Composition liquid for surface treatment, surface treatment material, metal coating resin, resin laminate, and method for producing resin

Abstract

The present invention addresses the problem of providing a general-purpose combination liquid that can be used in neutral to alkaline regions, which is a surface treatment liquid for securing adhesion, and also providing a method for producing a metal-coated resin or a resin laminate by plating or bonding using this combination liquid. In order to solve the above-mentioned problem, the present invention provides a combined liquid containing a diazide compound and a polymer provided with a first repeating unit having a primary amino group or a secondary amino group and a second repeating unit having one or more functional groups selected from the group consisting of a silanol group, an alkoxysilyl group, an epoxy group, an acryloyl group, and a methacryloyl group. The composition liquid contains a plurality of compounds such that the composition liquid can be subjected to a chemical reaction involving interfacial molecular bonding by heating and / or by irradiation with ultraviolet light after coating. It is preferable that at least two of the azide groups contained in the diazide compound are azide groups directly bonded to an aromatic ring. It is preferable that the second repeating unit comprises a polysiloxane skeleton.

Description

Technical Field

[0001] This invention relates to a combination liquid for surface treatment applied to a material to improve adhesion, a method for manufacturing a surface treatment material using the combination liquid, a method for manufacturing a metal-coated resin, a method for manufacturing a resin laminate, and a method for manufacturing a resin-coated material. Background Technology

[0002] Compounds with two or more functional groups can form chemical bonds by utilizing the properties of each functional group. Therefore, they can be used as interfacial molecular bonding agents for interface molecular bonding (IMB), where the interfacial molecular bond lies between two substances and binds them together through chemical bonds. Because the interfacial molecular bonding agent bonds the two substances through chemical bonds, the bond between the two substances is strong, and bond formation does not necessarily require high temperatures. Based on interfacial molecular bonding, the two substances can bond at a flat interface without relying on the anchoring effect caused by interface roughness. Furthermore, since only a small number of interfacial molecular bonding agent molecules are present at the interface, the problem of bond brittlement caused by volatile gases is less likely to occur, which also has environmental advantages.

[0003] Interfacial molecular bonding technology can be used in a variety of applications to bond two substances at the interface. It is particularly widely applied in the electrical / electronic fields. Examples include applications in the manufacture of printed circuit boards or lightweight spacers, probe sockets (test fixtures) for semiconductor testing equipment, and resin-core metal foil for battery plates.

[0004] For the use of interfacial molecular bonding technology, a combination liquid containing compounds having two or more functional groups is typically required. Patent Document 8, belonging to some of the inventors of this invention, discloses a combination liquid containing an azide aromatic carboxylic acid and an amine polymer, exhibiting a weakly acidic to acidic pH. This combination liquid is useful in ensuring adhesion between resins, resins and metals, and other substances, but is primarily suitable for use in the weakly acidic to acidic pH range. Additionally, Patent Document 9 discloses a combination liquid containing siloxane oligomers, which is prepared by hydrolyzing and dehydrating condensing silane monomers having aromatic azide and alkoxysilyl groups and silane monomers having amino and alkoxysilyl groups. This combination liquid is also useful in ensuring adhesion between resins, resins and metals, and other substances, but requires high manufacturing costs. A combination liquid is sought that can be used in a wide pH range beyond acidity and ensure adhesion for a wide variety of combinations of substances.

[0005] Patent Document 1 discloses an invention of a surface treatment agent for plastics containing an epoxy silane compound and a polyalkylene imide. This surface treatment agent is not an interfacial molecular bonding agent for binding the two substances, but rather a combination liquid for forming a cured coating on the plastic surface. Furthermore, this surface treatment agent does not contain azid compounds.

[0006] Patent Document 2 discloses an invention of a composition containing a silane-modified polymeric amine with biocidal activity. This composition is used to form a substantially non-sticky coating after being applied to a surface such as a resin film, and is not an interfacial molecular bonding agent for binding two substances. Furthermore, this composition does not contain diazid compounds.

[0007] Patent document 3 discloses a method for manufacturing a printed circuit board, which includes coating a substrate with a polyamine polymer and then contacting it with noble metal ions. The method is characterized by modifying the polyamine polymer with a compound containing a reactive functional group in the amino group before contact. However, this document does not describe the use of silane compounds to modify the polyamine polymer, nor does it describe diazid compounds.

[0008] Patent Document 4 discloses an invention for manufacturing composite materials such as metal nanowires, which includes the following steps: in an aqueous medium, by adding an epoxy-based alkoxysilane to an associative polymer having a linear polyethyleneimine backbone, a composite of the polymer associative polymer and silica is obtained; the composite is then contacted with a solution containing dissolved transition metal ions, causing the transition metal ions to coordinate and bind to the linear polyethyleneimine backbone in the polymer. However, Patent Document 4 does not describe the use of a combination solution containing silane-modified polyethyleneimine as a pretreatment solution for non-electrolytic plating of substrates such as resin films with a large expansion area, nor does it describe a diazid compound.

[0009] Patent Document 5 discloses a method for modifying the polymer surface of a substrate, showing a method of forming a grafted crosslinked network by contacting a polymer surface with functional groups with a polyamine compound and a crosslinking agent. Examples of crosslinking agents in this document include epoxy silanes, acryloyl silanes, and glycidyl acrylate, but diazid compounds are not mentioned. Furthermore, while this document describes the adhesion between the polymer and the metal coating, it does not describe the application of the above modification method to an electroless plating process.

[0010] Patent document 6 discloses an invention of a barrier polyamine coating for interlayer adhesion of a laminated film for packaging. The combination liquid used to form the coating may contain polyamine, silane acrylate, epoxy silane, glycidyl acrylate, etc. as crosslinking agents, but does not describe diazid compounds.

[0011] Patent document 7 discloses an invention containing a coating of an olefinic unsaturated acid, a polyamine, or a bissilane that has barrier properties useful for packaging applications. It describes that epoxy silane, acryloyl silane, glycidyl methacrylate, etc. are preferably added as crosslinking agents, but does not describe bisazide compounds.

[0012] Existing technical documents

[0013] Patent documents

[0014] Patent Document 1: Japanese Patent Publication No. 59-043051

[0015] Patent Document 2: Japanese Patent Publication No. 2008-540753

[0016] Patent Document 3: Japanese Patent Application Publication No. 03-173196

[0017] Patent Document 4: Japanese Patent No. 3978440

[0018] Patent Document 5: Japanese Patent Publication No. 2003-512490

[0019] Patent Document 6: Japanese Patent No. 3851354

[0020] Patent Document 7: Japanese Patent Publication No. 2004-528395

[0021] Patent Document 8: Japanese Patent No. 7120695

[0022] Patent Document 9: Japanese Patent Application Publication No. 2022-048068 Summary of the Invention

[0023] The problem that the invention aims to solve

[0024] The first object of this invention is to provide a composite liquid applied to a material to ensure adhesion during plating, bonding, etc. This composite liquid can be used primarily in neutral to alkaline environments and is applicable to multiple substances or combinations of substances. The second object of this invention is to provide a method for manufacturing a surface-treated material using the aforementioned composite liquid, a method for manufacturing a metal-coated resin by plating or bonding, a method for manufacturing a resin laminate, or a method for manufacturing a resin-coated material. The aforementioned composite liquid contains a compound or a combination of multiple compounds, enabling the composite liquid to undergo a chemical reaction involving interfacial molecular bonding after coating by heating and / or irradiation with ultraviolet light.

[0025] Methods for solving problems

[0026] The first aspect of the present invention is a combination liquid applied to at least one of two substances to improve the adhesion of the two substances, comprising a polymer and a diazid compound, wherein the polymer has a first repeating unit and a second repeating unit, the first repeating unit having a primary or secondary amino group, and the second repeating unit having one or more functional groups selected from silanol, alkoxysilyl, epoxy, acryloyl, and methacryloyl.

[0027] The second aspect of the present invention is a combination liquid of the first aspect described above, wherein the second repeating unit has a silanol group or an alkoxysilyl group.

[0028] The third aspect of the present invention is a combination liquid applied to the material to be plated in order to improve the adhesion of the plating, comprising a polymer having a first repeating unit and a second repeating unit, the first repeating unit having a primary amino or secondary amino group, and the second repeating unit having a silanol group or an alkoxysilyl group.

[0029] The fourth aspect of the present invention is a combination of the first, second or third aspects described above, wherein the polymer has a second repeating unit, and the second repeating unit has one or more functional groups selected from epoxy, acryloyl and methacryloyl.

[0030] The fifth aspect of the present invention is a combination of the second or third aspects described above, wherein the second repeating unit contains a polysiloxane backbone.

[0031] The sixth aspect of the present invention is a combination of the first, second or third aspects described above, wherein the polymer has a polyethyleneimine structure.

[0032] The seventh aspect of the present invention is a combination of the first or second aspect described above, wherein at least two of the azide groups contained in the bisazide compound are azide groups directly bonded to the aromatic ring.

[0033] The eighth aspect of the present invention is a method for manufacturing a surface treatment material, which includes a step of coating a combination liquid of the first, second or third aspects described above onto the surface of the material (coating step).

[0034] The ninth aspect of the present invention is a method for manufacturing a metal-coated resin, comprising: a step of coating a combination liquid of the first, second or third aspect onto a resin surface (coating step); a step of heating the surface or irradiating the surface with ultraviolet light (activation step); and then, a step of forming a metal coating on the surface by wet plating (wet plating) (plating step).

[0035] The tenth aspect of the present invention is a method for manufacturing a metal-coated resin, comprising: a step of coating the combined liquid of the first aspect onto the surface of at least one of the resin and the metal foil (coating step); a step of heating the surface or irradiating the surface with ultraviolet light (activation step); and then, a step of stacking the resin and the metal foil through the surface and integrating them under pressure (pressing step).

[0036] The eleventh aspect of the present invention is a method for manufacturing a resin laminate, comprising: a step of coating the combined liquid of the first aspect onto the surface of a first resin (coating step); a step of heating the surface or irradiating the surface with ultraviolet light (activation step); and then, a step of laminating a second resin onto the surface and pressing it to integrate them (pressing step).

[0037] The 12th aspect of the present invention is a method for manufacturing a resin-coated material, comprising: a step of coating the combined liquid of the first aspect onto the surface of the material (coating step); a step of heating the surface or irradiating the surface with ultraviolet light (activation step); a step of coating the surface with a resin varnish (resin coating step); and a step of curing the varnish (curing step).

[0038] Invention Effects

[0039] According to one embodiment of the present invention, a combination liquid is provided for application to a material to ensure adhesion in plating, bonding, etc. It is primarily usable in neutral to alkaline environments and is applicable to a variety of substances or combinations of substances. The aforementioned combination liquid contains compounds or combinations of compounds, enabling a chemical reaction involving interfacial molecular bonding to occur after coating by heating and / or ultraviolet irradiation.

