Resin adhesive and laminate

Abstract

Provided is an adhesive agent for resin, said adhesive agent having superior adhesion between a copper-based material substrate and a resin substrate. An adhesive agent for resin, said adhesive agent including one or both of a product (C) of a Maillard reaction in which a carbohydrate (A) and / or a reductone (B), and an amine compound (G) and / or an amine equivalent (H) served as source materials, and a product (D) of a caramelization reaction in which a carbohydrate (A) and / or a reductone (B) served as a source material or materials.

Description

[Technical Field]

[0001] The present invention relates to an adhesive for resins and a laminate. [Background technology]

[0002] Copper-clad laminates are made by laminating a copper-based material substrate (such as copper foil or copper alloy foil) on one or both sides of a resin substrate (such as prepreg, a composite material of organic and inorganic compounds, or resin film), and are widely used in the manufacture of printed wiring boards.

[0003] The copper-based material substrate used in copper-clad laminates generally has its surface roughened to ensure the required adhesion to the resin substrate. For example, Patent Document 1 discloses a surface treatment agent that is useful for roughening the copper surface or copper alloy surface and that can obtain a copper surface or copper alloy surface with deep irregularities that has good adhesion to resins such as prepregs and solder resists. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 7-292483 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, as communication speeds have increased, electrical signals have become increasingly frequent, creating a demand for printed wiring boards (high-frequency printed wiring boards) that can accommodate this. Specifically, copper-based material substrates and resin substrates that can suppress transmission loss are required. If the surface roughness of the copper-based material substrate is high, conductor loss tends to increase due to the skin effect, and it is therefore undesirable to roughen the surface of the copper-based material substrate to form deep irregularities, as in conventional copper-clad laminates.

[0006] Furthermore, in the high frequency range, materials with poor dielectric properties (high dielectric constant and dielectric dissipation factor) exhibit significant dielectric loss, so resin materials with excellent dielectric properties (low dielectric constant and dielectric dissipation factor) are desirable, but materials with excellent dielectric properties tend to have less electrostatic interaction with other materials and therefore less adhesive to other materials.

[0007] For these reasons, when copper-clad laminates are used in printed wiring boards for high-frequency applications, it is necessary to achieve sufficient adhesion between the copper-based material substrate (especially a copper-based material substrate with low surface roughness) and the resin substrate (especially a resin substrate with excellent dielectric properties).

[0008] In view of the above circumstances, an object of the present invention is, in one embodiment, to provide an adhesive for resins that exhibits excellent adhesion between a copper-based material substrate and a resin substrate. Also, an object of the present invention is, in another embodiment, to provide a laminate including such an adhesive for resins. [Means for solving the problem]

[0009] The present invention relates to the following items. [1] A resin adhesive containing one or both selected from a Maillard reaction product (C) made from carbohydrates (A) and / or reductones (B) and an amine compound (G) as raw materials, and a caramelization reaction product (D) made from carbohydrates (A) and / or reductones (B) as raw materials. [2] A laminate comprising, in this order, a copper-based material substrate, a layer of the adhesive for resin according to [1], and a resin substrate. [3] A resin adhesive containing one or both of a Maillard reaction product (C) made from carbohydrates (A) and / or reductones (B) and an amine compound (G) and / or an amine equivalent (H) as raw materials, and a caramelization reaction product (D) made from carbohydrates (A) and / or reductones (B) as raw materials. [4] A laminate comprising, in this order, a copper-based material substrate, a layer of the adhesive for resin according to [3], and a resin substrate. [Effects of the Invention]

[0010] According to one embodiment of the present invention, a resin adhesive can be provided that exhibits excellent adhesion between a copper-based material substrate and a resin substrate. In particular, a resin adhesive can be provided that exhibits excellent adhesion between a copper-based material substrate with low surface roughness and a resin substrate with excellent dielectric properties. Therefore, for example, by using this resin adhesive, a copper-clad laminate can be provided that exhibits excellent adhesion between a copper-based material substrate with low surface roughness and a resin substrate with excellent dielectric properties. This copper-clad laminate can be suitably used for printed wiring boards, particularly high-frequency printed wiring boards. DETAILED DESCRIPTION OF THE INVENTION

[0011] <1. Resin adhesive> An adhesive for resins according to one embodiment of the present invention contains one or both of a Maillard reaction product (C) made from carbohydrates (A) and / or reductones (B) and an amine compound (G) and / or an amine equivalent (H) as raw materials, and a caramelization reaction product (D) made from carbohydrates (A) and / or reductones (B) as raw materials. The adhesive for resins may contain additives other than the Maillard reaction product (C) and the caramelization reaction product (D). Examples of additives include a reaction accelerator (III), a crosslinking agent (IV), a pH adjuster, etc. added during the production of the adhesive, as well as inorganic compounds and organic compounds added during the production of the adhesive solution.

[0012] [1-1. Carbohydrates (A)] In the present invention, carbohydrate (A) refers to monosaccharides and polysaccharides (hereinafter referred to as compound (E)), as well as derivatives of compound (E) (hereinafter referred to as sugar derivative (F)). Monosaccharides refer to polyhydric alcohol compounds having three or more consecutive carbon atoms, one or more aldehyde or ketone groups, and two or more hydroxyl groups, and are carbohydrates that cannot be further hydrolyzed. Polysaccharides refer to compounds in which two or more monosaccharides are bonded. The bond type of the sugars that make up the polysaccharide is not particularly limited, and examples include ether bonds (particularly glycosidic bonds) and ester bonds. Carbohydrates (A) include those with chain structures and those with cyclic structures, and may be provided as a mixture of both.

[0013] In the present invention, the sugar derivative (F) refers to a compound in which the functional group of the compound (E) has been partially converted, and to salt compounds thereof. Partial conversion of the functional group refers to, for example, carboxylation, amination, etherification, esterification (e.g., carboxylic acid ester, phosphate ester, sulfate ester, nitrate ester, carbonate ester, etc.), acylation, silylation, siloxylation, aldehyde conversion, ketonization, or halogenation of a hydroxy group, hydroxylation or carboxylation of an aldehyde group, and dehydration by elimination of the hydroxy group and its β-hydrogen. Furthermore, the salt compounds thereof refer to, for example, alkali metal salts such as lithium, sodium, potassium, rubidium, and cesium; alkaline earth metal salts such as beryllium, magnesium, calcium, strontium, and barium; and transition metal salts such as titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, and molybdenum. Typical examples of the sugar derivative (F) include, but are not limited to, sugar acids, sugar alcohols, amino sugars, dehydrated sugar derivatives, and salt compounds thereof.

[0014] Specific examples of monosaccharides include, but are not limited to, dihydroxyacetone, glyceraldehyde, erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, erythrulose, xylulose, ribulose, psicose, fructose, sorbose, tagatose, sedoheptulose, coriose, deoxyribose, fucose, fuculose, rhamnose, allomethylose, quinovose, antiallose, talomethylose, digitalose, digitoxose, cymarose, tyvelose, abecose, paratose, colitose, and ascarylose.

[0015] Specific examples of polysaccharides and derivatives thereof include dihydroxyacetone dimer, glyceraldehyde dimer, sucrose, lactulose, lactose, maltose, trehalose, cellobiose, kojibiose, nigerose, isomaltose, isotrehalose, neotrehalose, sophorose, laminaribiose, gentiobiose, turanose, maltulose, palatinose, gentiobiulose, mannobiose, melibiose, Melibiulose, neolactose, galactosucrose, scillabiose, neohesperidose, rutinose, rutinulose, vicianose, xylobiose, primeverose, trehalosamine, maltitol, cellobionic acid, lactosamine, lactosediamine, lactobionic acid, lactitol, hyalobiuronic acid, sucralose, nigerotriose, maltotriose, melezitose, maltotriulose, raffinose, chesto Examples of suitable sugars include, but are not limited to, sucrose, nystose, nigerotetraose, stachyose, acarbose, lactose-fructose oligosaccharides, maltooligosaccharides, isomaltooligosaccharides, gentiooligosaccharides, nigerooligosaccharides, galactooligosaccharides, xylooligosaccharides, soybean oligosaccharides, fructooligosaccharides, mannan oligosaccharides, glycogen, starch, cellulose, glucan, fructan, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, salts of carboxymethyl cellulose (e.g., sodium salts), alginic acid, propylene glycol alginate, agarose, cellulose derivatives, guar gum, carrageenan, agar, chitosan, gellan gum, dextrin, dextran, starch, and pullulan.

