Adhesive for resin material having low dielectric properties, and laminate

Abstract

Provided is an adhesive for a resin material having low dielectric properties that is excellent in adhesiveness between a metal material (especially a metal material having a low surface roughness) and a resin material having low dielectric properties. Provided is an adhesive for bonding a metal material and a resin material having low dielectric properties, wherein the adhesive contains an organic amine compound (A) as a main component, and the organic amine compound (A) contains at least one selected from a compound (B) in which an amino group is directly bonded on a nitrogen-containing aromatic ring and a compound (C) having a polyalkylamine skeleton.

Description

Adhesive and laminate for low dielectric resin materials

[0001] The present invention relates to an adhesive for low dielectric resin materials and a laminate.

[0002] Metal-clad laminates are made by laminating a metal material (such as copper foil or copper alloy foil) on one or both sides of a resin material (such as a prepreg, which is a composite material of an organic compound and an inorganic compound, or a resin film), and are widely used in the manufacture of printed wiring boards, etc.

[0003] The surface of the metal material used in the metal-clad laminate is generally roughened to ensure adhesion to the resin material. For example, Patent Document 1 discloses a surface treatment method for roughening a copper foil to provide good adhesion to a resin film. Also, Patent Document 2 discloses a method for bonding a metal material to a resin material using a surface treatment solution containing a triazole silane compound.

[0004] In general, low-dielectric resin materials are used as resin materials in metal-clad laminates for high-frequency applications, but these materials have poor adhesive properties, and methods for improving adhesive properties include introducing specific functional groups into the resin or combining it with an adhesive resin. For example, Patent Document 3 discloses a technique for improving adhesive strength by mixing low-adhesion polytetrafluoroethylene (PTFE) particles with a highly adhesive epoxy resin.

[0005] JP 2007-46095 A International Publication No. 2018 / 186476 JP 2018-141053 A

[0006] In recent years, with the increase in communication speed, the frequency of electrical signals has been increasing, and there is a demand for printed wiring boards (high-frequency printed wiring boards) that can accommodate this. Specifically, there is a demand for printed wiring boards that are laminated with a metal material and a low-dielectric resin material that can suppress transmission loss. However, if the surface roughness of the metal material is high, conductor loss tends to increase due to the skin effect, and therefore it is undesirable to roughen the surface of the metal material to form deep irregularities, as disclosed in Patent Document 1. Furthermore, it is unclear whether the triazole silane compound described in Patent Document 2 is effective in bonding metal materials and low-dielectric resins.

[0007] Furthermore, in the high frequency region, materials with poor dielectric properties (high relative dielectric constant and dielectric dissipation factor) exhibit significant dielectric loss, and therefore there is a need for a technology that can bond low dielectric resins and metal materials without relying on the method shown in Patent Document 3.

[0008] In view of the above circumstances, one embodiment of the present invention aims to provide an adhesive for low dielectric resin materials that exhibits excellent adhesion between metal materials (particularly metal materials with low surface roughness) and low dielectric resin materials. In another embodiment, the present invention aims to provide a laminate including a metal material layer, an adhesive layer formed from such an adhesive, and a low dielectric resin material layer.

[0009] The present invention relates to the following items. [1] An adhesive for bonding a metal material and a low-dielectric resin material, the adhesive containing an organic amine compound (A) as a main component, the organic amine compound (A) containing at least one selected from a compound (B) having an amino group directly bonded to a nitrogen-containing aromatic ring and a compound (C) having a polyalkylamine skeleton. [2] The adhesive according to [1], wherein the mass ratio of the organic amine compound (A) to the non-volatile content of the adhesive is 20 mass % to 100 mass %. [3] A laminate comprising, in this order, a metal material layer, an adhesive layer formed from the adhesive according to [1] or [2], and a low-dielectric resin material layer. [4] The laminate according to [3], wherein the ten-point average roughness (Rzjis) of at least the surface of the metal material layer that is bonded to the low-dielectric resin material layer is 2.5 μm or less. [5] The laminate according to [3] or [4], wherein the dielectric loss tangent of the low dielectric resin material constituting the low dielectric resin material layer at a temperature of 23°C and 10 GHz is 0.0001 to 0.01. [6] A printed wiring board obtained by processing the metal material layer of the laminate according to any one of [3] to [5] into a wiring circuit. [7] The printed wiring board according to [6], which uses signals with a frequency of 25 GHz or more. [8] An electronic device having the printed wiring board according to [6] or [7]. [9] A method for manufacturing a laminate, comprising bonding a metal material and a low dielectric resin material via the adhesive according to [1] or [2].

[10] A method for manufacturing a laminate, comprising the steps of: bringing the adhesive according to [1] or [2] into contact with a metal material to form an adhesive layer on the metal material; optionally, after the contacting step, drying the adhesive layer; and bringing a low dielectric resin material into contact with the surface of the adhesive layer and applying heat and pressure.

[11] The amount of adhesion per unit area of ​​the adhesive layer is 0.1 to 4000 mg / m 2

[10] The method for producing a laminate according to

[10] ,

[0010] According to one embodiment of the present invention, an adhesive can be provided that exhibits excellent adhesion between a metal material and a low-dielectric resin material. In particular, an adhesive can be provided that exhibits excellent adhesion between a metal material with low surface roughness and a low-dielectric resin material with excellent dielectric properties. Furthermore, because the adhesive exhibits excellent adhesion even at an extremely low adhesion weight, the thickness of the adhesive layer can be minimized. For the reasons described above, in which the provision of an adhesive layer can reduce the deterioration of the dielectric properties of the laminate, the adhesive can be used to provide a metal-clad laminate that exhibits excellent adhesion between a metal material with low surface roughness and a low-dielectric resin material with excellent dielectric properties. This metal-clad laminate can be suitably used for printed wiring boards, particularly high-frequency printed wiring boards.

[0011] <1. Adhesive for Low Dielectric Resin Materials> An adhesive for low dielectric resin materials according to one embodiment of the present invention is characterized in that it contains an organic amine compound (A) as a main component, and the organic amine compound (A) includes at least one compound selected from the group consisting of a compound (B) having an amino group directly bonded to a nitrogen-containing aromatic ring and a compound (C) having a polyalkylamine skeleton.

[0012] In the present invention, the term "main component" refers to the component that accounts for the largest mass proportion among the components that contribute to adhesiveness. The mass proportion of the organic amine compound (A) in the nonvolatile content is preferably 20 mass% or more, more preferably 30 mass% or more, even more preferably 40 mass% or more, and even more preferably 50 mass% or more. There is no particular upper limit, but it may be 100 mass% or less. Therefore, the mass proportion of the organic amine compound (A) in the nonvolatile content is preferably 20 mass% to 100 mass%, more preferably 30 mass% to 100 mass%, even more preferably 40 mass% to 100 mass%, and even more preferably 50 mass% to 100 mass%.

[0013] In the present invention, the nonvolatile content refers to components having a boiling point of 170° C. or higher under an atmosphere of 760 mmHg.

[0014] In the adhesive of the present invention, the components other than the nonvolatile components are a solvent and / or a dispersion medium. The solvent and / or dispersion medium is not particularly limited, and it is preferable that the effect of uniformly dissolving or dispersing the organic amine compound (A) is obtained, and one or more solvents and / or dispersion mediums may be used in combination. A typical example is water.

[0015] In the present invention, the organic amine compound (A) (hereinafter also referred to simply as "amine compound (A)") refers to an organic compound having an amino group and a salt thereof. The amino group referred to here does not include an amino group derived from a nitrogen atom in the ring structure of an aromatic ring. For example, -NH- in the ring structure of pyrrole is not considered an amino group. The acid that forms a salt with the amino group may be either an inorganic acid or an organic acid. Examples of inorganic acids include hydrohalic acids, oxoacids, hydrocyanic acid, cyanic acid, and thiocyanic acid. Examples of hydrohalic acids include hydrofluoric acid, hydrochloric acid, hydrobromic acid, and hydroiodic acid. Examples of oxoacids include 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, carbonic acid, boric acid, silicic acid, chromic acid, dichromate, permanganic acid, molybdic acid, and tungstic acid. Examples of organic acids include carboxylic acids, percarboxylic acids, and sulfonic acids. Examples of carboxylic acids include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of sulfonic acids include aliphatic sulfonic acids and aromatic sulfonic acids. Examples of aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, gluconic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, and trifluoroacetic acid. Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, and gallic acid. Examples of percarboxylic acids include peracetic acid. Examples of aliphatic sulfonic acids include methanesulfonic acid. Examples of aromatic sulfonic acids include benzenesulfonic acid. The acids that form salts with amino groups may be used alone or in combination of two or more.