[0040] According to another embodiment of the present invention, a method for manufacturing a surface treatment substance using the combined liquid, a method for manufacturing a metal-coated resin by plating or bonding, a method for manufacturing a resin laminate, or a method for manufacturing a resin-coated substance can be provided. Attached Figure Description

[0041] Figure 1 This is an illustration of the interfacial molecular bonding mechanism.

[0042] Figure 2 This is a flowchart of the manufacturing method for surface-treated materials. Detailed Implementation

[0043] Next, the embodiments of the present invention will be described in detail. It should be noted that the present invention is not limited to the embodiments or examples described below, but should be understood to include various modifications or variations implemented within the scope of the technical concept of the present invention.

[0044] <Combination Solution>

[0045] According to one embodiment of the present invention, a combined liquid for coating on at least one of two substances to improve the adhesion of the two substances can be provided, comprising a polymer and a diazid compound, wherein the polymer has a first repeating unit and a second repeating unit, the first repeating unit having a primary or secondary amino group, and the second repeating unit having one or more functional groups selected from silanol, alkoxysilyl, epoxy, acryloyl, and methacryloyl.

[0046] (The purpose is to improve the seal)

[0047] "Applying the combined liquid to at least one of the two substances to improve their adhesion" refers to improving adhesion by introducing a compound from the combined liquid at the interface between the two substances. For example, the combined liquid of this embodiment is applied to resin, metal, or other inorganic materials to manufacture a resin film laminate formed by integrally bonding two resin films, to form a metal coating bonded to the resin surface by plating or lamination, or to form a coating on a resin varnish cured material bonded to inorganic materials such as metal, glass, or ceramics.

[0048] (Coating)

[0049] Here, "coating" is not limited to methods such as brushing, but generally refers to the application of liquid to the surface of a substance or the presence of liquid in a contact state. Preferably, "coating" includes the process of removing the solvent of the liquid by drying or other means after the liquid has been applied to or contacted with the surface of the substance, leaving the solute on the surface.

[0050] (The first repeating unit containing a primary or secondary amino group)

[0051] The composite liquid of the present invention contains a polymer having a first repeating unit, which is a primary amino (-NH2) or secondary amino (-NH-). After the coating and activation process of the composite liquid of the present invention, the polymer forms bonds with the surface of the above-mentioned substances and / or diazid compounds through a chemical reaction, which facilitates the formation of interfacial molecular bonds. An example of the first repeating unit is a repeating unit shown in any of the following formulas (1) to (6).

[0052] [Chemistry 1]

[0053]

[0054] In each of equations (1) to (6), a is an integer greater than or equal to 0, for example, an integer greater than or equal to 1 and less than 10, preferably an integer greater than or equal to 1 and less than 4, more preferably 1, R 1 R 2 and R3 Each independently represents a H atom, a substituted or unsubstituted alkyl group (e.g., having 1 to 25 carbon atoms, or 1 to 5 carbon atoms) or an aryl group (e.g., phenyl or benzyl), Z - This indicates anion in the solution that is not included in the aforementioned polymer. Preferably, in the formulas, R... 1 R 2 and R 3 At least one of them is a hydrogen atom.

[0055] In equations (1) to (6), R 1 R 2 and R 3 The alkyl or aryl group may have one or more substituents. Suitable substituents include, for example, cationic groups that are quaternary ammonium groups, or amino groups that are, for example, primary, secondary, or tertiary alkylamines or arylamines. Other suitable substituents include hydroxyl, alkoxy, alkyl, aryl, poly(ethyleneimine), and poly(alkyleneimine).

[0056] The first repeating unit is preferably selected from polyalkyleneimide ([C m H 2m NH] n The repeating unit is a polymer selected from one or more polymers of polyethyleneimine, polyvinylamine, and polyallylamine, where m is an integer of 1 to 4 and n is an integer of 2 or more. More preferably, the repeating unit is a polymer selected from one or more polymers of polyethyleneimine, polyvinylamine, and polyallylamine.

[0057] (Second repeating unit)

[0058] The composite liquid of the present invention contains a polymer having a second repeating unit, wherein the second repeating unit has a silanol group, an alkoxysilyl group, an epoxy group, an acryloyl group, or a methacryloyl group. Because the polymer has the aforementioned second repeating unit, after the coating and activation process of the composite liquid of the present invention is performed on a wider range of materials, it can form bonds with the surface and / or diazid compounds of the aforementioned materials through chemical reactions, thereby facilitating the formation of interfacial molecular bonds.

[0059] As a second repeating unit, for example, in equations (1) to (6) which are examples of the first repeating unit, R 1 R 2 and R 3 At least one of the used formulas -Z 1 -Q 1 The repeating unit represents the substitution of a group. Here, Z 1 It is a divalent linker, Q 1It includes groups such as silanol or alkoxysilyl, epoxy, acryloyl or methacryloyl.

[0060] "Groups including silanol or alkoxysilyl groups" are derived from the formula -Si(R 4 The group represented by )3, where there are 3 R 4 Each of the three R groups is independently selected from hydrogen atom, OH group, alkyl group with 4 or fewer carbon atoms, alkoxy group with 4 or fewer carbon atoms, phenyl group, phenoxy group, benzyl group, and phenoxy group, and the three R groups are... 4 At least one of them contains an O atom. Examples of "groups including silanol or alkoxysilyl" include: trimethoxysilyl, triethoxysilyl, trisilanol, etc.

[0061] Z 1 It is a substituted or unsubstituted straight-chain alkylene group, and is:

[0062] From the formula - (CR 5 R 6 ) b - represents a group (where b is an integer of 1 to 25, preferably 1 to 10, more preferably 1 to 5). Multiple R 5 R 6 Each can be independently a hydrogen atom, an alkyl group (with 1 to 10 carbon atoms, or 1 to 5 carbon atoms), or an aryl group (with 9 to 9 carbon atoms, or a phenyl or benzyl group).

[0063] In the above formula -(CR) 5 R 6 ) b - indicates a group formed by repeated insertion of one to three intercalation groups at one, two, or three selected locations, including the left and right ends of the group and any adjacent C atoms.

[0064] Each insert group is independently selected from -O-, -(C=O)-, -(C=O)NR-, -NR(C=O)-, -(C=O)O-, -O(O=C)-, -C(OH)-, and -NR-. R is a H atom, a substituted or unsubstituted alkyl group (with 1 to 10 carbon atoms, or 1 to 5 carbon atoms), or an aryl group (with 9 to 9 carbon atoms, or a phenyl or benzyl group). Here, the alkyl or aryl group represented by R may have more than one substituent. Suitable substituents include, for example, cationic groups as quaternary ammonium groups, or amino groups as primary, secondary, or tertiary alkylamines or arylamines. Other suitable substituents include hydroxyl, alkoxy, or alkyl groups (with 1 to 10 carbon atoms, or 1 to 5 carbon atoms), aryl groups (with 9 to 9 carbon atoms, or a phenyl or benzyl group), poly(ethyleneimine), poly(alkyleneimine), etc.

[0065] As another example of the second repeating unit, for example, in the various equations (1) to (6) which are examples of the first repeating unit, R 1 R 2 and R 3 At least one of the predicates -Z 1 -*-Q 1 The repeating unit represents the substitution of a group. Here, Z 1 and Q 1 The same group as above is indicated by *, which indicates a siloxane polymer (or oligomer) or an organic polymer (or oligomer).

[0066] Thus, in one embodiment of the present invention's composite liquid where the second repeating unit comprises a polymer or oligomer, the side chains of the polymer contained in the composite liquid have a functional group Q at their ends. 1 The polymer or oligomer has the following advantages: it can crosslink while absorbing the differences in position caused by the different distances between the surfaces of the two substances at the microscopic observation interface, thus stably ensuring the tightness of the interfacial molecular bonding. It should be noted that the combination liquid of this embodiment is generally applicable to interfacial molecular bonding where at least one of the two substances is an inorganic material when the second repeating unit contains a siloxane polymer, and to interfacial molecular bonding where at least one of the two substances is an organic material when the second repeating unit contains an organic polymer.

[0067] (Specific examples of the polymers of the present invention)

[0068] The polymer of this invention must have a first repeating unit. The first repeating unit has a primary amino or secondary amino group. The second repeating unit is a general term for repeating unit units having other functional groups, and various second repeating units may exist in the polymer.

[0069] Specific examples of polymers having a trimethoxysilyl group as the second repeating unit and having a polyethyleneimine structure include the following compound (hereinafter referred to as "Compound ET"). (n and m are positive real numbers representing natural numbers or composition ratios. The same applies below.)

[0070] [Chemistry 2]

[0071]

[0072] In addition, as a specific example of a polymer having both a second repeating unit containing a methacryloyl group and a second repeating unit containing an epoxy group and having a polyethyleneimine structure, the following compound (hereinafter referred to as "compound ETG") can be cited.

[0073] [Chemistry 3]

[0074]

[0075] In addition, as a specific example of a polymer that simultaneously has a second repeating unit containing trimethoxysilyl, a second repeating unit containing methacryloyl, and a second repeating unit containing an epoxy group and the above polymer has a polyethyleneimine structure, the following compound (hereinafter referred to as "compound ETMX") can be cited.

[0076] [Chemistry 4]

[0077]

[0078] (Polymer preparation method)

[0079] The method for preparing the polymer having a first repeating unit contained in the combination liquid of the present invention is well known, for example disclosed in Japanese Patent Application Publication No. 2016-047849 and the patent documents cited therein.

[0080] The polymer containing a first repeating unit and a second repeating unit in the combination liquid of the present invention, for example as shown later in the synthesis examples, can be prepared by first preparing a polymer having a first repeating unit, and then reacting it with an epoxy silane compound or an epoxy acrylate compound to modify a portion of the primary or secondary amino groups contained in the polymer.

[0081] The epoxy silane compound used in the above reaction is not limited, and examples include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane.

[0082] The epoxy acrylate compound used in the above reaction is not limited, but examples include glycidyl acrylate, glycidyl methacrylate, etc.

[0083] (The structure of the polymer)

[0084] The polymers containing the first and second repeating units in the composite liquid of the present invention can be of any type: linear, branched, or dendritic polymer structure. Alternatively, they can be cross-linked using a difunctional cross-linking agent such as epichlorohydrin.

[0085] (Weight-average molecular weight of the polymer)

[0086] From the viewpoint of suppressing uneven coating of the composite solution of the present invention, the weight-average molecular weight of the polymer having a first repeating unit and a second repeating unit contained in the composite solution of the present invention is preferably 20,000 or less, more preferably 3,000 or less, and even more preferably 1,500 or less. Furthermore, from the viewpoint of ensuring the tightness of interfacial molecular bonding while simultaneously allowing cross-linking to occur due to differences in position when absorbing the distance between the surfaces of the two substances facing each other at the microscopic observation interface, the aforementioned weight-average molecular weight is preferably 200 or more, more preferably 450 or more, and even more preferably 900 or more. It should be noted that in this specification, the weight-average molecular weight of the polymer refers to the weight-average molecular weight converted from polystyrene as determined by gel permeation chromatography (GPC).

