Non-silanol, non-ester surface treatment composition liquid, and method for producing surface treatment substances, metal coating resins, resin laminates, and cured coating substances.

Abstract

The objective is to provide a surface treatment liquid used to ensure adhesion between two substances through interfacial molecular bonding, and to provide a composition liquid capable of forming a bond with excellent moisture resistance, or a bond with excellent moisture and heat resistance, and to provide a method for manufacturing metal-coated resins or resin laminates by plating or bonding using the composition liquid. [Solution] The composition liquid comprises a polymer, a thermopolymerizable compound, and an azide compound, wherein the polymer comprises a first repeating unit having a primary or secondary amino group, a second repeating unit having an allyl group, and a third repeating unit having a hydrophobic functional group other than an allyl group. Preferably, the polymer, the thermopolymerizable compound, and the azide compound do not contain ester bonds, and preferably, the polymer and the azide compound do not contain amide bonds. The composition liquid may also contain an organosulfur compound. The polymer may also comprise a polyether block.

Description

[Technical Field]

[0001] The present invention relates to a surface treatment composition liquid used by applying it to a substance for the purpose of improving adhesion, and to a method for producing a surface treatment substance, a metal coating resin, a resin laminate, and a cured coating substance using the composition liquid. [Background technology]

[0002] Compounds having two or more functional groups can form chemical bonds by utilizing the properties of each functional group, making them useful as interfacial molecular bonding (IMB) agents for bonding two substances at their interface. Because interfacial molecular bonding agents bond two substances chemically, the bond is strong and does not necessarily require high temperatures for bond formation. Interfacial molecular bonding allows two substances to be bonded at a flat interface without relying on anchoring effects due to surface roughening. The flatness of the interface is useful in reducing transmission loss in the high-frequency range in electrical and electronic applications. Furthermore, because only a small amount of interfacial molecular bonding agent molecules are present at the interface, problems of bond weakening due to volatile gases are less likely to occur, which is an environmental advantage.

[0003] Interfacial molecular bonding technology can be used in many applications for bonding two materials at an interface. In particular, it has broad applications in the electrical and electronic fields. Examples include applications in the manufacture of electrical and electronic devices such as printed circuit boards, lightweight spacers, probe sockets (test fixtures) for semiconductor testing equipment, and resin core metal foils for battery electrodes. Other applications include packaging films and decorative plating.

[0004] Patent Document 1 discloses an invention of an interfacial molecular binder having a silanol group and an amino group in one molecule. When two substances are joined via this interfacial molecular binder, the silanol group undergoes dehydration condensation with a hydroxyl group present on the surface of at least one of the substances, for example, to form a (-Si-OM) type chemical bond. Here, M represents an atom such as C present on the surface of at least one of the substances. The amino group also undergoes dehydration condensation with a carboxyl group present on the surface of at least one of the substances, for example, to form a chemical bond (amide bond).

[0005] Conventional interfacial molecular binders, as seen in Patent Document 1, for example, often contain ester bonds, structures formed by dehydration condensation of silanol groups, or amide bonds within the bonding layer that connects two substances at the interface. In interfacial molecular bonding, the absolute amount of interfacial molecular binder present at the interface is far less than in ordinary adhesives. Therefore, these ester bonds, structures formed by dehydration condensation of silanol groups, and amide bonds decompose relatively easily through hydrolysis, solvolysis, or heating. Consequently, the bonding of two substances using conventional interfacial molecular binders lacked sufficient moisture resistance and heat resistance. The object of the present invention is to provide a novel interfacial molecular binder capable of forming a bond with excellent moisture resistance, or a bond with excellent moisture resistance and heat resistance.

[0006] Patent Document 2 discloses an invention of a photosensitive composition containing a nitrogen atom-containing resin, another resin, and a thermal crosslinking agent, wherein the nitrogen atom-containing resin has a predetermined functional group. This photosensitive composition is used for the purpose of forming a solder resist pattern with a thickness of about 30 μm on the surface of a substrate such as a printed circuit board, and is not used for the purpose of interposing a small amount as an interfacial molecular binder at the bonding interface of two substances to improve adhesion. Furthermore, the cured product of this photosensitive composition contains bonds such as ester bonds and amide bonds that decompose relatively easily by hydrolysis, solvolysis, or heating.

[0007] Patent Document 3 discloses an invention relating to a resin composition used as an adhesive, comprising a curing agent containing a novel thiol compound, an ene compound having a carbon-carbon double bond, and amines as curing accelerators. Furthermore, Japanese Patent Publication No. 2023-126883 and Japanese Patent Publication No. 2023-166744 each disclose similar inventions relating to other novel thiol compounds. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Re-tabled publication No. 2013-186941 [Patent Document 2] Japanese Patent Publication No. 2012-073598 [Patent Document 3] Japanese Patent Publication No. 2022-180364 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] The object of the present invention is, firstly, to provide a composition liquid for application to a substance for the purpose of ensuring adhesion in bonding, plating, etc., which can form a bond with excellent moisture resistance, or a bond with excellent moisture resistance and heat resistance; or secondly, to provide a method for producing a surface treatment substance, a method for producing a metal coating resin by bonding or plating, a method for producing a resin laminate, or a method for producing a cured coating substance using the above composition liquid. The above composition liquid contains a compound or a combination of multiple compounds such that, after application, a chemical reaction related to interfacial molecular bonding proceeds by heating and / or irradiation with light such as ultraviolet light. [Means for solving the problem]

[0010] This invention was made to solve the above problems, The first embodiment of the present invention is a composition liquid for coating and using on at least one of two substances for the purpose of improving the adhesion between the two substances, comprising a polymer, a thermally polymerizable compound, and an azide compound. The polymer comprises a first repeating unit having a primary amino group or a secondary amino group, a second repeating unit having an allyl group, and a third repeating unit having a hydrophobic functional group other than an allyl group.

[0011] The second embodiment of the present invention is the composition liquid according to the first embodiment, wherein the total concentration of the polymer, the thermally polymerizable compound, and the azide compound in the composition liquid is 0.02% by mass or more and 4% by mass or less.

[0012] The third embodiment of the present invention is the composition liquid according to the second embodiment, wherein the polymer, the thermally polymerizable compound, and the azide compound do not contain an ester bond.

[0013] The fourth embodiment of the present invention is the composition liquid according to the third embodiment, wherein the polymer and the azide compound further do not contain an amide bond.

[0014] The fifth embodiment of the present invention is the composition liquid according to the third embodiment, wherein the second repeating unit has an allylphenol group.

[0015] The sixth embodiment of the present invention is the composition liquid according to the third embodiment, wherein the polymer further comprises a polyether block formed by continuously linking 3 or more and 35 or less repeating units composed of C2 - C4 alkyleneoxy groups.

[0016] The seventh embodiment of the present invention is the composition liquid according to the sixth embodiment, wherein the polymer has two allylbenzoxazine rings at the terminals, and in the polymer, one of the allylbenzoxazine rings is opposite to the other allylbenzoxazine ring with respect to the polyether block. It is a composition liquid located on the opposite side.

[0017] The eighth embodiment of the present invention is a compositional solution in which, in the third embodiment, the hydrophobic functional group other than the allyl group is a C4-C14 alkyl group, a (hetero)aryl group, an alkyl(hetero)aryl group, or a (hetero)arylalkyl group.

[0018] The ninth embodiment of the present invention is a compositional liquid in which, in the third embodiment, the thermopolymerizable compound is an acrylamide derivative having two or more polymerizable double bonds.

[0019] A tenth embodiment of the present invention is a compositional liquid in which the thermopolymerizable compound is a maleimide compound, in the third embodiment.

[0020] An eleventh embodiment of the present invention is a compositional liquid in which, in the third embodiment, the thermopolymerizable compound is an allyl monomer having two or more allyl groups or allyloxy groups directly bonded to a (hetero)aryl group or hydrocarbon group.

[0021] A twelfth embodiment of the present invention is a compositional liquid in which, in the third embodiment, an organosulfur compound further comprises an organosulfur compound that does not have an ester bond.

[0022] A thirteenth embodiment of the present invention is a compositional solution in which, in the twelfth embodiment, the organosulfur compound is a compound having two or more thiol groups or a compound having a disulfide group.

[0023] A fourteenth embodiment of the present invention is a compositional solution in which, in the third embodiment, the azide compound is a compound having two or more azide groups directly bonded to an aromatic ring.

[0024] A fifteenth embodiment of the present invention is a compositional liquid in which the polymer is a compound represented by the following formula (12) in the third embodiment. (wherein n, m, and l are integers of 1 or more.) [ka]

[0025] A sixteenth embodiment of the present invention is a compositional liquid in which the polymer is a compound represented by the following formula (13) in the fourth embodiment. (wherein n, m, and l are integers of 1 or more.) [ka]

[0026] The seventeenth embodiment of the present invention is a compositional liquid in which the polymer is a compound represented by the following formula (14) in the fifth embodiment. (wherein n, m, and l are integers of 1 or more.) [ka]

[0027] The eighteenth embodiment of the present invention is a method for producing a surface-treated substance, comprising the step of applying a compositional liquid according to any of the first to seventeenth embodiments (coating step) to the surface of a substance.

[0028] A 19th embodiment of the present invention is a method for manufacturing a metal-coated resin, comprising the steps of: applying a compositional liquid according to any of the first to seventeenth embodiments to the surface of a resin; heating the surface or irradiating the surface with ultraviolet light; and then forming a metal plating layer on the surface by wet plating.

[0029] A 20th embodiment of the present invention is a method for producing a metal-coated resin, comprising the steps of: applying a compositional liquid according to any of the first to 17 embodiments to the surface of at least one of a resin and a metal foil; heating the surface or irradiating the surface with ultraviolet light; and then laminating the resin and metal foil via the surface and pressing them together to integrate them.

[0030] A 21st embodiment of the present invention is a method for manufacturing a resin laminate, comprising the steps of: applying a composition liquid according to any of the first to 17 embodiments to the surface of a first resin; heating the surface or irradiating the surface with ultraviolet light; and then bringing the first resin and the second resin into contact via the surface and pressing them together to integrate them.

[0031] A 22nd embodiment of the present invention is a method for producing a cured coating material, comprising the steps of: applying a composition liquid according to any of the 1st to 17th embodiments to the surface of a material; heating the surface or irradiating the surface with ultraviolet light; then applying a curing liquid onto the surface; and curing the curing liquid to form a cured material that covers the surface. [Effects of the Invention]

[0032] According to one embodiment of the present invention, a compositional liquid for application to a substance for the purpose of ensuring adhesion in bonding, plating, etc., can be provided, which is capable of forming a bond with excellent moisture resistance, or a bond with excellent moisture resistance and heat resistance. The above compositional liquid contains a compound or a combination of multiple compounds such that, after application, a chemical reaction related to interfacial molecular bonding proceeds by heating and / or irradiation with light such as ultraviolet light. According to another embodiment of the present invention, a method for producing a surface treatment substance, a method for producing a metal coating resin by bonding or plating, a method for producing a resin laminate, or a method for producing a cured coating substance can be provided using the above compositional liquid. [Brief explanation of the drawing]

[0033] [Figure 1] Figure 1 is a flow chart showing a method for manufacturing a surface treatment material. [Figure 2-1] Figure 2-1 is a conceptual diagram of the first half of the wet plating process using this composition solution. [Figure 2-2] Figure 2-2 is a continuation of Figure 2-1 and is a conceptual diagram of the latter half of the wet plating process using this composition solution. [Modes for carrying out the invention]

[0034] Next, embodiments of the present invention will be described in detail. It should be noted that the present invention is not limited to the embodiments and examples described below, but should be understood to include various modifications and variations implemented within the scope of the technical idea of ​​the present invention.

[0035] <Composition liquid> According to a first embodiment of the present invention, a compositional liquid for application to at least one of two substances for the purpose of improving the adhesion between the two substances is provided, comprising a polymer, a thermopolymerizable compound, and an azide compound, wherein the polymer comprises a first repeating unit having a primary amino group or a secondary amino group, a second repeating unit having an allyl group, and a third repeating unit having a hydrophobic functional group other than an allyl group.

