excellent corrosion prevention effect and adhesion can be formed, and migration can be further suppressed, and it is preferable to contain 0.1 to 30% by mass of the above-mentioned nitrogen-containing aromatic hetero compound containing a polymerizable functional group. The ring compound is more preferably contained in an amount of from 01 to 10% by mass.

The coating film having an excellent effect can be formed by the corrosion preventing effect and the adhesion, and the migration can be further suppressed. The content of the nitrogen-containing aromatic heterocyclic compound containing the polymerizable functional group is preferably 2% by mass or more. It is 3% by mass or more.

(A) Acrylic composition

The acrylic component is preferably at least one selected from the group consisting of an acrylic monomer and an acrylic polymer.

The acrylic monomer is preferably selected from the group consisting of (meth) acrylate, (meth) acrylate, hydroxyl group-containing (meth) acrylate, amine group-containing (meth) acrylate, and polyfunctional acryl monomer. At least one of the group formed.

In this specification, the single is described as "(meth)acrylic acid In the case of an ester, a hydroxyl group-containing (meth) acrylate, an amine group-containing (meth) acrylate, and a polyfunctional acryl monomer are not included.

The acrylic monomer is more preferably at least one selected from the group consisting of (meth) acrylate, (meth) acrylate, and polyfunctional acryl monomer, and more preferably selected from (meth) acrylate. At least one of the group consisting of an ester and a polyfunctional acrylic monomer. It is particularly preferable to use (meth) acrylate alone or both (meth) acrylate and polyfunctional acryl monomers.

The (meth) acrylate is preferably selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (methyl). N-butyl acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, (methyl) At least one of the group consisting of lauryl acrylate, cyclohexyl (meth) acrylate and benzyl (meth) acrylate is more preferably methyl (meth) acrylate.

As the polyfunctional acrylic monomer, a compound obtained by substituting a hydroxyl group of a polyhydric alcohol such as a diol, a triol or a tetraol with an acrylate group, a methacrylate group or an α-fluoroacrylate group is generally known. Specific examples thereof include 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, tripropylene glycol, neopentyl glycol, trimethylolpropane, and pentaerythritol. A compound in which two or more hydroxyl groups of individual polyols such as dipentaerythritol are substituted with any one of an acrylate group, a methacrylate group, and an α-fluoroacrylate group. Also, it is also possible to use a fluorine-containing alkyl group containing an ether bond. Two or more hydroxy groups of a fluorine-containing alkyl group, a fluorine-containing alkylene group or a polyether containing an ether-bonded fluorine-containing alkyl group are substituted with an acrylate group, a methacrylate group, and an α-fluoroacrylate group. The acrylic monomer is particularly preferred in that the refractive index of the low cured product can be maintained.

The polyfunctional acrylic monomer is preferably a polyfunctional (meth) acrylate, more preferably selected from the group consisting of ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethyl acrylate. Diol di(meth)acrylate, 1,2-propanediol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate , 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,9-nonanediol Di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol III At least one of a group consisting of (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and allyl (meth) acrylate, more preferably three Hydroxymethylpropane tri(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

The acrylic component can be an acrylic polymer. As the acrylic polymer, a homopolymer of (meth) acrylate or a copolymer of (meth) acrylate is preferred.

The copolymer of (meth) acrylate is preferably a (meth) acrylate and a (meth) acrylate selected from (meth)acrylic acid, a hydroxyl group-containing (meth) acrylate, and an amine group-containing (meth) acrylate. Multifunctional Acrylic monomer, alkyl vinyl ether, alkyl vinyl ester, crotonic acid, maleic acid, fumaric acid, itaconic acid, (meth)acrylonitrile, vinyl chloride, vinyl chloride and a copolymer of at least one of the group consisting of methyl) acrylamide.

Examples of the alkyl vinyl ether include methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether.

Examples of the alkyl vinyl ester include vinyl formic acid ester, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, and vinyl stearate.

Examples of the hydroxyl group-containing (meth) acrylate include hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate (HEA), 3-hydroxypropyl methacrylate, and 3-hydroxypropyl acrylate. , 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate And 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, etc., among them, HEMA and HEA are preferable.

The copolymer of a (meth) acrylate homopolymer and a (meth) acrylate is preferably 1 to 100 mol% based on the polymerization unit of the (meth) acrylate, relative to the total polymerization unit. Preferably, the polymerization unit of (meth) acrylate is 50 to 100 mol%.

The weight average molecular weight of the acrylic polymer is preferably in the range of 10,000 to 500,000. When the weight average molecular weight is too small, there is a fear that the gas barrier property (water vapor barrier property) is deteriorated, and when the weight average molecular weight is too large, the compatibility with the vinylidene fluoride resin (B) may be deteriorated.

The above weight average molecular weight is more preferably from 15,000 to 300,000.

The weight average molecular weight of the acrylic polymer (A) can be calculated, for example, by gel permeation chromatography (GPC).

The acrylic component (A) is preferably selected from the group consisting of (meth) acrylate monomers, polyfunctional acrylic monomers, unsaturated carboxylic acid monomers, homopolymers of (meth) acrylates, and (meth) acrylates. At least one selected from the group consisting of copolymers, more preferably selected from the group consisting of copolymers of (meth) acrylate monomers and polyfunctional (meth) acrylate monomers, and (meth) acrylates At least one of a group consisting of a polymer and a copolymer of (meth) acrylate and (meth)acrylic acid.

Further, the acrylic component (A) is preferably selected from the group consisting of a copolymer of a (meth) acrylate monomer and a polyfunctional (meth) acrylate monomer, a homopolymer of (meth) acrylate, (methyl) At least one of the group consisting of a copolymer of an acrylate and an unsaturated carboxylic acid.

(B) vinylidene fluoride (VdF) resin

The VdF-based resin (B) is a copolymer of one or two or more kinds of a homopolymer (PVdF) of VdF, or VdF, and another monomer copolymerizable with VdF.

The coating film obtained from the composition 2 of the present invention has excellent gas barrier properties by including the VdF-based resin (B).

Examples of other monomers copolymerizable with VdF include tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), trifluoroethylene (TrFE), monofluoroethylene, hexafluoropropylene (HFP), and perfluoro( Alkyl A fluorine-containing olefin such as an alkenyl ether) (PAVE); a fluorine-containing acrylate; and a functional group containing a fluorine-containing monomer. Among these, from the viewpoint of good solvent solubility, at least one selected from the group consisting of TFE, CTFE and HFP is preferred.

In other words, the VdF-based resin (B) is preferably a copolymer of VdF and a monomer selected from at least one selected from the group consisting of TFE, HFP, CTFE, and PAVE.

Further, the VdF-based resin (B) has a VdF unit of 50 mol% or more, preferably 60 mol% or more, but is preferably high in solvent solubility.

In the VdF-based resin (B), the upper limit of the VdF unit ratio may be, for example, 100 mol%. Since the transparency is good, the ratio of the VdF unit is preferably 95% by mole or less, more preferably 90% by mole or less.

The VdF-based resin (B) may, for example, be a VdF homopolymer (PVdF), a VdF/TFE copolymer, a VdF/TFE/HFP copolymer, a VdF/HFP copolymer, or a VdF/CTFE copolymer.

As the VdF-based resin (B), from the viewpoint of good transparency, it is preferable to contain 50 to 95 mol% of the VdF unit, 0 to 50 mol% of the TFE unit, and 0 to 50 mol% of the HFP unit. polymer. More preferably, it comprises a polymer having a VdF unit of 70 to 90 mol%, a TFE unit of 5 to 30 mol%, and a HFP unit of 5 to 30 mol%.

The VdF-based resin (B) is more preferably selected from the group consisting of a VdF/TFE copolymer, a VdF/HFP copolymer, and a VdF/TFE/HFP copolymer, from the viewpoint of good transparency. At least one, and more Preferably, it is a VdF/TFE copolymer.