[0016] In a laminate according to one embodiment of the present invention, discoloration of the resin material was observed after removing the metal portion of the laminate with an etching solution after thermocompression bonding. From this, it is speculated that the mechanism by which adhesiveness is obtained is that the amine compound (A) undergoes intermolecular and / or intramolecular elimination, addition, substitution, or oxidation reactions in the resin material softened and / or melted during thermocompression bonding, forming a network structure derived from the amine compound (A) in the resin material, thereby obtaining high adhesiveness. Note that the amine compound (A) is preferably a compound (C) having a structure having hydrogen at the β-position of the amino group, and from the viewpoint of enamine formation, it is preferable that the γ-position of the amino group is nitrogen.

[0017] In the present invention, the compound (B) having an amino group directly bonded to a nitrogen-containing aromatic ring and the compound (C) having a polyalkylamine skeleton may be used alone or in combination of two or more thereof.

[0018] In the present invention, a nitrogen-containing aromatic ring refers to an aromatic ring containing at least one nitrogen atom as an atom constituting a cyclic structure having aromaticity. The number of nitrogen atoms constituting the cyclic structure is not particularly limited. However, when the number of atoms constituting one cyclic structure is X and the number of nitrogen atoms is Y, the value of Y / X may be 0.07 or greater, preferably 0.11 or greater, more preferably 0.16 or greater, more preferably 0.33 or greater, and even more preferably 0.60 or greater. The value of Y / X is not particularly limited, but is preferably 0.8 or less. Therefore, the value of Y / X is, for example, preferably 0.16 to 0.8, more preferably 0.33 to 0.8, and even more preferably 0.60 to 0.8. For example, a pyridine ring is a six-membered ring containing one nitrogen atom, so X = 6 and Y = 1. Examples of compounds having a nitrogen-containing aromatic ring include, but are not limited to, azoles and azines. Examples of the ring structure of an azole include, but are not limited to, a pyrrole ring, a diazole ring, a triazole ring, a tetrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an oxadiazole ring, and a thiadiazole ring. Examples of the diazole ring include, but are not limited to, an imidazole ring and a pyrazole ring. Examples of the ring structure of an azine include, but are not limited to, a pyridine ring, a diazine ring, and a triazine ring. Examples of the diazine ring include, but are not limited to, a pyridazine ring, a pyrimidine ring, and a pyrazine ring. Furthermore, the nitrogen-containing aromatic ring may have a polycyclic ring structure, such as a bicyclic or tricyclic ring. Specific examples of the ring structure include, but are not limited to, an indole ring, an isoindole ring, a benzotriazole ring, a purine ring, an azaindole ring, a benzoxazole ring, a benzothiazole ring, a benzothiadiazole ring, a quinoline ring, a naphthyridine ring, a carbazole ring, an acridine ring, a phenazine ring, a phenoxazine ring, a phenothiazine ring, and a phenanthroline ring. The above examples also include isomers with different positions of heteroatoms (N, O, S) (for example, 1,2,3-triazole ring and 1,2,4-triazole ring). The azine may be in the form of a salt, and specific examples include pyridinium salts, diazinium salts, and triazinium salts. The acid that forms a salt with the azine may be either an inorganic acid or an organic acid.Specifically, the acids are the same as those that form salts with the amino group described above. The acids that form salts with the azines may be used alone or in combination of two or more. The azole may also be in the form of a salt, specifically, an alkali metal salt, an alkaline earth metal salt, or an onium salt. Examples of alkali metal salts include lithium salt, sodium salt, potassium salt, rubidium salt, and cesium salt. Examples of alkaline earth metal salts include magnesium salt, calcium salt, strontium salt, and barium salt. Examples of onium salts include ammonium salt and phosphonium salt. Examples of bases that form salts with the azole include alkali metal hydroxides, alkaline earth metal hydroxides, and ammonia. Examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. Examples of alkaline earth metal hydroxides include magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide.

[0019] In the present invention, the amino group in compound (B) (hereinafter also referred to simply as "compound (B)") in which an amino group is directly bonded to a nitrogen-containing aromatic ring is preferably primary to tertiary, more preferably primary or secondary. Furthermore, the amino group may be in the form of a salt, but is preferably not in the form of a salt. The number of amino groups bonded to one nitrogen-containing aromatic ring is not limited, but as long as they have the same ring structure, it is preferable that two or more amino groups are bonded to one nitrogen-containing aromatic ring. The element constituting the nitrogen-containing aromatic ring and to which the amino group is directly bonded is preferably carbon or nitrogen. Examples of compound (B) include, but are not limited to, aminoazoles and aminoazines. Examples of aminoazoles include aminoazoles having a primary amino group such as aminopyrrole, diaminopyrrole, aminodiazole, diaminodiazole, aminotriazole, diaminotriazole, triaminotriazole, aminotetrazole, diaminotetrazole, aminooxazole, diaminooxazole, aminoisoxazole, diaminoisoxazole, aminothiazole, diaminothiazole, aminoisothiazole, diaminoisothiazole, aminooxadiazole, diaminooxadiazole, aminothiadiazole, and diaminothiadiazole; N-methylaminopyrrole, N,N'-dimethyldiaminopyrrole, N-methylaminodiazole, N,N'-dimethyldiaminodiazole, and N-methylaminodiazole; aminoazoles having a secondary amino group such as thiazolinone triazole, N,N'-dimethyldiaminotriazole, N,N',N''-trimethyltriaminotriazole, N-methylaminotetrazole, N,N'-dimethyldiaminotetrazole, N-methylaminooxazole, N,N'-dimethyldiaminooxazole, N-methylaminoisoxazole, N,N'-dimethyldiaminoisoxazole, N-methylaminothiazole, N,N'-dimethyldiaminothiazole, N-methylaminoisothiazole, N,N'-dimethyldiaminoisothiazole, N-methylaminooxadiazole, N,N'-dimethyldiaminooxadiazole, N-methylaminothiadiazole, and N,N'-dimethyldiaminothiadiazole;N,N-dimethylaminopyrrole, N,N,N',N'-tetramethyldiaminopyrrole, N,N-dimethylaminodiazole, N,N,N',N'-tetramethyldiaminodiazole, N,N-dimethylaminotriazole, N,N,N',N'-tetramethyldiaminotriazole, N,N,N',N',N',N''-hexamethyltriaminotriazole, N,N-dimethylaminotetrazole, N,N,N',N'-tetramethyldiaminotetrazole, N,N-dimethylaminoxazole, N,N,N',N'-tetramethyldiaminoxazole, N,N-dimethylamino Examples of aminoazoles having a tertiary amino group include, but are not limited to, aminoazoles having a tertiary amino group such as isoxazole, N,N,N',N'-tetramethyldiaminoisoxazole, N,N-dimethylaminothiazole, N,N,N',N'-tetramethyldiaminothiazole, N,N-dimethylaminoisothiazole, N,N,N',N'-tetramethyldiaminoisothiazole, N,N-dimethylaminooxadiazole, N,N,N',N'-tetramethyldiaminooxadiazole, N,N-dimethylaminothiadiazole, or N,N,N',N'-tetramethyldiaminothiadiazole. Examples of aminoazines include aminoazines having a primary amino group, such as aminopyridine, diaminopyridine, triaminopyridine, aminodiazine, diaminodiazine, triaminodiazine, aminotriazine, diaminotriazine, and triaminotriazine; aminoazines having a secondary amino group, such as N-methylaminopyridine, N,N'-dimethyldiaminopyridine, tri-N-methylaminopyridine, N-methylaminodiazine, N,N'-dimethyldiaminodiazine, N,N',N''-trimethyltriaminodiazine, N-methylaminotriazine, N,N'-dimethyldiaminotriazine, and N,N',N''-trimethyltriaminotriazine;Examples of the compound (B) include, but are not limited to, aminoazines having a tertiary amino group, such as N,N-dimethylaminopyridine, N,N,N',N'-tetramethyldiaminopyridine, N,N,N',N',N'',N"-hexamethyltriaminopyridine, N,N-dimethylaminodiazine, N,N,N',N'-tetramethyldiaminodiazine, N,N,N',N',N',N"-hexamethyltriaminodiazine, N,N-dimethylaminotriazine, N,N,N',N'-tetramethyldiaminotriazine, and N,N,N',N',N',N"-hexamethyltriaminotriazine. Compound (B) may be used alone or in combination of two or more types, and compounds in which the amino group is in the form of a salt and compounds in which it is not in the form of a salt may be used in combination. The above examples also include isomers with different positions of heteroatoms (N, O, S) (e.g., 1,2,3-triazole ring and 1,2,4-triazole ring) and isomers with different positions of amino groups (e.g., 2,6-diaminopyridine and 3,4-diaminopyridine).