[0036] (Purpose of improving adhesion) "Applying to at least one of two substances for the purpose of improving the adhesion between the two substances" means improving adhesion by interposing a compound derived from the composition liquid at the interface between two substances. For example, the composition liquid according to this embodiment is applied to a resin, metal, or other inorganic material for the purpose of manufacturing a resin laminate in which two or more resins are integrally bonded, or for the purpose of forming a metal coating bonded to the surface of a resin by plating or lamination, or for the purpose of forming a coating consisting of a cured resin varnish bonded to a resin or an inorganic material such as a metal, glass, or ceramic, or for the purpose of forming a coating consisting of a cured conductive paste bonded to a resin or an inorganic material such as a metal, glass, or ceramic.

[0037] (Application) Here, "coating" is not limited to methods such as brush application, but generally refers to "adhering" or "having a liquid in contact with" the surface of a substance. Preferably, "coating" includes a step of adhering or contacting the liquid with the surface of the substance, and then removing the solvent of the liquid by drying or other means, leaving the solute on the surface.

[0038] <polymer> (A first repeating unit having a primary or secondary amino group) This composition solution contains a polymer, which comprises a first repeating unit having a primary amino group (-NH2) or a secondary amino group (-NH-). After the application and activation steps of this composition solution, the polymer forms bonds with the surface of the substance and / or the thermopolymerizable compound and / or the azide compound through chemical reactions, contributing to the formation of interfacial molecular bonds. Furthermore, the primary or secondary amino group increases intermolecular forces and improves adhesion. The first repeating unit is, for example, the repeating unit shown in equation (1) or equation (2) below.

[0039] [ka]

[0040] In formulas (1) and (2), A is an alkylene group of C1-C2, Z - * represents any anion in the composition solution, and * represents an atom in the polymer bonded to the repeating unit. Another example of the first repeating unit is the repeating unit shown in equation (3) or equation (4) below.

[0041] [ka]

[0042] In equations (3) and (4), A 1 C1-C2 alkylene group, Y 1 This represents N or C. L 1 L is a linear alkylene group of C1 to C14, or a linear alkylene group of C1 to C14 containing one or more ether bonds (-O-) or thioether bonds (-S-) between carbon atoms. 1 R may or may not have one or more hydrogen atoms bonded to the carbon atom substituted with hydroxyl groups. 1 is H, a C1-C6 alkyl group, or an aryl C1-C6 alkyl group. The aryl group in the aryl C1-C6 alkyl group is, for example, a phenyl group or a benzyl group. -represents an arbitrary anion in the composition liquid and is not included in the polymer. * represents an atom in the polymer bonded to the repeating unit.

[0043] The first repeating unit is preferably a repeating unit contained in one or more polymers selected from the group consisting of poly(lower alkyleneimine) ([C m H 2m NH] n , m is an integer of 1 or more and 4 or less, n is an integer of 2 or more), polyvinylamine, and polyallylamine, and more preferably a repeating unit contained in one or more polymers selected from the group consisting of polyethyleneimine, polyvinylamine, and polyallylamine. However, the first repeating unit is not limited to these repeating units.

[0044] (Second repeating unit) The polymer further comprises a second repeating unit having an allyl group. The allyl group is a functional group containing a polymerizable double bond, and its reactivity is large enough to ensure strong adhesion and is not so large as to impair storage stability, so it is suitable for a one-component interfacial molecular binder such as this composition liquid. Since the polymer has the second repeating unit, this composition liquid can improve the adhesion in bonding or plating, which is carried out after the application and activation steps of this composition liquid, by bonding the adherent substances to each other by chemical bonds. Also, since the allyl group is a hydrophobic functional group, the entire molecule of the polymer is hydrophobized by the polymer having the second repeating unit, and the moisture resistance of the bond is improved. The second repeating unit is, for example, a repeating unit represented by the following formula (5) or formula (6).

[0045]

Chemical formula

[0046] In formula (5) and formula (6), A 2 is a C1-C2 alkylene group, Y 2 represents N or C. L 2 and J2 Each of these is independently a linear alkylene group of C1 to C14, or a linear alkylene group of C1 to C14 containing one or more ether bonds (-O-) or thioether bonds (-S-) between carbon atoms. 2 and J 2 Each of these elements may have one or more hydrogen atoms bonded to the carbon atom substituted with a hydroxyl group, or it may not. - * represents any anion in the composition solution and is not included in the polymer. * represents an atom in the polymer bonded to the repeating unit.

[0047] (Third repeating unit) The polymer further comprises a third repeating unit having a hydrophobic functional group other than an allyl group. The presence of the third repeating unit makes the entire polymer molecule hydrophobic, improving the moisture resistance of the bond. The hydrophobic functional groups other than the allyl group are, for example, C4-C14 branched alkyl groups such as ethylhexyl groups. The third repeating unit is, for example, the repeating unit shown in formula (7) or formula (8) below.

[0048] [ka]

[0049] In equations (7) and (8), A 3 C1-C2 alkylene group, Y 3 L represents N or C. 3 and J 3 Each of these is independently a linear alkylene group of C1 to C14, or a linear alkylene group of C1 to C14 containing one or more ether bonds (-O-) or thioether bonds (-S-) between carbon atoms. 3 and J 3Each of these groups may independently have one or more hydrogen atoms bonded to the carbon atom substituted with a hydroxyl group, or may not be substituted. E is a hydrophobic functional group, C4-C14, and is a substituted or unsubstituted alkyl group, (hetero)aryl group, alkyl(hetero)aryl group, or (hetero)arylalkyl group. Z - * represents any anion in the composition solution and is not included in the polymer. * represents an atom in the polymer bonded to the repeating unit. In this specification, "(hetero)aryl group" means "aryl group or heteroaryl group," "alkyl(hetero)aryl group" means "alkylaryl group or alkylheteroaryl group," and "(hetero)arylalkyl group" means "arylalkyl group or heteroarylalkyl group." Generally, in this specification, A, B, and C are any words or empty letters, and "A(B)C" means "AC or ABC." In this specification, "aryl group" is exemplified by a 6- to 10-membered aromatic carbocyclic group. Specifically, this includes monocyclic or bicyclic aryl groups, such as phenyl and naphthyl groups. Phenyl groups are particularly preferred. Examples of "heteroaryl groups" include 5-10 membered aromatic heterocyclic groups containing 1-4 heteroatoms from sulfur, oxygen, or nitrogen. Monocyclic or bicyclic heteroaryl groups are preferred, and even more preferred are 5-10 membered monocyclic or bicyclic heteroaryl groups containing 1-2 heteroatoms from sulfur, oxygen, or nitrogen. In addition, 5-10 membered monocyclic or bicyclic heteroaryl groups containing at least one nitrogen atom and one further heteroatom selected from sulfur, oxygen, or nitrogen are also preferred. Specific examples include pyrrolyl group, furanyl group, thienyl group, imidazolyl group, pyrazolyl group, oxazolyl group, thiazolyl group, triazolyl group, tetrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridadinyl group, thiadinyl group, triazinyl group, indolyl group, isoindolyl group, indazolyl group, benzimidazolyl group, benzothiazolyl group, benzofuranyl group, quinolyl group, isoquinolyl group, imidazopyridyl group, and benzopyranyl group. E is, for example, an ethylhexyl group, a butyl group, a dodecyl group, a phenyl group, a diphenyl group, a 4-tert-butylphenyl group, a phthaloimide group, a substituted phenyl group, or a substituted heteroaryl group. The substituted phenyl group or substituted heteroaryl group is, for example, a functional group shown in the following formula (A1) or formula (A2).

[0050] [ka]

[0051] In formula (A1) or formula (A2), R1, R2, R3, and R4 are each independently a hydrogen group, a methyl group, a butyl group, an ethylhexyl group, a phenyl group, a vinyl group, an allyl group, a methoxy group, an N,N-dimethylamino group, or a sulfide group. From the viewpoint of ensuring adhesion of the bond, it is preferable that at least one of R1, R2, R3, and R4 is an allyl group, and it is more preferable that R1 is an allyl group. If the hydrophobic functional group E includes a (hetero)aryl group, this (hetero)aryl group also has the effect of increasing intermolecular forces and improving adhesion. Furthermore, if R1, R2, R3, and R4 are all hydrogen groups (H) or allyl groups, the repeating units represented by formulas (7) and (8) are classified as second repeating units.

[0052] (Further repeating units) The polymer may further include repeating units represented by the following formula (9) or formula (10).

[0053] [ka]

[0054] In equations (9) and (10), A 4 C1-C2 alkylene group, Y 4 L represents N or C. 4This refers to a linear alkylene group of C1 to C14, or a linear alkylene group of C1 to C14 containing one or more ether bonds (-O-) or thioether bonds (-S-) between carbon atoms. 4 Each of these elements may have one or more hydrogen atoms bonded to the carbon atom substituted with a hydroxyl group, or it may not. - * represents any anion in the composition solution and is not included in the polymer. * represents an atom in the polymer bonded to the repeating unit. If the polymer contains the above-mentioned further repeating units, the polymer will have a structure with many branched chains, improving the adhesion of the bond.

[0055] <Thermopolymerizable compounds> The compositional liquid according to this embodiment of the present invention further comprises a thermopolymerizable compound. The thermopolymerizable compound is a compound having a thermopolymerizable group, such as an acrylamide derivative, a maleimide compound, or an allyl compound. This composition solution contains a thermopolymerizable compound, and by interposing the components of this composition solution at the bonding surface of two substances and heating, an addition reaction can be induced, or a polymerization reaction can be initiated and carried out, thereby joining the two substances by interfacial molecular bonding. Here, the addition reaction or polymerization reaction can occur between the thermopolymerizable compound and the polymer, between thermopolymerizable compounds, between the thermopolymerizable compound and the azide compound, or between the thermopolymerizable compound, the polymer, or the azide compound and the adherend. The thermopolymerizable compound may also simply play the role of initiating the polymerization reaction. In that case, the polymerization reaction, once initiated, may proceed between two substances arbitrarily selected from the group consisting of the polymer, thermopolymerizable compound, azide compound, and adherend, with overlapping reactions permitted.

[0056] <Azide compounds> The compositional liquid according to this embodiment of the present invention further contains an azide compound. The azide compound is a compound having an azide group, such as diazidobenzene or 2,6-di(p-azidobenzal)-4-methylcyclohexanone. The azide group decomposes upon heating or irradiation with light such as ultraviolet light, releasing nitrogen molecules (N2) and generating nitrene. Since this compositional liquid contains an azide compound, by applying the components of this compositional liquid to the surface of at least one of the two substances to be joined and then heating or irradiating with light, nitrene is generated. Radical transfer occurs from the nitrene to molecules interposed on the surface, and a radical addition reaction or radical polymerization reaction proceeds with respect to the two substances, thereby joining the two substances by interfacial molecular bonding. Here, radical transfer from nitrene generated by external field stimuli such as heat and light can occur between the azide compound and the polymer, between azide compounds, between the azide compound and the thermopolymerizable compound, and between the azide compound and the adherend. Furthermore, an azide compound in a state where the radical is delocalized may simply play a role in initiating the polymerization reaction. In that case, the polymerization reaction, once initiated, may proceed between two arbitrarily selected components from the group consisting of the polymer, the thermopolymerizable compound, the azide compound, and the adherend, with some overlap allowed.

[0057] <Solvent of the compositional solution> The compositional solution according to the present invention (hereinafter referred to as "this compositional solution") contains a solvent. The solvent is not particularly limited, as long as it can dissolve the above-mentioned polymer, thermopolymerizable compound, and azide compound. For example, alcohols such as methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, cellosorb, carbitol, propylene glycol monomethyl ether, and 3-methoxy-3-methyl-1-butanol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, octane, decane, dodecane, and octadecane; esters such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, methyl propionate, and methyl phthalate; ethers such as tetrahydrofuran (THF), ethyl butyl ether, anisole, and propylene glycol monomethyl ether acetate (PGMEA); amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; and water can be used. Among these, alcohols, ethers, and water are preferred. The solvent may be used alone, or a mixture of two or more solvents may be used.