The total amount of the VdF/TFE copolymer relative to the VdF unit and the TFE unit is preferably 50 to 95 mol% in VdF units and 5 to 50 mol% in TFE units, and is excellent in VvF due to excellent water vapor barrier property. The unit is 70-95 mol% and the TFE unit is 5-30 mol%, and more preferably the VdF unit is 70-90 mol% and the TFE unit is 10-30 mol%.

Further, the VdF/TFE copolymer may be a polymer composed of only VdF units and TFE units, and is a polymerization unit other than the VdF unit and the TFE unit from the viewpoint of transparency and solvent solubility (however, according to HFP) Except for the polymerization unit, for example, may have a polymerization unit according to ethylene, propylene, alkyl vinyl ether, vinyl acetate, vinyl chloride, vinyl chloride, CH ₂ =CHCF ₃ , CH ₂ =CFCF _{3 ,} and the like. By.

The polymerization unit other than the VdF unit and the TFE unit is 0 to 10 mol% with respect to the total polymerization unit constituting the VdF/TFE copolymer.

The VdF/HFP copolymer is preferably 50 to 95 mol% in VdF unit and 5 to 50 mol% in HFP unit, and is preferably VdF because of excellent water vapor barrier property. The unit is 70-95 mol% and the HFP unit is 5-30 mol%, and more preferably the VdF unit is 70-90 mol% and the HFP unit is 10-30 mol%.

Further, the VdF/HFP copolymer may be a polymer composed of only VdF units and HFP units, and is a polymerization unit other than the VdF unit and the HFP unit from the viewpoint of transparency and solvent solubility (however, according to HFP) Except for the polymerization unit, for example, may have a polymerization unit according to ethylene, propylene, alkyl vinyl ether, vinyl acetate, vinyl chloride, vinyl chloride, CH ₂ =CHCF ₃ , CH ₂ =CFCF _{3 ,} and the like. By.

The polymerization unit other than the VdF unit and the HFP unit is 0 to 10 mol% with respect to the total polymerization unit constituting the VdF/HFP copolymer.

The total amount of the VdF/TFE/HFP copolymer relative to the VdF unit and the TFE unit and the HFP unit is preferably 50 to 95 mol% for the VdF unit and 1 to 50 mol% for the TFE unit and 1 to 50 for the HFP unit. The molar % is excellent in solvent solubility, more preferably 70 to 90 mol% in VdF units and 10 to 30 mol% in TFE units and 10 to 30 mol% in HFP units.

Further, the VdF/TFE/HFP copolymer may be a polymer composed only of VdF units, TFE units, and HFP units, and is in addition to VdF units, TFE units, and HFP units from the viewpoints of transparency and solvent solubility. The polymerization unit may be, for example, a polymerization unit having ethylene, propylene, alkyl vinyl ether, vinyl acetate, vinyl chloride, vinyl chloride, CH ₂ =CHCF ₃ , CH ₂ =CFCF ₃ or the like.

The polymerization unit other than the VdF unit, the TFE unit, and the HFP unit is 0 to 10 mol% with respect to the total polymerization unit constituting the VdF/TFE/HFP copolymer.

The weight average molecular weight of the VdF-based resin (B) is preferably in the range of 10,000 to 100,000,000. When the weight average molecular weight is too small, the coating film strength is deteriorated, and when the weight average molecular weight is too large, solvent solubility is deteriorated.

The above weight average molecular weight is more preferably 50,000 to 10,000,000.

The weight average molecular weight of the VdF-based resin (B) can be calculated, for example, by gel permeation chromatography (GPC).

The composition 2 of the present invention preferably has a mass ratio (A)/(B) of the acrylic component (A) to the VdF-based resin (B) of 1/99 to 99/1. By including the acrylic polymer (A) in the above specific range, a coating film excellent in corrosion prevention effect and adhesion can be formed. The mass ratio (A)/(B) is preferably from 1/99 to 70/30, more preferably from 1/99 to 50/50, and particularly preferably from 5/95 to 30/70.

In the composition 2 of the present invention, the total mass of the acrylic component (A) and the VdF-based resin (B) is preferably 90% by mass based on the total amount of the polymer component (the amount of the acrylic component when the acrylic component is a monomer). More preferably, it is 95 mass% or more. The composition of the present invention may be one in which the polymer component is composed only of the acrylic component (A) and the VdF resin (B).

The composition 2 of the present invention can be suitably used as a coating. Examples of the form of the coating material include a solvent-based paint, an aqueous paint, and a powder paint. In such a form, it can be modulated by a conventional method.

The composition 2 of the present invention is preferably a solvent-based paint from the viewpoints of easiness of film formation, curability, and goodness of drying property.

When the composition 2 of the present invention is a solvent-based paint, the composition of the present invention further contains a solvent. A solvent-based paint can be obtained by dissolving or dispersing the acrylic component (A) and the VdF-based resin (B) in a solvent.

The solvent is preferably a polar organic solvent, more preferably a ketone solvent, an ester solvent, a carbonate solvent, a cyclic ether solvent or a guanamine solvent. Specific examples thereof include methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), acetone, diethyl ketone, dipropyl ketone, ethyl acetate, methyl acetate, propyl acetate, and acetic acid. Butyl ester, ethyl lactate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethylformamide, dimethyl Indoleamine (DMAc), diacetone alcohol, and the like.

When the composition 2 of the present invention is a solvent-based paint, the total amount of the acrylic component (A) and the VdF-based resin (B) is preferably from 1 to 95% by mass, more preferably 5, based on 100% by mass of the total amount of the coating material. ~70% by mass.

When the composition 2 of the present invention is applied as a coating material, the coating temperature may be carried out under normal temperature conditions depending on the form of coating.

As the coating method, a doctor blade method, a roll coating method, a gravure coating method, a knife coating method, a reverse coating method, a rod coating method, an air knife coating method, a curtain coating method, a Feknelane coating method, a kiss roll may be employed. Coating method, screen coating method, spin coating method, spray coating method, extrusion coating method, micro gravure coating method, flow coating method, bar coating method, die coating method, dip coating method, etc., may consider a substrate The type, shape, productivity, and controllability of the film thickness are selected.

In the case of a solvent-based coating, the curing and drying are carried out at 10 to 300 ° C, usually at 30 to 200 ° C for 30 seconds to 3 days. After it is hardened and dried, it can be aged, and the aging is usually completed at 10 to 200 ° C for 1 minute to 3 days.

The hardening may be carried out by a method of curing the light by irradiating an active energy ray such as an ultraviolet ray, an electron beam or a radiation, in addition to heating.

The composition 2 of the present invention may contain a curing agent, a curing accelerator, a retarder, a pigment, a pigment dispersant, an antifoaming agent, a leveling agent, and ultraviolet rays in addition to the acrylic component (A) and the VdF resin (B). An absorbent, a light stabilizer, a tackifier, a adhesion improver, a matting agent, an active energy ray hardening initiator, and the like.

An active energy ray hardening initiator, for example, an electromagnetic wave in a wavelength region of 350 nm or less, that is, by first irradiating ultraviolet rays, electron beams, X-rays, γ-rays, etc., to generate radicals or cations for the first time, as a hardening (crosslinking) The reaction of a fluoropolymer with a carbon-carbon double bond is initiated by a catalyst, usually by the use of ultraviolet light to generate free radicals or cations, especially those that generate free radicals. For example, the following can be exemplified.

Acetophenone series: acetophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, α-aminoacetophenone, hydroxypropiophenone, 2-methyl-1-[4-( Methylthio)phenyl]-2-morpholinpropan-1-one and the like.

Benzoin: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

Benzophenone series: benzophenone, benzamidine benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propyl benzophenone , benzoated benzophenone, M. ketone, and the like.

Thioxanthone: thioxanthone, chlorothioxanthone, methylxanthone (Xanthone), diethyl thioxanthone, dimethyl thioxanthone, and the like.

Others: benzyl, α-mercaptodecyl ester, decylphosphine oxide, glyoxylate, 3-tocopherol (Ketocoumarin), 2-ethylhydrazine, camphorquinone, anthraquinone, and the like.