[0020] The amino group on the nitrogen-containing aromatic ring may be appropriately chemically modified. For example, the hydrogen atom of the amino group may be substituted with an alkyl group, a hydroxyalkyl group, a carboxyalkyl group, a phenyl group, or the like. Further examples include hydroxyalkylation (e.g., hydroxyethylation) by reaction with an epoxy compound. It is preferable that compound (B) itself does not contain Si, and it is preferable that the amino group on the nitrogen-containing aromatic ring is not chemically modified.

[0021] The nitrogen atom constituting the nitrogen-containing aromatic ring may be appropriately chemically modified. For example, the nitrogen atom may be modified with an alkyl group, a hydroxyalkyl group, a carboxyalkyl group, a phenyl group, or the like. It is preferable that the nitrogen atom constituting the nitrogen-containing aromatic ring is not chemically modified with a functional group containing Si, and is not chemically modified with an N—C bond formation.

[0022] In the present invention, compound (C) having a polyalkylamine skeleton (hereinafter also referred to simply as compound (C)) refers to a compound having two or more repeating units having an alkylamine structure. The number-average molecular weight of compound (C) is preferably 150 or more, more preferably 185 or more, and particularly preferably 250 or more. Furthermore, the number-average molecular weight is preferably 200,000 or less, more preferably 120,000 or less, even more preferably 100,000 or less, and particularly preferably 80,000 or less. Therefore, the number-average molecular weight of compound (C) is preferably, for example, 150 to 200,000, more preferably 185 to 120,000, even more preferably 250 to 100,000, and particularly preferably 250 to 80,000. The repeating unit may have a single structure or may contain two or more different repeating unit structures. Furthermore, the repeating units constituting compound (C) may be linear or branched. Specific examples of compound (C) include, but are not limited to, ethyleneamines, polyallylamine, and polydiallylamine. The ethyleneamines of the present invention have two or more ethylene groups (—CH2-CH2-) connecting amino groups together, and specific examples include polyethyleneimine, aminoethylpiperazine, tris(2-aminoethyl)amine, N,N'-bis-(2-aminoethyl)piperazine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexaethyleneheptamine. Compound (C) is preferably polyethyleneimine, with branched polyethyleneimine being more preferred than linear polyethyleneimine. Furthermore, the number of ethylene groups connecting amino groups in the ethyleneamines is preferably two or more, more preferably three or more, more preferably four or more, even more preferably five or more, and particularly preferably six or more.

[0023] When the mass of nitrogen in the repeating unit of compound (C) is p and the mass of the repeating unit is q, the value of p / q is preferably 0.08 or more, more preferably 0.10 or more, even more preferably 0.13 or more, particularly preferably 0.23 or more, and most preferably 0.30 or more. The value of p / q is preferably 0.4 or less, more preferably 0.35 or less. Therefore, the value of p / q is, for example, preferably 0.08 to 0.4, more preferably 0.10 to 0.4, even more preferably 0.13 to 0.4, particularly preferably 0.23 to 0.4, and most preferably 0.30 to 0.35.

[0024] The number average molecular weight of the compound (C) is measured by the GPC method. When the adhesive contains two or more types of compound (C) having different repeating units, the molecular weight is measured in a mixed state.

[0025] The compound (C) may or may not have a phenyl group in the repeating unit.

[0026] The amino group in compound (C) may be chemically modified as appropriate. For example, the hydrogen atom of the amino group may be substituted with an alkyl group, a hydroxyalkyl group, a carboxyalkyl group, a phenyl group, or the like. Further examples include hydroxyalkylation (e.g., hydroxyethylation) by reaction with an epoxy compound. It is preferable that the amino group is not chemically modified with a functional group containing Si, and it is more preferable that compound (C) itself does not contain Si, and it is even more preferable that the amino group is not chemically modified.

[0027] The organic amine compound (A) used in the present invention preferably has an ignition residue when heated at 265°C under atmospheric pressure for 1 hour, more preferably 10% or more, still more preferably 15% or more, particularly preferably 20% or more, and most preferably 25% or more.

[0028] The method for measuring the ignition residue in this embodiment is as follows: (1) The measurement sample is diluted with a solvent or dispersant to prepare a solution or dispersion of 1% by mass of the measurement sample. The solvent or dispersant used is the same as that used in the adhesive. If no solvent or dispersant is used in the adhesive, water is used. Water is usually the preferred solvent or dispersant. (2) The weight m of a fluororesin Petri dish is measured using an electronic balance capable of measuring in grams to four decimal places. Prior to measurement, the Petri dish is heated at 265°C for one hour to ensure no weight loss. (3) The solution or dispersion diluted in (1) is dropped onto the Petri dish, and the weight n of the dropped solution or dispersion is measured. (4) The Petri dish is placed in a stainless steel tray, the opening is covered with aluminum foil, and several holes with a diameter of approximately 1 cm are drilled to allow volatile components to escape. The dish is then placed in a hot air circulation drying oven and heated at 265°C for one hour. (5) After (4), remove the petri dish and allow the sample to cool to 30°C. After cooling, measure the weight M of the compound A and the petri dish after heating. (6) Calculate the ignition residue using the following formula (i): Ignition residue (%) = {(M - m) / (n x 0.01)} x 100 ... formula (i) (7) Perform the above measurement four times and use the arithmetic mean value as the evaluation value.

[0029] In addition, in the adhesive, when the number of moles of active hydrogen of the amino group in the organic amine compound (A) is x and the number of moles of the functional group that can easily undergo an addition reaction with the active hydrogen of the amino group in a 1:1 ratio is y, the ratio y / x is preferably 1.50 or less, more preferably 1.20 or less, even more preferably 1.00 or less, particularly preferably 0.80 or less, and most preferably 0.67 or less. There are no particular restrictions on the lower limit, but in general, the closer to 0 the value is, the more preferable. The functional group that can undergo an addition reaction with the active hydrogen of the amino group in a 1:1 ratio is a functional group that can undergo an addition reaction with the active hydrogen of the amino group in a 1:1 ratio under relatively mild conditions (for example, 25°C to 220°C, 1 kgf / cm 2 There is no particular limitation on the functional group as long as it is a functional group that undergoes nucleophilic attack by the unshared electron pair of the amino group at the amino group to form a covalent bond, and examples thereof include an isocyanate group, a blocked isocyanate group, an epoxy group, etc. There is no particular limitation on the blocking agent for the blocked isocyanate, and examples thereof include acetoxime, phenol, ε-caprolactam, an active methylene compound, triazole, pyrazole, etc.

[0030] 2. Laminate A laminate according to one embodiment of the present invention includes, in this order, a metal material layer, an adhesive layer formed from the adhesive for low dielectric resin materials, and a low dielectric resin material layer. Typically, the laminate is provided as a metal-clad laminate including, in this order, a copper-based material sheet or an aluminum-based material sheet, an adhesive layer formed from the adhesive for low dielectric resin materials, and a low dielectric resin sheet.