[0087] In the combined liquid of the present invention, one of the above polymers may be used, or two or more polymers may be used in combination.

[0088] (Polymer concentration)

[0089] In the combined solution of the present invention, from the viewpoint of ensuring the tightness of interfacial molecular bonding, the concentration of the polymer is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.05% by mass or more. Furthermore, from the viewpoint of suppressing uneven coating, the concentration is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. It should be noted that when two or more of the above-mentioned polymers are used in combination, "the concentration of the above-mentioned polymers" refers to the sum of the concentrations of each of the above-mentioned polymers.

[0090] (Diazide compound)

[0091] The combination solution of this invention comprises a bisazide compound. In this specification, a "bisazide compound" refers to a compound having two or more azido groups (-N3) located at different ends of a molecule. The azido groups can originate from the azide ion (N3... -The compound contains a diazid group. It should be noted that "the two diazid groups are located at different ends" means that the two diazid groups are not directly bonded to the same atom within a molecule. Because diazid compounds contain diazid groups, heating or light irradiation can produce nitrobenes as active substances. Considering that even low-temperature heating of around 80–160°C or irradiation with long-wavelength light of around 260–365 nm in ultraviolet light can promote nitrobene formation, diazid compounds preferably contain substituted or unsubstituted aromatic groups (aromatic rings), more preferably the aromatic ring is directly bonded to the diazid group, and even more preferably the aromatic ring directly bonded to the diazid group is a substituted or unsubstituted benzene ring. The combination liquid of the present invention, by containing a diazid compound, can promote the bonding reaction between the diazid compound and the aforementioned polymer and / or the bonding reaction between the diazid compound and the substance coated with the combination liquid of the present invention or other substances laminated on the substance, thereby improving the adhesion between the substance coated with the combination liquid of the present invention and other substances laminated on the substance.

[0092] If we exemplify preferred diazide compounds having two aromatic rings as components of the composite liquid of the present invention in ascending order of the distance between the two azido groups (where "distance" refers to the minimum number of atoms contained in the arrangement of atoms connecting the two azido groups. For example, in diazidomethane, the two azido groups are connected by one carbon atom, so the "distance" between the two azido groups is 1), the following examples are provided:

[0093] 3,3'-Diazidodiphenyl sulfone, 3,3'-Diazidodiphenyl sulfide, 3,3'-Diazidodiphenyl disulfide, 4,4'-Diazidobiphenyl, 4,4'-Diazidodiphenyl ether, 4,4'-Diazidobenzophenone, 4,4'-Diazidodiphenylmethane, 3,3'-Dichloro-4,4'-Diazidodiphenylmethane, 4,4'-Diazidodiphenyl sulfone, 4,4'-Diazidodiphenyl sulfide

[0094] 4,4'-Diazido group 4,4'-diazido group -2,2'-disulfonic acid (disodium salt), 4,4'-diazido group -2,2'-disulfonamide, 4,4'-diazido group -2,2'-Disulfonyl-N-(p-methoxyphenyl)amide, 4,4'-diazido- -2,2'-Disulfonyl-N-(p-hydroxyethylphenyl)amide, 4,4'-diazidoxy -2,2'-Disulfonyl-N-(p-hydroxyphenyl)amide, 4,4'-Diazidodiphenyl disulfide,

[0095] 4,4'-Diazidochalcone, 4,4'-Diazidochalcone-2-sulfonic acid (sodium salt)

[0096] 2,6-Bis(4'-azidobenzyl)cyclohexanone, 2,6-Bis(4'-azidobenzyl-2'-sulfonic acid (sodium salt))cyclohexanone, 2,6-Bis(4'-azidobenzyl)-4-methylcyclohexanone, 2,6-Bis(4'-azidobenzyl)-4-ethylcyclohexanone, 1,3-Bis(4'-azidobenzyl)-2-propanone, 1,3-Bis(4'-azidobenzyl-2'-sulfonic acid (sodium salt))-2-propanone, 4,4'-diazidobenzylacetone, 2,5-Bis(4'-diazidobenzyl-2'-sulfonic acid (sodium salt))cyclopentanone,

[0097] 2,6-bis(4'-azidocinimyl)cyclohexanone, 2,6-bis(4'-azidocinimyl)-4-methylcyclohexanone, 1,3-bis(4'-azidocinimyl)-2-propanone, etc.

[0098] If we exemplify preferred components of the composite liquid of the present invention, which are bisazide compounds having three or more aromatic rings or fused rings, in order of increasing distance between the two azide groups, examples include:

[0099] 2,7-Diazido-9H-fluorene-9-one, 6-azido-2-(4'-azidostyryl)benzimidazole, 1,4-bis(3'-azidostyryl)benzene, 1,4'-azidobenzyl-3-α-hydroxy-4''-azidobenzylindene, etc.

[0100] In the combined solution of the present invention, one type of diazid compound may be used, or two or more types may be used in combination.

[0101] As an example of a bis(4'-azidobenzylidene)-4-methylcyclohexanone (hereinafter referred to as "BABMC"), which is a bis(azidobenzylidene) compound having two azido groups directly bonded to a benzene ring and is a preferred embodiment of the present invention, the structural formula of 2,6-bis(4'-azidobenzylidene)-4-methylcyclohexanone (hereinafter referred to as "BABMC") is shown below.

[0102] [Chemistry 5]

[0103]

[0104] (Synthesis of diazide compounds)

[0105] The synthesis methods for the above-mentioned bisazide compounds are not particularly limited, and for example, they can be obtained by the following known methods: for aromatic compounds, (1) introducing the azido group using sodium azide, (2) introducing the azido group using tolyl azide or trifluoromethanesulfonyl azide, (3) introducing the azido group through a coupling reaction using a copper catalyst, etc. In addition, most of the above-mentioned bisazide compounds are commercially available.

[0106] (Concentration of diazide compounds)

[0107] From the viewpoint of ensuring the tightness of interfacial molecular bonding, the concentration of the diazid compound in the combined solution of the present invention is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.05% by mass or more. Furthermore, from the viewpoint of suppressing uneven coating, the above concentration is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. It should be noted that when two or more diazid compounds are used in combination, the "concentration of the diazid compound" refers to the sum of the concentrations of each diazid compound.

[0108] (The solvent of the combined solution of this invention)

[0109] The combined solution of this invention contains a solvent. The solvent can be any solvent capable of dissolving the aforementioned polymer and diazid compound, and is not particularly limited. Examples include: alcohols such as methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, cellosolve, carbitol, propylene glycol monomethyl ether, and 3-methoxy-3-methyl-1-butanol (hereinafter referred to as "SF"); 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); and water. Alcohols, ethers, and water are preferred. Only one solvent may be used, or two or more solvents may be used in combination.

[0110] (pH of the combined solution of this invention)

[0111] The pH of the composite solution of the present invention at 25°C is preferably 11.0 or lower, more preferably 10.0 or lower, and even more preferably 9.0 or lower. Furthermore, this pH is preferably 7.0 or higher, more preferably 7.5 or higher, and even more preferably 8.0 or higher. By ensuring the pH of the composite solution of the present invention meets the above conditions, the chemical stability of the composite solution in an atmospheric atmosphere is ensured, and the formation of interfacial molecular bonds after coating is promoted. It should be noted that in this specification, the pH of the composite solution refers to the value measured at 25°C using pH test paper (UNIVERSAL test paper, manufactured by Advantec Toyo Co., Ltd.), with a measurement error of approximately ±0.5.

[0112] (substance)

[0113] The two substances used in the preparation of the laminate using the combined liquid of the present invention can be composed of the same material or different materials. Each substance can be composed of multiple materials. Each substance can be a substance with a coating or the like on its surface. Each substance can be part of an object composed of multiple materials. Examples of materials constituting each substance include: organic materials such as resins and elastomers, and inorganic materials such as glass, ceramics, metals, silicon wafers, and coating substrates (catalysts).

[0114] As used in this specification, "resin" may include, for example, thermoplastic resins and thermosetting resins.

[0115] 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 methacrylate (PMMA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), and cyclic olefin polymers (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), polyether-imide (PEI), polyether-ether ketone (PEEK), thermoplastic polyimide (TPI), liquid crystal polymer (LCP), and polytetrafluoroethylene (PTFE).

[0116] Examples of thermosetting resins include: phenolic resin (PF), epoxy resin (EP), melamine resin (MF), urea-formaldehyde resin (UF), unsaturated polyester resin (UP), alkyd resin, polyurethane (PUR), polyimide (PI), modified polyimide (MPI), and thermosetting polyimide. Commercial forms of thermosetting resins include: C-stage (cured) sheets such as polyimide, laminated sheets, prepregs, chip bonding sheets, B-stage (uncured) sheets such as ACF (anisotropic conductive film), and A-stage materials such as conductive or insulating composites, pastes, or inks.

[0117] Examples of elastomers include: natural rubber, synthetic rubber, polyurethane rubber, silicone rubber, and fluororubber.

[0118] Examples of metals include copper, silver, gold, nickel, and aluminum.

[0119] Examples of glass include: ordinary sodium glass (whiteboard glass, etc.), borosilicate glass, lead glass, flint glass, optical glass, quartz glass, etc.

[0120] Examples of ceramic materials include: alumina, zirconium oxide, aluminum nitride, silicon carbide, silicon nitride, boron nitride, forsterite, talc, cordierite, seron (silicon aluminum oxy nitrogen), barium titanate, lead zirconate titanate, fir olivine, mullite, mica, etc.

[0121] There are no particular limitations on the shape of the two substances. Specific shapes of the substances used to coat the liquid mixture of the present invention include, for example, plate-like, sheet-like, film-like, tubular, columnar, linear (rope-like), irregular block-like, and any other shape formed into a specified form.

[0122] In some embodiments of the present invention, the material onto which the coating liquid is applied (the material for surface treatment) is preferably a non-fibrous substrate. A fiber refers to, for example, a linear solid with a maximum diameter of less than 0.1 mm and a length exceeding 10 times the maximum diameter. When the material onto which the coating liquid is applied in this embodiment is linear, its maximum diameter is preferably 0.1 mm or more, more preferably 1 mm or more. Furthermore, its length is preferably less than 10 times the maximum diameter, more preferably less than 5 times. By surface treating the non-fibrous material in this way, a combination of two materials can be effectively obtained.

[0123] (The bonding between silanol groups or alkoxysilyl groups and substances)

[0124] Alkoxysilyl groups are converted into silanol groups through hydrolysis or solvent decomposition.

[0125] Silanol groups can form Si-O bonds with carboxyl groups through silyl esterification, and can also form Si-O bonds with hydroxyl groups through silane coupling reactions.