[0016] In the present invention, the sugar acid refers to a compound in which one or more aldehyde groups or terminal hydroxy groups of compound (E) have been converted to a carboxyl group. Specific examples include, but are not limited to, glyceric acid, erythronic acid, threonic acid, ribonic acid, arabinonic acid, xylonic acid, lyxonic acid, allonic acid, altronic acid, gluconic acid, mannonic acid, gulonic acid, idonic acid, galactonic acid, talonic acid, erythronic acid, threonic acid, ribalic acid, arabinaric acid, xylaric acid, allaric acid, altraric acid, glucaric acid, mannaric acid, idaric acid, galactaric acid, glucuronic acid, mannuronic acid, guluronic acid, galacturonic acid, and iduronic acid.

[0017] In the present invention, the sugar alcohol refers to a compound in which one or more aldehyde or ketone groups of compound (E) have been converted to a hydroxy group. Specific examples include, but are not limited to, sorbitol, mannitol, erythritol, pentaerythritol, threitol, arabinitol, ribitol, xylitol, galactitol, rhamnitol, isomaltose, maltitol, lactitol, and palatinose.

[0018] In the present invention, the term "amino sugar" refers to a compound in which one or more hydroxy groups of compound (E) have been substituted with amino groups, and a compound in which the amino groups of the compound have been further acylated. Specific examples include, but are not limited to, glucosamine, galactosamine, N-acetylglucosamine, N-carbamoylglucosamine, N-acetylgalactosamine, chitin, chitosan, chondroitin, hyaluronic acid, and heparin. Some amino sugars also fall under the category of amine compound (G) or amine equivalent (H), which will be described later.

[0019] In the present invention, the dehydrated derivative of a sugar refers to a compound produced by an intramolecular dehydration reaction of compound (E). Specific examples include, but are not limited to, furfural and hydroxymethylfurfural.

[0020] The carbohydrate (A) used as the raw material for obtaining the Maillard reaction product (C) and / or the caramelization reaction product (D) is preferably a monosaccharide, a polysaccharide, a sugar acid, or a salt thereof. Among these, a reducing agent (e.g., a sugar that can be reacted with Cu in the Fehling reaction) is preferably used. 2+ Cu + A compound having the action of reducing to 1,2-dihydroxybenzoic acid (A) (typically a reducing sugar) is more preferred, and a monosaccharide is even more preferred. The carbohydrate (A) may be used alone or in combination of two or more.

[0021] [1-2. Reductones (B)] In the present invention, reductones (B) refer to compounds having a chemical structure represented by the following formula 1 in the molecule. Specific examples include, but are not limited to, ascorbic acid, erythorbic acid, and salts thereof (e.g., alkali metal salts, alkaline earth metal salts, or transition metal salts, and double salts of the above metal salts). Furthermore, as long as the compound has the following chemical structure in the molecule, it may be a compound in which a functional group has been partially converted, or a salt compound thereof. Examples of "a functional group that has been partially converted" are the same as those described in the explanation of carbohydrate (A). Reductones (B) may be used singly or in combination of two or more. [ka]

[0022] [1-3. Maillard reaction products (C)] In the present invention, the Maillard reaction product (C) refers to a brown substance produced by the reaction of the raw materials, carbohydrates (A) and / or reductones (B), with an amine compound (G). In the Maillard reaction, carbohydrates (A) and / or reductones (B) combine with an amine compound (G), and further reactions such as decomposition, oxidation, condensation, and polymerization are thought to be involved. However, the reaction pathway is complex, making it extremely difficult to analyze the components of the Maillard reaction product (C). For this reason, in the present invention, the Maillard reaction product (C) is considered to have been obtained by the reaction of carbohydrates (A) and / or reductones (B) with an amine compound (G) to produce a brown substance.

[0023] In the present invention, whether or not brown substances are produced is determined as follows. A liquid sample containing 10% by mass of the solute and / or dispersoid of the resin adhesive to be measured is prepared, and if the yellowness index (YI) of the liquid sample is 2.5 or higher, it is determined that "brown substances are produced." YI can be measured using a commercially available spectrophotometer. For example, using a spectrophotometer (SD7000) manufactured by Nippon Denshoku Industries Co., Ltd., tristimulus values ​​(X, Y, Z) in the XYZ color system are determined from the transmittance measured using auxiliary illuminant C and a 2-degree visual field by spectrophotometric colorimetry, and the tristimulus values ​​are applied to the following formula based on ASTM D1925 to calculate YI: YI=100(1.28X-1.06Z) / Y When diluting the resin adhesive to prepare a liquid sample, the solvent and / or dispersant should be pure water. When concentrating the resin adhesive to prepare a liquid sample, the resin adhesive can be placed in a container and left to stand at 35°C or below in the open air to evaporate the solvent and / or dispersant, or the solvent and / or dispersant can be removed under reduced pressure using a rotary evaporator at 35°C or below. The mass concentration of the liquid sample can be calculated from the weight of the resin adhesive before and after drying. Furthermore, in measurements using a spectrophotometer, if the color of the liquid sample is too dark when the resin adhesive concentration is adjusted to 10% by mass and the transmittance cannot be measured, the resin adhesive is diluted until the transmittance can be measured, and if the measured YI is 2.5 or higher, it is determined that "brown substances have been produced."

[0024] In the present invention, the amine compound (G) refers to ammonia, primary amines, secondary amines, and salts thereof. The amine compound (G) also encompasses amino acids, peptides, proteins, and salts thereof. As the amine compound (G), primary or lower amines (specifically, primary amines and ammonia) and salts thereof are preferred over secondary amines, with ammonia and salts being particularly preferred. In addition, the carbon adjacent to the amino group in the amine compound (G) is preferably a primary, secondary, or tertiary carbon. Examples of the amine compound (G) include arylamines and salts thereof, alkylamines and salts thereof, heteroarylamines and salts thereof, and ammonia and salts thereof. Among these, one or more selected from arylamines, alkylamines, heteroarylamines, and ammonia are preferred, one or more selected from alkylamines, heteroarylamines, and ammonia are more preferred, and ammonia is particularly preferred. The amine compound (G) may be used alone or in combination with two or more, and may also be used in combination with one or more amine equivalents (H) described below.

[0025] As the ammonia and its salts, ammonia and a salt compound composed of ammonia and an acid are used. Examples of acids that form salts with ammonia include inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, nitric acid, nitrous acid, sulfuric acid, sulfurous acid, peroxomonosulfuric acid, peroxodisulfuric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, hydrocyanic acid, cyanic acid, thiocyanic acid, carbonic acid, boric acid, silicic acid, chromic acid, dichromate, permanganic acid, molybdic acid, and tungstic acid, as well as formic acid, acetic acid, propionic acid, butyric acid, Examples of organic acids that can form a salt with ammonia include valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, lactic acid, malic acid, citric acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, gluconic acid, methanesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, and peracetic acid. The acids that form a salt with ammonia may be used alone or in combination of two or more.

[0026] Examples of the secondary amine include R 1 R 2 A compound having the chemical structure NH, 1 , R 2are independently any one of an alkyl group, an aryl group, and a heteroaryl group having a substituent or no substituent. Also included are saturated heterocyclic amines having a substituent or no substituent, and unsaturated heterocyclic amines having an aromatic or no aromatic group or no aromatic group having a substituent or no aromatic group. Examples of the substituent include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, mercapto groups, carbonyl groups (e.g., aldehyde groups, ketone groups, carboxyl groups, acyl groups, ester groups, amide groups, etc.), imino groups, thiocarbonyl groups, fluoro groups, chloro groups, bromo groups, iodo groups, nitro groups, sulfo groups, cyano groups, alkoxy groups, trifluoromethyl groups, azo groups, silyl groups, siloxy groups, etc. Examples of secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, diallylamine, diphenylamine, dibenzylamine, diethanolamine, ethylmethylamine, N-methylaniline, methylbenzylamine, aziridine, azetidine, pyrrolidine, piperidine, morpholine, pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, indoline, indole, and proline.