[0031] In a metal-clad laminate, a copper-based or aluminum-based material sheet (hereinafter also referred to as a "metal material sheet") may be laminated on one or both sides of a resin sheet, or on the entire surface or part of the surface of the resin sheet.

[0032] The adhesive layer (hereinafter referred to as "adhesive layer") formed from the adhesive for low dielectric resin materials is usually formed on the entire surface of the metal material sheet to be bonded to the resin sheet, but may also be formed on a portion of the surface of the metal material sheet to be bonded to the resin sheet. Similarly, the adhesive layer may be formed on the entire surface of the resin sheet to be bonded to the metal material sheet, or may also be formed on a portion of the surface to be bonded. When a metal material sheet is laminated on both sides of a resin sheet, it is sufficient that at least one of the metal material sheets is laminated to the resin sheet via the adhesive layer according to one embodiment of the present invention, but it is preferable that both metal material sheets are laminated to the resin sheet via the adhesive layer according to one embodiment of the present invention. The two metal material sheets laminated on both sides of the resin sheet may be the same or different, and the two adhesive layers may also be the same or different. When a metal 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 metal material sheet is laminated. Examples of other layers include, but are not limited to, a release film layer for protecting the resin sheet. The metal-clad laminate may further include another layer laminated on the surface of the metal material sheet opposite to the surface on which the resin sheet is laminated. This other layer may be a layer of an adhesive for low dielectric resin materials, i.e., an adhesive layer formed from an adhesive containing the organic amine compound (A) as a main component.

[0033] [2-1. Metallic Material] The metallic material is not particularly limited, but may be a material containing copper, a copper alloy, aluminum, or an aluminum alloy as a main component (the total concentration of copper, copper alloy, aluminum, or aluminum alloy in the material is 50% by mass or more, preferably 60% by mass or more, more preferably 75% by mass or more, even more preferably 85% by mass or more, for example, 50 to 100% by mass), and a material containing copper or a copper alloy as a main component is preferred (the total concentration of copper and copper alloy in the material is 50% by mass or more, preferably 60% by mass or more, more preferably 75% by mass or more, even more preferably 85% by mass or more, for example, 50 to 100% by mass). The metallic material 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 aluminum content in the aluminum alloy is not particularly limited, 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 aluminum alloys include, but are not limited to, known alloys such as those specified by JIS H4000:2014 and JIS H4160:1994. The copper content in the copper alloy is not particularly limited, 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, but are not limited to, copper-zinc alloys, copper-iron-phosphorus alloys, copper-tin alloys, copper-zirconium alloys, copper-nickel alloys, and copper-silver alloys, as specified in JIS H3100:2012 or the CDA (Copper Development Association) standard. The metal material may be one that has undergone a surface treatment typically applied to copper foil or copper alloy foil in metal-clad laminates used in printed wiring boards. Examples of the surface treatment include plating treatment such as single metal plating treatment or alloy plating treatment, and chromate treatment.The plating process may be any known plating process, such as a single-metal plating process or an alloy plating process 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 process may be a single-layer plating or a multi-layer plating process consisting of two or more layers. Furthermore, the metal material may be surface-treated with a coupling agent such as a silane coupling agent. However, according to the present invention, excellent adhesion between the metal material and the low-dielectric resin material can be achieved without surface treatment of the metal material with a coupling agent. Such surface treatments can be performed according to known methods.

[0034] The form of the metal material is not particularly limited, and examples include plates, foils, strips, and ingots. Examples of the plate include rolled plates, and examples of the foil include electrolytic metal foils. These may also be surface-treated as described above. Foils may also include metal foils with carriers, and foils with surface treatments as described above. In this case, metal foils that are not the carrier of the carrier-supported metal foil may be used as the metal material according to one embodiment of the present invention. The carrier of the carrier-supported metal foil is not particularly limited, and commonly used carriers, such as electrolytic copper foils and electrolytic aluminum foils, and resin films, may be used. The thickness of the carrier is also not particularly limited and may be selected appropriately. Carrier-supported electrolytic copper foils and carrier-supported electrolytic copper alloy foils are common carrier-supported metal foils, but are not limited thereto. In the present invention, plates, foils, strips, and ingots of copper, copper alloys, aluminum, or aluminum alloys are preferred. Laminates having metal materials such as plated materials and clad materials on their surfaces, as well as metal materials whose surfaces are surface-treated as described above, may also be used. In this case, the metal material contained in the laminate is the metal material of the laminate according to one embodiment of the present invention. In the present invention, plated materials and clad materials of copper, copper alloys, aluminum, or aluminum alloys are preferred. Also, a low dielectric resin material can be laminated onto the metal material contained in the metal-clad laminate produced by an existing method or by this embodiment via the adhesive for low dielectric resin materials, and the laminate obtained in this manner is also a laminate according to an embodiment of the present invention.

[0035] It is generally preferred that the surface of a metal material be smooth. In particular, when the metal material is provided in the form of a sheet such as a plate or foil, it is preferred that at least the surface to be bonded to the low-dielectric resin material layer be smooth, and it is more preferred that both surfaces be smooth. Specifically, the ten-point average roughness (Rzjis) of at least the surface of the metal material to be bonded to the low-dielectric resin material layer, preferably both surfaces, is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 2.5 μm or less, particularly preferably 1.8 μm or less, and most preferably 1.0 μm or less. It is also generally preferred that the surface of a metal material is not roughened. The lower limit of the ten-point average roughness (Rzjis) of the metal material surface is not particularly limited, and generally, the closer to 0 μm, the more preferable. The ten-point average roughness of the metal material surface is, for example, in the range of 0.0001 μm to 10 μm, preferably in the range of 0.001 μm to 5 μm, and more preferably in the range of 0.01 μm to 2.5 μm. The ten-point average roughness (Rzjis) can be measured in accordance with JIS B0601:2001 using a laser microscope (VK-X1000 manufactured by Keyence Corporation) or the like.

[0036] When the metal material is in the form of a sheet, the thickness is not particularly limited and can be selected appropriately 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 metal material with the low dielectric resin material is not particularly limited and can be selected appropriately depending on the application.

[0037] [2-2. Low-Dielectric Resin Material] The low-dielectric resin material may be any material containing a low-dielectric resin. It may be composed solely of resin, but may also contain components other than resin. When the low-dielectric resin material contains components other than resin, the resin may be the main component (resin concentration is 50% by mass or more), or it may not be the main component. Examples of components other than resin include inorganic fibers, specifically carbon fibers and glass fibers. Examples of low-dielectric resin materials containing components other than resin include materials in which inorganic fibers (which may be in the form of woven or nonwoven fabric) are impregnated with a resin or a resin composition, typically prepreg. Low-dielectric resin materials 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 layers laminated together. The sheets may be flexible or rigid. The resin contained in the low-dielectric resin material may be one type or a mixture of two or more types of resins. Furthermore, the low dielectric resin material may contain inorganic particles (fillers), various other additives, etc. Components other than the resin that can be contained in the low dielectric resin material are not particularly limited, and components other than those mentioned above may also be used.

[0038] In the present invention, the term "low dielectric resin material" refers to a resin material having a dielectric constant of 4.0 or less and a dielectric loss tangent of 0.01 or less at 23°C and 10 GHz. The low dielectric resin material can be selected appropriately depending on the application, but thermoplastic resins are suitable. Resins having a dielectric constant of 4.0 or less at 23°C and 10 GHz are preferred, with resins having a dielectric constant of 3.4 or less being more preferred, and resins having a dielectric loss tangent of 3.1 or less being particularly preferred. Typically, resins having a dielectric constant of greater than 1.0 to 4.0, more typically 1.1 to 4.0, at 23°C and 10 GHz can be used. The dielectric constant of the resin can be measured by a cavity resonator method in accordance with IEC 62810. The dielectric loss tangent at 23°C and 10 GHz is preferably 0.01 or less, more preferably 0.008 or less, even more preferably 0.006 or less, particularly preferably 0.004 or less, and most preferably 0.003 or less. Typically, a resin having a dielectric loss tangent of 0.0001 to 0.01, more typically 0.0003 to 0.01, and even more typically 0.0005 to 0.01 at a temperature of 23° C. and 10 GHz can be used. The dielectric loss tangent of the resin can be measured by a cavity resonator method in accordance with IEC 62810.