[0126] The combination solution of embodiments such as those having silanol or alkoxysilyl groups in the second repeating unit described above can be used for interfacial molecular bonding of substances such as resins having carboxyl and / or hydroxyl groups. Furthermore, since carboxyl and / or hydroxyl groups are formed on the surface of various substances that have undergone pretreatment processes as described later, the combination solution of this embodiment can be used for interfacial molecular bonding of various substances that have undergone pretreatment processes.

[0127] Examples of resins containing carboxyl and / or hydroxyl groups include polyallylamine (PAA).

[0128] (The bonding of primary or secondary amino groups with substances)

[0129] Primary or secondary amino groups can form CN bonds with carboxyl groups through amidation, or they can form CN bonds with epoxy groups through ring-opening amidation, or they can form CN bonds with ester groups -(C=O)O- through trans-amidation.

[0130] Since the first repeating unit described above has a primary or secondary amino group, the combination solution of the present invention can be used for interfacial molecular bonding of substances such as resins having carboxyl, epoxy, or ester groups. Furthermore, since carboxyl groups are formed on the surface of various organic materials that have undergone pretreatment processes (described later), the combination solution of this embodiment can be used for interfacial molecular bonding of various organic materials that have undergone pretreatment processes. Examples of various organic materials that have undergone pretreatment processes include: organic materials treated with atmospheric plasma or polyimide (PI) treated with alkali.

[0131] Examples of resins containing carboxyl groups are as described above.

[0132] Examples of resins containing epoxy groups include various epoxy resins.

[0133] Examples of resins containing ester groups include liquid crystal polymers (LCP), polycarbonate (PC), polymethyl methacrylate (PMMA), and polyethylene terephthalate (PET).

[0134] (The bonding properties of epoxy groups with substances)

[0135] Epoxy groups can form CO bonds with carboxyl groups through esterification, and CO bonds with hydroxyl groups through etherification. They can also form CN bonds with amino groups through ring-opening amylation, and CC bonds with epoxy groups through ring-opening polymerization.

[0136] The combination solution of the embodiment described above, where the second repeating unit has an epoxy group, can be used for interfacial molecular bonding of substances such as resins having carboxyl, hydroxyl, amino, or epoxy groups. Furthermore, since carboxyl and / or hydroxyl groups are formed on the surface of various substances that have undergone the pretreatment process described later, the combination solution of this embodiment can be used for interfacial molecular bonding of various substances that have undergone the pretreatment process.

[0137] Examples of resins having carboxyl or hydroxyl groups and examples of resins having epoxy groups are as described above.

[0138] Examples of resins containing amino groups include polyallylamine (PAA) and various resins modified to contain amino groups.

[0139] (The bonding of the acryloyl or methacryloyl group with the substance)

[0140] Acryloyl or methacryloyl groups can form CN bonds through an aza-Michael addition reaction with an amino group.

[0141] Combinations of embodiments having acryloyl or methacryloyl groups, as described above, can be used for interfacial molecular bonding of substances such as resins containing amino groups.

[0142] Examples of resins containing amino groups are as described above.

[0143] (The bonding properties of azide groups with substances)

[0144] The azide group is removed from the nitrogen molecule by heating or light irradiation, becoming a nitro group.

[0145] Azide (azide) can form a CN bond with an alkenyl group (-CH=CH-) through aziridinization, and can also form a CN bond with a methylene group (-CH2-) through CH amination. Furthermore, it can form a CN bond with a methyl group (-CH3) through hydrogen abstraction amination, and can also form a CN bond with a phenyl group through a [2+1] addition cyclization reaction.

[0146] The azide group can also form a triazole ring by [3+2] addition cyclization reaction with the alkenyl group (-CH=CH-) to form a CN bond.

[0147] The combination solution containing the diazid compound can be used for interfacial molecular bonding of substances such as resins having alkenyl, methylene, methyl, or phenyl groups.

[0148] Examples of resins containing alkenyl groups include ABS resin or polyolefins with double bonds at the polymerization ends.

[0149] Examples of resins containing methylene groups include ABS resin, polypropylene (PP), polyethylene (PE), polystyrene (PS), and polymethyl methacrylate (PMMA).

[0150] Examples of resins containing methyl groups include polypropylene (PP), polycarbonate (PC), and polymethyl methacrylate (PMMA).

[0151] Examples of resins containing phenyl groups include: polystyrene (PS), polyphenylene sulfide (PPS), liquid crystal polymer (LCP), carbon nanotubes (CNT), polyimide (PI), polycarbonate (PC), polyether ether ketone (PEEK), etc.

[0152] As described above, the at least two azide groups in the bisazide compound contained in the combined liquid of this embodiment can form CN bonds with polymers having a first repeating unit and a second repeating unit, respectively. Therefore, the bisazide compound acts as a crosslinking agent for the polymer, making the interfacial molecules of any two substances firmly bonded.

[0153] (Mechanism of interfacial molecular bonding)

[0154] Although the mechanism of interfacial molecular bonding of the present invention is not easy to verify, it is speculated that at the interface containing the combined liquid of the present invention, a bonding mechanism such as... is generated. Figure 1 Chemical bonds as illustrated in the diagram. Figure 1 This figure shows the state in which a condensate layer 3 of the composite liquid of the present invention is interposed at the interface between substances 2 and 4 in a laminate 1 composed of substances 2, 4, and 5. Substances 4 and 5 can be bonded via interfacial molecular bonds in the same way as substances 2 and 4 are bonded, or they can be bonded by other methods such as high-temperature pressing. In the figure, A1 to A4 represent the portions of the composite liquid of the present invention derived from the diazid compound, and P1 and P2 represent the polymers (hereinafter referred to as amine polymers) of the composite liquid of the present invention having a first repeating unit and a second repeating unit. P1 is a linear amine polymer, and P2 is a branched amine polymer.

[0155] The surfaces of substances 2 and 4 contain functional groups such as OH, carboxyl, carbonyl, primary amino, or secondary amino groups, either naturally occurring or generated during the pretreatment process. The amino, silanol, epoxy, and acryloyl functional groups contained in amine polymers P1 and P2 react with these surface functional groups to form bonds.

[0156] A portion A1 from the diazid compound, through the decomposition of the azido group at one end of the diazid compound, generates a nitrogen bene that radically binds to the surface of substance 4. The other end of A1 radically binds to the amine polymer P1. Similarly, one end of portion A2 from the diazid compound radically binds to the surface of substance 4, and the other end of A2 radically binds to the amine polymer P2. One end of portion A3 from the diazid compound radically binds to the surface of substance 2, and the other end of A3 radically binds to the amine polymer P2. One end of portion A4 from the diazid compound radically binds to the amine polymer P1, and the other end of A4 radically binds to the amine polymer P2. Thus, the diazid compound in the composite liquid of the present invention crosslinks the two substances with the amine polymer to form bonds.

[0157] To explain, although Figure 1Although not shown, bonds can be formed between amine polymers P1 and P2, or between the branches of P2, through reactions between the functional groups they possess. For example, when P1 and P2 have silanol groups, they can be bonded via siloxane bonds. Furthermore, bonds can be formed between amine polymers, for example, through reactions between epoxy groups and amino groups, or between (meth)acryloyl groups and amino groups.

[0158] <Methods for manufacturing surface treatment materials>

[0159] Reference Figure 2 The flowchart illustrates a method for manufacturing a surface-treated substance according to an embodiment of the present invention, comprising a step of coating a combination liquid of any of the above embodiments onto a substance surface (coating step (S2)). This manufacturing method preferably includes a pretreatment step S1 and an activation step. The activation step may include: a step of heating the surface of the substance coated with the combination liquid (heating activation step (S4)); and a step of irradiating the surface of the substance coated with the combination liquid with ultraviolet light (UV activation step (S6)). This manufacturing method may include a post-activation washing step (S8).

[0160] (Coating process)

[0161] In the coating process (S2), the treatment liquid, such as the combination liquid of the present invention, is coated onto a material such as a polyimide film. Here, "coating" means that the treatment liquid is "attached" to the surface of the material or that the treatment liquid is "in contact with" the material. Examples of coating methods include conventionally known coating methods, such as brush coating, inkjet coating, gravure coating, lip-sealing coating, comma-blade coating, blade coating, roller coating, knife coating, spray coating, bar coating, spin coating, and dip coating. From the viewpoint of ensuring the adhesion of the surface-treated material to other materials (substances or metals), the lower limit of the coating thickness (wet film thickness) when coating with the combination liquid of the present invention is preferably, for example, 0.5 μm, more preferably 1.5 μm, and even more preferably 5 μm. The lower limit of the coating thickness (dry film thickness) is preferably, for example, 1 nm, more preferably 3 nm, and even more preferably 10 nm. On the other hand, from the viewpoint of ease of coating and suppression of uneven coating, the upper limit of the thickness of the coating (wet film thickness) is preferably, for example, 500 μm, more preferably 150 μm, and even more preferably 50 μm. The upper limit of the thickness of the coating (dry film thickness) is preferably, for example, 1 μm, more preferably 300 nm, and even more preferably 100 nm. As for the immersion time when using the dip coating method, it is preferably, for example, 3 seconds or more and 60 seconds or less. "Coating" can be performed on a part of the surface of the material or on the entire surface of the material. In addition, when the material is in the form of a film or sheet, "coating" can be performed on only one side of the front or back of the material, or on both the front and back sides of the material.

[0162] It should be noted that after "coating", the following steps (drying steps) are usually performed: the surface of the material coated with the treatment solution is dried by natural drying in an atmospheric atmosphere, air drying, or blowing warm air at about 40°C to 70°C. Through the above coating and drying steps, the amine polymer and diazid compound contained in the combination solution of the present invention are disposed on the surface of the above material.

[0163] (Heating activation process)

[0164] In the heat activation step (S4), the surface of the material coated with the combination liquid of the present invention is heated. Heating makes the surface suitable for bonding with other materials via heat pressing or metal plating. The surface temperature during heating is, for example, 80–160°C, preferably 90–120°C, and the surface is maintained at this temperature for, for example, 30 seconds–60 minutes, preferably 5–20 minutes. Analysis of the phenomena occurring in the heat activation step is difficult, but it is speculated that the following phenomena occur: The azido groups in the diazid compound decompose due to heat treatment, N2 molecules are released, and nitrides are generated, making the diazid compound suitable for bonding with substances such as resins or metals and amine polymers. Furthermore, heating makes the various functional groups in the amine polymer suitable for bonding with the diazid compound and substances such as resins or metals. The diazid compound and the amine polymer bond to each other and to the material to form an extremely thin layer of condensate on the surface of the material. Therefore, it is believed that during the heating activation process, an extremely thin layer of condensate is formed that adheres closely to the surface of the material, and the surface of the condensate becomes suitable for bonding with other substances such as resins or metals.