[0058] <pH of the compositional solution> The pH of this composition solution at 25°C is preferably 11.0 or less, more preferably 10.0 or less, and even more preferably 9.0 or less. Furthermore, the pH is preferably 7.0 or higher, more preferably 7.5 or higher, and even more preferably 8.0 or higher. By satisfying the above conditions for the pH of this composition solution, the chemical stability of the composition solution in an atmospheric environment is ensured, and the formation of interfacial molecular bonds after application is promoted. In this specification, the pH of the composition solution refers to the value measured at 25°C using pH test paper (UNIVERSAL test paper, manufactured by Advantec Toyo Co., Ltd.), and the measurement error is not considered. The range is approximately ±0.5.

[0059] <Concentration of each component> According to a second embodiment of the present invention, in the first embodiment, a compositional liquid can be provided in which the total concentration of the polymer, the thermopolymerizable compound, and the azide compound in the compositional liquid is 0.02% by mass or more and 4% by mass or less. From the viewpoint of ensuring adhesion, the total concentration of the polymer, the thermopolymerizable compound, and the azide compound in the composition liquid is preferably 0.02% by mass or more, more preferably 0.04% by mass or more, even more preferably 0.1% by mass or more, and especially preferably 0.2% by mass or more. Furthermore, from the viewpoint of ease of application and storage stability, the total concentration of the polymer, the thermopolymerizable compound, and the azide compound in the composition liquid is preferably 4% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and especially preferably 1.5% by mass or less. Furthermore, from the viewpoint of ensuring adhesion, the ratio D1 / D2 of the concentration D1 of the polymer in the composition liquid to the total concentration D2 of the polymer, the thermopolymerizable compound, and the azide compound in the composition liquid is preferably 0.2 or more and 0.9 or less, more preferably 0.3 or more and 0.8 or less, and even more preferably 0.4 or more and 0.7 or less.

[0060] <Non-ester> According to a third embodiment of the present invention, in the second embodiment, the polymer, the thermopolymerizable compound, and the azide compound can provide a compositional solution that does not contain ester bonds. In conventional interfacial molecular binders, if the composition liquid contains compounds with ester bonds, ester bonds will be present in the bonding layer formed by joining two substances at the interface. In interfacial molecular bonding, the absolute amount of interfacial molecular binder present at the interface is far less than in ordinary adhesives, so these ester bonds decompose relatively easily through hydrolysis or solvolysis. Therefore, the bonding of two substances using conventional interfacial molecular binders did not have sufficient moisture resistance. In the composition liquid according to this embodiment, the polymer, the thermopolymerizable compound, and the azide compound do not contain ester bonds, so by using this composition liquid, it is possible to form an interfacial molecular bond with excellent moisture resistance.

[0061] <Non-amide> According to a fourth embodiment of the present invention, in the third embodiment, the polymer and the azide compound can further provide a compositional solution that does not contain amide bonds. If the composition liquid contains compounds with amide bonds, as in conventional interfacial molecular binders, then amide bonds will be present in the bonding layer formed by joining two substances at the interface. In interfacial molecular bonding, the absolute amount of interfacial molecular binder present at the interface is far less than in ordinary adhesives. Therefore, although these amide bonds are not as easily decomposed as ester bonds, they will decompose by hydrolysis or solvolysis under harsh conditions such as acids, alkalis, and heat. Consequently, the bonding of two substances using conventional interfacial molecular binders did not have sufficient moisture resistance or heat resistance under harsh conditions. In the composition liquid according to this embodiment, the polymer and the azide compound do not contain amide bonds. Therefore, by using this composition liquid, it is possible to form an interfacial molecular bond with excellent moisture resistance, or an interfacial molecular bond with excellent moisture resistance and heat resistance.

[0062] <Non-silanol> According to one embodiment of the present invention, in the third embodiment, a compositional solution can be provided in which each component of the compositional solution, such as the polymer, the thermopolymerizable compound, and the azide compound, does not contain any silanol groups or silanol-producing groups. Here, a silanol-producing group is a group that generates a silanol group by hydrolysis or solvolysis, such as an alkoxysilyl group or a silyl halogenated group. Unlike conventional silane-containing interfacial molecular binders, the components of the composition solution are silanol groups or silanol When a compound containing a silanol-producing group is present, the bonding layer formed by the dehydration condensation of OH groups and silanol groups is included within the bonding layer between the two substances at the interface. In interfacial molecular bonding, the absolute amount of interfacial molecular binder present at the interface is far less than in ordinary adhesives, so the bonds formed by this dehydration condensation are relatively easily decomposed by hydrolysis or solvolysis. Therefore, conventional bonding of two substances using silane-containing interfacial molecular binders did not have sufficient moisture resistance. In the compositional solution according to this embodiment, each component of the compositional solution, such as the polymer, the thermopolymerizable compound, and the azide compound, does not contain silanol groups or silanol-producing groups, so by using this compositional solution, it is possible to form interfacial molecular bonds with excellent moisture resistance.

[0063] (allylphenol group) According to a fifth embodiment of the present invention, in the third embodiment, the second repeating unit can provide a compositional solution having an allylphenol group. Since the allylphenol group is a hydrophobic functional group, the presence of an allylphenol group in the second repeating unit increases the overall hydrophobicity of the polymer molecule, thereby improving the moisture resistance of the bond in the composition solution of this embodiment. Furthermore, because the allylphenol group contains a benzene ring with high electron density and a phenol group, which is a hydrogen-bonding functional group, the intermolecular forces between the adherend and the interfacial molecular bonding layer increase, improving the adhesion of the bond, especially the adhesion to metals.

[0064] (Polyether block) According to the sixth embodiment of the present invention, in the third embodiment, the polymer can further provide a compositional liquid comprising a polyether block in which 3 to 35 repeating units, each consisting of C2 to C4 alkylene oxy groups, are continuously linked together. The repeating units constituting the polyether block are, for example, the repeating units shown in the following equation (11).

[0065] [ka]

[0066] Here, A 5 * represents a C2-C4 alkylene group, and * represents an atom in the polymer bonded to that repeating unit. A polyether block, formed by the continuous linkage of multiple C2-C4 alkylene oxy groups, has a stable structure that is resistant to hydrolysis, solvolysis, and thermal decomposition. In this embodiment of the composition, since the polymer has the polyether block, it can form interfacial molecular bonds with excellent moisture resistance, or interfacial molecular bonds with excellent moisture and heat resistance. From the viewpoint of ensuring the moisture resistance of the interfacial molecular bonds in the composition liquid of this embodiment, the number of repeating units consisting of C2-C4 alkylene oxy groups contained in the polyether block is preferably 3 or more, more preferably 6 or more, and even more preferably 9 or more. On the other hand, if the number of repeating units is too large, the chain of the polyether block becomes long, and the molecular motion of the chain becomes too vigorous at high temperatures, impairing the adhesion of the bond. From the viewpoint of ensuring the heat resistance of the interfacial molecular bonds in the composition liquid of this embodiment, the number of repeating units is preferably 35 or less, more preferably 25 or less, and even more preferably 15 or less.

[0067] (A configuration in which allylbenzoxazine rings are provided on both sides of the polyether block) According to the seventh embodiment of the present invention, in the sixth embodiment, the polymer has two allylbenzoxazine rings at its terminals, and in the polymer, one of the allylbenzoxazine rings The ring can provide a compositional solution that is located opposite each other with respect to the polyether block, along with the other allylbenzoxazine ring. The allylbenzoxazine ring has a hydrophobic and polymerizable structure, improving the moisture resistance and adhesion of the bond in the compositional solution of this embodiment. Furthermore, the allylbenzoxazine ring improves the adhesion of the bond in the compositional solution of this embodiment not only through the addition reaction of the allyl group, but also through the ring-opening addition reaction of the benzoxazine ring. Since the two allylbenzoxazine rings located opposite each other with respect to the polyether block are bonded to the adherend, the polymer, the thermopolymerizable compound, or the azide compound by the above addition reaction, the polyether block has both ends of its chain fixed directly or indirectly, restricting the molecular motion of the chain at high temperatures and improving the heat resistance of the bond in the compositional solution of this embodiment.

[0068] (Hydrophobic functional group) According to the eighth embodiment of the present invention, in the third embodiment, a compositional solution can be provided in which the hydrophobic functional group other than the allyl group is a C4-C14 alkyl group, a (hetero)aryl group, an alkyl(hetero)aryl group, or a (hetero)arylalkyl group.

[0069] (Acrylamide derivative) According to the ninth embodiment of the present invention, in the third embodiment, a compositional solution can be provided in which the thermopolymerizable compound is an acrylamide derivative having two or more polymerizable double bonds. Since the thermally polymerizable compound is an acrylamide derivative such as an acrylamide monomer having two or more polymerizable double bonds, the acrylamide derivative can crosslink any two substances arbitrarily selected from the group consisting of the adherend, the polymer, the thermally polymerizable compound, and the azide compound, thereby improving the adhesion of the bond in the composition liquid of this embodiment. The acrylamide derivative relating to the composition liquid of this embodiment only needs to have two or more polymerizable double bonds and is not particularly limited in other respects, but from the viewpoint of ensuring moisture resistance of the bond, it is preferable that it does not have an ester bond. For example, N,N'-methylenebisacrylamide, N-[tris(3-acrylamidopropoxymethyl)methyl]acrylamide, N,N-bis(2-acrylamidoethyl)acrylamide, N,N'-1,2-ethanediylbis[N-[2-(acryloylamino)ethyl]acrylamide], etc., can be suitably used as acrylamide derivatives in the compositional solution of this embodiment.

[0070] (Maleimide compounds) According to the tenth embodiment of the present invention, in the third embodiment, a compositional solution can be provided in which the thermopolymerizable compound is a maleimide compound. Since the thermally polymerizable compound is a maleimide compound having a polymerizable double bond, the maleimide compound can bond to the adherend, the polymer, the thermally polymerizable compound, or the azide compound by an addition reaction, thereby improving the adhesion of the bond in the composition liquid of this embodiment. The maleimide compound is preferably a bismaleimide compound having two or more polymerizable double bonds. If the thermopolymerizable compound is a bismaleimide compound having polymerizable double bonds, the bismaleimide compound can crosslink any two substances arbitrarily selected from the group consisting of the adherend, the polymer, the thermopolymerizable compound, and the azide compound by an addition reaction, thereby improving the adhesion of the bond in the composition liquid of this embodiment. The maleimide compound in this embodiment of the compositional solution only needs to have one or more polymerizable double bonds and is not particularly limited in other respects, but it is preferable that it does not have an ester bond from the viewpoint of ensuring moisture resistance of the bond. For example, N-phenylmaleimide, N-cyclohexylmaleimide, bismaleimide compounds, etc. can be suitably used as the maleimide compound in this embodiment of the compositional solution. Examples of the bismaleimide compounds include 4,4'-diphenylmethanebismaleimide, m-phenylenebismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'- Diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, etc., can be suitably used as the maleimide compound in the compositional solution of this embodiment.

[0071] (allyl monomer) According to the eleventh embodiment of the present invention, in the third embodiment, a compositional solution can be provided in which the thermopolymerizable compound is an allyl monomer having two or more allyl groups or allyloxy groups directly bonded to a (hetero)aryl group or hydrocarbon group. Since the thermopolymerizable compound is an allyl monomer having two or more allyl or allyloxy groups directly bonded to a (hetero)aryl group or hydrocarbon group, the allyl monomer can crosslink any two substances arbitrarily selected from the group consisting of the adherend, the polymer, the thermopolymerizable compound, and the azide compound by addition or polymerization reactions, thereby improving the adhesion of the bond in the composition liquid of this embodiment. Furthermore, since the allyl or allyloxy groups directly bonded to the (hetero)aryl group or hydrocarbon group are hydrophobic functional groups, the moisture resistance of the bond in the composition liquid of this embodiment is improved. Moreover, because the (hetero)aryl group has a high electron density, the intermolecular forces become stronger, improving the adhesion of the bond in the composition liquid of this embodiment, especially the adhesion to metals. The allyl monomer in the composition liquid of this embodiment only needs to have two or more allyl or allyloxy groups directly bonded to a (hetero)aryl group or hydrocarbon group, and is not particularly limited in other respects, but it is preferable that it does not have an ester bond from the viewpoint of ensuring moisture resistance of the bond. Examples of allyl monomers in the composition liquid of this embodiment include triallyl isocyanurate, Triaryl cyanurate, 2,2'-diallylbisphenol A, diallylbisphenol A bisallyl ether, and the like can be suitably used.