[0027] Examples of the primary amine include compounds having a chemical structure of RNH2, where R is any of an alkyl group having no or an optionally substituted group, an aryl group, and a heteroaryl group having no -NH- partial structure in the ring structure. Illustrative primary amines include methylamine, ethylamine, propylamine, butylamine, octylamine, cyclohexylamine, allylamine, ethanolamine, propanolamine, benzylamine, furfurylamine, phenylethylamine, aniline, methoxyaniline, trifluoromethylaniline, aminobenzoic acid, aminosalicylic acid, nitroaniline, cyanoaniline, fluoroaniline, chloroaniline, bromoaniline, iodoaniline, aminophenol, aminothiophenol, naphthylamine, aminopyridine, hydroxylamine, ...methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine, methylamine Examples include amines, aminotriazines, aminothiazoles, amino-1,3,4-thiadiazoles, amino-1,2,3-thiadiazoles, 2-amino-5-mercapto-1,3,4-thiadiazoles, aminopyrazines, aminopyrimidines, amino-1,2,4-triazines, amino-1,3,5-triazines, levodopa, dopamine, noradrenaline, glycine, alanine, valine, leucine, isoleucine, cysteine, methionine, serine, threonine, aspartic acid, glutamic acid, glutamine, arginine, phenylalanine, and tyrosine.

[0028] The amine compound (G) may be a monovalent amine having one amino group per molecule and its salt, or a polyvalent amine having two or more amino groups and its salt. The amine compound (G) may be a monomer or a polymer. The amino group of the polyvalent amine may contain a primary amino group, a secondary amino group, or a combination of both. Examples of polyvalent amines include ethylenediamine, diethylenetriamine, hexamethylenediamine, triethylenetetramine, piperazine, phenylenediamine, aminobenzylamine, diaminonaphthalene, diaminopyridine, triaminopyridine, diaminopyrimidine, triaminopyrimidine, diamino-1,3,5-triazine, triamino-1,3,5-triazine, aminopyrazole, aminoimidazole, aminobenzimidazole, amino-1H-tetrazole, and amino-1,2,4- Examples include triazole, diamino-1,2,4-triazole, diaminodiphenylmethane, dimethylthiotoluenediamine, diaminodiphenyl sulfone, diaminodiphenyl ether, bis(3-aminophenoxy)benzene, bis[2-(4-aminophenyl)-2-propyl]benzene, adenine lysine, histidine, tryptophan, gelatin, albumin, casein, fibroin, keratin, egg yolk protein, egg white protein, yeast protein, collagen, chitosan, and hydrazine.

[0029] In the present invention, the amine equivalent (H) refers to a compound that easily generates an amine compound (G) by hydrolysis. In the present invention, ammonia, a primary amine, or a secondary amine is generated from the amine equivalent (H), and the resulting amine compound undergoes a Maillard reaction with a carbohydrate (A) and / or a reductone (B). To promote hydrolysis, heating or warming conditions may be applied, or a catalyst, acid, or base may be added. Examples of the amine equivalent (H) include R 1 R 2 NC(=O)NR 3 R 4 Urea derivatives represented by R 1 R 2 NC(=S)NR 3 R 4 Thiourea derivatives represented by R 1 OC(=O)NR2 R 3 Carbamate compounds represented by R 1 OC(=S)NR 2 R 3 O-thiocarbamate compounds represented by R 1 SC(=O)NR 2 R 3 S-thiocarbamate compounds represented by R 1 OC(=NR 2 )NR 3 R 4 an isourea derivative represented by R 1 SC(=NR 2 )NR 3 R 4 isothiourea derivatives represented by R 1 SC(=S)NR 2 R 3 Dithiocarbamate compounds represented by R 1 C(=NR 2 )NR 3 R 4 and amidine compounds represented by R 1 R 2 NC(=NR 3 )NR 4 R 5 Examples of the guanidine derivatives include urea, thiourea, carbamic acid, amidine, acetamidine, guanidine, and derivatives thereof. 1 R 2 (e.g., 3-amino-1H-1,2,4-triazole, melamine, etc.) are not amine equivalents (H), but amine compounds (G). 1 ~R 5 each independently represents any one of hydrogen, an unsubstituted or optionally substituted alkyl group, an aryl group, and a heteroaryl group, and the amine equivalent (H) may be used alone or in combination with two or more kinds, and may also be used in combination with the above-mentioned amine compound (G).

[0030] [1-4. Maillard reaction conditions] The reaction conditions for the Maillard reaction are not particularly limited, as long as the raw materials, carbohydrate (A) and / or reductones (B), react with the amine compound (G) generated from the amine compound (G) and / or amine equivalent (H), producing a brown substance. The concentrations of carbohydrate (A), reductones (B), and amine compound (G) during the reaction, the reaction time, the reaction pressure, the presence or absence and type of solvent and / or dispersion medium (I), the reaction temperature (II), the addition of a reaction accelerator (III), the addition of a crosslinking agent (IV), adjustment of the pH (V), etc., can be appropriately set. When an amine equivalent (H) is used, the reaction conditions may be appropriately adjusted so that the amine equivalent (H) decomposes in the reaction system to produce the amine compound (G) and the Maillard reaction occurs simultaneously. Alternatively, the reaction conditions for the Maillard reaction may be appropriately adjusted after the amine compound (G) is produced in the reaction system.

[0031] The solvent and / or dispersion medium (I) is not particularly limited, but is preferably a polar aprotic or protic solvent and / or dispersion medium, more preferably a polar protic solvent, and particularly preferably water. The solvent and / or dispersion medium (I) may be used alone or in combination of two or more, but the content of water in the solvent and / or dispersion medium is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, even more preferably 70% by mass or more, particularly preferably 90% by mass or more, and most preferably water alone.

[0032] The reaction temperature (II) is not particularly limited, but is preferably heated. The reaction temperature (II) is preferably set to, for example, 40°C to 200°C, 60°C to 200°C, 70°C to 200°C, 80°C to 200°C, 90°C to 200°C, or 95°C to 200°C.

[0033] The reaction promoter (III) (e.g., Lewis acid catalyst, radical initiator, oxidizing agent, etc.) is not particularly limited and may or may not be added, but any additive that generally promotes the Maillard reaction can be used. Examples of Lewis acid catalysts include metal salts that generate metal ions such as zinc ions, lead ions, iron ions, and copper ions in aqueous solution. Examples of radical initiators include peroxides and their salts such as hydrogen peroxide, tert-butyl hydroperoxide, peroxodisulfuric acid, and ethane peroxoic acid, as well as oxoacids and their salts such as perchloric acid and periodic acid. Examples of oxidizing agents include nitric acid and its salts, permanganate, chromate, dichromate, hypochlorite, iron(III) chloride, iron(III) fluoride, iron(III) nitrate, and iron(III) sulfate. Other examples of the reaction accelerator (III) include sodium chloride, phosphoric acid and its salts, ammonium sulfite, ammonium metabisulfite, sodium sulfite, sodium metabisulfite, potassium sulfite, potassium metabisulfite, sulfurous acid gas, etc. The reaction accelerator (III) may be used alone or in combination of two or more.

[0034] A known crosslinking agent (IV) may or may not be used in the Maillard reaction. The crosslinking agent is not particularly limited, and any compound may be used as long as it is incorporated into the structure of the Maillard reaction product to form a crosslinked structure. Examples of crosslinking agents include zirconium carbonate salts, titanium alkoxides, silane coupling agents, colloidal silica, isocyanates, blocked isocyanates, glyoxal, polycarboxylic acids and their anhydrides, phosphoric acid and phosphate salts, polycarboxylic acids (e.g., succinic acid, citric acid, maleic anhydride, etc.) and their salts, epoxy compounds, aziridine compounds, urethane compounds, hydrazide compounds, oxazoline compounds, carbodiimide compounds, methylolmelamine compounds (e.g., methylolmelamine and alkylated methylolmelamine, etc.), and acetoacetyl compounds. The crosslinking agent (IV) may be used alone or in combination of two or more.