[0165] (UV activation process)

[0166] In the aforementioned heating activation process, heating decomposes the azido groups of the diazid compound. However, in the UV activation process, it is believed that irradiation with ultraviolet light decomposes the azido groups of the diazid compound, causing N2 molecules to detach and generating nitrobenes. This makes the diazid compound suitable for bonding with resins, metals, or amine polymers. From the viewpoint of ensuring tight adhesion and preventing the deterioration of resins such as polyimide films due to ultraviolet radiation, the wavelength of the irradiated ultraviolet light is preferably 260–420 nm, more preferably 330–365 nm. As the ultraviolet light source, any of a mercury lamp, a metal halide lamp, or a UV-LED lamp can be used.

[0167] In cases where the amine polymer in the combined liquid of the present invention has a photosensitive functional group such as (meth)acryloyl, it is believed that by irradiation with ultraviolet light, the amine polymer becomes suitable for bonding with substances such as resins or metals and diazid compounds.

[0168] In this invention, in addition to the UV activation step, the aforementioned heat activation step can also be performed. In this case, regardless of the order of the heat activation step and the UV activation step, either step can be performed first or simultaneously. Furthermore, the coating step, the heat activation step, and the UV activation step can be combined with other treatments such as the post-activation washing treatment step (S8) for removing byproducts, or not combined, and can be repeatedly applied in any order. Removing byproducts that are detrimental to bonding through washing can improve adhesion.

[0169] (Pre-treatment process)

[0170] According to one embodiment of the present invention, a method for manufacturing a surface treatment substance can be provided, which further includes a pretreatment step (S1) of the substance being subjected to one or more of the following: washing treatment, acid treatment, alkali treatment, corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, silicon oxidation flame treatment (also known as "ITRO treatment"), and defluorination treatment.

[0171] The pretreatment process involves pretreating the surface of materials such as polyimide films. This is done to facilitate the fixation of azido compounds and amine polymers deposited on the surface during subsequent coating and drying processes, and to more effectively perform subsequent heat activation and / or UV activation processes. By performing the pretreatment process, the material becomes activated, possessing functional groups such as OH, carboxyl, carbonyl, primary or secondary amine groups on its surface, making it easier to form bonds with azido compounds and amine polymers. The pretreatment process can include one or more treatments selected from: washing, acid treatment, alkali treatment, corona discharge treatment (irradiating the surface of the material with corona discharge), plasma treatment (treating the surface of the material with plasmas such as argon plasma, oxygen plasma, or atmospheric plasma), ultraviolet irradiation treatment, and silicon oxide flame treatment (ITRO treatment) (exposing the surface of the material to a combustion flame containing a coupling agent such as a silane compound). Only one treatment may be performed, or multiple treatments may be combined.

[0172] <Metal Coating Resin Manufacturing Method (Wet Plating)>

[0173] According to one embodiment of the present invention, a method for manufacturing a metal-coated resin can be provided, comprising: a step of coating a combination liquid of any embodiment of the present invention onto a resin surface (coating step); a step of heating the surface or irradiating the surface with ultraviolet light (activation step); and then a step of forming a metal coating on the surface by wet plating (plating step).

[0174] In this embodiment, a metal coating is formed on the surface of the resin that has undergone coating and activation processes, for example, by electroless plating, vapor deposition, or sputtering (seed layer formation process). Then, this metal coating layer can be thickened by electrolytic plating (electrolytic plating process). The metal coating can be formed on the entire surface or patterned using known methods such as photolithography. The metal-coated resin manufactured according to this embodiment is suitable as a flexible metal-coated laminate or printed circuit board. 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 layer is thickened by electrolytic plating, the thickness of the thickened metal coating layer is preferably 0.2 to 50 μm, more preferably 0.5 to 20 μm. Examples of metals used in electroless plating include Cu and Ni. Examples of metals used in metal coatings formed by vapor deposition or sputtering include Al, Cr, Sn, Ti, Cu, In, Au, Pt, and Ag. Furthermore, when the metal coating includes a layer formed by electroplating, the electroplated metal may be, for example, Cu, Ni, Ag, Pd, Au, Pt, Zn, Cr, Sn, Bi, etc. The metal coating can be a metal monomer or an alloy. To improve the adhesion between the resin and the plated metal in the metal coating resin obtained by this method, it is preferable to perform an annealing treatment 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.

[0175] <Manufacturing Method of Metal-Coated Resin (Lamination of Metal Foil)>

[0176] According to one embodiment of the present invention, a method for manufacturing a metal-coated resin can be provided, comprising: a step of coating a combination liquid of any embodiment of the present invention onto the surface of at least one of a resin and a metal foil (coating step); a step of heating the surface or irradiating the surface with ultraviolet light (activation step); and then, a step of laminating the resin and the metal foil through the surface and pressing them together to obtain a metal-coated resin (pressing step). The thickness of the laminated metal foil is preferably 0.2 to 50 μm, more preferably 0.5 to 20 μm. Examples of metals constituting the metal foil include: Cu, Ni, Ag, Pd, Au, Pt, Zn, Cr, Sn, Bi, Al, Ti, In, especially Cu, Ag, Au, Pt, Al, etc. The metal foil can be an elemental metal or an alloy. The surface of the metal foil laminated with the resin can be roughened or unroughened. The metal-coated resin manufactured by this embodiment is suitable as a flexible metal-coated laminate or a printed circuit board.

[0177] The pressing process includes the following steps: a process of overlapping the resin and metal foil (overlapping process) on a surface treated with the combined liquid of the present invention, and a process of bonding the two together by applying force (pressurizing process). In the pressing process, flat pressing, rolling, etc., are performed, for example, under atmospheric atmosphere, nitrogen atmosphere, or vacuum. From the viewpoint of improving productivity and reducing processing costs, flat pressing or rolling under atmospheric atmosphere is preferred. From the viewpoint of the quality stability of the manufactured metal-coated resin, pressing under nitrogen atmosphere or vacuum is preferred. The pressing pressure is preferably 1 to 100 MPa, more preferably 20 to 70 MPa. Generally, the higher the pressing pressure, the greater the bonding strength of the manufactured metal-coated resin, which is preferred; however, excessive pressing pressure may damage the support. The time for applying the above pressure is, for example, 5 to 60 minutes, more preferably 10 to 20 minutes. Heating is preferably performed simultaneously in this pressing process. The temperature of the resin in the pressing process is set to not exceed its heat resistance temperature. The aforementioned 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.

[0178] <Manufacturing Method of Resin Laminates>

[0179] According to one embodiment of the present invention, a method for manufacturing a resin laminate can be provided, comprising: a step of coating a combination liquid according to any embodiment of the present invention onto the surface of a first resin (coating step); a step of heating the surface or irradiating the surface with ultraviolet light (activation step); and then, a step of laminating a second resin onto the surface and applying pressure to integrate them (pressing step). Examples of resin shapes include resin films, resin sheets, and resin blocks.

[0180] The pressing process includes the following steps: a step of overlapping the surfaces of the two resins through a surface-treated liquid of the present invention (overlapping step), and a step of bonding the two together by applying force (pressurizing step). In the pressurizing step, flat pressing, rolling, etc., are performed, for example, under atmospheric atmosphere, nitrogen atmosphere, or vacuum. From the viewpoint of improving productivity and reducing processing costs, flat pressing or rolling under atmospheric atmosphere is preferred. From the viewpoint of the quality stability of the manufactured resin laminate, pressing under nitrogen atmosphere or vacuum is preferred. The pressing pressure is preferably 1 to 100 MPa, more preferably 20 to 70 MPa. Generally, the higher the pressing pressure, the greater the bonding strength of the manufactured laminate, which is preferred; however, excessive pressing pressure may damage the support. The time for applying the above pressure is, for example, 5 to 60 minutes, more preferably 10 to 20 minutes. Heating is preferably performed simultaneously in this pressurizing step. The temperature of the resin film in the pressurizing step is set to not exceed its heat resistance temperature. The aforementioned 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.

[0181] <Method for manufacturing resin-coated materials>

[0182] According to one embodiment of the present invention, a method for manufacturing a resin-coated material can be provided, comprising: a step of coating a combination liquid of any embodiment of the present invention onto the surface of the material (coating step); a step of heating the surface or irradiating the surface with ultraviolet light (activation step); a step of coating the surface with a resin varnish (resin coating step); and a step of curing the varnish (curing step).

[0183] In this embodiment, a resin-coated material is manufactured by coating a resin varnish onto the surface of a material that has undergone the coating and activation processes of the present invention's combined liquid and then curing it. The resin varnish preferably comprises a thermosetting resin or a UV-curable resin. The resin-coated material manufactured through this embodiment exhibits excellent adhesion. In a variation of this embodiment, the resin varnish contains conductive fillers and is coated (printed) onto the material in a patterned manner; the resin-coated material obtained after the curing process described above has patterned conductive portions.

[0184] (Polyimide)

[0185] Among resins, polyimide is a thermosetting resin with high heat resistance. Because its physical properties change very little over a wide temperature range from -269°C to +300°C, its applications in the electrical and electronic fields are expanding. In the electrical field, it can be used, for example, as insulation for coils or superconducting wires in industrial motors. In the electronic field, it can be used, for example, as a base film for flexible printed circuit boards, lightweight spacers, and probe sockets (test fixtures) for semiconductor testing equipment.

[0186] The polyimide used as the resin in this invention is a known substance, which can be obtained through a polycondensation reaction using diamine and tetracarboxylic dianhydride as the main components. Polyimide films are generally obtained by coating a polyamic acid solution, obtained by reacting diamine and tetracarboxylic dianhydride in a solvent, onto a support, drying to form a green film, followed by high-temperature heat treatment, and then a dehydration and ring-closing reaction. Regarding the diamine and tetracarboxylic dianhydride components used as raw materials, the most suitable components are appropriately selected based on the characteristics required for the application of the resin film laminate or metal-coated resin.

[0187] As the tetracarboxylic dianhydride component constituting polyamic acid, aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides 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.

[0188] As an aromatic tetracarboxylic acid dianhydride, there is no particular limitation. In the case that the diazid compound has a benzene ring, from the viewpoint of affinity and ease of bonding with the diazid compound, an acid dianhydride containing a benzene ring or a benzene ring with a substituent is preferred, and an acid dianhydride that does not contain "an aromatic ring other than a benzene ring or a benzene ring with a substituent" is more preferred.

[0189] Examples of aromatic tetracarboxylic acid dianhydrides that do not contain "aromatic rings other than benzene rings or benzene rings with substituents" include: pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 4,4'-hydroxyphthalic acid dianhydride, 3,4,3',4'-benzophenone tetracarboxylic acid dianhydride, 3,4,3',4'-diphenylsulfone tetracarboxylic acid dianhydride, bis(3,4-dicarboxyphenyl)sulfide dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride.

[0190] p-Triphenyl-3,4,3',4'-tetracarboxylic dianhydride, m-Triphenyl-3,4,3',4'-tetracarboxylic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phenyl dianhydride,

[0191] p-Tetraphenyl-3,4,3''',4'''-tetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2-bis[4-(3,4-dicarboxyphenyl)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride.