[0072] (Types and concentrations of thermopolymerizable compounds) In this composition solution, one type of thermopolymerizable compound may be used, or two or more types may be used in combination. In this composition solution, the concentration of the thermopolymerizable compound is preferably 0.2% by mass or more and 0.8% by mass or less, and more preferably 0.3% by mass or more and 0.6% by mass or less, from the viewpoint of ensuring adhesion, ease of application, and storage stability. When two or more types of thermopolymerizable compounds are used in combination, the "concentration of thermopolymerizable compounds" mentioned above refers to the sum of the concentrations of each thermopolymerizable compound contained in the composition solution.

[0073] <Organic sulfur compounds> According to a twelfth embodiment of the present invention, a compositional solution can be provided that further comprises an organic sulfur compound in the third embodiment, wherein the organic sulfur compound does not have an ester bond. According to a thirteenth embodiment of the present invention, a compositional solution can be provided in the twelfth embodiment, wherein the organic sulfur compound is a compound having two or more thiol groups, or a compound having a disulfide group. The organic sulfur compounds in these forms of compositional solutions contain a thiol group or a group that generates a thiol group upon decomposition (e.g., a disulfide group -SS-). Furthermore, the components of this form of compositional solution contain polymerizable double bonds, such as allyl groups. The adherend, such as a resin, may also contain polymerizable double bonds. A chemical bond can be formed between the thiol group and the polymerizable double bond through a thiol-ene reaction or a thio-michael addition reaction. The organic sulfur compounds can form chemical bonds with adherends, polymers, thermopolymerizable compounds, or azide compounds containing polymerizable double bonds through a thiol-ene reaction or a thio-michael addition reaction, thereby improving the adhesion of the bond in this form of compositional solution. The aforementioned organic sulfur compound preferably has two or more thiol groups. The aforementioned organic sulfur compound having two or more thiol groups can crosslink any two substances selected from the group consisting of a substrate containing a polymerizable double bond, the polymer, a thermopolymerizable compound, and an azide compound by a thiol-ene reaction or a thiomichael addition reaction, thereby improving the adhesion of the bond relating to the composition liquid of this embodiment. Furthermore, since the aforementioned organic sulfur compound does not have ester bonds, the moisture resistance of the bond in the composition liquid of this embodiment is improved.

[0074] As the aforementioned organic sulfur compound, for example, 3-mercaptopropionic acid can be used. Examples of the organic sulfur compounds having two or more thiol groups that can be suitably used include bis(2-mercaptoethyl)sulfide, 1,2-bis(mercaptoethyloxy)ethane, 1,3-dimercapto-2-propanol, 2,4,6-trimercapto-1,3,5-triazine, 2-dibutylamino-4,6-dimercapto-1,3,5-triazine, and 2,4-dimercapto-1,3,5-triazine. Suitable organic sulfur compounds having a disulfide group include, for example, 1,2-bis(3-sulfopropyl) disulfide sodium salt, 2,2'-dithiodianiline, dibenzothiazole disulfide, 2-(morpholinodithio)benzothiazole, morpholine disulfide, and the like.

[0075] (Types and concentrations of organosulfur compounds) In the compositional solution according to the present invention, one type of organic sulfur compound may be used, two or more types may be used in combination, or none may be used at all. When an organic sulfur compound is used in this compositional solution, its concentration is preferably 0.02% by mass or more and 0.8% by mass or less, and more preferably 0.05% by mass or more and 0.4% by mass or less, from the viewpoint of ensuring adhesion, ease of application, and storage stability. When two or more types of organic sulfur compounds are used in combination, the above-mentioned "concentration of organic sulfur compounds" means the sum of the concentrations of each organic sulfur compound contained in the compositional solution.

[0076] (Aromatic bisazide compounds) According to the fourteenth embodiment of the present invention, in the third embodiment, the azide compound is a compound having two or more azide groups directly bonded to an aromatic ring (hereinafter referred to as an aromatic bisazide compound). The aromatic bisazide compound in this embodiment contains highly reactive azide groups directly bonded to substituted or unsubstituted aromatic rings. Therefore, even by heating at low temperatures of about 80 to 160°C or irradiation with long-wavelength light of about 260 to 365 nm in ultraviolet light, the azide groups decompose to generate nitrenes, which can then form chemical bonds with the adherend, the polymer, the thermopolymer, or the azide compound via radical addition reactions, thereby improving the adhesion of the bond in this embodiment. Since the aromatic bisazide compound contains two or more azide groups, the azide groups decompose upon contact with heat or light to generate nitrenes, which can then crosslink and bond any two substances selected from the group consisting of the adherend, the polymer, the thermopolymer, and the azide compound via radical addition reactions, thereby improving the adhesion of the bond in this embodiment. From the viewpoint of ensuring moisture resistance of the bond, it is desirable that the aromatic bisazide compound does not have an ester bond.

[0077] Aromatic bisazide compounds having one or two aromatic rings or fused rings, and preferred as components of the compositional liquid according to this embodiment, are listed below in order of increasing distance between two azide groups (where "distance" means the minimum number of atoms included in the sequence of atoms linking the two azide groups. For example, in diazidomethane, the two azide groups are linked via one carbon atom, so the "distance" between the two azide groups is 1): 1,4-Diazidobenzene, 3,3'-Diazidodiphenylsulfone, 3,3'-Diazidodiphenylsulfide, 3,3'-Diazidodiphenyldisulfide, 4,4'-Diazidobiphenyl, 4,4'-Diazidediphenyl ether, 4,4'-Diazidebenzophenone, 4, 4'-Diazidediphenylmethane, 3,3'-Dichloro-4,4'-Diazidediphenylmethane, 4,4'-Diazidediphenylsulfone, 4,4'-Diazidediphenylsulfide, 4,4'-Diazidostilbene, 4,4'-Diazidostilbene-2,2'-Disulfonic Acid (Disodium Salt Tetrahydrate), 4,4'-Diazidostilbene-2,2'-Disulfonylamide, 4,4'-Diazidostilbene-2,2'-Disulfonyl-N-(p-Methoxyphenyl)amide, 4,4'-Diazidostilbene-2,2'-Disulfonyl-N-(p-Hydroxyethylphenyl)amide, 4,4'-Diazidodiphenyldisulfide, 4,4'-Diazidochalcone, 4,4'-Diazidochalcone-2-sulfonic acid (sodium salt), 2,6-Bis(4'-azidobenzylidene)cyclohexanone, 2,6-Bis(4'-azidobenzylidene-2'-sulfonic acid (sodium salt))cyclohexanone, 2,6-Bis(4'-azidobenzylidene)-4-methylcyclohexanone, 2,6-Bis(4'-azidobenzylidene)-4-ethylcyclohexanone, 1,3-Bis(4'-azidobenzylidene)-2-propanone, 1,3-Bis(4'-azidobenzylidene-2'-sulfonic acid (sodium salt))-2-propanone, 4,4'-Diazidobenzylideneacetone, 2,5-Bis(4'-azidobenzylidene-2'-sulfonic acid (sodium salt))cyclopentanone, Examples include 2,6-bis(4'-azidocinnamyridene)cyclohexanone, 2,6-bis(4'-azidocinnamyridene)-4-methylcyclohexanone, and 1,3-bis(4'-azidocinnamyridene)-2-propanone.

[0078] Aromatic bisazide compounds having three or more aromatic rings or fused rings, and preferred as components of this composition solution, are exemplified in order of increasing distance between two azide groups: Examples include 2,7-diazido-9H-fluoren-9-one, 6-azido-2-(4'-azidostyryl)benzimidazole, 1,4-bis(3'-azidostyryl)benzene, and 1,4'-azidobenzylidene-3-α-hydroxy-4"-azidobenzylindene.

[0079] (Types and concentrations of aromatic bisazide compounds) In this composition solution, one aromatic bisazide compound may be used, or two or more may be used in combination. In this composition solution, the concentration of the aromatic bisazide compound is preferably 0.02% by mass or more and 0.1% by mass or less, and more preferably 0.03% by mass or more and 0.08% by mass or less, from the viewpoint of ensuring adhesion, ease of application, and storage stability. When two or more aromatic bisazide compounds are used in combination, the "concentration of aromatic bisazide compounds" mentioned above refers to the sum of the concentrations of each aromatic bisazide compound contained in the composition solution.

[0080] As an example of an aromatic bisazide compound having two azide groups directly bonded to a benzene ring, and suitable for carrying out the present invention, the structural formula of 2,6-bis(4'-azidobenzylidene)-4-methylcyclohexanone (hereinafter referred to as "BAC-M") is shown in the following formula (A3).

[0081] [ka]

[0082] (Synthesis of aromatic bisazide compounds) The method for synthesizing the aromatic bisazide compounds described above is not particularly limited, but they can be obtained by known methods such as (1) introducing an azide group using sodium azide, (2) introducing an azide group using tosyl azide or trifluoromethanesulfonyl azide, or (3) introducing an azide group by a coupling reaction using a copper catalyst. Furthermore, many of the above aromatic bisazide compounds are available on the market.

[0083] (Polyethyleneimine polymer) According to the 15th embodiment of the present invention, in the third embodiment, a compositional liquid can be provided in which the polymer is a compound represented by formula (12) (hereinafter referred to as "polyethyleneimine-type IMB agent (containing polymer)"). Formula (12) schematically represents the structure of the compound. The compound is formed by the polymerization of (n+m+l) repeating units, where n, m, and l are integers of 1 or more, consisting of n repeating units containing an allyl group (let's call them A), m repeating units containing an ethylhexyl group (let's call them B), and l repeating units containing a primary amino group (let's call them C), in any order. In other words, formula (12) schematically represents not only compounds formed by the polymerization of these repeating units in the order "AA··BB··CC··", but also compounds formed by polymerization in any order, such as "ABCBCA··". By using the compositional solution in this form, it is possible to form a bond with excellent adhesion and "excellent moisture resistance, or a bond with excellent moisture resistance and heat resistance" through interfacial molecular bonding.

[0084] (Polyether block polymer) According to the sixteenth embodiment of the present invention, in the fourth embodiment, a compositional solution can be provided in which the polymer is a compound represented by formula (13). Formula (13), like formula (12), schematically represents the structure of the compound. The compound is formed by the polymerization of (n+m+l) repeating units, where n, m, and l are integers of 1 or more, consisting of n repeating units containing an allyl group, m repeating units containing a methyleneoxy group, and l repeating units containing an ethylhexyl group. Of these, m repeating units containing a methyleneoxy group are bonded together in a continuous manner to form a polyether block. On the other hand, the n repeating units containing an allyl group, the l repeating units containing an ethylhexyl group, and the polyether block can be polymerized in any order to form the compound. By using the compositional liquid of this form, it is possible to form a bond with excellent adhesion and "excellent moisture resistance, or a bond with excellent moisture resistance and heat resistance" through interfacial molecular bonding.

[0085] (Polyetheramine-type polymer) According to the 17th embodiment of the present invention, in the 5th embodiment, the polymer is a compound represented by formula (14) (hereinafter referred to as "polyetheramine type IMB agent (polymer containing)" and We can provide a liquid composition that is called (or called). Formula (14), like formula (13), schematically represents the structure of the compound. The compound comprises a polyether block in which m ethyleneoxy groups are continuously bonded, where m is an integer of 1 or more. The compound also comprises n repeating units containing allylphenol groups and l repeating units having secondary amino groups, where n and l are integers of 1 or more. The compound is formed by polymerizing n repeating units containing allylphenol groups, l repeating units having secondary amines, the polyether block, and two allylbenzoxazine rings in any order. However, in the compound, one allylbenzoxazine ring is located opposite the other allylbenzoxazine ring with respect to the polyether block. By using the compositional liquid of this form, it is possible to form a bond with excellent adhesion and "excellent moisture resistance, or a bond with excellent moisture resistance and heat resistance" through interfacial molecular bonding.