[0035] The pH (V) at the start of the reaction is not particularly limited, but the pH range in which the reaction proceeds easily may vary depending on the amine compound (G) or amine equivalent (H) used, and can be adjusted accordingly. The Maillard reaction generally proceeds easily in a pH range that is not strongly acidic (e.g., pH 2.0 to pH 14.0, pH 3.0 to pH 13.5, pH 4.0 to pH 13.5, or pH 5.0 to pH 13.5). However, when using an amine compound (G) that undergoes a radical reaction, such as ammonium peroxodisulfate, the reaction proceeds even at strongly acidic pH, so the pH can be selected from a wide range (e.g., pH 0.1 to pH 14.0, pH 0.2 to pH 14.0, pH 0.3 to pH 14.0, or pH 1.0 to pH 14.0). A pH adjuster may be added as needed to adjust the pH, but this is not essential. Examples of pH adjusters include, but are not limited to, inorganic acids, organic acids, inorganic bases, and organic bases. Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid. Examples of organic acids include acetic acid, propionic acid, oxalic acid, maleic acid, adipic acid, gallic acid, butyric acid, salicylic acid, benzoic acid, methanesulfonic acid, benzenesulfonic acid, chloroacetic acid, formic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, acrylic acid, and methacrylic acid. Examples of inorganic bases include ammonia, ammonium bicarbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide. Examples of organic bases include the amine compound (G) described above. pH adjusters may be used alone or in combination of two or more.

[0036] [1-5. Caramelization reaction product (D)] In the present invention, the caramelization reaction product (D) refers to a brown substance produced by reactions such as decomposition, oxidation, condensation, and polymerization of the raw material carbohydrates (A) and / or reductones (B) themselves due to heat or other factors. The caramelization reaction has a complex reaction pathway, making it extremely difficult to analyze the components of the caramelization reaction product (D). For this reason, in the present invention, the caramelization reaction product (D) is considered to have been obtained when the carbohydrates (A) and / or reductones (B) themselves react to produce a brown substance. Whether or not a brown substance has been produced is determined by the method described above.

[0037] [1-6. Caramelization reaction conditions] The reaction conditions for the caramelization reaction are not particularly limited as long as brown substances are produced by heating the raw materials, saccharides (A) and / or reductones (B), and the reaction conditions can be appropriately set by, for example, adjusting the concentrations of saccharides (A) and reductones (B) during the reaction, the reaction time, the reaction pressure, the presence or absence and type of solvent and / or dispersion medium (i), the reaction temperature (ii), the addition of a reaction accelerator (iii), the addition of a crosslinking agent (iv), and the adjustment of the pH (v).

[0038] The reaction conditions (i) to (iv) are the same as the reaction conditions (I) to (IV) in [1-4. Reaction conditions for the Maillard reaction], and therefore a description thereof will be omitted.

[0039] The pH (v) at the start of the reaction is not particularly limited, and a pH adjuster may be added as appropriate to adjust the pH, but this is not essential. Examples of pH adjusters include, but are not limited to, inorganic acids, organic acids, inorganic bases, and organic bases. Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid. Examples of organic acids include acetic acid, propionic acid, oxalic acid, maleic acid, adipic acid, gallic acid, butyric acid, salicylic acid, benzoic acid, methanesulfonic acid, benzenesulfonic acid, chloroacetic acid, formic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, acrylic acid, and methacrylic acid. Examples of inorganic bases include ammonia, ammonium bicarbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide. Examples of organic bases include the amine compound (G) described above. One pH adjuster may be used alone, or two or more may be used in combination.

[0040] Commercially available Maillard reaction products (C) and caramelized reaction products (D) can also be used. Examples of commercially available products include commercially available caramel colors. Caramel colors are generally classified into four types: caramel I, caramel II, caramel III, and caramel IV (Ministry of Health, Labor, and Welfare, Consumer Affairs Agency, "Official Standards of Food Additives 2018, 9th Edition").

[0041] Commercially available caramel colorants can be used in either liquid or powder form.

[0042] Caramel I is obtained by heat-treating edible carbohydrates such as starch hydrolysate, molasses, or sugars, or by heat-treating them with the addition of acid or alkali, and does not contain sulfite compounds or ammonium compounds. Caramel II is obtained by adding sulfite compounds during the caramel I reaction. Caramel I and caramel II fall under the category of caramelization reaction products (D). Specific commercially available products include liquid caramel manufactured by Morita Food System Co., Ltd. (product names: S-70, S-65, S-60, S-60S, SS, SSS, SM, SB, MK, and F), powdered caramel manufactured by the same company (product names: SAP and FP), liquid caramel manufactured by Senba Toka Kogyo Co., Ltd. (product names: Caramel KS-S, Caramel KS-SB, Caramel KS-SNT, Caramel KS-NB, and Caramel KS-45), powdered caramel manufactured by the same company (product names: Powdered Caramel SW, Powdered Caramel S-180W, Powdered Caramel KS-W, Powdered Caramel KS-SS, Powdered Caramel C-85, Powdered Caramel KS-LW, Powdered Caramel KS-SSW, Powdered Caramel MW, and Powdered Caramel BD-W), and caramel color I manufactured by Kanto Chemical Co., Ltd.

[0043] Caramel III is obtained by adding an ammonium compound or an acid or alkali to edible carbohydrates such as starch hydrolysate, molasses, or sugars and then heat treating the carbohydrates. Caramel III does not contain sulfite compounds. Caramel IV is obtained by adding sulfite compounds during the caramel III reaction. Caramel III and caramel IV are Maillard reaction products (C). Specific commercially available products include liquid caramel manufactured by Morita Food System Co., Ltd. (product names: SL, MC, MR, MU, CL, CL-150, MS, MH, and DS), powdered caramel manufactured by the same company (product name: MRP), liquid caramel manufactured by Senba Toka Kogyo Co., Ltd. (product names: Caramel TO, Caramel MG-18, Caramel S, Caramel TB, Caramel KD, Caramel BD-2, Caramel Z-80, Caramel Z-100, Caramel Z-35, and Caramel WH-N-92), powdered caramel manufactured by the same company (product names: Powdered Caramel MG-18W, Powdered Caramel KD-W, and Powdered Caramel Z-35W), and caramel color III manufactured by Kanto Chemical Co., Ltd.

[0044] [1-7. Manufacturing method of resin adhesive] According to one embodiment of the present invention, there is provided a method for producing a resin adhesive, which includes, for example, one or both of step 1 and step 2. Step 1: A Maillard reaction occurs in a reaction system containing carbohydrates (A) and / or reductones (B) and amine compounds (G) and / or amine equivalents (H) as raw materials to produce brown substances. The raw materials in the reaction system may be in a gaseous, liquid, or solid state, or a combination thereof. The reaction system may contain any of a gaseous, liquid, and solid phases, but preferably contains a liquid phase. A solvent and / or a dispersion medium may or may not be used. Step 2: A caramelization reaction occurs in a reaction system containing carbohydrates (A) and / or reductones (B) as raw materials, producing a brown substance. The raw materials in the reaction system may be in a gaseous, liquid, or solid state, or a combination thereof. The reaction system may contain any of a gaseous, liquid, and solid phases, but preferably contains a liquid phase. A solvent and / or a dispersion medium may or may not be used. The carbohydrates (A), reductones (B), amine compounds (G), amine equivalents (H), Maillard reaction, and caramelization reaction are as described above.