[0192] Examples of aromatic tetracarboxylic dianhydrides containing an aromatic ring other than a benzene ring or a benzene ring with substituents include: naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, and 2,3,6,7-tetrachloronaphthalene-1,4,5 8-Tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-3,7-dihydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,5-dihydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, -2,3,8,9-Tetracarboxylic acid dianhydride, -3,4,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride.

[0193] Examples of alicyclic tetracarboxylic dianhydrides include: cyclobutane-1,2,3,4-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, dicyclohexyl-3,3',4,4'-tetracarboxylic dianhydride, 1-carboxymethyl-cyclopentane-2,3,5-carboxylic acid-2,6∶3,5-dianhydride, and pyrrolidine-2,3,4,5-tetracarboxylic dianhydride.

[0194] Examples of aliphatic tetracarboxylic dianhydrides include: ethane-1,1,2,2-tetracarboxylic dianhydride, ethylene-tetracarboxylic dianhydride, propane-1,1,3,3-tetracarboxylic dianhydride, and butane-1,2,3,4-tetracarboxylic dianhydride.

[0195] Tetracarboxylic acid dianhydride can be used alone or in combination with two or more other components.

[0196] As the diamine component constituting polyamic acid, aromatic diamines, alicyclic diamines, and aliphatic diamines commonly used in the synthesis of polyimides 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.

[0197] As an aromatic diamine, there is no particular limitation. In the case that the diazid compound has a benzene ring, from the viewpoint of affinity and ease of bonding with the diazid compound, an aromatic diamine containing a benzene ring or a benzene ring with a substituent is preferred, and an aromatic diamine that does not contain "an aromatic ring other than a benzene ring or a benzene ring with a substituent" is more preferred.

[0198] Examples of aromatic diamines that do not contain "an aromatic ring other than a benzene ring or a benzene ring with substituents" include: p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,6-dihydroxy-1,3-phenylenediamine, 3,5-diaminobenzoic acid, m-aminobenzylamine, and p-aminobenzylamine.

[0199] 3,3'-Dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3',4,4'-tetraaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diamino-5,5'-diethyldiphenylmethane, 4,4'-diaminodiphenyl-difluoromethane, bis( 2-Methyl-4-aminophenyl)methane, bis(3-methyl-4-aminophenyl)methane, bis(2-ethyl-4-aminophenyl)methane, bis(3-ethyl-4-aminophenyl)methane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, 4,4'-diaminodiphenylamine Sulfone, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminobenzoylaniline, 4,4'-diamino-1'-methoxybenzoylaniline, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)n-butane, 1,5-bis(4-aminophenoxy)n-pentane, 1,3-bis(4-aminophenoxy)-2,2-dimethylpropane, 1,2-bis[2-(4-aminophenoxy)ethoxy]ethane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane Alkane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 1,3-bis(4-aminophenoxy)-2,2-dimethylpropane, 5-amino-1-(4-aminophenyl)-1,3,3-trimethylindene, 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide, 2,6-diaminoanthraquinone, 2,7-diaminoanthraquinone, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone,

[0200] 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene,

[0201] 9,9-bis(4-aminophenyl)fluorene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 9,10-bis(4-aminophenyl)anthracene.

[0202] Examples of aromatic diamines containing an aromatic ring other than a benzene ring or a benzene ring with substituents include 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 1,5-diaminonaphthalene, and 1,4-diaminonaphthalene.

[0203] Examples of alicyclic diamines include 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 1,4-diaminocyclohexane, and bis(4-amino-2,6-dimethylcyclohexyl)methane.

[0204] Examples of aliphatic diamines include: 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane.

[0205] Diamine components can be used alone or in combination with two or more.

[0206] In this invention, from the viewpoint of heat resistance, polyimide films containing aromatic rings are preferred as the polyimide film used as the resin. The type is not particularly limited, whether it is non-thermoplastic or thermoplastic. For specific examples, non-thermoplastic polyimide films such as the Kapton series manufactured by Toray-DuPont, the Upirex series manufactured by Ube Industries, Ltd., the Apical series manufactured by Kanebuchi Chemical Co., Ltd., the U-Film series manufactured by Nitto Denko Corporation, and the Xenomax series manufactured by Xenomax Japan Co., Ltd. are preferred. When the aforementioned diazid compound and the aforementioned amine polymer have benzene rings, from the viewpoint of ensuring affinity and adhesion, films composed of polyimides containing benzene rings are preferred, and films composed of polyimides containing only benzene rings as aromatic rings are particularly preferred. 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. In addition, the thickness of the polyimide film is not particularly limited, and examples include: 12.5μm, 25μm, 30μm, 40μm, 50μm, 75μm, 100μm, 125μm, 250μm, etc.

[0207] Example

[0208] <Synthetic Example 1> (Synthetic example of compound ET)

[0209] In a glass reactor, 1 g of polyethyleneimine (trade name: EpoMinutes (registered trademark), trade number: SP-012, manufactured by Nippon Catalyst Co., Ltd., average molecular weight: 1200, amine value: 19 mmol / g, amine ratio: primary amine 35%, secondary amine 35%, tertiary amine 30%) was dissolved in 19 g of 3-methoxy-3-methyl-1-butanol (hereinafter referred to as "SF"). The glass reactor was purged with dry nitrogen while the internal temperature was raised to 150°C with stirring. When the internal temperature reached 150°C, a solution containing 1 g of 3-(glycidoxy)propyltrimethoxysilane was immediately added dropwise to 9 g of SF over 30 minutes. The mixture was then stirred at 150°C for another 3 hours. The reaction batch in the glass reactor was then slowly cooled. A pale yellow solution with an active ingredient content of 6.7% was obtained.

[0210] The solution was analyzed by gas chromatography, and no signal was detected from the starting material 3-(glycidoxy)propyltrimethoxysilane, therefore the reaction was considered complete. Based on the molar ratio of primary or secondary amino groups in the starting material polyethyleneimine, approximately 31.8% of the generated target compound was estimated to have been modified by silane. This compound will be referred to as "Compound ET" below. (See formula (7)).

[0211] Example 1 (Preparation of ETBA Combined Solution)

[0212] 2,6-bis(4'-azidobenzylene)-4-methylcyclohexanone (trade name: BAC-M, manufactured by Toyo Synthetic Industries, Ltd., hereinafter referred to as "BABMC") powder, designated as a "diazid compound," was dissolved in methyl benzoate and adjusted to a 2% solution. The required mass of the adjusted 2% solution and the aforementioned synthesized compound ET, designated as a "polymer containing repeating units having primary or secondary amino groups and repeating units having silanol or alkoxysilyl groups," were weighed separately and mixed in ethanol to obtain a pale yellow composite solution. Regarding the concentration of each component (as a percentage of the total mass of the composite solution, hereinafter abbreviated as "%)," the aforementioned diazid compound was 0.2%, the aforementioned polymer was 0.60%, and the pH of the composite solution, measured using pH paper, was 8.0. This composite solution is hereinafter referred to as "composite solution ETBA."

[0213] <Example 1> (Preparation of the combined liquid ET)

[0214] The required mass of the synthesized compound ET was weighed and dissolved in ethanol to obtain a pale yellow solution. Regarding the concentration of the components, the polymer was 0.60%, and the pH of the solution, measured using pH paper, was 8.0. This solution will be referred to below as "Combination Solution ET".

[0215] <Synthesis Example 2> (Synthesis example of compound ETG)

[0216] In a glass reactor, 1 g of liquid polyethyleneimine (as above) was dissolved in 19 g of SF. The reactor was purged with dry nitrogen while stirring to raise the internal temperature to 150°C. Once the internal temperature reached 150°C, a solution containing 0.5 g of glycidyl methacrylate was immediately added dropwise to 9 g of SF over 30 minutes. The mixture was then stirred at 150°C for another 3 hours. The reaction batch in the glass reactor was then slowly cooled. A pale yellow solution containing 5.1% active ingredient was obtained.

[0217] The solution was analyzed by gas chromatography, and no signal of glycidyl methacrylate was detected, thus the reaction was considered complete. Based on the molar ratio of primary or secondary amino groups in the raw material polyethyleneimine, approximately 26.5% of the target compound was modified. IR analysis suggested that the ratio of epoxy groups to acryloyl groups (or methacryloyl groups) in the generated compound was approximately 1:7. This compound will be referred to as "Compound ETG" below. (See Equation (8))

[0218] <Example 2> (Preparation of Combined Liquid ETGBA)

[0219] BABMC powder, designated as a "diazid compound," was dissolved in methyl benzoate and adjusted to a 2% solution. The required masses of the adjusted 2% solution and the aforementioned synthesized compound ETG, designated as a "polymer containing repeating units having primary or secondary amino groups, repeating units having epoxy groups, and repeating units having acryloyl or methacryloyl groups," were weighed and mixed in ethanol to obtain a pale yellow combined solution. Regarding the concentrations of each component, the diazid compound was 0.20%, the polymer was 0.60%, and the pH of the combined solution, measured using pH paper, was 8.0. This combined solution will be referred to below as "Combined Solution ETGBA."

[0220] <Example 2> (Preparation of Combined Liquid ETG)

[0221] The required mass of the synthesized compound ETG was weighed and dissolved in ethanol to obtain a pale yellow solution. Regarding the concentration of the components, the polymer was 0.60%, and the pH of the solution, measured using pH paper, was 8.0. This solution will be referred to below as "ETG solution".

[0222] <Synthesis Example 3> (Synthesis example of compound ETMX)

[0223] In a glass reactor, 1 g of liquid polyethyleneimine (as above) was dissolved in 19 g of SF. The reactor was purged with dry nitrogen while stirring to raise the internal temperature to 150°C. When the internal temperature reached 150°C, a solution containing 0.5 g of 3-(glycidoxy)propyltrimethoxysilane was immediately added dropwise to 4.5 g of ethanol over 30 minutes, followed by the addition of a solution containing 0.25 g of glycidyl methacrylate over 30 minutes. The mixture was then stirred at 150°C for 3 hours. The reaction batch in the glass reactor was then slowly cooled. A pale yellow solution with 5.9% active ingredient was obtained.

[0224] The solution was analyzed by gas chromatography, and no signals were detected from the starting materials 3-(glycidoxy)propyltrimethoxysilane and glycidyl methacrylate, thus indicating that the reaction was complete. Based on the molar ratio of primary or secondary amino groups in the starting material polyethyleneimine, approximately 29.1% of the target compound was modified. IR analysis suggested that the ratio of epoxy groups to acryloyl groups (or methacryloyl groups) in the generated compound was approximately 1:8. This compound will be referred to as "Compound ETMX" below. (See Equation (9)).