[0039] Examples of low dielectric resin materials include fluororesins, polyphenylene ether resins (PPE), maleimide resins, hydrocarbon resins, modified polyimide resins, aromatic polyether resins, and polyphenylene sulfide resins (PPS). Examples of fluororesins include polytetrafluoroethylene (PTFE), perfluoroalkoxyalkanes (PFA), perfluoroethylenepropene copolymers (FEP), ethylene-tetrafluoroethylene copolymers (ETFE), ethylene-chlorotrifluoroethylene copolymers (ECTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorotrifluoroethylene (PCTFE), and ethylene-chlorotrifluoroethylene copolymers (ECTFE). Examples of hydrocarbon resins include butadiene-based hydrocarbons, cycloolefin polymers (COP), and cycloolefin copolymers (COC). Examples of butadiene-based hydrocarbons include liquid polybutadiene and styrene-butadiene-styrene (SBS). Examples of aromatic polyether resins include liquid crystal polymers, polyether ether ketone (PEEK), etc. In the present invention, among low dielectric resin materials, PEEK and fluororesin are preferred, fluororesin is more preferred, and PTFE is particularly preferred.

[0040] As the low dielectric resin material, resin films and prepregs commercially available as low dielectric resin materials for printed wiring boards can also be used.

[0041] When the low dielectric resin material 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.

[0042] [2-3. Manufacturing Method of Laminate] A laminate according to one embodiment of the present invention, typically a metal-clad laminate, can be produced by sandwiching and adhering a metal material and a low-dielectric resin material with the above-described adhesive for low-dielectric resin materials. While the method for sandwiching the adhesive between the metal material and the low-dielectric resin material is not particularly limited, it can be produced preferably by forming a layer of adhesive for low-dielectric resin materials (adhesive layer) on the surface of the metal material and then adhering the low-dielectric resin material onto the adhesive layer. When forming an adhesive layer on the surface of the low-dielectric resin material, an appropriate leveling agent may be added to the adhesive or the surface of the low-dielectric resin material may be subjected to an activation treatment in advance to improve the applicability of the adhesive to the low-dielectric resin material. Specific examples of activation treatments include corona treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, plasma treatment, and primer treatment. The adhesive for low-dielectric resin materials may be provided in liquid form or in sheet form (e.g., a hot-melt adhesive sheet). When the adhesive for low dielectric resin materials is in liquid form, an example of the method is to form an adhesive layer on the surface of a metal material, as described below, and then adhere the low dielectric resin material onto the adhesive layer. When the adhesive for low dielectric resin materials is in sheet form, an example of the method is to sandwich the sheet-like adhesive between the metal material and the low dielectric resin material. Below, an exemplary method for producing a laminate according to one embodiment of the present invention is described, but the method for producing a laminate is not limited to the following method.

[0043] First, a layer of adhesive is formed on a metal material, typically a copper-based material sheet or an aluminum-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 on the metal material (which may have been subjected to the above-mentioned surface treatment) when a laminate having a metal material on its surface is used.

[0044] The adhesive layer can be formed, for example, by dissolving or dispersing an adhesive for low dielectric resin materials containing an organic amine compound (A) in a solvent or dispersion medium to prepare a liquid adhesive for forming an adhesive layer, applying this to the surface of the metal material, and then drying it.

[0045] The content of each compound in the adhesive is not particularly limited and can be selected appropriately.

[0046] The solvent or dispersion medium used in the adhesive 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 or dispersion media can also be used in combination.

[0047] The adhesive may contain, as needed, 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, defoamers, leveling agents, antibacterial agents, antifungal agents, dyes, pigments, fragrances, antiblocking agents, release agents, rust inhibitors, etc., or may not contain such additives.

[0048] The application of the adhesive 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 dip coating method, or a dipping method.

[0049] The drying conditions after application of the adhesive are not particularly limited and can be selected as appropriate, but it is usually preferable to heat and dry the metal material so that the maximum temperature (PMT) of the metal material is 60°C to 300°C. The drying temperature is not particularly limited as long as the adhesive can be dried to form an adhesive layer, but the maximum temperature (PMT) of the metal material is more preferably in the range of 60°C to 250°C, and particularly preferably in the range of 60°C to 180°C. The drying time is not particularly limited as long as the adhesive can be dried to form an adhesive layer, but it may be, for example, 0.5 minutes or more, 1 minute or more, 5 minutes or more, 10 minutes or more, 120 minutes or less, 60 minutes or less, or 20 minutes or less.

[0050] Before forming the adhesive layer, the metal material may be subjected to cleaning treatment such as solvent degreasing, acid degreasing, alkali degreasing, solvent washing, acid washing, alkali washing, or water washing, and drying after the cleaning treatment, etc. Such cleaning treatment and drying can be performed according to known methods.

[0051] The amount of adhesive per unit area of ​​the adhesive layer is not particularly limited, but from the viewpoint of adhesiveness and taking advantage of the properties of the low dielectric resin material, it is preferably 0.1 to 4000 mg / m 2 is preferred, and 0.3 to 2000 mg / m 2 More preferably, 0.3 to 1500 mg / m 2 is more preferably 0.3 to 1000 mg / m 2 is more preferably 0.3 to 700 mg / m 2 is more preferably 0.3 to 600 mg / m 2 is more preferably 0.3 to 500 mg / m 2 is more preferably 0.3 to 250 mg / m 2 is more preferably 0.3 to 125 mg / m 2 is particularly preferred.

[0052] The adhesive layer adhesion weight is the adhesion weight per one side (one layer). The adhesive layer adhesion weight is calculated by burning all organic matter in the adhesive using a total organic carbon (TOC) meter and quantifying the amount of carbon. A specific calculation method is shown below. The solid content concentration a (mass%) of a measurement sample (e.g., 5000-fold dilution) obtained by diluting the adhesive (e.g., solid content 3 mass%, 10 mass%, or 30 mass%), the carbon content measured by the TOC meter b (mg / L) per volume of the measurement sample, and the density c (g / L) of the measurement sample are applied to the following equation 1 to calculate the carbon content ratio d (%) in the solid content of the adhesive. d = [b / {c × (a / 100) × 1000}] × 100 ... Equation 1 Next, the carbon content of the adhesive layer of the measurement sample on which the adhesive layer has been formed is measured using the TOC meter, and the measured carbon content e (mg) and the area f (m ) on the measurement sample on which the adhesive layer has been formed are calculated. 2 ) is applied to the following formula 2 to obtain the coating amount g (mg / m 2g = {e / (d / 100)} / f Formula 2 Furthermore, when the coating amount is 2000 mg / m using the above calculation method, 2 In the above cases, the adhesion amount is calculated by the weight method using the following formula 3: The weight of the copper foil before treatment, h (mg), the weight of the copper foil after forming the adhesive layer, i (mg), and the measured area of ​​the part of the copper foil where the adhesive layer is formed, j (m 2 ), adhesion amount k (mg / m 2 ) k = (i - h) / j ... Equation 3

[0053] The thickness of the adhesive layer is not particularly limited and can be selected as appropriate so that the amount of adhesion falls within the above range, but is preferably 0.1 nm or more, more preferably 0.3 nm or more, even more preferably 1 nm or more, preferably 4000 nm or less, more preferably 2000 nm or less, even more preferably 1500 nm or less, even more preferably 1000 nm or less, particularly preferably 700 nm or less, and most preferably 500 nm or less.