[0045] <2. Laminate> A laminate according to one embodiment of the present invention comprises a copper-based material substrate, a layer of the resin adhesive, and a resin substrate, in this order. Typically, the laminate is provided as a copper-clad laminate comprising a copper-based material sheet, a layer of the resin adhesive, and a resin sheet, in this order. In the copper-clad laminate, the copper-based material sheet may be laminated on one side of the resin sheet, or may be laminated on both sides of the resin sheet. Furthermore, the copper-based material sheet may be laminated on the entire surface of one or both sides of the resin sheet, or may be laminated only on a portion of the surface. The resin adhesive layer is usually formed on the entire surface of the copper-based material sheet to be bonded to the resin sheet, but it may also be formed on only a portion of the surface of the copper-based material sheet to be bonded to the resin sheet. Similarly, the resin adhesive layer may be formed on the entire surface of the resin sheet to be bonded to the copper-based material sheet, or may also be formed on only a portion of the surface of the resin sheet to be bonded to the copper-based material sheet. When copper-based material sheets are laminated on both sides of a resin sheet, it is sufficient that at least one of the copper-based material sheets is laminated to the resin sheet via a layer of the adhesive for resin according to one embodiment of the present invention. However, it is preferable that both copper-based material sheets are laminated to the resin sheet via a layer of the adhesive for resin according to one embodiment of the present invention. The two copper-based material sheets laminated on both sides of the resin sheet may be the same or different, and the two resin adhesive layers may also be the same or different. When a copper-based material sheet is laminated on one side of a resin sheet, another layer may be laminated on the surface of the resin sheet opposite to the surface on which the copper-based material sheet is laminated. Examples of the other layer include, but are not limited to, a release film layer for protecting the resin sheet. Furthermore, the copper-clad laminate may further have another layer laminated on the surface of the copper-based material sheet opposite to the surface on which the resin sheet is laminated. This other layer may be a layer of adhesive for resin, i.e., a layer containing one or both of a Maillard reaction product (C) and a caramelization reaction product (D).

[0046] [2-1.Copper-based material base material] The copper-based material substrate is a substrate containing copper or a copper alloy as a main component (the concentration of copper or copper alloy is 50% by mass or more, preferably 60% by mass or more, more preferably 75% by mass or more, and even more preferably 85% by mass or more, for example, 50 to 100% by mass), and is typically provided in the form of a sheet such as a plate or foil. The sheet may be composed of a single layer, or may be composed of two or more laminated layers. The copper content of the copper alloy is not particularly limited as long as it contains copper, but is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 75% by mass or more, and particularly preferably 85% by mass or more. Specific examples of copper alloys include copper-zinc alloys, copper-iron-phosphorus alloys, copper-tin alloys, copper-zirconium alloys, copper-nickel alloys, and copper-silver alloys, as defined in JIS H3100:2012 or the Copper Development Association (CDA) standard, but are not limited thereto. The copper-based material substrate may be one that has undergone a surface treatment typically applied to copper foil or copper alloy foil in copper-clad laminates used in printed wiring boards. Examples of surface treatments include single-metal plating, alloy plating, and chromate treatment. The plating may be any known plating treatment, such as a single-metal plating or alloy plating containing one or more elements selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. The plating may be single-layer plating or multi-layer plating (two or more layers). The copper-based material substrate may also be surface-treated with a coupling agent such as a silane coupling agent. However, according to the present invention, excellent adhesion between the copper-based material substrate and the resin substrate can be achieved without surface treatment with a coupling agent. Such surface treatments can be performed according to known methods.

[0047] The copper-based material substrate is not particularly limited, and examples thereof include copper plates, copper alloy plates, copper foils, and copper alloy foils, such as rolled copper plates, rolled copper alloy plates, rolled copper foils, rolled copper alloy foils, electrolytic copper foils, and electrolytic copper alloy foils, as well as those having the above-described surface treatments applied thereto. Carrier-attached copper foils and carrier-attached copper alloy foils, as well as those having the above-described surface treatments applied thereto, can also be used. In this case, copper foils that are not carriers for carrier-attached copper foils and copper alloy foils that are not carriers for carrier-attached copper alloy foils, can be used as the copper-based material substrate of the laminate according to one embodiment of the present invention. Laminates having copper-based material substrates on their surfaces, such as copper-plated materials, copper alloy-plated materials, copper-clad materials, and copper alloy-clad materials, as well as those having the above-described surface treatments applied thereto, can also be used. In this case, the copper-based material substrate included in the laminate serves as the copper-based material substrate of the laminate according to one embodiment of the present invention. The carrier of the carrier-attached copper foil or carrier-attached copper alloy foil is not particularly limited, and any commonly used metal foil such as electrolytic copper foil or resin film can be used. The thickness of the carrier is also not particularly limited and can be selected appropriately. Carrier-attached copper foil and carrier-attached copper alloy foil are generally, for example, electrolytic copper foil with a carrier and electrolytic copper alloy foil with a carrier, but are not limited thereto. Furthermore, a resin substrate can be laminated via the above-mentioned resin adhesive to a copper-based material substrate contained in a copper-clad laminate produced by an existing method or according to this embodiment, and the laminate obtained in this manner is also a laminate according to an embodiment of the present invention.

[0048] The copper-based material substrate usually preferably has a smooth surface. In particular, when the copper-based material substrate is provided in the form of a sheet such as a plate or foil, both surfaces are preferably smooth. Specifically, the ten-point mean roughness (Rzjis) of the surface is preferably 15 μm or less, more preferably 10 μm or less, even more preferably 5 μm or less, particularly preferably 2.5 μm or less, and most preferably 1.5 μm or less. In addition, the copper-based material substrate usually preferably has a surface that has not been roughened. The lower limit of the ten-point mean roughness (Rzjis) of the copper-based material substrate surface is not particularly limited, and typically, the closer to 0 μm, the more preferable. The ten-point mean roughness of the copper-based material substrate surface is, for example, in the range of 0.0001 μm to 14 μm, preferably in the range of 0.001 μm to 12 μm, and more preferably in the range of 0.01 μm to 10 μm. The ten-point average roughness (Rzjis) can be measured in accordance with JIS B0601:2001.

[0049] When the copper-based material substrate is in the form of a sheet, the thickness is not particularly limited and can be appropriately selected depending on the application, etc., but is usually preferably 0.5 μm to 1000 μm, more preferably 1 μm to 100 μm. In addition, the adhesive area of ​​the copper-based material substrate with the resin substrate is not particularly limited and can be appropriately selected depending on the application.

[0050] [2-2. Resin adhesive layer] The amount of adhesion per unit area of ​​the resin adhesive layer, i.e., the layer containing one or both of the Maillard reaction product (C) and the caramelization reaction product (D), is not particularly limited as long as it is an amount that provides a desired adhesive strength, but is preferably 0.1 to 3,000 mg / m 2 is preferably 0.5 to 2000 mg / m 2 More preferably, it is 0.5 to 1500 mg / m 2 More preferably, the concentration is 0.5 to 1000 mg / m 2 More preferably, it is 0.5 to 700 mg / m 2 More preferably, it is 0.5 to 600 mg / m 2It is particularly preferable that the concentration is 0.5 to 500 mg / m 2 It is most preferable that:

[0051] The adhesion weight of the resin adhesive layer is the adhesion weight per one surface (one layer). The adhesion weight of the resin adhesive layer can be indirectly measured by adding an element not contained in the adhesive to the adhesive using X-ray fluorescence spectroscopy (XRF). Specifically, a compound (hereinafter referred to as compound β) containing a known amount of an element not contained in the adhesive (hereinafter referred to as element α) is added to the adhesive at a specific ratio, and the adhesion weight per unit area of ​​the adhesive layer is calculated from the adhesion amount of the known amount of element α per unit area using X-ray fluorescence spectroscopy. The addition amount of compound β to the adhesive is, for example, 5% to 40% by mass based on the total solid content. The content of element α in compound β is, for example, 30% to 80% by mass. Compound β is not particularly limited, and an example is zirconium ammonium carbonate, in which case element α can be Zr. Compound β may also be used in the form of an aqueous solution.