The composition 2 of the present invention can form a coating film having excellent corrosion preventing effect, transparency, and metal adhesion, and is particularly suitable as a rust preventive coating for protecting a metal surface.

Examples of the metal include copper, silver, aluminum, iron, SUS, nickel, molybdenum, chromium, zinc, and various other steel sheets. In particular, copper or silver is preferred because it exhibits excellent metal adhesion and rust resistance. It is especially good for copper. Accordingly, the composition 2 of the present invention is more suitable as a coating composition for rust prevention of copper or silver. Copper is not only a copper plate, but also a copper-plated copper substrate, and may be a laminated copper foil on a substrate. Silver is not only a silver plate, but also a person who deposits silver on a substrate, and may be a laminated silver foil on a substrate.

The composition 2 of the present invention can also be used for a printed circuit board, a conductive portion of a multilayer substrate, an electrode of a connector, a silver or copper pattern, a conductive film of silver or copper mesh, a metal fine particle such as silver or copper, or a metal. A conductive film composed of a nanowire and various conductive portions suppress migration, and are also suitable as a coating composition for suppressing migration.

Examples of the use of the composition 2 of the present invention include a touch panel, an LED, a solar cell, an organic EL, an electronic device used outdoors, wiring of other electronic devices, electric wires, electrical contacts, electronic devices, antennas, and components. The protection of the metal part. More specifically, it can be exemplified by copper or silver, the protection of the wiring taken out of the touch panel, and the touch panel are transparent. Protection of the bright electrode, protection of the LED lead frame, and protection of the removed wiring of the solar cell.

The composition 2 of the present invention contains a vinylidene fluoride resin (B). When the vinylidene fluoride-based resin (B) is contained, the water repellency, the moisture resistance, the environmental resistance, and the chemical resistance are improved. Accordingly, the composition 2 of the present invention can be expected from the composition 3 of the present invention described later. It can improve the effect of preventing corrosion of metals and also improve the effect of suppressing migration.

The present invention is also a composition comprising the above novel compound and an optical adhesive (hereinafter also referred to as "composition 3").

The composition 3 described above can form a coating film or sheet which is excellent in adhesion prevention against metal and which is excellent in adhesion to metal. The obtained coating film or sheet is also excellent in transparency.

Further, the coating film or sheet obtained from the composition 3 can be suppressed to various conductive portions of the printed circuit board, the conductive portion of the multilayer substrate, the electrode of the connector, the silver or copper pattern, the conductive film of silver or copper mesh, and the like. The migration took place.

The novel compound containing the above composition 3 is as a compound represented by the formula (1) or (2) as described above.

The composition 3 can form a coating film having excellent corrosion prevention effect and adhesion, and can further inhibit migration, and preferably contains 0.1 to 30% by mass of the above-mentioned nitrogen-containing aromatic heterocyclic compound containing a polymerizable functional group. More preferably, it contains 01 to 10% by mass.

An excellent coating film can be formed by the corrosion preventing effect and the adhesion, and migration can be further suppressed, and the above-mentioned nitrogen-containing aromatic group containing a polymerizable functional group The content of the heterocyclic compound is more preferably 2% by mass or more, particularly preferably 3% by mass or more.

Examples of the optical adhesive include an ethylene-vinyl acetate copolymer, an ethylene-vinyl acetate copolymer denature, polyethylene, an ethylene-propylene copolymer, an ethylene-acrylic copolymer, an ethylene-acrylate copolymer, and ethylene. Cerium acrylate copolymer, acrylate rubber, polyisobutylene, random polypropylene, polyvinyl butyral, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer, styrene-isoprene Diene block copolymer, polybutadiene, ethyl cellulose, phenoxy resin, polyester, epoxy resin, polyamine, polyvinyl ether, polyethylene glycol, polyisoprene , a mixture of a siloxane rubber, a polychloroprene or a (meth) acrylate.

As the above optical adhesive, since it has excellent transparency and optical properties, among them, a copolymer of (meth) acrylate is preferable.

In the present specification, when it is described as "(meth) acrylate", a hydroxyl group-containing (meth) acrylate, an amine group-containing (meth) acrylate, and a polyfunctional acryl monomer are not included.

The (meth) acrylate is preferably selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (methyl). N-butyl acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, (methyl) Lauryl acrylate, cyclohexyl (meth) acrylate and (meth) acrylate At least one of the group consisting of benzyl esters is more preferably n-butyl (meth)acrylate or 2-ethylhexyl (meth)acrylate.

The copolymer of (meth) acrylate is preferably a (meth) acrylate and a (meth) acrylate selected from (meth)acrylic acid, a hydroxyl group-containing (meth) acrylate, and an amine group-containing (meth) acrylate. , polyfunctional acrylic monomer, alkyl vinyl ether, alkyl vinyl ester, crotonic acid, maleic acid, fumaric acid, itaconic acid, (meth)acrylonitrile, vinyl chloride, chloride a copolymer of a monomer of at least one of ethylene and (meth) acrylamide.

Examples of the alkyl vinyl ether include methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether.

Examples of the alkyl vinyl ester include vinyl formic acid ester, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, and vinyl stearate.

Examples of the hydroxyl group-containing (meth) acrylate include hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate (HEA), 3-hydroxypropyl methacrylate, and 3-hydroxypropyl acrylate. , 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate And 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, etc., among them, HEMA and HEA are preferable.

The copolymer of (meth) acrylate is preferably 1 to 100 mol% based on the polymerization unit of (meth) acrylate, more preferably polymerized according to (meth) acrylate, with respect to the total polymerization unit. unit It is 50~100% by mole.

The weight average molecular weight of the (meth) acrylate copolymer is in the range of 5,000 to 2,000,000, preferably in the range of 10,000 to 1.7 million, more preferably in the range of 500,000 to 1,500,000. When the weight average molecular weight is too small, the gas barrier property and the water vapor barrier property are deteriorated, and when the weight average molecular weight is too large, the solubility in a solvent and the coatability are deteriorated.

The weight average molecular weight of the acrylic polymer (A) can be calculated, for example, by gel permeation chromatography (GPC).

The above composition 3 can be suitably used as a coating material. Examples of the form of the coating material include a solvent-based paint, an aqueous paint, and a powder paint. In such a form, it can be modulated by a conventional method.

The composition 3 is preferably a solvent-based paint from the viewpoints of easiness of film formation, curability, and goodness of drying property.

When the composition 3 is a solvent-based paint, the composition further contains a solvent. A solvent-based paint can be obtained by dissolving or dispersing the above optical adhesive in a solvent. Further, in the presence of the above-mentioned nitrogen-containing aromatic heterocyclic compound containing a polymerizable functional group, a solution may be obtained by polymerizing a monomer constituting the optical adhesive in a solution.

The solvent is preferably a polar organic solvent, more preferably a ketone solvent, an ester solvent, a carbonate solvent, a cyclic ether solvent or a guanamine solvent. Specific examples thereof include methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), acetone, diethyl ketone, dipropyl ketone, ethyl acetate, methyl acetate, propyl acetate, and acetic acid. Butyl ester, ethyl lactate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, tetrahydrogen Furan, methyltetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide (DMAc), diacetone alcohol, and the like.

When the composition 3 is a solvent-based paint, the total amount of the optical adhesive is preferably from 1 to 95% by mass, and more preferably from 5 to 70% by mass, based on 100% by mass of the total amount of the coating material.

When the composition 3 is applied as a coating material, the coating temperature may be carried out under normal temperature conditions depending on the form of coating.

As the coating method, a doctor blade method, a roll coating method, a gravure coating method, a knife coating method, a reverse coating method, a rod coating method, an air knife coating method, a curtain coating method, a Feknelane coating method, a kiss roll may be employed. Coating method, screen coating method, spin coating method, spray coating method, extrusion coating method, micro gravure coating method, flow coating method, bar coating method, die coating method, dip coating method, etc., may consider a substrate The type, shape, productivity, and controllability of the film thickness are selected.