[0086] (Method of producing polymers) The method for producing the polymer (hereinafter also referred to as the polyamine polymer) contained in the compositional liquid according to the first embodiment of the present invention (hereinafter referred to as the compositional liquid) is publicly known and is disclosed, for example, in Japanese Patent Application Publication No. 2016-047849 and the documents cited therein. The polymers contained in this composition solution, which have a first repeating unit, a second repeating unit, and a third repeating unit, can be produced, for example, by first preparing or creating a polymer having the first repeating unit, and then reacting it with an epoxy compound having an allyl group or an epoxy compound having a hydrophobic functional group to modify a portion of the primary amino groups or secondary amino groups contained in the polymer, as will be shown in the synthesis example later.

[0087] (Structure of polymers) Unless otherwise specified, the polymers contained in this composition solution may have linear, branched, or dendrimer structures. They may also be crosslinked with a bifunctional crosslinking agent such as epichlorohydrin.

[0088] (Weight-average molecular weight of polymers) The weight-average molecular weight of the polymer contained in this composition solution is preferably 20,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less, from the viewpoint of suppressing uneven coating of this composition solution. Furthermore, the weight-average molecular weight is preferably 200 or more, more preferably 450 or more, and even more preferably 900 or more, from the viewpoint of ensuring adhesion in interfacial molecular bonding by crosslinking while absorbing the microscopic locational difference in the distance between the surfaces of two materials facing each other at the interface. In this specification, the weight-average molecular weight of the polymer refers to the weight-average molecular weight in terms of polystyrene, measured by gel permeation chromatography (GPC).

[0089] (Type and concentration of polymer) In this composition, one polymer may be used, or two or more polymers may be used in combination. In this composition solution, the concentration of the polymer is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, even more preferably 0.1% by mass or more, and especially preferably 0.3% by mass or more, from the viewpoint of ensuring adhesion at the interfacial molecular bond. Furthermore, from the viewpoint of suppressing uneven coating and storage stability, the concentration is preferably 4% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and especially preferably 1% by mass or less. When two or more of the above polymers are used in combination, "the concentration of the above polymers" means the sum of the concentrations of the various polymers.

[0090] (material) The two substances (adhered materials) used in the manufacturing method of laminates using this composition liquid may be made of the same material or of different materials. Each substance may be composed of multiple materials. Each substance may have a coating or the like formed on its surface. Each substance may be part of an object made of multiple materials. Examples of materials that make up each substance include organic materials such as resins and elastomers, and inorganic materials such as glass, ceramics, metals, silicon wafers, and plating substrates (catalysts).

[0091] Examples of "resins" as used herein include thermoplastic resins and thermosetting resins. Examples of thermoplastic resins include general-purpose resins, engineering resins, and super engineering resins. Examples of general-purpose resins include polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), acrylonitrile butadiene styrene (ABS), acrylonitrile styrene (AS), polymethyl methacrylic (PMMA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), and cycloolefin polymer (COP). Examples of engineering resins include polyamide (PA), polyacetal (POM), polycarbonate (PC), polyphenylene ether (PPE (modified PPO)), polybutylene terephthalate (PBT), ultra-high molecular weight polyethylene (U-PE), and polyvinylidene fluoride (PVDF). Examples of super engineering resins include polysulfone (PSU), polyethersulfone (PES), polyphenylene sulfide (PPS), polyarylate (PAR), polyamide-imide (PAI), polyetherimide (PEI), polyetheretherketone (PEEK), thermoplastic polyimide (TPI), liquid crystal polymer (LCP), and polytetrafluoroethylene (PTFE). Examples of thermosetting resins include phenolic resins (PF), epoxy resins (EP), melamine resins (MF), urea resins (urea resins, UF), unsaturated polyester resins (UP), alkyd resins, polyurethanes (PUR), polyimides (PI), modified polyimides (MPI), and thermosetting polyimides. Examples of thermosetting resin product forms include C-stage (cured) sheets such as polyimides, B-stage (uncured) sheets such as build-up sheets, prepregs, die bond sheets, and ACF (anisotropic conductive sheets), and A-stage materials such as conductive or insulating compounds, pastes, or inks.

[0092] Examples of elastomers include natural rubber, synthetic rubber, urethane rubber, silicone rubber, and fluororubber.

[0093] Examples of metals include copper, silver, gold, nickel, and aluminum. These metals can take various forms, such as metal sheets, metal foils, vapor-deposited films, sputtering layers, and plated metal layers obtained by wet plating (electroless plating and / or electrolytic plating).

[0094] Examples of glass include general soda-lime glass (such as white plate glass), borosilicate glass, lead glass, flint glass, optical glass, and quartz glass.

[0095] Examples of ceramics include aluminum oxide, zirconium oxide, aluminum nitride, silicon carbide, silicon nitride, boron nitride, forsterite, steatite, cordierite, sialon, barium titanate, lead zirconate titanate, ferrite, mullite, and mica.

[0096] The shapes of the two substances are not particularly limited. Specific shapes of the substance to which the composition liquid according to the present invention is applied include, for example, plate-like, sheet-like, film-like, tubular, columnar, string-like, irregularly shaped mass-like, fibrous, and any other shape formed into a predetermined shape.

[0097] (Bonding properties between primary or secondary amino groups and substances) A primary or secondary amino group can form a CN bond with a carboxyl group through amidation, a CN bond with an epoxy group through ring-opening amination, and a CN bond with an ester group -(C=O)O- through transamidation. Because the first repeating unit of this composition has a primary or secondary amino group, it is useful for interfacial molecular bonding of substances such as resins having carboxyl groups, epoxy groups, or ester groups. Furthermore, since carboxyl groups are formed on the surface of various organic materials that have undergone the pretreatment process described later, this form of composition is useful for interfacial molecular bonding of various organic materials that have undergone the pretreatment process. Examples of various organic materials that have undergone the pretreatment process include organic materials treated with atmospheric plasma and polyimide (PI) treated with alkali. Examples of resins containing carboxyl groups include polyallylamine (PAA). Examples of resins containing epoxy groups include various epoxy resins. Examples of resins containing ester groups include liquid crystal polymer (LCP), polycarbonate (PC), polymethyl methacrylic (PMMA), and polyethylene terephthalate (PET).

[0098] (Bonding properties between azide groups and substances) The azide group detaches a nitrogen molecule upon heating or irradiation with light, becoming a nitrene. The azide group (nitrene) can form a CN bond with an alkenyl group (-CH=CH-) through aziridination, a methylene group (-CH2-) through CH amination, a methyl group (-CH3) through hydrogen abstraction amination, and a phenyl group through a [2+1] cycloaddition reaction. The azide group can also form a triazole ring and a CN bond through a [3+2] cycloaddition reaction with an alkenyl group (-CH=CH-). The composition solution containing azide compounds is useful for interfacial molecular bonding of substances such as resins having alkenyl groups, methylene groups, methyl groups, or phenyl groups. Examples of resins containing alkenyl groups include ABS resin and polyolefins that have double bonds at their polymerization ends. Examples of resins containing a methylene group include ABS resin, polypropylene (PP), polyethylene (PE), polystyrene (PS), and polymethyl methacrylic (PMMA). Examples of resins containing methyl groups include polypropylene (PP), polycarbonate (PC), and polymethyl methacrylic (PMMA). Examples of resins containing phenyl groups include polystyrene (PS), polyphenylene sulfide (PPS), liquid crystal polymer (LCP), carbon nanotube (CNT), polyimide (PI), polycarbonate (PC), and polyetheretherketone (PEEK). Since at least two azide groups in an aromatic bisazide compound contained in one form of this composition solution can each form a CN bond with the polymer, thermopolymerizable compound, azide compound, adherend, or (if present) an organosulfur compound after activation, as described above, the aromatic bisazide compound acts as a crosslinking agent to strengthen the interfacial molecular bond between any two substances.

[0099] (Bonding properties between allyl groups and substances) The allyl group has a double bond structure and contains regions with high and low electron density, making it useful in a variety of reactions. In particular, it is used in radical reactions, ene reactions, electrophilic substitution reactions, and nucleophilic addition reactions. It is important in response. The allyl group can form bonds through its double bond via the following reactions. CC bond: The allyl group can bond with other carbon atoms to form a carbon-carbon bond through radical polymerization reactions or ene reactions. CN bond: The allyl group can form a CN bond through a reaction with a nitrene group generated by an external field stimulus such as light or heat. CS bond: The allyl group can also form a CS bond through a thiol-ene reaction with a thiol radical generated by external field stimulation such as light or heat. Examples of compounds that can form CC bonds with an allyl group include the resin having the methylene group and the resin having the methyl group. Examples of compounds that can form a CN bond with an allyl group include the azide compounds in this composition. Examples of compounds that can form CS bonds with an allyl group include organosulfur compounds in one form of this composition solution.

[0100] (Bonding properties between thiol groups and substances) Thiol groups are functional groups containing sulfur atoms and have properties similar to alcohols, but their high reactivity makes them useful in a variety of chemical reactions. In particular, thiol groups are easily oxidized and have a high affinity for metals, so they are often used for strong bonding with metal surfaces and in cross-linking reactions. Thiol groups can form bonds through the following reactions: CS bond: Thiol groups generate thioradicals via radical generators that produce radicals in response to external stimuli such as heat and light. These thioradicals then bond with polymerizable double-bonded compounds such as allyl groups to form CS bonds. Additionally, electron-deficient olefins, a type of polymerizable double bond, can bond with thiol groups to form CS bonds. This reaction is induced by light and heat and is used in polymer crosslinking reactions, among other applications. SS bond: Thiol groups, upon oxidation, bond with other thiol groups to form disulfide bonds (SS bonds). Disulfide bonds are reversible, and their dissociation and formation are repeatedly carried out through oxidation-reduction reactions. Bonding with metals: Thiol groups have strong bonds with metals such as gold (Au), silver (Ag), and copper (Cu), making them useful for protecting metal surfaces and bonding interfacial molecules. Examples of compounds that can form CS bonds with thiol groups include compounds having allyl groups, such as polymers and allyl monomers in this composition solution.

[0101] <Method for manufacturing surface-treated materials> Referring to the flowchart in Figure 1, according to the 18th embodiment of the present invention, a method for producing a surface-treated substance is provided, comprising the step of applying a compositional liquid according to any of the first to 17 embodiments to the surface of a substance (application step (S2)). This production method preferably includes an activation step. The activation step may include a step of heating the surface of the substance to which the compositional liquid has been applied (heating activation step (S4)) and a step of irradiating the surface of the substance to which the compositional liquid has been applied with ultraviolet light (UV activation step (S6)). This production method may further include a pretreatment step (S1) and a post-activation cleaning step (S8).

[0102] (Coating process) In the coating process (S2), a treatment solution such as the composition solution is applied to a material such as a polyimide film. Here, "applying" means "adhering" or "being in contact with" the surface of the material. Methods of application include conventionally known coating methods, such as brush coating, inkjet coating, gravure coating, lip coating, comma coating, blade coating, roll coating, knife coating, spray coating, bar coating, spin coating, and dip coating. The lower limit of the coating thickness (wet film thickness) when the liquid is applied is preferably 0.5 μm, more preferably 1.5 μm, and even more preferably 3 μm, from the viewpoint of ensuring adhesion between the surface treatment material and other materials (materials or metals). Similarly, the lower limit of the coating thickness (dry film thickness) is preferably 1 nm, more preferably 3 nm, and even more preferably 6 nm. On the other hand, the upper limit of the coating thickness (wet film thickness) is preferably 200 μm, more preferably 50 μm, and even more preferably 20 μm, from the viewpoint of ease of application and suppression of uneven application. Similarly, the upper limit of the coating thickness (dry film thickness) is preferably 0.4 μm, more preferably 100 nm, and even more preferably 40 nm. When using the dip-coating method, the immersion time is preferably 3 seconds or more and 60 seconds or less. "Application" may be performed on a part of the surface of the material or on the entire surface of the material. Furthermore, if the substance is in the form of a film or sheet, the "coating" may be performed on only one side of the substance, either the front or the back, or on both the front and back sides of the substance. Following the "coating" step, a drying step is usually performed to dry the surface of the material to which the treatment solution has been applied, either by natural drying in an air atmosphere, air drying, or by blowing hot air at approximately 40°C to 70°C. Through the above coating and drying steps, the polymers, thermopolymerizable compounds, and azide compounds contained in the composition solution, and any organic sulfur compounds present, are arranged on the surface of the material.