[0054] Next, a low-dielectric resin material is brought into contact with the surface of the adhesive layer formed on the surface of the metal material in this manner, and a low-dielectric resin material, typically a resin sheet such as a resin film or prepreg, is placed on the adhesive layer, and the layers are heated and pressed to bond them together, thereby producing a laminate according to this embodiment. The adhesive layer is altered by the evaporation and polymerization of volatile components during heating and pressing, so the adhesive layer after heating and pressing is referred to as the adhesive layer. When producing a laminate in which a metal material is laminated on both sides of a low-dielectric resin material, the metal material may be bonded simultaneously to both sides of the low-dielectric resin material, such as a resin film or prepreg, via the adhesive layer, or each side may be bonded sequentially.

[0055] The method for bonding a metal material having an 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 pressing device. The pressing conditions (pressing pressure) are not particularly limited and can be appropriately selected depending on the material and type of resin used, and are generally 1 to 1000 kgf / cm. 2 is sufficient, and 5 to 100 kgf / cm 2is preferred. The heating conditions are not particularly limited and can be selected appropriately depending on the material used, the type of resin, etc., and may be 80°C to 600°C, preferably 150°C to 450°C, but a temperature above the temperature at which the resin becomes fluid upon heating is desirable. After the resin temporarily becomes fluid, it may become non-fluid due to thermal curing or the like. Furthermore, from the viewpoint of polymerizing and / or condensing the amine compound during adhesion, the temperature is preferably 150°C or higher, more preferably 180°C or higher, even more preferably 200°C or higher, particularly preferably 230°C or higher, and most preferably 260°C or higher. Furthermore, from the viewpoint of thermal decomposition of the resin substrate and adhesive, the temperature is preferably 800°C or lower, more preferably 700°C or lower, and particularly preferably 600°C or lower. The adhesion time is not particularly limited, but may be 0.1 to 1,440 minutes, preferably 0.5 to 600 minutes.

[0056] During the heating and pressurization, the pressure may be reduced from normal pressure, or the heating and pressurization may be carried out in a state where air is blocked, or the heating and pressurization may be carried out in an inert gas (e.g., nitrogen gas, helium gas, or argon gas) atmosphere.

[0057] The peel strength (peel strength) between the metal material layer and the resin material layer of a metal-clad laminate can be measured in accordance with JIS C5012:1993. The peel strength is preferably from 2.5 N / cm to the breaking strength of the resin material layer, more preferably from 5.0 N / cm to the breaking strength of the resin material layer, and most preferably from 7.5 N / cm to the breaking strength of the resin material layer. The breaking strength of the resin material layer is generally 8.0 N / cm or more. In other words, the peel strength of the metal-clad laminate is preferably higher than the breaking strength of the resin material layer.

[0058] A printed wiring board can be manufactured by wiring and circuit processing the metal material layer of the laminate according to this embodiment. The laminate according to this embodiment can be suitably used for printed wiring boards that use signals with high frequencies, for example, frequencies of 25 GHz or higher. The printed wiring board can be mounted on various electronic devices.

[0059] 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.

[0060] The raw materials used in the examples and comparative examples are shown below. Unless otherwise specified, compounds manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. were used.

[0061] [Raw Materials] [Compound (B) in which an amino group is directly bonded to a nitrogen-containing aromatic ring] (B-1) 3,5-diamino-1,2,4-triazole (Tokyo Chemical Industry Co., Ltd.) (B-2) 3-amino-1,2,4-triazole (B-3) 5-aminotetrazole (B-4) Na salt of 5-aminotetrazole (5-aminotetrazole neutralized with sodium hydroxide) (B-5) 2,6-diaminopyridine (B-6) 2,4,6-Triaminopyrimidine [Compound (C) having a polyalkylamine skeleton] (C-1) Triethylenetetramine (C-2) Tetraethylenepentamine (C-3) Pentaethylenehexamine (C-4) PAA (registered trademark)-1 (polyallylamine) (manufactured by Nittobo Medical Co., Ltd.) (C-5) PAS (registered trademark)-21 (polydiallylamine) (manufactured by Nittobo Medical Co., Ltd.) (C-6) Epomin (registered trademark) SP-003 (polyethyleneimine, number average molecular weight 300) (manufactured by Nippon Shokubai Co., Ltd.) (C-7) Epomin (registered trademark) SP-006 (polyethyleneimine, number average molecular weight 600) (manufactured by Nippon Shokubai Co., Ltd.) (C-8) Epomin (registered trademark) P-1000 (polyethyleneimine, number average molecular weight 70,000) (manufactured by Nippon Shokubai Co., Ltd.) (C-9) Lupasol (registered trademark) FG (polyethyleneimine weight average molecular weight 800) (manufactured by BASF SE) [Metallic materials] (D-1) Electrodeposited copper foil (thickness 18 μm, Rzjis 0.15 μm, Ra 0.04 μm) having a surface provided with a heat-resistant plating layer and an electrolytic chromate layer in this order from the outside to the inside (D-2) Electrodeposited copper foil (thickness 18 μm, Rzjis 0.09 μm, Ra 0.02 μm) (D-3) Pure aluminum plate (thickness 0.8 mm, Rzjis 0.14 μm, Ra 0.01 μm) (D-4) Electrodeposited copper foil (thickness 18 μm, Rzjis 0.16 μm, Ra 0.04 μm) having a silane coupling agent layer, a heat-resistant plating layer and an electrolytic chromate layer in this order from the outside to the inside [Low dielectric resin material] (E-1) PTFE prepreg (manufactured by Rogers Corporation, trade name "RO3003 Bondply", thickness 0.1 mm) (catalog values: relative dielectric constant 3.0±0.04, dielectric dissipation factor 0.0010 at 23°C, 10 GHz) (measured values: relative dielectric constant 2.44, dielectric dissipation factor 0.00063 at 23°C, 10 GHz) (E-2) PEEK-based prepreg (thickness 0.05 mm) (catalog values: relative dielectric constant 3.1, dielectric dissipation factor 0.0033 at 23°C, 10 GHz) (measured values: relative dielectric constant 2.88, dielectric dissipation factor 0.00337 at 23°C, 10 GHz) [Compound (F)] (F-1) Imidazole (F-2) 1,2,4-Triazole (F-3) Tetrazole (F-4) Oxalate of aniline (aniline neutralized with oxalic acid) (F-5) Bismarck Brown [Water-based resins (G)] (G-1) MODEPIX (registered trademark) 302 (manufactured by Arakawa Chemical Industries, Ltd.) (epoxy resin) (G-2) GOHSENEX (registered trademark) LW-100 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) (sulfo-modified PVOH) (G-3) ARROWBASE (registered trademark) YA-6010 (manufactured by Unitika Ltd.) (modified polypropylene) (G-4) AQUALIC (registered trademark) HL415 (manufactured by Nippon Shokubai Co., Ltd.) (polyacrylic acid) (G-5) BONCOAT (registered trademark) CF-6140 (manufactured by DIC Corporation) (acrylic resin) (G-6) ELITEL (registered trademark) KT-507 (manufactured by Unitika Ltd.) (ester resin) [Epoxy adhesives (H)] (H-1) ThreeBond (registered trademark) 2086M main agent (epoxy resin) / curing agent (polythiol) (H-2) jER (registered trademark) 828EL (Mitsubishi Chemical Corporation) (epoxy compound (bisphenol A type epoxy resin)) / pentaethylenehexamine (used as amine curing agent) (H-3) jER (registered trademark) 828EL (Mitsubishi Chemical Corporation) (epoxy compound (bisphenol A type epoxy resin)) / Epomin SP-006 (used as amine curing agent) (H-4) Denacol (registered trademark) EX313 (Mitsubishi Chemical Corporation) (epoxy compound (glycerol polyglycidyl ether)) / pentaethylenehexamine (used as amine curing agent) [High dielectric property resin material (I)] (I-1) Epoxy resin prepreg (manufactured by Showa Denko Materials Co., Ltd., trade name "GEA-679N") (measured values: relative permittivity 3.20, dielectric dissipation factor 0.0225 at 23°C and 10 GHz) [Materials other than resin] (J-1) Glass fiber cloth (J-2) SUS foil (manufactured by AS ONE Corporation, thickness 0.1 mm) For the glass fiber cloth of (J-1), epoxy resin prepreg (manufactured by Showa Denko Materials Co., Ltd., trade name "GEA-679N") was placed in chloroform heated to 60°C, the epoxy resin was completely dissolved, and only the glass fiber cloth was extracted. This was then immersed again in another 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.