In the case of a solvent-based coating, the curing and drying are carried out at 10 to 300 ° C, usually at 30 to 200 ° C for 30 seconds to 3 days. After it is hardened and dried, it can be aged, and the aging is usually completed at 10 to 200 ° C for 1 minute to 3 days.

The hardening may be carried out by a method of curing the light by irradiating an active energy ray such as an ultraviolet ray, an electron beam or a radiation, in addition to heating.

The composition 3 may include a hardener, a hardening accelerator, a retarder, a pigment, a pigment dispersant, an antifoaming agent, a leveling agent, an ultraviolet absorber, a light stabilizer, a tackifier, and the like, in addition to the optical adhesive. Adhesion improver, matting agent, active energy ray hardening initiator, and the like.

The above composition 3 may contain a hardener. Hardening as above The agent is preferably an isocyanate-based curing agent, a melamine resin, a phthalate compound, or an isocyanate group-containing decane compound.

Examples of the isocyanate-based curing agent include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), benzodimethyl diisocyanate (XDI), isophorone diisocyanate (IPDI), and lysine. Methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate (HDI), n-pentane-1,4-diisocyanate, etc. A volume, such an adduct, an isocyanurate body, a biuret body, and the like.

An active energy ray hardening initiator, for example, an electromagnetic wave in a wavelength region of 350 nm or less, that is, by first irradiating ultraviolet rays, electron beams, X-rays, γ-rays, etc., to generate radicals or cations for the first time, as a hardening (crosslinking) The reaction of a fluoropolymer with a carbon-carbon double bond is initiated by a catalyst, usually by the use of ultraviolet light to generate free radicals or cations, especially those that generate free radicals. For example, the following can be exemplified.

Acetophenone series: acetophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, α-aminoacetophenone, hydroxypropiophenone, 2-methyl-1-[4-( Methylthio)phenyl]-2-morpholinpropan-1-one and the like.

Benzoin: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

Benzophenone series: benzophenone, benzamidine benzoic acid, benzamidine benzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propyl benzophenone Acrylate benzophenone, Michler's ketone Wait.

Thioxanthone: thioxanthone, chlorothioxanthone, Xanthone, diethylthioxanthone, dimethylthioxanthone, and the like.

Others: benzyl, α-mercaptodecyl ester, decylphosphine oxide, glyoxylate, 3-tocopherol (Ketocoumarin), 2-ethylhydrazine, camphorquinone, anthraquinone, and the like.

The composition 3 can form a coating film having an excellent corrosion preventing effect, transparency, and adhesion, and can be suitably used as an adhesive for subsequent use of the optical member. Further, since it is excellent in adhesion to a metal substrate, it is also suitable as an anticorrosive paint for protecting a metal surface. The above-described composition 3 is not limited to being used for the optical member, and can be suitably used as an adhesive.

Further, from the above-mentioned composition 3, a sheet having excellent corrosion preventing effect, transparency, and adhesion can be formed, and the obtained sheet can be suitably used as an adhesive sheet or a sheet for subsequent use for the optical member. Further, since it is excellent in adhesion to a metal substrate, it is also suitable as a rust-proof sheet for protecting a metal surface. The obtained sheet is not limited to being used for the optical member, and may be suitably used as an adhesive sheet or a sheet.

Examples of the metal include copper, silver, aluminum, iron, SUS, nickel, molybdenum, chromium, zinc, and various other steel sheets. In particular, copper or silver is preferred because it exhibits excellent metal adhesion and rust resistance. It is especially good for copper. Accordingly, the above composition 3 is more suitable as a coating composition for rust prevention of copper or silver. Copper may be not only a copper plate but also a vapor deposition or sputtering copper on a substrate, and may be a laminated copper foil on a substrate. Silver is not only silver plate, but also can be evaporated or sputtered on the substrate. It can be laminated silver foil on the substrate.

The composition 3 can also be used for a printed circuit board, a conductive portion of a multilayer substrate, an electrode of a connector, a silver or copper pattern, a conductive film of silver or a copper mesh, a metal fine particle such as silver or copper, or a metal nanoparticle. A conductive film composed of a wire or the like, various conductive portions suppress migration, and is also suitable as a coating composition for suppressing migration.

Examples of the use of the composition 3 include a touch panel, an LED, a solar cell, an organic EL, an electronic device used outdoors, wiring of other electronic devices, wires, electrical contacts, electronic devices, antennas, and metal components. Protection of the Ministry. More specifically, it is made of copper or silver, the protection of the wiring taken out by the touch panel, the protection of the transparent electrode of the touch panel, the protection of the LED lead frame, and the protection of the wiring taken out by the solar cell.

The above composition 3 does not need to contain a vinylidene fluoride resin (B). When the composition 3 does not contain the vinylidene fluoride-based resin (B), it is expected to be more excellent in adhesion to the above-described composition 2 and other layers, more excellent in solubility in various solvents, and more excellent in optical characteristics.

The present invention is also a coated article comprising a substrate and a coating film formed on the substrate of the composition 2 described above. Preferably, the substrate is a resin which is dispersed or partially dispersed, a whole resin surface or a metal/resin laminate covered with metal, glass, polyethylene terephthalate, cycloolefin polymer, Polyimine polymer, urethane polymer, acrylic polymer, or a mixed polymer of a urethane polymer and an acrylic polymer, preferably gold It is a laminate of a resin or a resin which is dispersed or partially dispersed, or a metal/resin laminated body covered with a metal. Examples of the metal include copper, silver, aluminum, iron, SUS, nickel, molybdenum, chromium, zinc, and the like. In particular, copper or silver is preferred because it exhibits an excellent corrosion preventing effect and adhesion. It is especially good for copper.

Examples of the coated article of the present invention include a touch panel, an LED, a solar cell, an organic EL, an electronic device used outdoors, a metal wiring of another electronic device, an electronic device, an antenna, an element, and the like. More specifically, it is made of copper or silver, the protection of the wiring taken out by the touch panel, the protection of the transparent electrode of the touch panel, the wiring of the LED lead frame, and the wiring taken out by the solar cell.

The present invention is also a sheet characterized by being formed of the above composition 2 or the above composition 3.

The sheet of the present invention can be produced by applying the above-mentioned composition 2 or the above-mentioned composition 3 to a substrate, drying the obtained coating film, and curing it as desired. A single layer of the sheet can also be produced by peeling the dried and hardened sheet from the substrate.

When the above-mentioned compositions 2 and 3 are solvent-based paints, the curing and drying are carried out at 10 to 300 ° C, usually at 30 to 200 ° C for 30 seconds to 3 days. After it is hardened and dried, it can be aged, and the aging is usually completed at 10 to 200 ° C for 1 minute to 3 days.

The hardening may be carried out by a method of curing the light by irradiating an active energy ray such as an ultraviolet ray, an electron beam or a radiation, in addition to heating.

The sheet of the present invention is disposed on or disposed on other layers After the other two layers, it can be followed by the other layers by pressing.

The sheet formed from the above composition 2 and the sheet formed from the above composition 3 may be used in combination. After the two sheets which have been overlapped in advance are placed on the other layers or are disposed between the other two layers, they can be brought into contact with the other layers by pressing.

The present invention is also a laminated sheet characterized by comprising a release sheet and a sheet formed on the release sheet from the composition 2 or the composition 3. The release sheet may be disposed on one side of the coating film and may be disposed on both sides of the coating film.

The laminated sheet of the present invention can be produced by applying the above-mentioned composition 2 or the above-mentioned composition 3 onto a release sheet, drying the obtained coating film, and curing it as desired. The conditions for drying and hardening are as described above.

As the release sheet, a sheet obtained by applying a release agent to a substrate, a fluororesin sheet, or the like can be used. The base material may be a polyester resin such as polyethylene terephthalate. Examples of the release agent include a siloxane oxide, a fluorine-based, a fluorononane-based, and no hydrazine. An olefin system, an alkyd system, an alkyl group or a long chain alkyl group of an oxyalkylene.