[0052] The thickness of the resin adhesive layer is not particularly limited and can be selected appropriately so that the amount of adhesion falls within the above range, but is preferably 0.5 to 3000 nm, more preferably 0.5 to 2000 nm, even more preferably 0.5 to 1500 nm, particularly preferably 0.5 to 1000 nm, and most preferably 0.5 to 700 nm.

[0053] [2-3. Resin substrate] The resin substrate may be any substrate containing a resin. Accordingly, the resin substrate may be composed solely of a resin, or may contain components other than a resin. When the resin substrate contains components other than a resin, the resin may be the main component (resin concentration of 50% by mass or more), or may not be the main component. Examples of components other than a resin include inorganic fibers such as carbon fiber and glass fiber. Examples of resin substrates containing components other than a resin include substrates in which inorganic fibers (which may be in the form of woven fabric or nonwoven fabric) are impregnated with a resin or a resin composition, typically prepregs. Resin substrates are typically provided in the form of sheets such as films and prepregs. The sheets may be composed of a single layer or two or more laminated layers. The sheets may be flexible or rigid. The resin contained in the resin substrate may be one type or a mixture of two or more types of resin. The resin substrate may also contain inorganic particles (fillers) and various other additives, as necessary. The components other than the resin that the resin substrate can contain are not particularly limited, and components other than those listed above may also be used.

[0054] The resin contained in the resin substrate is not particularly limited and can be appropriately selected depending on the intended use, but thermoplastic resins are preferably used. Furthermore, resins having a relative dielectric constant of 5.0 or less at 25°C and 10 GHz are preferred, more preferably 4.0 or less, and even more preferably 3.5 or less. Typically, resins having a relative dielectric constant of more than 1.0 to 5.0, more typically 1.1 to 5.0, at 25°C and 10 GHz can be used. The relative dielectric constant of the resin can be measured by a cavity resonator method in accordance with JIS C2565:1992.

[0055] Specific examples of resins include fluororesins such as polytetrafluoroethylene (PTFE), perfluoroalkoxy fluororesin (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, liquid crystal polymer (LCP), aromatic polyether ketones such as polyether ether ketone (PEEK), polyphenylene ether (PPE), epoxy resins, bismaleimide triazine resins, cycloolefin polymers, and polyimides. Among these, PEEK and fluororesins (e.g., PTFE, PFA, FEP, ETFE, ECTFE, and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers) are preferred, with fluororesins being more preferred and PTFE being particularly preferred.

[0056] As the resin substrate, resin films and prepregs commercially available as resin substrates for printed wiring boards can also be used.

[0057] When the resin substrate is in the form of a sheet, the thickness is not particularly limited and can be appropriately selected depending on the application, but is usually preferably 10 μm to 1000 μm, more preferably 20 μm to 500 μm.

[0058] [2-4. Manufacturing method of laminate] A laminate according to one embodiment of the present invention, typically a copper-clad laminate, can be produced by bonding a copper-based material substrate and a resin substrate together using the resin adhesive. Preferably, the laminate can be produced by forming a layer of resin adhesive on the surface of the copper-based material substrate and then bonding the resin substrate onto the layer of resin adhesive. The resin adhesive may be provided in liquid form or in sheet form (e.g., a sheet-like hot-melt adhesive). When the resin adhesive is in liquid form, an example of a method is to form a layer of resin adhesive on the surface of the copper-based material substrate, as described below, and then bond the resin substrate onto the layer of resin adhesive. When the resin adhesive is in sheet form, an example of a method is to sandwich a sheet-like adhesive between the copper-based material substrate and the resin substrate to bond them. A preferred method for producing a laminate according to one embodiment of the present invention is described below, but the method for producing a laminate is not limited to the following method.

[0059] First, a layer of resin adhesive is formed on a copper-based material substrate, typically a copper-based material sheet such as copper foil, copper plate, copper alloy foil or copper alloy plate (which may have been subjected to the above-mentioned surface treatment), or, in the case of using a laminate having a copper-based material substrate on its surface, on the copper-based material substrate (which may have been subjected to the above-mentioned surface treatment).

[0060] The resin adhesive layer can be formed, for example, by dissolving or dispersing a resin adhesive containing one or both of the Maillard reaction product (C) and the caramelization reaction product (D) in a solvent (e.g., water) to prepare an adhesive liquid for forming the resin adhesive layer, applying this to the surface of the copper-based material substrate, and then drying it.

[0061] The content of each compound in the adhesive liquid is not particularly limited and can be selected appropriately.

[0062] The solvent used in the adhesive liquid is not particularly limited and can be appropriately selected from commonly used solvents. Organic solvents can also be used, but water is usually preferred. Two or more solvents may be used in combination.

[0063] The adhesive liquid may, if necessary, contain various commonly used additives, for example, inorganic compounds, organic compounds such as resins (for example, acrylic resins, epoxy resins, urethane resins, ether resins, amide resins, alkylene vinyl acetate copolymers, polyvinyl alcohols, polyalkylene glycols, styrene-maleic anhydride copolymers, oxidatively modified polyalkylene resins, thickening polysaccharides, and cellulose nanofibers, which are commonly used as binders), surfactants, antifoaming agents, leveling agents, antibacterial and antifungal agents, dyes, pigments, fragrances, antiblocking agents, release agents, rust inhibitors, etc.

[0064] The application of the adhesive liquid is not particularly limited and can be carried out by a known method, such as a bar coating method, a spray method, a spin coating method, a roll coating method, a curtain coating method, an electrostatic powder coating method, a fluidized bed coating method, or a dipping method.

[0065] The drying conditions after application of the adhesive liquid are not particularly limited and can be selected as appropriate, but it is usually preferable to heat and dry the copper-based material substrate so that the maximum temperature reached (PMT) is 60°C to 300°C. The drying temperature is not particularly limited as long as the adhesive liquid can be dried to form a layer of resin adhesive, but the maximum temperature reached (PMT) of the copper-based material substrate is more preferably in the range of 60°C to 250°C, and particularly preferably in the range of 60°C to 200°C. The drying time is not particularly limited as long as the adhesive liquid can be dried to form a layer of resin adhesive, but may be, for example, 1 minute or more, 5 minutes or more, 10 minutes or more, 30 minutes or more, 180 minutes or less, 120 minutes or less, or 60 minutes or less.

[0066] Before forming the layer of the adhesive for resin, the copper-based material substrate may be subjected to a cleaning treatment such as acid degreasing, alkali degreasing, acid cleaning, alkali cleaning, or water washing, and drying after the cleaning treatment, etc. Such cleaning treatment and drying can be performed according to known methods.

[0067] Next, a resin substrate, typically a resin sheet such as a resin film or prepreg, is superimposed on the layer of adhesive for resin formed on the surface of the copper-based material substrate in this manner, and the layers are heated and pressed to bond them together, thereby producing a laminate according to the present embodiment. When producing a laminate in which copper-based material substrates are laminated on both sides of a resin substrate, the copper-based material substrates may be bonded simultaneously to both sides of the resin substrate such as a resin film or prepreg via the layer of adhesive for resin, or may be bonded to each side in turn.

[0068] The method for bonding a copper-based material substrate having a resin adhesive layer formed on its surface to a resin film or prepreg is not particularly limited, and can be carried out using a known heating and pressure device. The pressure and heating conditions are also not particularly limited, and can be selected appropriately depending on the material and type of resin used. For example, the pressing pressure can be set to 1 to 1000 kgf / cm. 2 The pressing time can be 0.1 to 1440 minutes, the pressing temperature can be 80°C to 600°C, and the pressing pressure can be typically 5 to 100 kgf / cm 2 The pressing time can be set to 0.5 to 600 minutes or less, and the pressing temperature can be set to 120°C to 450°C.