[0103] (heat activation process) In the heating activation step (S4), the surface of the material to which the composition solution has been applied is heated. Heating makes the surface suitable for bonding such as heat-pressure bonding with other materials or metal plating. The surface temperature of the material during heating is, for example, 80 to 160°C, preferably 90 to 120°C, and the time the surface of the material is maintained at that temperature is, for example, 30 seconds to 60 minutes, preferably 1 to 20 minutes. Although it is difficult to analyze the phenomena occurring in the heating activation step, it is presumed that the following phenomena occur: The polymerization reaction is initiated by the heating treatment, and a bonding layer is formed at the interface. The reaction forms include thermal polymerization of polymerization groups, ring-opening polymerization of benzoxazine rings, chemical reactions starting from nitrene groups due to thermal decomposition of azide groups (such as CH insertion reactions), thiol-ene reactions, thiomichael addition reactions, and amidation reactions with amino groups, and it is sufficient for any of these reactions to occur. The (bis)azide compound, polyamine polymer, thermopolymerizable compound, and (if present) organosulfur compound will bond with each other and with the adherend to form an extremely thin layer of condensate on the surface of the material. In this way, the heating activation process forms an extremely thin layer of condensate that adheres closely to the surface of the material, and the surface of this condensate is considered to be in a state suitable for bonding with other materials such as resins or metals.

[0104] (UV activation process) In the UV activation step (S6), ultraviolet light is irradiated onto the surface of the material coated with this composition solution. The irradiation of ultraviolet light prepares the surface for bonding, such as adhesion to other materials or metal plating. While it is difficult to analyze the phenomena occurring in the UV activation step, it is presumed that the following phenomena occur: The irradiation of ultraviolet light triggers a polymerization reaction, forming a bonding layer at the interface. The reaction can take the form of photopolymerization of polymer groups, a chemical reaction starting from a nitrene group due to photodecomposition of azide groups (such as CH insertion reactions), a thiol-ene reaction, or a thiomichael addition reaction; any of these reactions is sufficient. The (bis)azide compound, polyamine polymer, thermopolymerizable compound, and (if present) organosulfur compound will bond with each other and with the adherend, forming an extremely thin layer of condensate on the surface of the material. In this way, the UV activation step forms an extremely thin layer of condensate that adheres closely to the surface of the material, and the surface of this condensate is considered to be in a state suitable for bonding with other materials such as resins or metals. The wavelength of the ultraviolet light to be irradiated is preferably 260 to 420 nm, and more preferably 330 to 365 nm, from the viewpoint of ensuring adhesion and preventing degradation of resins such as polyimide films due to ultraviolet light. As an ultraviolet light source, a mercury lamp, Either a metal halide lamp or a UV-LED may be used. In the present invention, the above-mentioned heating activation step may be performed in addition to the UV activation step. In this case, the order of the heating activation step and the UV activation step is not important; either can be performed first, or they can be performed simultaneously. Furthermore, the coating step, the heating activation step, and the UV activation step may be applied repeatedly in any order, either in combination with other treatments such as a post-activation washing treatment step (S8) for removing by-products, or without combination. By washing away by-products that do not contribute to bonding, adhesion can be improved.

[0105] (Pre-treatment process) According to one embodiment of the present invention, a method for producing a surface-treated substance is provided, further comprising the step of performing one or more pretreatment (pretreatment step (S1)) on the substance before applying a compositional liquid according to any embodiment of the present invention to the surface of the substance, the pretreatment of one or more pretreatments selected from the group consisting of cleaning, acid treatment, alkali treatment, corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, silicate flame treatment (also called "ITRO treatment"), and defluorination treatment. The pretreatment step is a process of pre-treating the surface of a material such as a polyimide film. This is done to facilitate the fixation of polyamine polymers, thermopolymerizable compounds, (bis)azide compounds, and (if present) organic sulfur compounds, which will be placed on the surface of the material in the subsequent coating and drying steps, and also to efficiently carry out the subsequent heating activation step and / or UV activation step. By performing the pretreatment step, the material becomes an activated state in which functional groups such as OH groups, carboxyl groups, carbonyl groups, primary or secondary amino groups, and polymerizable double bonds are present on its surface, making it easier to form bonds with polyamine polymers, thermopolymerizable compounds, (bis)azide compounds, and (if present) organic sulfur compounds. The pretreatment step can be one or more treatments selected from the group consisting of washing, acid treatment, alkali treatment, corona discharge treatment in which corona discharge is irradiated onto the surface of the substance, plasma treatment in which the surface of the substance is treated with plasma such as argon plasma, oxygen plasma, or atmospheric plasma, ultraviolet irradiation treatment, and silicate flame treatment (Itro treatment) in which the surface of the substance is exposed to the combustion flame of combustion gas mixed with a coupling agent such as a silane compound. Only one treatment may be performed, or a combination of these treatments may be performed. In another embodiment of the present invention, the pretreatment step is omitted to avoid the formation of bonds with poor moisture resistance, such as ester bonds or amide bonds, in the bonding layer at the interface.

[0106] <Method for manufacturing metal-coated resin (wet plating)> According to the 19th embodiment of the present invention, a method for manufacturing a metal-coated resin is provided, comprising the steps of: applying a compositional liquid according to any of the first to 17 embodiments to the surface of a resin (coating step); heating the surface or irradiating the surface with ultraviolet light (activation step); and then forming a metal plating layer on the surface by wet plating (plating step). In this embodiment, a metal coating is formed on the surface of the resin after the coating and activation steps, for example, by electroless plating, vapor deposition, or sputtering (seed layer formation step). Subsequently, the metal coating may be thickened by electrolytic plating (electrolytic plating step). The metal coating may be formed over the entire surface, or it may be formed in a pattern by known methods such as photolithography. The metal-coated resin produced by this embodiment is suitable for flexible metal-clad laminates and printed circuit boards. From the viewpoint of processing time and processing cost, the thickness of the metal coating formed by electroless plating, vapor deposition, or sputtering is preferably 0.1 to 2 μm, more preferably 0.2 to 1 μm. When the metal coating is thickened by electrolytic plating, the thickness of the metal coating after thickening is preferably 0.2 to 50 μm, more preferably 0.5 to 20 μm. Examples of metals to be electrolessly plated are Cu, Ni, etc. The metals used for the metal coating formed by vapor deposition or sputtering are, for example, Al, Cr, Sn, Ti, Cu, In, Au, Pt, Ag, etc. Furthermore, if the metal coating includes a layer formed by electroplating, the metals used for electroplating are, for example, Cu, Ni, Ag, Pd, Au, Pt, Zn, Cr, Sn, Bi, etc. The metal coating may be a single metal or an alloy. The materials obtained by this method... To improve the adhesion between the resin and the plated metal of the metal-coated resin, preferably, an annealing treatment is performed at a temperature of 100°C to 250°C for 5 to 60 minutes after the seed layer formation step and / or the electroplating step.

[0107] Figures 2-1 and 2-2 are a series of conceptual diagrams illustrating the chemical reactions that occur in the wet plating process in chronological order. (i) Surface treatment liquid application process A surface treatment solution (here, as an example, a polyetheramine-type IMB agent containing an organic sulfur compound) is applied to the substance (substrate). As shown in the upper part of Figure 2-1, reactive functional groups such as alkylene groups and polymerizable double bonds are present on the surface of the substrate from the beginning, or as a result of the aforementioned pretreatment. (ii) Heat activation step It is presumed that the following reactions occur when each component contained in the surface treatment liquid is thermally activated. The benzoxazine group of the polyamine polymer undergoes an addition reaction to aromatic compounds upon thermal activation. The benzoxazine group undergoes an addition reaction to the aromatic compound on the substrate, forming a chemical bond with the substrate. Azide compounds are thermally activated, generating nitrenes. These nitrenes form chemical bonds with methylene groups on the substrate via CH insertion reactions. In the case of (bis)azide compounds, this reaction can also result in crosslinking. Organic sulfur compounds (in this case, disulfide compounds) are highly thermally reactive, generating organic sulfur radicals, which then undergo a thiol-ene reaction with the allyl group. Following this reaction, carbon radicals are produced. These carbon radicals then undergo radical polymerization of nearby thermally polymerizable compounds. The state after these reactions have occurred is shown in the middle diagram of Figure 2-1. (iii) Catalyst process (catalyst application process) As shown in the lower diagram of Figure 2-1, a metal catalyst such as palladium, used for plating, is supported on the surface of the substrate after surface treatment. It is presumed that amino groups, aromatic rings, aromatic hydroxyl groups, etc., hold the metal catalyst. (iv) Electroless plating process As shown in the upper part of Figure 2-2, plating metals such as copper and nickel are deposited around a metal catalyst, forming an electroless plating layer. (v) Electrolytic plating process As shown in the lower diagram of Figure 2-2, an electroless plating layer is used as a seed layer, and an electroplating layer is formed on top of the electroless plating layer by electroplating, thereby increasing the thickness of the plating layer. The adhesion, moisture resistance, and heat resistance of the plating layer to the substrate are determined using this surface treatment solution. It is presumed that this depends on the state of the substrate interface.

[0108] <Manufacturing method for metal-coated resin (lamination of metal foils)> According to the 20th embodiment of the present invention, a method for manufacturing a metal-coated resin is provided, comprising the steps of: applying a compositional liquid according to any of the first to 17 embodiments to the surface of at least one of a resin and a metal foil (coating step); heating the surface or irradiating the surface with ultraviolet light (activation step); and then laminating the resin and metal foil via the surface, pressing them together to integrate them, and obtaining a metal-coated resin (pressing step). The thickness of the metal foil to be bonded is preferably 0.2 to 50 μm, more preferably 0.5 to 20 μm. The metals constituting the metal foil are, for example, Cu, Ni, Ag, Pd, Au, Pt, Zn, Cr, Sn, Bi, Al, Ti, and In, with Cu, Ag, Au, Pt, and Al being particularly noteworthy. The metal foil may be a single metal or an alloy. The surface of the metal foil bonded to the resin may be roughened or unroughened. The metal-coated resin produced by this embodiment is suitable as a flexible metal-clad laminate or a printed circuit board. The above pressing process comprises a step of overlapping the resin and metal foil via the surface of the resin or metal foil that has been surface-treated with the composition liquid (overlapping step), and a step of integrally bonding the two by applying force (pressurization step). In the pressurization step, for example, flat plate pressing, roll pressing, etc., are performed in an atmospheric atmosphere, a nitrogen atmosphere, or a vacuum. From the viewpoint of improving productivity and reducing processing costs, flat plate pressing or roll pressing in an atmospheric atmosphere is preferred. From the viewpoint of quality stability of the manufactured metal-coated resin, pressing in a nitrogen atmosphere or a vacuum is preferred. The pressing pressure is preferably 1 to 100 MPa, and more preferably 2 to 30 MPa. Generally, the greater the pressing pressure, the greater the adhesion strength of the manufactured metal-coated resin, which is preferable, but if the pressing pressure is too high, there is a risk of damaging the support. The time for applying the above pressure is, for example, 0.5 to 60 minutes, more preferably 1 to 20 minutes. In the pressurization step, it is preferable to heat simultaneously. The temperature of the resin in the pressurization step should not exceed its heat resistance temperature. The temperature is, for example, 40°C or higher and 350°C or lower, preferably 120°C or higher and 250°C or lower, and more preferably 150°C or higher and 230°C or lower.