The laminated sheet of the present invention is used to peel off the release sheet at the time of use, and can be used by laminating the sheet formed of the above composition 2 or the above composition 3 with another layer. Further, the sheet formed of the above-mentioned composition 2 or the above-mentioned composition 3 is provided on the other layer or between the other two layers, and can be bonded to the other layers by pressing.

The laminated sheet of the present invention may be a sheet comprising a release sheet formed on the release sheet from the composition 2, and formed from the above On the sheet formed by the composition 2, the sheet formed from the above composition 3 is formed. Further, the laminated sheet of the present invention may be formed of a release sheet, a sheet formed on the release sheet from the composition 3, and formed on the sheet formed from the composition 3, and formed from the composition 2 Slicer.

The sheet formed of the above composition 2 or the above-mentioned composition 3 has an effect of preventing corrosion of metal, is excellent in adhesion to metal, and is excellent in transparency.

Further, the sheet may suppress migration from occurring in various conductive portions of the printed circuit board, the conductive portion of the multilayer substrate, the electrode of the connector, the silver or copper pattern, the conductive film of silver or copper mesh, and the like.

Among the above-mentioned sheets, in particular, the sheet formed of the above composition 2 contains a vinylidene fluoride-based resin (B). According to this, it is expected that the sheet formed of the above-described composition 3 can improve the effect of preventing corrosion of the metal, and the effect of suppressing the occurrence of migration can be enhanced. Accordingly, it can be suitably used as a rust preventive sheet used for protecting a metal surface.

Among the above-mentioned sheets, in particular, the sheet formed of the above composition 3 does not need to contain a vinylidene fluoride-based resin (B). When the sheet formed of the above-mentioned composition 3 does not contain the vinylidene fluoride-based resin (B), it is expected that the sheet formed of the above-mentioned composition 2 is more excellent in adhesion to other layers. Accordingly, it can be suitably used as a subsequent sheet for use as an optical member.

By using the above-described compositions 2 and 3, and the above-described sheets and laminated sheets, lamination having the laminated structure shown in Figs. 1 to 6 can be produced. body.

In the embodiment shown in FIG. 1, the insulating layer 11, the sheet 12 formed of the above-mentioned composition 3, the metal layer 13, and the insulating layer 14 are sequentially disposed. The sheet formed of the above composition 3 is used as an optically transparent adhesive sheet (OCA sheet). That is, the sheet 12 is such that the insulating layer 11 and the metal layer 13 are strongly adhered while protecting the metal layer 13 from corrosion. The insulating layers 11 and 14 are preferably transparent substrates, and may be made of glass, polyethylene terephthalate, cycloolefin polymer, polyimine polymer, urethane polymer, acrylic polymer, or amine group. It is formed of a mixed polymer of an ethyl formate polymer and an acrylic polymer. The metal layer 13 may be formed of copper, silver, aluminum, iron, SUS, nickel, molybdenum, chromium, zinc, or the like, and is preferably formed of copper or silver. A primer layer for improving adhesion can be provided on one or both sides of the insulating layers 11 and 14. The primer layer can be a sheet formed from the composition of the present invention.

In the embodiment shown in FIG. 2, the insulating layer 21, the sheet 22 formed of the above-mentioned composition 2, the metal layer 23, and the insulating layer 24 are sequentially disposed. The sheet 22 formed of the above composition 2 protects the metal layer 23 from corrosion while the insulating layer 21 and the metal layer 23 are strongly adhered. The insulating layers 21 and 24 are preferably transparent substrates, and may be made of glass, polyethylene terephthalate, cycloolefin polymer, polyimine polymer, urethane polymer, acrylic polymer, or amine group. It is formed of a mixed polymer of an ethyl formate polymer and an acrylic polymer. The metal layer 23 may be formed of copper, silver, aluminum, iron, SUS, nickel, molybdenum, chromium, zinc, or the like, and is preferably formed of copper or silver. On one or both sides of the insulating layers 21 and 24 Set a primer layer that enhances adhesion. The primer layer can be a sheet formed from the composition of the present invention.

In the embodiment shown in FIG. 3, the insulating layer 31, the sheet 32 formed of the above composition 3, the metal layer 33, the insulating layer 34, the metal layer 35, and the sheet 36 formed of the above composition 3 are formed. Set in order. In this way, two metal layers can also be provided through the insulating layer. The sheet formed of the above composition 3 is used as an optically transparent adhesive sheet (OCA sheet). That is, the sheets 32 and 36 are such that the insulating layer 31 and the metal layer 33 are strongly adhered while protecting the metal layers 33 and 35 from corrosion. Further, the sheet 36 can be passed through with other optical members. The insulating layers 31 and 34 are preferably transparent substrates, and may be made of glass, polyethylene terephthalate, cycloolefin polymer, polyimine polymer, urethane polymer, acrylic polymer, or amine group. It is formed of a mixed polymer of an ethyl formate polymer and an acrylic polymer. The metal layers 33 and 35 may be formed of copper, silver, aluminum, iron, SUS, nickel, molybdenum, chromium, zinc, or the like, and among them, copper or silver is preferably formed. A primer layer for improving adhesion can be provided on one or both sides of the insulating layers 31 and 34. The primer layer can be a sheet formed from the composition of the present invention.

In the embodiment shown in FIG. 4, the insulating layer 41, the sheet 42 formed of the above composition 2, the metal layer 43, and the insulating layer 44, the metal layer 45, and the sheet 46 formed of the above composition 2 are used. Set in order. In this way, two metal layers can also be provided through the insulating layer.

The sheets 42 and 46 formed of the above composition 2 protect the metal layers 43 and 45 from corrosion while making the insulating layer 41 and the metal layer 43 strong. Solid up. Further, the laminate of this embodiment can be passed through the sheet 46 and the other optical members. The insulating layers 41 and 44 are preferably transparent substrates, and may be made of glass, polyethylene terephthalate, cycloolefin polymer, polyimine polymer, urethane polymer, acrylic polymer, or amine group. It is formed of a mixed polymer of an ethyl formate polymer and an acrylic polymer. The metal layers 43 and 45 may be formed of copper, silver, aluminum, iron, SUS, nickel, molybdenum, chromium, zinc, or the like, and are preferably formed of copper or silver. A primer layer for improving adhesion can be provided on one or both sides of the insulating layers 41 and 44. The primer layer can be a sheet formed from the composition of the present invention.

In the embodiment shown in FIG. 5, the insulating layer 51, the sheet 52 formed of the above-mentioned composition 3, the sheet 53 formed of the above-mentioned composition 2, the metal layer 54 and the insulating layer 55 are sequentially provided. The sheet 52 formed of the above composition 3 is used as an optically transparent adhesive sheet (OCA sheet), and the insulating layer 51 and the metal layer 53 are strongly adhered thereto. The sheet 52 is not limited to the sheet formed of the above-described composition 3, and may be Commercially available optical adhesives, OCA sheets. The sheet 53 formed of the above composition 2 protects the metal layer 54 from corrosion while holding the sheet 52 and the metal layer 54. The insulating layers 51 and 55 are preferably transparent substrates, and may be made of glass, polyethylene terephthalate, cycloolefin polymer, polyimine polymer, urethane polymer, acrylic polymer, or amine group. It is formed of a mixed polymer of an ethyl formate polymer and an acrylic polymer. The metal layer 54 may be formed of copper, silver, aluminum, iron, SUS, nickel, molybdenum, chromium, zinc, or the like, and is preferably formed of copper or silver. A primer layer for improving adhesion can be provided on one or both sides of the insulating layers 51 and 55. The primer layer can be made up of A sheet formed from the composition of the present invention.