[0225] <Example 3> (Preparation of the combined liquid ETMXBA)

[0226] BABMC powder, designated as a "diazid compound," was dissolved in methyl benzoate and adjusted to a 2% solution. The required masses of the adjusted 2% solution and the aforementioned synthesized compound ETMX, designated as a "polymer containing repeating units having primary or secondary amino groups, repeating units having silanol or alkoxysilyl groups, repeating units having epoxy groups, and repeating units having acryloyl or methacryloyl groups," were weighed and mixed in ethanol to obtain a pale yellow solution. Regarding the concentrations of each component, the diazid compound was 0.20%, the polymer was 0.60%, and the pH of the solution, measured using pH paper, was 8.0. This solution will be referred to below as "Combination Solution ETMXBA".

[0227] <Example 3> (Preparation of the combined liquid ETMX)

[0228] The required mass of the synthesized compound ETMX was weighed and mixed in ethanol to obtain a pale yellow solution. Regarding the concentration of the components, the polymer was 0.60%, and the pH of the solution, measured using pH paper, was 8.0. This solution will be referred to below as "Combined Solution ETMX".

[0229] <Synthetic Example 4> (Synthetic example of compound ETX (organic chain type))

[0230] In a glass reactor, 1 g of liquid polyethyleneimine (as above) was dissolved in 19 g of SF. The glass reactor was purged with dry nitrogen while the internal temperature was raised to 150°C with stirring. When the internal temperature reached 150°C, a solution containing 1 g of an organic chain silane coupling agent with epoxy and ethoxysilyl groups (trade code: X-12-981S, manufactured by Shin-Etsu Chemical Industry Co., Ltd., epoxy equivalent: 290 g / mol) was immediately added dropwise to 9 g of SF over 30 minutes. The mixture was then stirred at 150°C for 3 hours. The reaction batch in the glass reactor was then slowly cooled. A pale yellow solution with 6.7% active ingredient was obtained.

[0231] The solution was analyzed by high-performance liquid chromatography (HPLC), and no signal of X-12-981S was detected, therefore the reaction was considered complete. Based on the molar ratio of primary or secondary amines in the raw material polyethyleneimine, approximately 25.9% of the generated target compound was estimated to have been modified by silane. This compound will be referred to below as "Compound ETX (Organic Chain Type)".

[0232] <Example 4> (Preparation of the combined liquid ETXBA (organic chain type))

[0233] BABMC powder, designated as a "diazid compound," was dissolved in methyl benzoate and adjusted to a 2% solution. The required masses of the adjusted 2% solution and the aforementioned synthesized compound ETX (organic chain type), a "polymer containing repeating units having primary or secondary amino groups and repeating units having silanol or alkoxysilyl groups," were weighed separately and mixed in ethanol to obtain a pale yellow solution. Regarding the concentrations of each component, the diazid compound was 0.20%, the polymer was 0.60%, and the pH of the solution, as determined by pH paper, was 8.0. This solution will be referred to below as "Combination Solution ETXBA (Organic Chain Type)".

[0234] <Example 4> (Preparation of a combined liquid ETX (organic chain type))

[0235] The synthesized compound ETX (organic chain form) was weighed to the required mass and dissolved in ethanol to obtain a pale yellow solution. Regarding the concentration of the components, the polymer was 0.60%, and the pH of the solution, measured using pH paper, was 8.0. This solution will be referred to below as "ETX (organic chain form) solution".

[0236] <Synthetic Example 5> (Synthetic example of compound ETKR (inorganic chain type))

[0237] In a glass reactor, 1 g of liquid polyethyleneimine (as above) was dissolved in 19 g of SF. The glass reactor was purged with dry nitrogen while the internal temperature was raised to 150°C with stirring. When the internal temperature reached 150°C, a solution containing 3 g of an inorganic chain-type (polysiloxane backbone) silane coupling agent (trade code: KR-517, manufactured by Shin-Etsu Chemical Industry Co., Ltd., epoxy equivalent: 830 g / mol) with epoxy and methoxysilyl groups was immediately added dropwise to 9 g of SF over 30 minutes. The mixture was then stirred at 150°C for 3 hours. The reaction batch in the glass reactor was then slowly cooled. A pale yellow solution with 12.5% ​​active ingredient was obtained.

[0238] Analysis of the solution by high-performance liquid chromatography (HPLC) showed no detected signal of KR-517, thus indicating that the reaction was complete. Based on the molar ratio of primary or secondary amines in the raw material polyethyleneimine, approximately 27.2% of the generated target compound was estimated to have been modified by silane. This compound will be referred to below as "Compound ETKR (Inorganic Chain Type)".

[0239] <Example 5> (Preparation of the combined liquid ETKRBA (inorganic chain type))

[0240] BABMC powder, designated as a "diazid compound," was dissolved in methyl benzoate and adjusted to a 2% solution. The required masses of the adjusted 2% solution and the aforementioned synthesized compound ETKR (inorganic chain type), a "polymer containing repeating units having primary or secondary amino groups and repeating units having silanol or alkoxysilyl groups," were weighed separately and mixed in ethanol to obtain a pale yellow combined solution. Regarding the concentrations of each component, the aforementioned diazid compound was 0.20%, the aforementioned polymer was 0.60%, and the pH of the combined solution, measured using pH paper, was 8.0. This combined solution will be referred to below as "Combined Solution ETKRBA (Inorganic Chain Type)".

[0241] <Example 5> (Preparation example of combined liquid ETKR (inorganic chain type))

[0242] The synthesized compound ETKR (inorganic chain form) was weighed to the required mass and dissolved in ethanol to obtain a pale yellow solution. Regarding the concentration of the components, the polymer was 0.60%, and the pH of the solution, measured using pH paper, was 8.0. This solution will be referred to below as "ETKR (inorganic chain form) solution".

[0243] <Comparative Example 1> (Example of preparation of solution IMB-KP)

[0244] According to Patent Document 9, a 1% ethanol solution of compound IMB-KP is prepared. The pH is approximately 4.5. Compound IMB-KP is a siloxane oligomer containing amino, alkoxysilyl, and azide phenyl groups. This solution will be referred to below as "solution IMB-KP".

[0245] <Comparative Example 2> (Example of the preparation of combined liquid IMB-8)

[0246] According to Patent Document 8, an SF solution containing 0.10% 4-azidobenzoic acid, 0.10% polyethyleneimine, and 0.15% maleic anhydride was prepared. The pH was approximately 4.0. This solution will be referred to as "Combined Solution IMB-8" below.

[0247] The functional groups of the compounds that make up each combined liquid (or solution) are summarized below.

[0248] [Table 1]

[0249]

[0250] <Example 6-1>

[0251] (Manufacturing of surface treatment resin)

[0252] As the resin, two 3cm × 6cm polyimide films (trade name "Kapton 200H", 50μm thick, manufactured by Toray-DuPont) were prepared. After washing with acetone, each film was subjected to argon plasma treatment on one side (argon flow rate 100mL / min, 5 minutes, 200W) (pretreatment step). Next, using a rod coater, a pre-prepared combined solution ETGBA (component concentrations: 0.05% azido compound, 0.4% polymer) was coated onto the argon plasma-treated surface to a wet film thickness of 25μm (coating step). Then, the two polyimide films were held in a constant temperature bath at 100°C for 10 minutes (heat activation step).

[0253] (Manufacturing of resin laminates)

[0254] Two surface-treated polyimide films are overlapped with their surface-treated sides facing each other, and then pressed together using a flatbed press at a pressing temperature of 200°C, a pressing time of 5 minutes, and a pressing pressure of 27.2 MPa, with buffer plates added above and below, to create a polyimide film laminate (resin laminate) (pressing process). The polyimide film laminate is then placed in an oven at 250°C for 30 minutes (annealing process).

[0255] (Determination of peel strength)

[0256] After natural cooling, a 90° peel strength test was performed on a 30mm wide polyimide film laminate. A ZTA-50N force gauge was mounted on a vertical electric measuring stand MX2-500N (manufactured by Imada, Japan), forming a 90° peel strength tester. The peel speed was 50mm / min. For the 4cm section after removing 1cm from both ends from the total length of 6cm, the peel strength was continuously measured, and the average value was calculated.

[0257] <Examples 6-2 and 6-3>

[0258] As the resin, two 3cm × 6cm polyimide films were used. Otherwise, the same procedure as in Example 6-1 was followed to prepare the polyimide film laminate and the average peel strength was measured.

[0259] Example 6-2 Trade name "Kapton EN-Y", thickness 50μm, manufactured by Toray-DuPont Co., Ltd. (Low-CTE)

[0260] Example 6-3 Trade name "Xenomax", thickness 38μm, manufactured by Xenomax Japan Co., Ltd. (high heat resistance, Low-CTE)

[0261] <Comparative Examples 6-1 to 6-3>

[0262] Using IMB-8 instead of ETBBA, the polyimide film laminates were fabricated in the same manner as in Examples 6-1 to 6-3, and the average peel strength was measured.

[0263] (Measurement results)

[0264] The peel strength (average) measurement results are shown below.

[0265]

[0266] As shown in Examples 6-1 to 6-3, when using the ETGBA composite liquid of the present invention, all polyimide resins achieved adhesion. On the other hand, as shown in Comparative Examples 6-1 to 6-3, for the IMB-8 composite liquid, only Kapton H200 achieved adhesion. It should be noted that "base material failure" refers to peeling occurring not within the condensate layer from the coated composite liquid, but rather due to the destruction of the base material (polyimide film) during a 90° peel strength test. "Base material failure" indicates a strong bond resulting from the interfacial molecular bonding between the two substances.

[0267] <Example 6-1>

[0268] Instead of the heating activation step in Example 6-1, an air-drying and UV activation step were performed. Otherwise, the process was the same as in Example 6-1 to fabricate a polyimide film laminate and measure the average peel strength. In the UV activation step, the film was irradiated from a UV irradiation device at an energy of 1000 mJ / cm². 2 Irradiate the coated surface with ultraviolet light.

[0269] As a result, similar to Example 6-1, a tight seal was obtained that resulted in the degree of damage to the parent material.

[0270] <Example 7-1>

[0271] (Manufacturing of resin coating on metal through plating)

[0272] Prepare a polyimide film identical to that in Example 6-1, and apply the same combination solution as in Example 6-1 to one side of it, performing the same surface treatment as in Example 1. However, the heat activation treatment is changed to 160°C for 10 minutes.

[0273] Next, the surface-treated polyimide film was used as a sample for an electroless plating process. The electroless plating process included the following treatments: pre-immersion treatment in a pre-immersion solution; catalyst treatment in Inducer AM (manufactured by Okuno Pharmaceutical Co., Ltd.); accelerator treatment in an OPC-150 Crystal-RW (manufactured by Okuno Pharmaceutical Co., Ltd.); electroless plating of copper; and post-electroless annealing treatment at 100°C for 30 minutes to reduce plating stress. The electroless plating thickness was 0.1 μm.