[0062] <Production of Metal-Clad Laminate> [Formation of Adhesive Layer for Low Dielectric Resin Material] [Example 1] As the metal material, an electrolytic copper foil (thickness 18 μm, RzJIS 0.15 μm, Ra 0.04 μm) (D-1) having a surface provided with a heat-resistant plating layer and an electrolytic chromate layer in this order from the outside to the inside was prepared. The adhesive layer formed on the copper foil surface was 12 mg / m 2 The solids concentration of compound (B-1) in which an amino group is directly bonded to a nitrogen-containing aromatic ring was adjusted with ion-exchanged water so that the adhesion amount was 100%. The resulting aqueous solution was used to prepare an adhesive, which was then applied (by bar coating) to the surface of a copper foil having a plating layer and an electrolytic chromate layer. The mass ratio of compound (B-1) excluding water in the adhesive is shown in Table 1. The adhesive was then dried at 100°C for 1 minute in a hot air circulating drying oven to form an adhesive layer on the copper foil surface.

[0063] [Adhesion between a metal material having an adhesive layer formed thereon and a low dielectric resin material] A PTFE prepreg (manufactured by Rogers Corporation, trade name "RO3003 Bondply", thickness 0.1 mm) (E-1) was laminated to the surface of the adhesive layer formed on the metal material, and a matte surface of an electrolytic copper foil having a thickness of 35 μm was laminated as a ground layer to the backside of the laminated surface of the (E-1), and the metal material, adhesive layer, (E-1), and ground layer were laminated in this order. The ground layer was provided because it was necessary for the adhesion evaluation described below. Thereafter, the metal clad laminate was produced by wrapping it in aluminum foil and adhering it while blocking the atmosphere. The adhesion conditions were a press pressure of 30 kgf / cm 2 The pressing time was 45 minutes and the pressing temperature was 370°C.

[0064] [Examples 2 to 30] An adhesive layer was formed in the same manner as in Example 1, except that an aqueous solution of the compounds (B-1 to 6) and (C-1 to 9) shown in Table 1 was used as an adhesive to form an adhesive layer on one surface of the metal material (D-1, 2) shown in Table 1. When the solubility of compound (B) and compound (C) was low and the compound concentration in the aqueous solution could not be increased, the adhesion amount shown in Table 1 was obtained by coarsening the mesh of the bar used for bar coating or by overcoating the dried adhesive layer. Thereafter, metal-clad laminates were produced in the same manner as in Example 1, except that bonding was performed under the press time and press temperature conditions shown in Table 1. [Examples 31 to 36] An adhesive layer was formed using an aqueous solution of the compounds (B-1, C-8) shown in Table 1 as an adhesive, and metal-clad laminates were produced in the same manner as in Example 1, except that bonding was performed under the press time and press pressure conditions shown in Table 1. [Examples 37 and 38] Metal-clad laminates were produced in the same manner as in Example 1, except that an aqueous solution of the compounds (B-1, C-8) shown in Table 1 was used as the adhesive to form an adhesive layer, and the resin material (E-2) shown in Table 1 was used and bonded under the conditions of the press time, press temperature, and press pressure shown in Table 1. [Examples 39 and 40] Metal-clad laminates were produced in the same manner as in Example 1, except that an aqueous solution of the compounds (B-1, C-8) shown in Table 1 was used as the adhesive to form an adhesive layer, and the metal material (D-3) shown in Table 1 was used for bonding.

[0065] [Comparative Examples 1 to 3, 9, 16, and 28] Metal-clad laminates were produced in the same manner as in Example 1, except that no adhesive layer was formed, and that bonding was performed using the metal materials (D-1 to 4), low-dielectric resin materials (E-1 and E-2), or resin material I-1 shown in Table 2 under the conditions of press time and press temperature shown in Table 2. [Comparative Examples 4 to 8] Metal-clad laminates were produced in the same manner as in Example 1, except that an adhesive layer was formed using an aqueous solution of the compounds (F-1 to F-5) shown in Table 2 as the adhesive. [Comparative Examples 10 to 15] Metal-clad laminates were produced in the same manner as in Example 1, except that an adhesive layer was formed using an aqueous solution of the water-based resins (G-1 to G-6) shown in Table 2 as the adhesive. [Comparative Examples 17 and 18] Metal-clad laminates were produced in the same manner as in Example 1, except that an adhesive layer was formed using an aqueous solution of the compounds (B-1 and C-8) shown in Table 2 as the adhesive, and bonding was performed using resin material I-1 under the conditions of press time and press temperature shown in Table 2. Comparative Example 19 Epoxy adhesive H-1 (ThreeBond (registered trademark) 2086M main agent (epoxy resin) / curing agent (polythiol)) was used as the adhesive, and 10 g / m 2 A metal-clad laminate was produced in the same manner as in Example 1, except that an adhesive layer was formed, and then, without drying, it was laminated to a resin material and bonded under the conditions of the press time and press temperature shown in Table 2. [Comparative Example 20] jER828EL (epoxy compound) was diluted with toluene, and pentaethylenehexamine (amine curing agent) was added to the toluene solution and stirred until homogeneous so that the molar ratio of the number of active hydrogen atoms in the epoxy group to the amino group was 1.2:1.0. This toluene solution was used as an adhesive and applied (bar coating method) to one surface of copper foil. The adhesive was then dried at 40°C for 3 minutes in a hot air circulating drying oven to form an adhesive layer on the copper foil surface. A metal-clad laminate was produced in the same manner as in Example 1, except that the concentration at the time of dilution was 106 mg / m2, so that the adhesive layer formed on the copper foil surface was 106 mg / m2. 2 The concentration was adjusted so that the amount of adhesion of pentaethylenehexamine alone in the total adhesion amount of the adhesive layer was 12 mg / m. 2 [Comparative Example 21] The adhesive layer formed on the copper foil surface was 1762 mg / m 2A metal-clad laminate was produced in the same manner as in Comparative Example 20, except that the concentration was adjusted so that the adhesion amount of pentaethylenehexamine alone in the total adhesion amount of the adhesive layer was 200 mg / m. 2 Comparative Example 22 A metal-clad laminate was produced in the same manner as in Comparative Example 20, except that Epomin SP-006 was used as the amine curing agent and an adhesive layer was formed on the copper foil surface so as to have the adhesion amount shown in Table 2. The adhesion amount of Epomin SP-006 alone in the total adhesion amount of the adhesive layer at this time was 12 mg / m 2 [Comparative Example 23] A metal-clad laminate was produced in the same manner as in Comparative Example 20, except that Denacol EX313 was used as the epoxy compound and an adhesive layer was formed on the copper foil surface so as to have the adhesion amount shown in Table 2. The adhesion amount of pentaethylenehexamine alone in the total adhesion amount of the adhesive layer at this time was 12 mg / m 2 Comparative Examples 24 to 27 A metal-clad laminate was produced in the same manner as in Example 1 except that an adhesive layer was formed using an aqueous solution of the compound (B-1, C-8) shown in Table 2 as an adhesive, and materials (J-1, 2) other than resin were used.

[0066] [Ten-point average roughness (Rzjis) of metal material surfaces] The ten-point average roughness (Rzjis) and arithmetic mean roughness (Ra) of the bonded surfaces of the metal materials (D-1 to D-4) used above with resin were measured using a laser microscope (Keyence Corporation, VK-X1000) in accordance with JIS B0601:2001. The measurement method is described in detail below. The measurement environment temperature for the laser microscope was 23 to 25°C. (1) The metal material surface to be measured was placed on the stage. (2) The focus was adjusted to 50x objective lens and an image was taken using the shape measurement mode. The image was taken using [Basic Settings], with [Scan Mode: Laser Confocal], [Measurement Size: Standard], and [Measurement Quality: High Precision]. (3) The measurement area was the 202 μm x 270 μm area captured (1200x magnification on the monitor), and the surface roughness was measured within this area. (4) Launch the [Multi-File Analysis Application VK-X], select [Image Processing], and correct the surface. (5) To measure surface roughness, select [Line Roughness] and display five horizontal and five vertical lines at different locations within the surface image, obtaining the ten-point average roughness Rzjis and arithmetic mean roughness Ra values ​​for each. The cutoff value of each profile curve filter was set to λc = 0.25 μm. (6) Calculate the average of each of the 10 values ​​obtained to obtain the ten-point average roughness Rzjis and arithmetic mean roughness Ra.