In the embodiment shown in FIG. 6, the insulating layer 61, the sheet 62 formed of the above composition 3, the sheet 63 formed of the above composition 2, the metal layer 64, the insulating layer 65, the metal layer 66, The sheet 67 formed of the above composition 2 and the sheet 68 formed of the above composition 3 are sequentially provided. In this way, two metal layers can also be provided through the insulating layer. The sheets 62 and 68 formed of the above composition 3 are used as an optically transparent adhesive sheet (OCA sheet), and the sheets 62 and 68 are not limited to the sheet formed of the above-mentioned composition 3, and may be a commercially available optical adhesive. , OCA sheet. That is, the sheet 62 is made to adhere to the insulating layer 61 and the sheet 63, and the permeable sheet 68 is used to join the laminate of the embodiment to the other optical members. The sheets 63 and 67 formed by the above composition 2 protect the metal layers 64 and 66 from corrosion while reinforcing the sheet 62 and the metal layer 64, thereby reinforcing the metal layer 66 and the sheet 68. The insulating layers 61 and 65 are preferably transparent substrates, and may be made of glass, polyethylene terephthalate, cycloolefin polymer, polyimine polymer, urethane polymer, acrylic polymer, or amine group. It is formed of a mixed polymer of an ethyl formate polymer and an acrylic polymer. The metal layers 64 and 66 may be formed of copper, silver, aluminum, iron, SUS, nickel, molybdenum, chromium, zinc, or the like, and are preferably formed of copper or silver. A primer layer for improving adhesion can be provided on one or both sides of the insulating layers 61 and 65. The primer layer can be a sheet formed from the composition of the present invention.

The "sheet formed of the above composition 2" in each of the above-described embodiments may be "coated by the above composition 2" The film "the sheet formed of the above composition 3" may be "the coating film formed of the above composition 3".

The above-mentioned nitrogen-containing aromatic heterocyclic compound containing a polymerizable functional group may be added to a conductive paste, a conductive ink, a conductive paint or an electrode paste.

A composition comprising at least one selected from the group consisting of a nitrogen-containing aromatic heterocyclic compound containing a polymerizable functional group, and a metal nanowire, a metal nanoparticle, and a metal sol particle may be suitably used as the composition. The way to illustrate. The above composition can be suitably used as a conductive paste, a conductive ink, a conductive paint, or an electrode paste.

The nitrogen-containing aromatic heterocyclic compound containing a polymerizable functional group can be used in the above-described compositions 2 and 3, but the composition can also be used in the same manner.

The above-mentioned metal nanowire refers to a material having conductivity and having a sufficiently long shape in comparison with the diameter (length in the short axis direction) in the longitudinal direction. The metal nanowire can be a medium fiber and can be a hollow fiber.

The material of the above metal nanowire is not particularly limited and may be appropriately selected depending on the purpose. For example, it is preferably selected from the fourth cycle, the fifth cycle, and the sixth cycle of the long-period law table (IUPAC 1991). The metal of at least one of the group is more preferably selected from the group consisting of at least one of the group consisting of the fourth cycle, the fifth cycle, and the sixth cycle, and is selected from the group 2 to the 14th. The metal of at least one of the group is more preferably selected from the group consisting of at least one of the group consisting of the fourth cycle, the fifth cycle, and the sixth cycle, and is selected from the group consisting of the second group and the eighth group. 9th A metal of at least one of the group, the group 10, the group 11, the group 12, the group 13 and the group 14 is particularly preferably contained as a main component.

Examples of the metal include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, ruthenium, iron, osmium, iridium, manganese, molybdenum, tungsten, rhenium, ruthenium, titanium, osmium, iridium, and lead. , such alloys, etc. Among these, in terms of excellent electrical conductivity, silver and an alloy with silver are particularly preferable.

Examples of the metal used for the alloy with the above silver include platinum, rhodium, palladium, iridium, tin, iridium, nickel, and the like. These may be used alone or in combination of two or more.

The shape of the metal nanowire is not particularly limited, and may be appropriately selected depending on the purpose. For example, the shape may be a columnar shape, a rectangular parallelepiped shape, or a columnar shape having a polygonal cross section, but high transparency is required. The use is preferably a cylindrical shape or a polygonal shape in which the polygonal shape of the polygonal shape is a circular shape.

The cross-sectional shape of the above-mentioned metal nanowire is coated with a metal nanowire aqueous dispersion on a substrate, and the cross-section slice produced by the microtome can be investigated by transmission electron microscopy (TEM) observation.

The above metal nanoparticle system comprises silver, copper, gold, zinc, cadmium, palladium, rhodium, iridium, osmium, iridium, platinum, iron, nickel, cobalt, indium, silver oxide, copper oxide, gold oxide, zinc oxide, oxidation. Cadmium, palladium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, platinum oxide, iron oxide, nickel oxide, cobalt oxide, indium oxide, or any combination thereof.

The metal nanoparticle group may have individual nanoparticles, particle aggregates composed of 2 or more individual nanoparticles, Flocculation particles composed of 2 or more individual nanoparticles, or any combination thereof. The particle agglomerate of the group of individual metal nanoparticles, by weight ratio of from about 1:99 to 99:1, relative to the flocculated particles of the individual metal nanoparticles, by weight It is generally in the range of from 1:99 to 99:1. In other embodiments, substantially all of the aforementioned nanoparticles are aggregates. In other embodiments, substantially all of the nanoparticles are individual nanoparticles that are separated.

The above metal nanoparticle can be used as a metal particle sol. Preferably, the metal particle sol is 0.1 to 10% by weight of a metal selected from the group consisting of silver nanoparticles, and a group consisting of ruthenium, rhodium, palladium, osmium, iridium, and platinum (in the case of the metal nanoparticle) The silver content of the particles is contained in the form of a metal and/or at least one metal compound.

In a preferred embodiment, the silver nanoparticle in the metal particle sol is at least 80% of a metal selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, and platinum. Preferably, at least 90%. The metal particle sol does not have metal nanoparticles selected from silver of the metal in the group consisting of ruthenium, rhodium, palladium, iridium, osmium, and platinum, or only a small amount of metal compound nano particles. Preferably, the metal particle sol is selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum, and the content of the metal is less than 20%, particularly preferably less than 10% (in terms of the content of the metal) It is contained in the form of a metal nanoparticle which does not have silver of this metal or a metal compound nanoparticle.

The conductive ink preferably contains the above metal nanoparticles, a binder resin, and a solvent. Also, if necessary, blending and reducing Agents, dispersants, defoamers, and other various additives.

[Examples]

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the examples.

The values of the examples are determined by the following methods.

Haze determination

The coating liquids obtained in Examples 1 to 10, 13, and 14 and Comparative Examples 1 to 4 were applied to a PET film (manufactured by Toray Industries, Inc., Lumilar U-46 100 μm) by bar coating No. 10 at 70 ° C. Allow to dry for 20 minutes.

Further, the coating liquids obtained in the examples 11 and 12 were applied to a PET film (manufactured by Toray Industries, Inc., Lumilar U-46 100 μm) by bar coating No. 10, and dried at 70 ° C for 20 minutes. The dried coating film was irradiated with UV (manufactured by Oxtail Electric Co., Ltd.; cumulative light amount: 615 mJ/cm ² ).

Next, the Haze meter (Haze Gard II manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used for the film formed on the PET to measure the Haze value.

Copper adhesion test

The coating liquids obtained in Examples 1 to 10, 13, and 14 and Comparative Examples 1 to 4 were applied to a copper vapor-deposited surface of a film on which PET was vapor-deposited on PET by bar coating No. 10 at 120 ° C. After drying for 5 minutes, a copper substrate coating was obtained. sample.

Further, the coating liquids obtained in Examples 11 and 12 were applied to a copper vapor-deposited surface of a film on which a copper film was deposited on PET by bar coating No. 10, and dried at 120 ° C for 5 minutes. The dried coating film was irradiated with UV (manufactured by Oxtail Electric Co., Ltd.; cumulative light amount: 615 mJ/cm ² ) to obtain a copper substrate coated sample.

For the film formed on the copper vapor-deposited surface of the vapor-deposited copper film on PET, the number of the mesh which can be maintained in the 100-screen sieve was investigated by the base tape method according to JIS K5600. Among the 100 sieves, 70 or more of which were not peeled off from the coating film were marked as ○, and those who did not peel off the adhesive to 70 were marked as ×.