[0109] <Method for manufacturing resin laminates> According to the 21st embodiment of the present invention, a method for manufacturing a resin laminate is provided, comprising the steps of: applying a composition liquid according to any of the first to 17 embodiments to the surface of a first resin (coating step); heating the surface or irradiating the surface with ultraviolet light (activation step); and then bringing the first resin and the second resin into contact via the surface and pressing them together to integrate them (pressing step). Examples of resin shapes include resin films, resin sheets, resin blocks, etc. The above pressing process comprises a step of bringing two resins into contact via surfaces treated with the composition liquid (contact step) and a step of applying force to integrally bond the two (pressure step). In the pressure step, for example, flat plate pressing, roll pressing, etc., are performed in an atmospheric atmosphere, a nitrogen atmosphere, or a vacuum. From the viewpoint of improving productivity and reducing processing costs, flat plate pressing or roll pressing in an atmospheric atmosphere is preferred. From the viewpoint of quality stability of the manufactured resin laminate, pressing in a nitrogen atmosphere or a vacuum is preferred. The pressing pressure is preferably 1 to 100 MPa, and more preferably 2 to 30 MPa. Generally, the greater the pressing pressure, the greater the adhesion strength of the manufactured laminate, which is preferable, but if the pressing pressure is too high, there is a risk of damaging the support. The time for applying the above pressure is, for example, 0.5 to 60 minutes, more preferably 1 to 20 minutes. In the above pressurizing step, it is preferable to heat simultaneously. The temperature of the resin film in the pressurizing step should not exceed its heat resistance temperature. The temperature is, for example, 40°C or higher and 350°C or lower, preferably 120°C or higher and 250°C or lower, and more preferably 150°C or higher and 230°C or lower.

[0110] <Method for producing a cured coating material> According to the 22nd embodiment of the present invention, a method for producing a cured material coating is provided, comprising the steps of: applying a composition liquid according to any of the first to 17 embodiments to the surface of a substance (coating step); heating the surface or irradiating the surface with ultraviolet light (activation step); then applying a curing liquid onto the surface (curing liquid coating step); and curing the curing liquid to form a cured material that covers the surface (curing step). In this embodiment, a cured coating material is produced by applying a curing liquid, such as a resin varnish, to the surface of a substance that has undergone a coating step and an activation step related to the composition liquid, and then curing it. The curing liquid, such as a resin varnish, preferably contains a thermosetting or UV-curable resin. The cured coating material produced by this embodiment has excellent adhesion and excellent moisture resistance, or moisture resistance and heat resistance. In a modified form of this embodiment, the curing liquid is a conductive paste containing a conductive filler in a resin varnish, which is applied (printed) in a pattern on the substance, and the cured coating material obtained through the curing step has a patterned conductive portion. El.

[0111] (Polyimide) Among resins, polyimide is a thermosetting resin with high heat resistance, and its physical properties change very little over a wide temperature range from low temperatures of -269°C to high temperatures of +300°C, leading to its expanding use in the electrical and electronic fields. In the electrical field, for example, it is used in the insulation of coils in industrial motors and superconducting wires, while in the electronic field, for example, it is used in the base film of flexible printed circuit boards, lightweight spacers, and probe sockets (test fixtures) for semiconductor testing equipment.

[0112] The polyimide used as a resin in this invention is a known substance that can be obtained by a polycondensation reaction using a diamine component and a tetracarboxylic dianhydride component as the main components. Polyimide films are generally obtained by reacting a diamine component and a tetracarboxylic dianhydride component in a solvent to obtain a polyamic acid solution, which is then applied to a support, dried to form a green film, and further subjected to high-temperature heat treatment to carry out a dehydration and ring-closing reaction. The diamine component and tetracarboxylic dianhydride component used as raw materials are appropriately selected considering the various properties required depending on the application of the resin film laminate or metal coating resin.

[0113] As the tetracarboxylic dianhydride component constituting polyamic acid, aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides, which are commonly used in polyimide synthesis, can be used. Among these, aromatic tetracarboxylic dianhydrides and alicyclic tetracarboxylic dianhydrides are preferred. From the viewpoint of heat resistance, aromatic tetracarboxylic dianhydrides are more preferred, and from the viewpoint of light transmittance, alicyclic tetracarboxylic dianhydrides are more preferred. The aromatic tetracarboxylic dianhydrides are not particularly limited, but if the (bis)azide compound has a benzene ring, it is preferable that the acid dianhydride has a benzene ring or a benzene ring with a substituent, from the viewpoint of affinity and ease of bonding with the (bis)azide compound, and it is more preferable that the acid dianhydride does not have any aromatic rings other than a benzene ring or a benzene ring with a substituent. Examples of compounds that can be used as the tetracarboxylic dianhydride component are described, for example, in the specification of international application PCT-JP2024-013371. The tetracarboxylic dianhydride component may be used alone or in combination of two or more.

[0114] As the diamine component constituting polyamic acid, aromatic diamines, alicyclic diamines, and aliphatic diamines commonly used in polyimide synthesis can be used. Among these, aromatic diamines and alicyclic diamines are preferred. From the viewpoint of heat resistance, aromatic diamines are more preferred, and from the viewpoint of light transmittance, alicyclic diamines are more preferred. The aromatic diamines are not particularly limited, but if the (bis)azide compound has a benzene ring, it is preferable that the aromatic diamine has a benzene ring or a benzene ring with a substituent, from the viewpoint of affinity and ease of bonding with the (bis)azide compound, and it is more preferable that the aromatic diamine does not have any aromatic rings other than a benzene ring or a benzene ring with a substituent. Examples of compounds that can be used as the diamine component are described, for example, in the specification of the PCT application. The diamine component may be used alone or in combination of two or more types.

[0115] In the present invention, the polyimide film used as a resin is preferably one containing an aromatic ring from the viewpoint of heat resistance, and is not particularly limited in type, regardless of whether it is non-thermoplastic or thermoplastic, but to give specific examples, for example, the Kapton series from Toray DuPont Co., Ltd., the Upirex series from Ube Industries, Ltd., the Apical series from Kanegafuchi Chemical Co., Ltd., the U-Film series from Nitto Denko Corporation, and Xenomax Japan Non-thermoplastic polyimide films such as the Xenomax series manufactured by NI Corporation can be suitably used. When the bisazide compound and the polyamine polymer have a benzene ring, a film made of polyimide containing a benzene ring, particularly a film made of polyimide containing only a benzene ring as an aromatic ring, can be suitably used from the viewpoint of ensuring affinity and adhesion. The glass transition temperature of the polyimide constituting the film for high heat resistance applications is preferably 300°C or higher, more preferably 350°C or higher. The thickness of the polyimide film is not particularly limited, but examples include 12.5 μm, 25 μm, 30 μm, 40 μm, 50 μm, 75 μm, 100 μm, 125 μm, 250 μm, etc.

[0116] (General-purpose resins and resins that are difficult to bond) Generally, general-purpose resins with aliphatic carbon chains, such as PE, PP, and ABS, have reactive functional groups such as alkylene groups and polymerizable double bonds on their surface. Even if they do not have reactive functional groups on their surface, the aforementioned pretreatment process allows for the easy formation of reactive functional groups such as carboxyl groups, hydroxyl groups, and polymerizable double bonds on the surface. Therefore, by interposing the interfacial molecular binder in this composition solution, they can be bonded relatively easily with other organic materials such as resins or inorganic materials such as metals by lamination, plating, or resin varnish coating, ensuring good adhesion and "moisture resistance, or moisture resistance and heat resistance." However, difficult-to-bond resins such as polyimide (PI) and polyether ether ketone (PEEK) generally have a structure in which aromatic rings, fused rings, polyethers, etc. are linked together, and often do not have aliphatic carbon chains on their surface. Therefore, they do not have reactive functional groups on their surface, and it is not easy to form reactive functional groups at high density on their surface even by the aforementioned pretreatment process. Therefore, in the following examples, we will verify the adhesion, moisture resistance, and heat resistance of bonding using this composition liquid, using polyimide, a resin that is difficult to bond, as an example. [Examples]

[0117] <Synthesis Example 1> (Synthesis example of compound MPEI) In a glass reactor, 5 g of liquid polyethyleneimine (trade name: Epomin®, product number: SP-012, manufactured by Nippon Shokubai Co., Ltd., average molecular weight: 1200, amine value: 19 mmol / g, amine ratio: primary amino groups 35%, secondary amino groups 35%, tertiary amino groups 30%) was dissolved in 35 g of propylene glycol monomethyl ether (trade name: PGM propylene glycol monomethyl ether, manufactured by Daishin Chemical Co., Ltd., hereinafter referred to as "PGM"). The glass reactor was purged with dry nitrogen, and the internal temperature was raised while stirring until the PGM refluxed. As soon as the internal temperature reached the reflux temperature, a solution containing 3 g of allyl glycidyl ether and 2 g of 2-ethylhexyl glycidyl ether in 2 g of PGM was added dropwise over 30 minutes. The mixture was then stirred at reflux temperature for a further 9 hours. After this, the reaction batch in the glass reactor was slowly cooled. A pale yellow solution with an active ingredient concentration of 21.3% was obtained. When this solution was measured by gas chromatography, no signals for the starting materials, allyl glycidyl ether and ethylhexyl glycidyl ether, were detected, so it was determined that the reaction was complete. In the resulting target compound, it can be estimated that approximately 55.7% of the primary or secondary amino groups contained in the starting material polyethyleneimine were modified. This compound will be referred to as "compound MPEI" below. Compound MPEI is the polyethyleneimine-type IMB agent (or the polymer it contains), and its chemical structure is schematically represented by formula (12).

[0118] <Synthesis Example 2> (Synthesis example of compound PEA) In a glass reactor, 5 g of liquid pentaethylenehexamine was dissolved in 57 g of dipropylene glycol dimethyl ether (hereinafter referred to as "DPDM"). The glass reactor was purged with dry nitrogen, and the internal temperature was raised to 80°C while stirring. As soon as the temperature reached 80°C, 5.4 g of poly(ethylene glycol) diglycidyl ether (Average Mn 500) was added dropwise over 30 minutes. The mixture was then stirred at 80°C for a further 24 hours. After this, the reaction batch in the glass reactor was slowly cooled. When this solution was measured using high-performance liquid chromatography, a shift in the peaks of pentaethylenehexamine and poly(ethylene glycol) diglycidyl ether was observed, leading to the conclusion that the prepolymerization reaction was complete. Next, 5 g of 2-allylphenol and 6.3 g of paraformaldehyde were dissolved in a glass reactor containing the prepolymer. The glass reactor was purged with dry nitrogen, and the internal temperature was raised to 100°C while stirring. The mixture was then stirred at 100°C for a further 24 hours. After this, the reaction batch in the glass reactor was slowly cooled. A yellow solution with an active ingredient concentration of 27.6% was obtained. When this solution was measured by gas chromatography, no signal for the starting material 2-allylphenol was detected, so it was determined that the reaction was complete. Furthermore, IR analysis revealed signals for the C=C stretching vibration of the resulting compound, a signal originating from the benzoxazine ring, and an out-of-plane bending signal of the aromatic compound, so it was determined that the reaction was complete. This compound will be referred to as "compound PEA" below. Compound PEA is the polyetheramine-type IMB agent (or polymer containing it), and its chemical structure is schematically represented by formula (14).

[0119] To further illustrate the present invention, examples of preparations, embodiments, and comparative examples are given below. However, the present invention is not limited to these examples of preparations and embodiments, and can be implemented in other forms. The abbreviations for each component in the examples of preparations, embodiments, and comparative examples are as follows. (1) Polyamine polymer MPEI: The polyethyleneimine-type IMB agent (containing polymers) mentioned above. PEA: The above polyetheramine-type IMB agent (containing polymers) PEI: Polyethyleneimine (Product name: Epomin (registered trademark), Part number: SP-012, Manufactured by Nippon Shokubai Co., Ltd., Average molecular weight: 1200, Amine value: 19 mmol / g, Amine ratio: Primary amino groups 35%, Secondary amino groups 35%, Tertiary amino groups 30%) (For comparative example) (2)Thermopolymerizable compound BIS:N,N'—Methylenebis(acrylamide) BMI: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide TAIC: Triallyl isocyanurate DABPA:2,2'-Diallylbisphenol A (3) Azide compounds BAC-M:2,6-di(p-azidobenzal)-4-methylcyclohexanone (4)Organic sulfur compounds DTD: 2-Dibutylamino-4,6-Dimercapto-1,3,5-Triaidine DA:2,2'-Dithioaniline Furthermore, in the following, the symbol "wt%" will be used to mean "mass%".