[0067] The adhesion weight of the adhesive layer was determined using the following method. The amount of carbon in the liquid adhesive was measured using a TOC meter (Total Organic Carbon Analyzer ON-LINE TOC-VCSH (Shimadzu Corporation)), and the proportion of carbon in the solids was calculated using the method described above. A coating film was formed on the metal material used in each Example and Comparative Example using an aqueous adhesive solution by the bar coating method, and then dried at 100°C for 1 minute in a hot air circulation drying oven to form a dry coating film. The copper foil on which the above-mentioned dry coating film was formed was cut into two pieces measuring 1 cm wide x 3 cm long to serve as measurement samples. These were analyzed using a Total Organic Carbon Analyzer TOC-5000A (Shimadzu Corporation) to measure the carbon content per unit area. Since the adhesion weight per unit area can be calculated using the method described above from the carbon content per unit area, the solids concentration of the adhesive that would give the adhesion weights shown in Table 1 was determined, and metal-clad laminates having adhesive layers for adhesion evaluation were prepared. In addition, if the solubility of the adhesive component is low and the desired adhesion weight cannot be obtained by forming a coating film using the bar coating method once, the coating film formation using the bar coating method was repeated, and the adhesion weight was calculated using a TOC meter as described above. After confirming that the desired adhesion weight was achieved, a metal-clad laminate for adhesion evaluation was prepared. Similarly to the above method, for each of the other adhesives, the solids concentration of the adhesive was determined using a TOC meter each time so that the adhesive layer formed on the surface of each metal material had the adhesion weight shown in Tables 1 and 2. The solids concentration was determined for each combination of the compound used to form the adhesive layer and the metal material shown in Tables 1 and 2.

[0068] [Evaluation of Ignition Residue] The ignition residues of Compound (B) and Compound (C) used in the above examples were measured using the following procedure. (1) A measurement sample was prepared into a 1% by mass solution in deionized water. (2) The weight m (approximately 25 g) of a PFA petri dish was measured using an electronic balance capable of measuring in grams to four decimal places. (3) The solution diluted in (1) was dripped onto the petri dish, and the weight n (approximately 5 g) of the dripped solution was measured. (4) The petri dish was placed in a stainless steel tray, the opening was covered with aluminum foil, and multiple holes with a diameter of approximately 1 cm were drilled to allow volatile components to escape. The dish was then placed in a hot air circulation drying oven and heated at 265°C for 1 hour. (5) After (4), the petri dish was removed and allowed to cool to 30°C. After cooling, the weight M of the petri dish was measured. (6) The ignition residue was measured using the above formula (i). (7) The above measurement was carried out four times, and the arithmetic mean value was used as the evaluation value. (8) The evaluation values ​​calculated in (7) were rated according to the following criteria. The results are shown in Table 1. D: Ignition residue is 0% or more and less than 10% C: Ignition residue is 10% or more and less than 20% B: Ignition residue is 20% or more and less than 30% A: Ignition residue is 30% or more

[0069] <Adhesion Evaluation> The metal-clad laminates using the metal materials (D-1), (D-2), and (D-4) prepared in the above Examples and Comparative Examples were cut to a width of 0.3 cm and a length of 7 cm, and the peel strength was measured when the tip of the metal material layer was gripped and peeled with a jig of a tensile tester. Specifically, the peel strength (peel strength) was plotted in 0.1 mm increments over the peel length (the length perpendicular to the width of the cut metal-clad laminate) from 2.75 mm to 15.25 mm, and the arithmetic mean was used as the evaluation value. The peel strength (peel strength) of the metal material in the 90° direction was measured in accordance with JIS C5012:1993, and the adhesion was evaluated according to the following evaluation criteria. For metal-clad laminates using the metal material (D-3), peel strength was measured and adhesiveness was evaluated in the same manner as described above, except that the tip of the laminated portion of the resin material layer and the ground layer was gripped with the jig of the tensile tester. In this evaluation, taking into account the adhesiveness when no adhesive was used, metal materials (D-1), (D-2), and (D-4) were evaluated as having poor adhesiveness if they received a rating of 2 or less, and metal materials (D-3) were evaluated as having poor adhesiveness if they received a rating of 4 or less. In addition, since the resin material layer underwent cohesive failure at 10.0 N or more using the tensile tester, making measurement difficult, a test was further conducted in which the metal material was peeled off in a 90° direction with the metal materials (D-1), (D-2), and (D-4), and the layer formed by bonding the resin material and the ground layer with the metal material (D-3) was peeled off with fingers at a speed of approximately 600 mm / min, and the degree of adhesion of the resin material to the metal material surface after peeling was rated. The results are shown in Tables 1 and 2.[Evaluation criteria: peel strength and appearance of metal material surface after peeling] 1 point: 0 N / cm or more and less than 1.0 N / cm 2 points: 1.0 N / cm or more and less than 2.5 N / cm 3 points: 2.5 N / cm or more and less than 5.0 N / cm 4 points: 5.0 N / cm or more and less than 7.5 N / cm 5 points: 7.5 N / cm or more and less than 10.0 N / cm 6 points: 10.0 N / cm or more, and the area of ​​the resin material that has cohesively failed and spread to the metal material surface after peeling is 20% or more and less than 40% of the area of ​​the metal material surface 7 points: 10.0 N / cm or more, and the area of ​​the resin material that has cohesively failed and spread to the metal material surface after peeling is 40% or more and less than 70% of the area of ​​the metal material surface 8 points: 10.0 N / cm or more, and the area of ​​the resin material that has cohesively failed and spread onto the metal surface after peeling is 70% or more of the area of ​​the metal surface.

[0070]

[0071]

Claims

1. An adhesive for bonding a metal material and a low dielectric constant resin material, wherein the adhesive contains an organic amine compound (A) as a main component, and the organic amine compound (A) contains at least one selected from a compound (B) in which an amino group is directly bonded to a nitrogen-containing aromatic ring and a compound (C) having a polyalkylamine skeleton.

2. The adhesive according to claim 1, wherein the mass ratio of the organic amine compound (A) in the non-volatile matter of the adhesive is 20% by mass to 100% by mass.

3. A laminate comprising a metal material layer, an adhesive layer formed from the adhesive according to claim 1 or 2, and a low dielectric constant resin material layer in this order.

4. The laminate according to claim 3, wherein the ten-point average roughness (Rzjis) of at least the bonding surface with the low dielectric constant resin material layer among the surfaces of the metal material layer is 2.5 μm or less.

5. The laminate according to claim 3, wherein the dielectric tangent of the low dielectric constant resin material constituting the low dielectric constant resin material layer is 0.0001 to 0.01 at a temperature of 23 °C and a frequency of 10 GHz.

6. A printed wiring board obtained by processing the metal material layer of the laminate according to claim 3 into a wiring circuit.

7. The printed wiring board according to claim 6, which uses a signal having a frequency of 25 GHz or higher.

8. An electronic device having the printed wiring board according to claim 6.

9. A method for manufacturing a laminate, which includes bonding a metal material and a low dielectric constant resin material with the adhesive according to claim 1 interposed therebetween.

10. A method for manufacturing a laminate, which includes a step of bringing the adhesive according to claim 1 into contact with a metal material to form a layer of the adhesive on the metal material, an optional step of drying the layer of the adhesive after the contacting step, and a step of bringing a low dielectric constant resin material into contact with the surface of the layer of the adhesive and heating and pressing it.

11. The adhesion amount per unit area of the adhesive layer is 0.1 to 4000 mg / m 2 The method for producing a laminate according to claim 10, wherein the laminate is as described above.

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