[0274] Next, to achieve a thicker plating layer, an electrolytic copper plating process was performed on the sample. The plating thickness was 20 μm. Then, to reduce plating stress, an annealing treatment was performed, maintaining the sample at 150°C for 30 minutes after electrolytic plating. This yielded a metal-coated polyimide film. The metal-coated polyimide film was then cut to a width of 10 mm, and the peel strength (average value) was measured in the same manner as in Example 6-1. It should be noted that the solution used in the above catalyst-attributing treatment was an alkaline solution containing a Pd catalyst, suitable for forming microwires.

[0275] <Examples 7-2 to 7-5>

[0276] Instead of the combination liquid ETGBA used in Example 7-1, other combination liquids of the present invention, namely combination liquids ET, ETBA, ETMXBA or ETKRBA, were used. Otherwise, the same procedure as in Example 7-1 was followed to prepare the plated metal-coated polyimide film and measure the peel strength (average value).

[0277] <Comparative Examples 7-1 and 7-2>

[0278] Instead of the combined liquid ETGBA used in Example 7-1, other combined liquids such as combined liquid IMB-8 or solution IMB-KP, which are used as comparative examples, were used. Otherwise, the same procedure was followed as in Example 7-1 to prepare the metal-coated polyimide film and measure the peel strength (average value).

[0279] (Measurement results)

[0280] The peel strength (average) measurement results are shown below.

[0281]

[0282] These five examples exhibit adhesion equal to or better than that of the two comparative examples. A comparison of the combined solutions ET and ETBA shows that adding a diazid compound to the combined solution improves adhesion. Furthermore, a comparison of the combined solutions ETBA, ETMXBA, and ETGBA shows that silanol groups improve plating adhesion. It is speculated that the combined solution of Comparative Example 7-2, with a pH of approximately 4.5 (acidic), exhibits weak adhesion in alkaline Pd plating. In contrast, the five examples have a pH of approximately 8.0 (alkaline), thus demonstrating good compatibility with alkaline Pd plating for micro-wires.

[0283] <Examples 7-1' to 7-4'>

[0284] Instead of the heating activation steps in Examples 7-1 to 7-4, an air-drying and UV activation step was performed; biaxially oriented polypropylene (OPP) was used instead of Kapton H200 as the resin; and the electrolytic annealing conditions were changed to 100°C for 60 minutes. Otherwise, the OPP film laminate was produced in the same manner as in Examples 7-1 to 7-4. In the UV activation step, the UV irradiation device was used with 1000 mJ / cm². 2 The irradiation energy is used to irradiate the coated surface with ultraviolet light. These are referred to as Examples 7-1' to 7-4' in sequence.

[0285] As a result, similar to Examples 7-1 to 7-4, good plating performance was confirmed.

[0286] <Example 8-1>

[0287] (Made by laminating metal-coated resin)

[0288] Prepare one piece of polyimide film and unroughened copper foil with a size of 6cm×3cm (i.e., copper foil that has not undergone surface roughening treatment).

[0289]

[0290] The same combination solution as in Example 7-1 was used to perform the same surface treatment on one side of the polyimide film. No surface treatment was performed on the copper foil described above.

[0291] Next, the above-mentioned bonding process of surface-treated polyimide film and copper foil is performed. The copper foil is superimposed on the surface-treated polyimide film, and the copper foil is heated and pressed together using a flatbed press with a pressing temperature of 230°C, a pressing time of 5 minutes, and a pressing pressure of 58.3 MPa through the addition of buffer plates on the top and bottom, to produce a metal-coated polyimide film (pressing process).

[0292] After natural cooling, without performing an annealing process, the metal-coated polyimide film was cut to a width of 10 mm, and the peel strength was measured in the same manner as in Example 6-1.

[0293] <Examples 8-2 to 8-4>

[0294] Instead of the combined liquid EGBA used in Example 8-1, other combined liquids of the present invention, namely combined liquid ETBA, combined liquid ETMXBA or combined liquid ETXBA, were used. Otherwise, the same procedure as in Example 8-1 was followed to prepare the metal-coated polyimide film obtained by lamination and to measure the peel strength (average value).

[0295] <Comparative Examples 8-1 and 8-2>

[0296] Instead of the combined liquid ETGBA used in Example 8-1, other combined liquids such as combined liquid IMB-8 or solution IMB-KP, which are used as comparative examples, were used. Otherwise, the same procedure as in Example 8-1 was followed to prepare a metal-coated polyimide film obtained by lamination and to measure the peel strength (average value).

[0297] <Examples 8-5 and 8-6>

[0298] Instead of the resin (polyimide film "Kapton EN") used in Example 8-1, another polyimide film "Xenomax" was used. Otherwise, the same procedure as in Example 8-1 was followed to prepare the metal-coated polyimide film obtained by lamination and to measure the peel strength (average value).

[0299] <Comparative Examples 8-3 and 8-4>

[0300] Instead of the polyimide film “Kapton EN” used in Comparative Examples 8-1 and 8-2, the polyimide film “Xenomax” was used. Otherwise, the same procedure was followed as in Comparative Examples 8-1 and 8-2 to prepare metal-coated polyimide films obtained by lamination, and the peel strength (average value) was measured.

[0301] (Measurement results)

[0302] The peel strength (average) measurement results are shown below.

[0303]

[0304] The comparative example's combined solution IMB-8 exhibited poor adhesion, while the solution IMB-KP showed high adhesion. The Kapton EN of the present invention, although exhibiting slightly lower adhesion than the comparative example's solution IMB-KP, showed a similar level of adhesion. Furthermore, the Xenomax of the present invention showed higher adhesion than the comparative example's solution IMB-KP. In Examples 8-4, using combined solutions containing polymers having repeating units (which have organic chains in their side chains), strong adhesion was observed in a portion of the sample.

[0305] (Coating thickness dependence)

[0306] In Examples 8-3, the relationship between coating thickness (wet film thickness) and peel strength was investigated when the combined solution ETMXBA was coated onto a polyimide film. The results are shown below.

[0307]

[0308] When the coating thickness is less than 7 μm, the thinner the coating, the lower the peel strength. On the other hand, when the coating thickness is between 7 μm and 25.0 μm, the peel strength remains unchanged.

[0309] <Example 9> (Preparation of resin-coated material)

[0310] (Surface treatment)

[0311] Prepare a silicon wafer and wash it with ethanol. Then, using a rod coater, apply a pre-prepared ETBA mixture (component concentrations: 0.05% azido compound, 0.4% polymer) to one side of the silicon wafer with a wet film thickness of 25 μm (coating step). Next, hold the silicon wafer in a constant temperature bath at 100°C for 10 minutes (heat activation step).

[0312] (Manufacturing of resin-coated materials)

[0313] Prepare a polyimide varnish (UPIA-AT, manufactured by Ube Industries, solids concentration 18±1%, viscosity 5±1 Pa·s, solvent NMP, heat curing conditions 350℃, 20 minutes), and spin-coat it onto the coated surface of a silicon S-wafer (1500 rpm, 20 seconds). Next, heat-treat the polyimide varnish under the recommended heat curing conditions to cure it. Then, cut the resulting coating into 5×5 squares, 1 mm wide, and perform a tape peel test (cross-cut test) to confirm the grid adhesion number (=25 - peel number). The adhesion number is 25, and the coating thickness is 33 μm.

[0314] <Comparative Examples 9-1 and 9-2>

[0315] Prepare a silicon wafer identical to that in Example 9, and instead of the ETBA combination solution, use a combination solution as described below (or none at all). Otherwise, operate in the same manner as in Example 9 to form a coating on the silicon wafer. Then, confirm the adhesion of the coating by a tape peel test. The results are shown below; in the ETBA combination solution of the present invention, an adhesion improvement effect of the same degree as Comparative Example 9-1 can be confirmed.

[0316]

[0317] Industrial practicality

[0318] The combined liquid of this invention can be used in a variety of applications because it is primarily usable in a neutral to alkaline pH range and can improve the adhesion between various substances through interfacial molecular bonding. In particular, it has wide applications in the electrical and electronic fields. Examples include applications in the manufacture of electrical / electronic devices such as printed circuit boards or lightweight spacers, probe sockets (test fixtures) for semiconductor testing equipment, and resin core metal foils for battery plates.

[0319] Explanation of reference numerals in the attached figures

[0320]

Claims

1. A combination liquid, which is applied to at least one of two substances to improve the adhesion of the two substances, comprising: A polymer having a first repeating unit and a second repeating unit, the first repeating unit having a primary or secondary amino group, and the second repeating unit having one or more functional groups selected from silanol, alkoxysilyl, epoxy, acryloyl, and methacryl; and Diazide compounds.

2. The combined liquid according to claim 1, wherein, The second repeating unit has a silanol group or an alkoxysilyl group.

3. A combination liquid applied to a material to be plated for improving plating adhesion, comprising a polymer having a first repeating unit and a second repeating unit, the first repeating unit having a primary or secondary amino group, and the second repeating unit having a silanol group or an alkoxysilyl group.

4. The combined liquid according to claim 1, 2, or 3, wherein, The polymer has a second repeating unit, which has one or more functional groups selected from epoxy, acryloyl and methacryloyl.

5. The combined liquid according to claim 2 or 3, wherein, The second repeating unit comprises a polysiloxane backbone.

6. The combined liquid according to claim 1, 2 or 3, wherein, The polymer has a polyethyleneimine structure.

7. The combined liquid according to claim 1 or 2, wherein, At least two of the azide groups in the bisazide compound are azide groups that are directly bonded to the aromatic ring.

8. A method for manufacturing a surface treatment substance, comprising a coating step: a step of coating the combined liquid according to claim 1, 2 or 3 onto the surface of the substance.

9. A method for manufacturing a metal-coated resin, comprising: Coating process: The process of coating the resin surface with the combined liquid according to claim 1, 2 or 3. Activation process: the process of heating the surface or irradiating the surface with ultraviolet light, and Plating process: Next, a process of forming a metal plating layer on the surface by wet plating.

10. A method for manufacturing a metal-coated resin, comprising: Coating process: A process of coating the surface of at least one of the resin and the metal foil with the combined liquid according to claim 1. Activation process: the process of heating the surface or irradiating the surface with ultraviolet light, and Pressing process: Next, the resin and metal foil are laminated on the surface and pressed together to form an integral unit.

11. A method for manufacturing a resin laminate, comprising: Coating process: The process of coating the combined liquid according to claim 1 onto the surface of the first resin. Activation process: the process of heating the surface or irradiating the surface with ultraviolet light, and Pressing process: Next, a second resin is laminated on the surface and pressed to form an integral unit.

12. A method for manufacturing a resin-coated material, comprising: Coating process: The process of coating the surface of a substance with the combined liquid according to claim 1. Activation process: The process of heating the surface or irradiating the surface with ultraviolet light. Resin coating process: Next, the process of coating the surface with a resin varnish, and Curing process: The process of curing the varnish.

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