[0120] <Preparation Examples 1-6> (Preparation of surface treatment solutions for metal-coated resin manufacturing) DABPA and TAIC were dissolved in PGM as "thermopolymer compounds" and each was prepared as a 2 wt% solution. DA was also dissolved in PGM as an "organosulfur compound" and prepared as a 2 wt% solution. Furthermore, BMI was dissolved in anisole as a "thermopolymer compound" and BAC-M as an "azide compound" and each was prepared as a 2 wt% solution. For the surface treatment solution used in the comparative example, PEI, a "polyamine polymer," was used, and PEI was dissolved in 3-methoxy-3-methyl-1-butanol (product name: Solfit, manufactured by Kuraray Co., Ltd., hereafter referred to as...). It was dissolved in (referred to as "SF") and adjusted to a 2 wt% solution. Each of these prepared 2 wt% solutions and the compound PEA synthesized in Synthesis Example 2 were weighed in the required mass and mixed with denatured ethanol (product name: Neoethanol PM, manufactured by Daishin Chemical Co., Ltd., hereinafter referred to as "MEtOH") to the concentrations shown in Table 1 to obtain the compositional solution. Hereafter, each prepared surface treatment solution for metal coating resin production will be used according to the "Name of Prepared Solution" listed in Table 1.

[0121] [Table 1]

[0122] <Examples 1-5 and Comparative Example 1> (Method for producing metal-coated resin and evaluation of adhesion reliability) The manufacturing method for the metal-coated resin consists of a cleaning step, a coating step, a heat activation step, and a pressurizing step. One 3cm x 10cm polyimide film (product name "Kapton 200H", thickness 50μm, manufactured by Toray DuPont Co., Ltd.) and one 3cm x 10cm unroughened copper foil (thickness 18μm, surface roughness Sa 0.19μm, manufactured by Fukuda Metal Foil & Powder Industry Co., Ltd.) were prepared, and each was treated to remove dust and other adhering substances using an air duster (cleaning step). Next, using a bar coater, the pre-prepared surface treatment solutions 1 to 6 were applied to the polyimide film and the unroughened copper foil surface to a wet film thickness of 12μm (coating step). After that, the polyimide film and the unroughened copper foil surface coated with surface treatment solutions 1 to 6 were held in a constant temperature bath at 85°C for 5 minutes (heat activation step). These surface-treated polyimide films and the unroughened copper foil surface were superimposed so that the surface-treated sides faced each other, and then heated and pressed together in a flat plate press machine at a press temperature of 210°C, a press time of 5 minutes, and a press pressure of 8.0 MPa, with cushion plates placed above and below, to produce a metal-coated resin (pressure process). The adhesion strength of the obtained metal-coated resin was measured by a 90° peel strength test on a 10 mm (1 cm) wide metal-coated resin. A 90° peel strength tester was constructed by attaching a force gauge ZTA-50N to a vertical electric measuring stand MX2-500N (manufactured by Imada Co., Ltd.). The peel speed was set to 50 mm / min. The peel strength was continuously measured over 3 cm of the 10 cm total length, excluding the 3.5 cm at both ends, and the average value was calculated. For the heat resistance test, which evaluates the reliability of adhesion, three samples of the metal-coated resin were prepared in the same manner as described above. These samples were placed in a 150°C heating furnace and left to stand for 168 hours before being removed. After removal, the adhesion strength was measured. For the humidity resistance test, which also evaluates the reliability of adhesion, three samples of the metal-coated resin were prepared in the same manner as described above. These samples were placed in a constant temperature and humidity chamber at 85°C and 85% humidity and left to stand for 168 hours before being removed. After removal, the samples were thoroughly dried and the adhesion strength was measured. The average value of the obtained adhesion strength was evaluated in four stages as described below, and the results are shown in Table 2. ◎: Adhesion retention rate after reliability evaluation test (%): 100-95% ○: Restoration rate of adhesion after reliability evaluation test (%): 94-75% △: Adhesion retention rate after reliability evaluation test (%): 74-50% ×: Adhesion retention rate after reliability evaluation test (%): 49-0%

[0123] [Table 2]

[0124] <Preparation Examples 7-15> (Preparation of surface treatment solutions for resin laminate manufacturing) BIS and TAIC were dissolved in PGM as "thermopolymerization compounds" and each was prepared as a 2 wt% solution. Similarly, DTD and DA were dissolved in PGM as "organosulfur compounds" and prepared as 2 wt% solutions. Furthermore, BMI as a "thermopolymerization compound" and BAC-M as an "azide compound" were dissolved in anisole and each was prepared as a 2 wt% solution. The required masses of each of these prepared 2 wt% solutions, along with the compounds MPEI and PEA synthesized in Synthesis Example 1 and Synthesis Example 2, were weighed and mixed with MEtOH to the concentrations shown in Table 3 to obtain the compositional solutions. Hereafter, each prepared surface treatment solution for metal coating resin production will be used according to the "Name of Prepared Solution" listed in Table 3.

[0125] [Table 3]

[0126] <Examples 6-14 and Comparative Example 2> (Method for manufacturing resin laminates and evaluation of adhesion reliability) Two 10cm x 10cm polyimide films, the same as those used in Examples 1-5, were prepared as the resin, and each was treated to remove dust and other contaminants using an air duster (cleaning step). Next, using a bar coater, the pre-prepared surface treatment solutions 6-15 were applied to a wet film thickness of 3. A single polyimide film was coated with a surface treatment solution 6-15 at a thickness of μm (coating step). Subsequently, the polyimide film coated with surface treatment solutions 6-15 was held in a constant temperature bath at 100°C for 5 minutes (heat activation step). These surface-treated polyimide films and untreated polyimide films were stacked so that the washed surfaces and surface-treated surfaces faced each other, and a resin laminate was fabricated by heating and pressing them together in a flat plate press machine at a press temperature of 200°C, a press time of 1 minute, and a press pressure of 8.0 MPa, with cushion plates placed above and below (pressure step). The obtained resin laminates were cut to a width of 2 cm, and the adhesion strength was measured for a 20 mm (2 cm) wide resin laminate using the same method as in Examples 1 to 5 and Comparative Example 1. Furthermore, in resin laminates with very high adhesion strength, a phenomenon was observed where the base material fractured at adhesion strengths of 15 N / 2 cm or higher. When this phenomenon occurred, the adhesion strength was defined as 15 N / 2 cm. For the heat resistance test, which evaluates the reliability of adhesion, a resin laminate was prepared using the above manufacturing method, and three samples were created by cutting it into 2 cm widths. These samples were placed in a 200°C heating furnace and left to stand for 168 hours before being removed. After sample removal, the adhesion strength was measured. For the moisture resistance test, which evaluates the reliability of adhesion, the same method as in Examples 1 to 6 was used. The average value of the obtained adhesion strength was evaluated in four stages as shown below, and the results are shown in Table 4. ◎: Adhesion retention rate after reliability evaluation test (%): 100-95% ○: Restoration rate of adhesion after reliability evaluation test (%): 94-75% △: Adhesion retention rate after reliability evaluation test (%): 74-50% ×: Adhesion retention rate after reliability evaluation test (%): 49-0%

[0127] [Table 4] [Industrial applicability]

[0128] The composition of the present invention is characterized by being non-silanol and non-ester, can be used mainly in a neutral to basic pH range, can improve the adhesion between various materials through interfacial molecular bonding, and ensures moisture resistance and heat resistance in the bonding, making it usable in many applications. In particular, it has a wide range of applications in the electrical and electronic fields. For example, it can be used in the manufacture of electrical and electronic devices such as printed circuit boards, lightweight spacers, probe sockets (test fixtures) for semiconductor testing equipment, and resin core metal foils for battery electrode plates. Other applications such as packaging films and decorative plating are also being considered. [Explanation of Symbols]

[0129] S1 Pretreatment process S2 coating process S4 Heat activation process S6 UV activation process S8 Post-activation cleaning process S3, S5, S7, S9 Branching decision steps

Claims

1. This is a compositional liquid intended to be applied to at least one of two substances for the purpose of improving the adhesion between them. Polymers and, Thermopolymerizable compounds, Azide compounds and, The polymer includes, A first repeating unit having a primary amino group or a secondary amino group, A second repeating unit having an allyl group, A third repeating unit having hydrophobic functional groups other than allyl groups, The thermally polymerizable compound comprises, Acrylamide derivatives having two or more polymerizable double bonds, maleimide compounds, and allyl monomers having two or more allyl or allyloxy groups directly bonded to a (hetero)aryl group or hydrocarbon group. A compositional liquid that is one of the following selected from the group consisting of the above.

2. The compositional liquid according to claim 1, wherein the total concentration of the polymer, the thermopolymerizable compound, and the azide compound in the compositional liquid is 0.02% by mass or more and 4% by mass or less.

3. The compositional solution according to claim 2, wherein the polymer, the thermopolymerizable compound, and the azide compound do not contain ester bonds.

4. The compositional solution according to claim 3, further comprising the polymer and the azide compound, and further lacking an amide bond.

5. The compositional solution according to claim 3, wherein the second repeating unit has an allylphenol group.

6. The compositional liquid according to claim 3, wherein the polymer further comprises a polyether block in which three or more and 35 or fewer repeating units consisting of C2 to C4 alkylene oxy groups are continuously linked together.

7. The compositional solution according to claim 6, wherein the polymer has two allylbenzoxazine rings at its terminals, and in the polymer, one of the allylbenzoxazine rings is located opposite to the other allylbenzoxazine ring with respect to the polyether block.

8. The compositional solution according to claim 3, wherein the hydrophobic functional group other than the allyl group is a C4 to C14 alkyl group, a (hetero)aryl group, an alkyl(hetero)aryl group, or a (hetero)arylalkyl group.

9. The compositional solution according to claim 3, wherein the thermally polymerizable compound is an acrylamide derivative having two or more polymerizable double bonds.

10. The compositional solution according to claim 3, wherein the thermally polymerizable compound is a maleimide compound.

11. The compositional solution according to claim 3, wherein the thermally polymerizable compound is an allyl monomer having two or more allyl groups or allyloxy groups directly bonded to a (hetero)aryl group or hydrocarbon group.

12. The compositional solution according to claim 3, further comprising an organic sulfur compound, wherein the organic sulfur compound does not have an ester bond.

13. The compositional solution according to claim 12, wherein the organic sulfur compound is a compound having two or more thiol groups, or a compound having a disulfide group.

14. The compositional solution according to claim 3, wherein the azide compound is a compound having two or more azide groups directly bonded to an aromatic ring.

15. The compositional solution according to claim 3, wherein the polymer is a compound represented by the following formula (12). (wherein n, m, and l are integers of 1 or more.) 【Chemistry 1】

16. The compositional solution according to claim 4, wherein the polymer is a compound represented by the following formula (13). (wherein n, m, and l are integers of 1 or more.) 【Chemistry 2】

17. The compositional solution according to claim 5, wherein the polymer is a compound represented by the following formula (14). (wherein n, m, and l are integers of 1 or more.) 【Transformation 3】

18. A method for producing a surface-treated substance, comprising the step of applying a compositional liquid according to any one of claims 1 to 17 to the surface of a substance.

19. A step of applying the compositional liquid according to any one of claims 1 to 17 to the surface of a resin, A step of heating the surface or irradiating the surface with ultraviolet light, Next, a step of forming a metal plating layer on the surface by wet plating, A method for producing a metal-coated resin having the properties of a metal.

20. A step of applying the compositional liquid according to any one of claims 1 to 17 to the surface of at least one of the resin and the metal foil, A step of heating the surface or irradiating the surface with ultraviolet light, Next, the resin and metal foil are laminated via the surface and pressed together to integrate them; A method for producing a metal-coated resin having the properties of a metal.

21. A step of applying the compositional liquid according to any one of claims 1 to 17 to the surface of a first resin, A step of heating the surface or irradiating the surface with ultraviolet light, Next, the first resin and the second resin are brought into contact via the surface and pressed together to integrate them. A method for manufacturing a resin laminate having [the specified characteristic].

22. A step of applying the compositional liquid according to any one of claims 1 to 17 to the surface of a substance, A step of heating the surface or irradiating the surface with ultraviolet light, Next, the process involves applying a hardening liquid onto the surface, A step of curing the aforementioned curing liquid to form a cured material that covers the surface, A method for producing a cured coating material having the properties of a cured product.

Images