Evaluation of copper corrosion prevention

The same samples as those of the copper substrate coated sample prepared by the adhesion test with the copper substrate were subjected to the conditions; high temperature and high humidity test (85 ° C, 85% RH, 240 hours). The surface resistance value of the metal was measured using a non-contact surface resistance measuring device (EC-80P manufactured by Napuson Co., Ltd.).

Evaluation of inhibition of migration

The electrode portions of the copper beryllium electrode (L/S = 300 um / 300 um) and the silver samarium electrode (L / S = 300 um / 300 um) were coated in Examples 1 to 10, 13, 14 and Comparative Examples 1 to 4. The cloth liquid was applied by bar coating No. 10, and dried at 120 ° C for 5 minutes to obtain a ruthenium-shaped electrode coating sample.

Further, the coating liquids obtained in Examples 11 and 12 were coated with No. 10, dried at 120 ° C for 5 minutes, and then irradiated with UV on a dried coating film (manufactured by Oxtail Electric Co., Ltd.; cumulative light amount: 615 mJ/cm) ² ), and a sample was coated with a ruthenium-type electrode. Here, the wiring was attached by soldering, and 18.2 MΩ/cm of ultrapure water was dropped by one drop of the drop tube at the application site, and a DC voltage of 5 V was applied. After the application, the time (seconds) at which the current (0.001 mA or more) started to flow was measured. When the current is less than 40 seconds, the current is short-circuited as ×, and when 40 seconds or more and less than 900 seconds are short-circuited, it is denoted as Δ, and even if it has not been short-circuited for 900 seconds or more, it is denoted as ◎.

Synthesis Example 1 Compound having an unsaturated group Synthesis of Compound a~f

Compound a

In a 30 ml eggplant type flask, weighed 0.5 g of 1,2,3-benzotriazole and 10 g of acetone, and stirred at room temperature for 30 minutes to dissolve the 1,2,3-benzotriazole. Propylene oxirane ethyl isocyanate (Karenz AOI, manufactured by Showa Denko Co., Ltd.) was dropped 0.59 g (1 equivalent to 1,2,3-benzotriazole). After stirring at room temperature for 4 hours, 0.1 g of the reaction solution was dropped on a KBr plate, and it was measured by FT-IR (Perkin Elmer precisely Spectrum 100 FT-IR Spectrometer manufactured by Fourier Transform Infrared Spectrophotometer Co., Ltd. Perkin Elmer Japan Co., Ltd.) to confirm that it was not The isocyanate group derived from propylene oxirane ethyl isocyanate remains.

Compound b, compound d, compound f

In the same manner as the compound a, for the nitrogen-containing alloy shown in Table 1. The reaction was carried out in such a manner that the isocyanate monomer became 1 equivalent.

Compound c

In a 30 ml eggplant type flask, weighed 0.5 g of 1,2,3-benzotriazole, 10 g of acetone, and further 0.01 g of dibutyltin dilaurate, and stirred at room temperature for 30 minutes to make 1,2,3-benzene. After the triazole was dissolved, a cooling ring was attached and the mixture was heated to 70 degrees using a water bath. After dropping 1.0 g of 1,1-(bisacryloxymethyl)ethyl isocyanate, the mixture was stirred at 70 °C for 10 hours, and then subjected to FT-IR measurement in the same manner as in the compound a, and it was confirmed that no isocyanate group remained. .

Compound e

The reaction was carried out in the same manner as in the compound a except that the nitrogen-containing compound was reacted in such a manner that the isocyanate monomer was 2 equivalents.

The vinylidene fluoride-based resin to be used in the examples is shown in Table 2.

The acrylic components used in the examples are shown in Table 3.

Examples 1 to 10, 13, and 14 and Comparative Examples 1 to 4

A compound having an unsaturated group, a vinylidene fluoride-based resin, an acrylic component, butyl acetate, and methyl ethyl ketone were mixed to prepare a coating having a solid content concentration of 30% by mass as shown in Table 4 or 5. Liquid (butyl acetate / methyl ethyl ketone = 1 / 1).

Examples 11, 12

Mixing a compound having an unsaturated group, a vinylidene fluoride resin, and C The olefin component, butyl acetate and methyl ethyl ketone were prepared to have a composition having a solid content of 30% by mass as shown in Table 5 (butyl acetate / methyl ethyl ketone = 1 / 1). Then, Irgacure 184 (manufactured by BASF Corporation) was added to the solid content of the obtained coating liquid (the solvent of butyl acetate and methyl ethyl ketone was removed) to prepare a coating liquid.

Example C

In a 250 mL eggplant type flask, 25 parts by mass of 2-ethylhexyl acrylate, 30 parts by mass of n-butyl acrylate, 30 parts by mass of 2-hydroxyethyl acrylate, 10 parts by mass of methyl acrylate, and 5 parts by mass are added. The compound a prepared in Synthesis Example 1 and 150 parts by mass of ethyl acetate and 0.15 parts by mass of azobisisobutyronitrile (AIBN) were used as a polymerization initiator, and stirred at 80 ° C for 6 hours in a nitrogen atmosphere. Ethyl acetate was added to the obtained solution, and the solid content concentration of the polymer was adjusted to 20% by mass. Next, 1 part by mass of Colonate L (manufactured by Nippon Polyethylene Acetate Co., Ltd.) was added as a crosslinking agent and stirred to prepare a coating liquid. The coating liquid contained the compound a in an amount of 4.9% by mass based on the solid content.

The obtained coating liquid was applied by a bar coater on the release agent surface of the release sheet composed of PET (Lintec GS38) to which a naphthenic type release agent was applied, and dried at 80 ° C. After 3 minutes, a laminated sheet composed of a release sheet/following sheet was obtained. Then, on the copper vapor-deposited surface of the film on which the copper film was deposited on the PET having a thickness of 100 μm, the thinned single side of the laminated sheet was bonded to form a peeling sheet/following sheet/copper evaporation layer/PET layer. Laminate.

Example A

The coating liquid obtained in Example 1 was applied by a bar coater on the release agent side of the release sheet composed of PET (Lintec GS38) which was applied with a oxoxane-based release agent on one side. Allow it to dry for 3 minutes while A laminated sheet composed of a release sheet/rust-proof sheet was obtained. Thereafter, a rust-proof thin single side of the laminated sheet was bonded to a copper vapor-deposited surface of a film on which a copper film was deposited on a film having a thickness of 100 μm to prepare a release sheet/rust-proof sheet/copper vapor-deposited layer/PET. 4-layer laminate.

Example B

The coating liquid obtained in Example 11 was coated on one side on a release agent surface of a release sheet composed of PET (Lintec GS38) to which a decane-based release agent was applied, by a bar coater. Allow to dry for 3 minutes at °C. On the coated side of the coating, the release agent surface of the release sheet composed of PET (Lintec GS38) coated with a siloxane-based release agent was bonded to the surface to form a bonding surface, and the cumulative amount of light was irradiated. A UV of 800 mJ/m ² was obtained to obtain a laminated sheet B-1 composed of a release sheet/rust-proof sheet/release sheet. Next, the peeling sheet of one side of B-1 was peeled off, and the commercially available OCA (8146-3 high transparency adhesive transfer tape made by 3M company) was bonded to the rustproof sheet to prepare a release sheet/rustproof sheet/OCA. The three-layer laminate was bonded to the OCA, and a laminate of four layers of a release sheet/rust-proof sheet/OCA/glass was produced. Further, the rust-preventive thin-sided release sheet was peeled off, and the thin-sided single side of the laminated sheet was bonded to the copper-deposited surface of the copper-deposited film on PET having a thickness of 100 μm to prepare a PET/copper deposition layer. / rust-proof sheet / OCA / glass 5 layer laminate.

[Industrial availability]

The novel compound of the present invention can be added to the resin as The paint of the car is used. A coating material containing a novel compound can be formed into a coating film which is excellent in the effect of preventing corrosion of metal and excellent in adhesion to metal.