[0069] During the above heating and pressurization, the pressure may be reduced from normal pressure and then the heating and pressurization may be performed. [Example]

[0070] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0071] <1. Production of Maillard reaction product (C) and caramelization reaction product (D)> The following carbohydrates (A) or reductones (B) and amine compounds (G) or amine equivalents (H) were used as raw materials for the Maillard reaction product (C), and the following carbohydrates (A) or reductones (B) were used as raw materials for the caramelization reaction product (D). The following additive (I) was used as an additive during the reaction. Unless otherwise specified, the carbohydrates (A), reductones (B), amine compounds (G), amine equivalents (H), and additives (I) were manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. [Carbohydrate (A)] (A-1) Dihydroxyacetone (monosaccharide / ketose / triose) (A-2) Xylose (monosaccharide / aldose / pentose) (A-3) Arabinose (monosaccharide / aldose / pentose) (A-4) Glucose (monosaccharide / aldose / hexose) (A-5) Fructose (monosaccharide / ketose / hexose) (A-6) Maltose (disaccharide) (A-7) Gluconic acid (50% by mass aqueous solution) (sugar acid) (A-8) Pullulan (Hayashibara Co., Ltd.) (polysaccharide) (A-9) Cellogen 5A (registered trademark) (Na salt of carboxymethylcellulose) (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (polysaccharide) (A-10) Gum arabic (Sumitomo Pharma Food & Chemical Co., Ltd.) (polysaccharide) (A-11) Sorbitol (sugar alcohol) [Reductones (B)] (B-1) Ascorbic acid (reductone) (B-2) Sodium ascorbate (reductone salt) [Amine compound (G)] (G-1) Ammonia water (28.0 to 30.0 mass%) (G-2) Dibutylamine (G-3) Aniline (G-4) Trimethylenetetramine (G-5) Epomin (registered trademark) P-1000 (manufactured by Nippon Shokubai Co., Ltd.) (G-6) Ammonium chloride (G-7) Ammonium nitrate (G-8) Glycine (G-9) L-Asparagine Monohydrate (G-10) 3-amino-1H-1,2,4-triazole (G-11) 3,5-diamino-1H-1,2,4-triazole (G-12) Ammonium peroxodisulfate [Amine equivalent (H)] (H-1)Urea (H-2) Thiourea [Additives (I)] (I-1) 30% by mass hydrogen peroxide solution (I-2) 35% by mass hydrochloric acid (I-3) 50% by mass sodium hydroxide aqueous solution

[0072] [Maillard reaction product (C) production conditions] [Manufacturing conditions 1: C-1~C-16, C-18~C-36] Based on the formulations shown in Tables 1 and 2, ion-exchanged water, carbohydrates (A) or reductones (B), and amine compounds (G) or amine equivalents (H) were mixed to prepare aqueous solutions. For Maillard reaction products (C-13, C-23 to C-25) that required additives, the additives were added at this stage. The pH of the aqueous solution at room temperature at this stage is shown in Tables 1 and 2. The pre-reaction aqueous solution was then placed in a 100 mL polypropylene container, sealed, and heated in a circulating hot air oven at a liquid temperature of 95°C for the time shown in Tables 1 and 2 to produce a solution containing a Maillard reaction product (C). The Maillard reaction products produced were designated C-1 to C-16 and C-18 to C-36, respectively. The production of Maillard reaction products was determined by determining whether or not brown substances were produced using a spectrophotometer (SD7000) manufactured by Nippon Denshoku Industries Co., Ltd., using the method described above. When brown substances were produced, they were marked as "present" in Tables 1 and 2. The same applies to the following production examples.

[0073] [Manufacturing condition 2: C-17] Based on the formulation shown in Table 1, ion-exchanged water, reductones (B-1), and 30% by mass ammonia water (G-1) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed to prepare an aqueous solution. The pH of the aqueous solution at room temperature at this point is shown in Table 1. This aqueous solution and stirrer chips were placed in a 100 mL glass beaker, and the liquid temperature was raised to 90°C and heated with stirring for 8 hours to produce a solution containing a Maillard reaction product (C). The produced Maillard reaction product was designated C-17.

[0074] [Conditions for producing caramelized reaction product (D)] [Manufacturing conditions 3: D-1~D-8] Based on the formulation shown in Table 3, ion-exchanged water and carbohydrate (A) were mixed to prepare an aqueous solution. For caramelization reaction products (D-6 to D-8) using additives, the additives were added at this stage. The pH of the aqueous solution at room temperature at this stage is shown in Table 3. The pre-reaction aqueous solution was then placed in a 100 mL polypropylene container, sealed, and heated in a circulating hot air drying oven at a liquid temperature of 95°C for the time shown in Table 3 to produce a solution containing caramelization reaction product (D). The produced caramelization reaction products were designated (D-1 to D-8). The production of a caramelization reaction product was determined by the presence or absence of a brown substance using a spectrophotometer (SD7000) manufactured by Nippon Denshoku Industries Co., Ltd., using the method described above. If a brown substance was produced, this was marked "present" in Table 3. The same applies to the following production examples.

[0075] [Manufacturing condition 4: D-9~D-10] Ion-exchanged water and reductones (B) were mixed according to the formulation shown in Table 3 to prepare an aqueous solution. The pH of the aqueous solution at room temperature at this point is shown in Table 3. This aqueous solution and stirrer chips were placed in a 100 mL glass beaker, and the liquid temperature was brought to 90°C, followed by heating and stirring for 8 hours to produce a solution containing a caramelization reaction product (D). The produced caramelization reaction products were designated (D-9 to D-10).

[0076] [Table 1]

[0077] [Table 2]

[0078] [Table 3]

[0079] <2. Manufacturing of copper clad laminates> [Formation of resin adhesive layer] [Example 1] As the copper-based material substrate, electrolytic copper foil (thickness 18 μm, Rzjis 0.14 μm, Ra 0.05 μm) (K-1) was prepared, which had a heat-resistant plating layer and an electrolytic chromate layer in this order from the outside to the inside. The adhesive layer formed on the copper foil surface was 12 mg / m 2 The solid content of the Maillard reaction product (C-1) was adjusted with ion-exchanged water to a coating amount of 100°C, and the resulting coating was applied to one surface of the copper foil (by bar coating). The resulting coating was then dried at 100°C for 1 minute in a circulating hot air drying oven to form an adhesive layer on the copper foil surface.

[0080] [Adhesion between copper foil with an adhesive layer and a resin substrate] A PTFE prepreg (manufactured by Rogers Corporation, product name "RO3003 Bondply", thickness 0.1 mm) (L-1) was attached to the surface of the adhesive layer of the copper foil on which the adhesive layer was formed, and then the copper foil was wrapped in aluminum foil and sealed off from the atmosphere, thereby producing a copper-clad laminate. The bonding conditions were a press pressure of 30 kgf / cm. 2 The pressing time was 45 minutes and the pressing temperature was 370°C.

[0081] [Examples 2 to 67] For Examples 2 to 67, adhesives shown in Table 4 (Maillard reaction products (C-2 to C-36), caramelization reaction products (D-1 to D-10), and commercially available caramel colors (J-1 to J-3 shown below)) were used, and the solids concentration was adjusted with ion-exchanged water so that the adhesive layer formed on the copper foil surface would have the adhesion amount shown in Table 4. The adhesive layer was formed in the same manner as in Example 1, except that it was applied (by bar coating) to one surface of the copper-based material substrate (K-1 to K-3 shown below) shown in Table 4. Then, copper-clad laminates were produced in the same manner as in Example 1, except that the resin substrates (L-1 to L-3 shown below) shown in Table 4 were used and bonded under the conditions of the press time and press temperature shown in Table 4. [Caramel color] (J-1) Commercially available caramel color, Caramel I (J-2) Commercially available caramel color, Caramel III (J-3) Commercially available caramel color, Caramel IV [Copper-based material base material] (K-1) Electrolytic copper foil (thickness 18 μm, Rzjis 0.14 μm, Ra 0.05 μm) with a heat-resistant plating layer and an electrolytic chromate layer in this order from the outside to the inside (K-2) Electrolytic copper foil with heat-resistant plating layer (thickness 18 μm, Rzjis 1.05 μm, Ra 0.20 μm) (K-3) Electrolytic copper foil (thickness 18μm, Rzjis 0.89μm, Ra 0.17μm) [Resin substrate] (L-1) PTFE prepreg (manufactured by Rogers Corporation, product name "RO3003 Bondply", thickness 0.1 mm) (relative permittivity at 10 GHz: 3.0 ± 0.04, dielectric dissipation factor: 0.0010) (L-2) ETFE sheet (manufactured by AS ONE Corporation, thickness 0.05 mm) (relative permittivity 2.6 at 10 GHz, dielectric dissipation factor 0.0150) (L-3) PEEK-based prepreg (thickness 0.05 mm) (relative permittivity 3.1 at 10 GHz, dielectric dissipation factor 0.0033)

[0082] [Comparative Examples 1 to 4] Copper-clad laminates were produced in the same manner as in Example 1, except that aqueous solutions of carbohydrates (A-4, A-5, A-8) or reductones (B-1) shown in Table 5 were used to form the adhesive layer.

[0083] [Comparative Examples 5, 7 to 8, 16, 21, and 26] Copper-clad laminates were manufactured in the same manner as in Example 1, except that no adhesive layer was formed, and that the resin substrates (L-1 to L-3) shown in Table 5 or non-resin material substrates (O-1 to O-3 shown below) were used and bonded under the pressing time and pressing temperature conditions shown in Table 5.

[0084] Comparative Example 6 A copper-clad laminate was produced in the same manner as in Example 1, except that the copper-based material substrate (M-1) shown below was used, no adhesive layer was formed, and bonding was performed under the pressing time and pressing temperature conditions shown in Table 5. (M-1) Electrodeposited copper foil (thickness 18 μm, Rzjis 1.77 μm, Ra 0.19 μm) having, from the outside to the inside, a silane coupling agent adhesive layer, a heat-resistant plating layer, and an electrolytic chromate layer in that order.

[0085] [Comparative Examples 9 to 15, 17 to 20, 22 to 25, 27 to 30] An adhesive layer was formed in the same manner as in Example 1 using the adhesives shown in Table 5 (Maillard reaction products (C-4, C-17), caramelization reaction product (D-1), commercially available caramel color (J-2)) or commercially available water-based resins (N-1 to N-7 shown below). The solid content was adjusted with ion-exchanged water so that the adhesive layer formed on the copper foil surface had the adhesion amount shown in Table 5. Then, a copper-clad laminate was produced in the same manner as in Example 1, using the resin substrates (L-1 to L-3) shown in Table 5 or material substrates other than resin (O-1 to O-3 shown below). The copper-clad laminate was bonded under the conditions of the pressing time and pressing temperature shown in Table 5.

[0086] [Water-based resin] (N-1) MODEPIX (registered trademark) 302 (manufactured by Arakawa Chemical Industries, Ltd.) (epoxy resin) (N-2) Gohsenex (registered trademark) LW-100 (manufactured by The Nippon Synthetic Chemical Industry Co., Ltd.) (sulfo-modified PVOH) (N-3) Arrowbase (registered trademark) YA-6010 (manufactured by Unitika Ltd.) (modified polypropylene) (N-4) Pitzcol (registered trademark) V-7154 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (PVP / PVA) (N-5) AQUALIC (registered trademark) HL415 (manufactured by Nippon Shokubai Co., Ltd.) (polyacrylic acid) (N-6) Boncoat (registered trademark) CF-6140 (DIC Corporation) (acrylic resin) (N-7) Eliter (registered trademark) KT-507 (manufactured by Unitika Ltd.) (ester resin)

[0087] [Materials other than resin] (O-1) Glass fiber cloth (O-2) SUS foil (manufactured by AS ONE Corporation, thickness 0.1 mm) (O-3) Aluminum foil (MA Aluminum Co., Ltd., thickness 12 μm) The glass fiber cloth (O-1) was prepared by placing an epoxy resin prepreg (manufactured by Showa Denko Materials Co., Ltd., product name "GEA-679N") in chloroform heated to 60°C, completely dissolving the epoxy resin, and then extracting only the glass fiber cloth. This was then immersed again in chloroform heated to 60°C to remove the remaining epoxy resin, and then dried at 80°C for 1 minute in a circulating drying oven.

[0088] [Ten-point average roughness of copper foil surface (Rzjis)] The ten-point average roughness (Rzjis) and arithmetic mean roughness (Ra) of the surface of the copper foil to be bonded to the resin used above were measured using a laser microscope (VK-8701 manufactured by Keyence Corporation) in accordance with JIS B0601:2001.

[0089] [Adhesive layer adhesion amount on copper foil with adhesive layer formed] The adhesion weight of the adhesive layer was determined by the following method. A predetermined amount of ammonium zirconium carbonate aqueous solution was added to a Maillard reaction product (C-1) with a known solid content concentration to prepare a coating treatment agent for adhesion weight measurement. The solid content ratio of ammonium zirconium carbonate to the total solid content was 15% by mass. Next, using the prepared coating treatment agent, a coating film was formed on an electrolytic copper foil (K-1), a copper-based material substrate, by bar coating, and then dried at 100°C for 1 minute in a circulating hot air drying oven to form a dry coating film. The copper foil with the dry coating film formed thereon was cut into a measurement sample of 4 cm width x 4 cm length, and analyzed using an X-ray fluorescence analyzer (ZSX Primus II, manufactured by Rigaku Corporation) to measure the zirconium adhesion weight per unit area. Based on these results, the adhesion weight per unit area of ​​the entire dried coating film at a known solid content concentration can be calculated. The same procedure was repeated for several solid content concentrations without changing the type of bar coating, and a two-axis graph (calibration curve) was created with solid content concentration versus adhesion weight. The target adhesion weight was confirmed to be interpolated within the range of the actually measured adhesion weight values ​​in the two-axis graph, and the solid content concentration corresponding to the target adhesion weight was calculated. A copper-clad laminate for adhesion evaluation was then produced using a Maillard reaction product (C-1) of known solid content concentration without the addition of an aqueous solution of ammonium zirconium carbonate. Using the same method as above, the relationship between solid content concentration and adhesion weight was determined for each adhesive (C-2 to C-36, D-1 to D-10, J-1 to J-3, and N-1 to N-7), and the solid content was adjusted so that the adhesive layer formed on the copper foil surface had the adhesion weight shown in Tables 4 and 5. The relationship between the solid content concentration and the adhesion amount was determined for each combination of adhesive (C-2 to C-36, D-1 to D-10, J-1 to J-3, and N-1 to N-7) and electrolytic copper foil (K-1, K-2, or K-3) shown in Tables 4 and 5.

[0090] <3. Adhesion evaluation> The copper-clad laminates prepared in the above Examples and Comparative Examples were cut into 0.3 cm wide x 7 cm long pieces, and the peel strength of the copper foil in the 90° direction was measured in accordance with JIS C5012:1993. The adhesion was evaluated according to the following evaluation criteria. In this evaluation, a score of 2 or less was considered to have poor adhesion. The results are shown in Tables 4 and 5. [Evaluation criteria: peel strength] 1 point: 0N / cm or more and less than 1.0N / cm 2 points: 1.0N / cm or more and less than 2.5N / cm 3 points: 2.5N / cm or more and less than 5.0N / cm 4 points: 5.0N / cm or more and less than 7.5N / cm 5 points: 7.5N / cm or more and less than 10.0N / cm 6 points: 10.0N / cm or more

[0091] [Table 4]

[0092] [Table 5]

Claims

1. The adhesive for resins contains one or both selected from a Maillard reaction product (C) made from carbohydrates (A) and / or reductones (B) and an amine compound (G) as raw materials, and a caramelization reaction product (D) made from carbohydrates (A) and / or reductones (B) as raw materials.

2. A laminate comprising, in this order: a copper-based material substrate; a layer of the adhesive for resin according to claim 1; and a resin substrate.

3. A resin adhesive containing one or both selected from a Maillard reaction product (C) made from carbohydrates (A) and / or reductones (B) and an amine compound (G) and / or an amine equivalent (H) as raw materials, and a caramelization reaction product (D) made from carbohydrates (A) and / or reductones (B) as raw materials.

4. A laminate comprising, in this order, a copper-based material substrate, a layer of the adhesive for resin according to claim 3, and a resin substrate.

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