The composition of the present invention can be used as a coating material for forming a coating film on the surface of a metal, and the obtained coating film is excellent in the effect of preventing corrosion of metal, and is excellent in adhesion to metal and transparency.

Claims (27)

a compound of the formula (1) or (2), In the formula (1), the ring A is a substituted five or six membered nitrogen-containing aromatic heterocyclic ring, the L ¹ is an n1+1 valent linking group, and the R ¹ is a hydrogen atom, a halogen atom or a C _1-6 alkane. Base, n1 is an integer from 1 to 6, Q ¹ is -O- or -NH-, l1 is 0 or 1, and ring B is a substituted aromatic ring. In the formula (2), the ring C is a substituted five or six membered nitrogen-containing aromatic heterocyclic ring, a L ² -based n2+1 valent linking group, an R ² -based hydrogen atom, a halogen atom or a C _1-6 alkane. Base, n2 is an integer from 1 to 6, Q ² is -O- or -NH-, and l2 is 0 or 1. The compound of claim 1, wherein the ring A in the formula (1) is a five-membered nitrogen-containing aromatic heterocyclic ring containing two or three nitrogen atoms. The compound of claim 1 or 2, wherein L ¹ in formula (1) is represented by formula (3), [Chemical 3]-Cm ₁ H2m ₁ +1-n ₁ - (3) in formula (3) M1 is an integer from 1 to 20, and n1 is an integer from 1 to 6. However, when m1 is 1, n1 is an integer from 1 to 3. When m1 is 2, n1 is an integer from 1 to 5. The compound of claim 1, 2 or 3, wherein ring B in formula (1) is via a hydroxyl group, an amine group, a carboxylic acid group, a nitro group, a halogen group, a thiol group, a cyano group, a decyl group, a sulfonic acid group. An aromatic ring substituted with a group, a methylsulfonyl group, an alkyl group, or a substituent represented by the formula (4), In the formula (4), the L ^{3 group} includes a n3+1 valent linking group bonded by -CO-NH-, -CO-O-, -O-CO-NH- or -NH-CO-NH- R ³ is a hydrogen atom, a halogen atom or a C _1-6 alkyl group, and n 3 is an integer of 1 to 6. A compound according to claim 1, 2, 3 or 4, wherein the ring B in the formula (1) is a benzene ring. A compound according to claim 1, 2, 3, 4 or 5, wherein the ring C in the formula (2) is a five-membered nitrogen-containing aromatic heterocyclic ring containing two or three nitrogen atoms. A compound according to claim 1, 2, 3, 4, 5 or 6, wherein the L ² in the formula (2) is represented by the formula (5), [Chem. 5]-Cm ₂ H2m ₂ + 1-n ₂ - (5) In the formula (5), m2 is an integer from 1 to 20, and n2 is an integer from 1 to 6. However, when m2 is 1, n2 is an integer from 1 to 3, and when m2 is 2, n2 is 1 An integer of ~5. A composition comprising: a compound of claim 1, 2, 3, 4, 5, 6 or 7, and an optical adhesive. A composition comprising: a nitrogen-containing aromatic heterocyclic compound containing a polymerizable functional group, a vinylidene fluoride-based resin (B), and a group selected from the group consisting of an acrylic monomer and an acrylic polymer. At least one acrylic component (A). The composition of claim 9, wherein the nitrogen-containing aromatic heterocyclic compound containing a polymerizable functional group is a compound represented by the formula (14) or the formula (15), In the formula (14), the ring A is a substituted five or six membered nitrogen-containing aromatic heterocyclic ring, and the R ¹ is a hydrogen atom, a halogen atom or a C _1-6 alkyl group, and the n1 is an integer of 1 to 6, L ^{The 4} series includes a n1+1 valent linking group represented by -CO-NH-, -CO-O-, -O-CO-NH- or -NH-CO-NH-, and the ring B system may be substituted Aromatic ring, In the formula (15), the ring C is a substituted five or six membered nitrogen-containing aromatic heterocyclic ring, an R ² -based hydrogen atom, a halogen atom or a C _1-6 alkyl group, and the n2 is an integer of 1 to 6, L ^{The 5} series includes a n1+1-valent linking group bonded by -CO-NH-, -CO-O-, -O-CO-NH- or -NH-CO-NH-. The composition of claim 10, wherein the ring A in the formula (14) is a five-membered nitrogen-containing aromatic heterocyclic ring containing two or three nitrogen atoms. The composition of claim 10 or 11, wherein L ⁴ in the formula (14) is represented by the formula (16), In the formula (16), Q ¹ is -O- or -NH-, l1 is 0 or 1, m1 is an integer from 1 to 20, and n1 is an integer from 1 to 6, but when m1 is 1, n1 is 1 An integer of ~3, when m1 is 2, n1 is an integer from 1 to 5. The composition of claim 10, 11 or 12, wherein ring B in formula (14) is via a hydroxyl group, an amine group, a carboxylic acid group, a nitro group, a halogen group, a thiol group, a cyano group, a decyl group, a sulfonate group. An aromatic ring substituted with an acid group, a methanesulfonyl group, an alkyl group, or a substituent represented by the formula (17), In the formula (17), the L ^{6 group} includes a n3+1 valent linking group bonded by -CO-NH-, -CO-O-, -O-CO-NH- or -NH-CO-NH- R ³ is a hydrogen atom, a halogen atom or a C _1-6 alkyl group, and n 3 is an integer of 1 to 6. The composition of claim 10, 11, 12 or 13, wherein the ring B in the formula (14) is a benzene ring. The composition of claim 10, 11, 12, 13 or 14, wherein ring C in formula (15) is a five-membered nitrogen-containing aromatic heterocyclic ring containing two or three nitrogen atoms. The composition of claim 10, 11, 12, 13, 14, or 15, wherein L ⁵ in the formula (15) is represented by the formula (18), In the formula (18), Q ² is -O- or -NH-, l2 is 0 or 1, m2 is an integer from 1 to 20, and n2 is an integer from 1 to 6, but when m2 is 1, n2 is 1 An integer of ~3, when m2 is 2, n2 is an integer from 1 to 5. The composition of claim 9, 10, 11, 12, 13, 14, 15, or 16, wherein the content of the nitrogen-containing aromatic heterocyclic compound containing a polymerizable functional group is 0.1 to 30% by mass of the composition. The composition of claim 9, 10, 11, 12, 13, 14, 15, 16 or 17, wherein the acrylic component (A) is selected from the group consisting of (meth) acrylate monomers, polyfunctional acrylic monomers, At least one of the group consisting of an unsaturated carboxylic acid monomer, a homopolymer of (meth) acrylate, and a copolymer of (meth) acrylate. The composition of claim 9, 10, 11, 12, 13, 14, 15, 16 or 17, wherein the acrylic component (A) is selected from the group consisting of (meth) acrylate monomers and polyfunctional (meth) acrylates Copolymer of ester monomer, homopolymer of (meth) acrylate, (meth) acrylate and unsaturated At least one of the group of copolymers of carboxylic acids. The composition of claim 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19, wherein the vinylidene fluoride resin (B) is vinylidene fluoride and is selected from the group consisting of tetrafluoroethylene a copolymer of at least one of a group of hexafluoropropylene, chlorotrifluoroethylene, and perfluoro(alkyl vinyl ether). The composition of claim 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, wherein the vinylidene fluoride resin (B) is vinylidene fluoride and tetrafluoroethylene Copolymer. A composition of claim 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or 21 which is a coating. A composition of claim 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 or 22 which is a rust preventive coating. A coated article, comprising: a substrate, and a request item 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, formed on the substrate A coating film formed by the composition of 21, 22 or 23. The coated article of claim 24, wherein the substrate is formed of a metal. A sheet characterized by the composition of claim 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 or 23. A laminated sheet, characterized by comprising: a release sheet, and a request item 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, formed on the release sheet, A sheet formed by the composition of 21, 22 or 23.