Adhesive for resin material having low dielectric properties, and laminate

Abstract

To provide 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.SOLUTION: 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.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] A metal-clad laminate is one in which a metal material (such as a copper foil and a copper alloy foil) is laminated 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, and a resin film), and is widely used in the manufacture of printed wiring boards and the like.

[0003] In order to ensure the adhesiveness with the resin material, the surface of the metal material used for the metal-clad laminate is generally roughened. For example, Patent Document 1 discloses a surface treatment method for roughening a copper foil having good adhesion to a resin film. Further, Patent Document 2 discloses a method of adhering a metal material and a resin material using a surface treatment liquid containing a triazole silane compound.

[0004] As the resin material in a metal-clad laminate for high-frequency applications, a low dielectric constant resin material is generally used, but it has poor adhesiveness, and techniques such as a method of introducing a predetermined functional group into the resin and a method of compounding with a resin exhibiting adhesiveness are known. For example, Patent Document 3 discloses a technique for improving the adhesive force by mixing low-adhesion polytetrafluoroethylene (PTFE) particles with a high-adhesion epoxy resin.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] In recent years, with the increase in communication speed, the high-frequency of electrical signals has been progressing, and a printed wiring board (high-frequency printed wiring board) capable of corresponding to this has been demanded. Specifically, a printed wiring board in which a metal material capable of suppressing transmission loss and a low-dielectric constant resin material are laminated is required. However, when the surface roughness of the metal material is large, the conductor loss tends to increase due to the skin effect, and as disclosed in Patent Document 1, it is not desirable to roughen the surface of the metal material to form deep irregularities. Further, it is unclear whether the triazole silane compound described in Patent Document 2 is effective in bonding the metal material and the low-dielectric constant resin.

[0007] Further, in the high-frequency region, since the dielectric loss becomes remarkable in a material having inferior dielectric properties (high relative permittivity and dielectric tangent), a technique capable of bonding a low-dielectric constant resin and a metal material is required regardless of the method shown in Patent Document 3.

[0008] In view of the above circumstances, an object of the present invention in one embodiment is to provide an adhesive for a low-dielectric constant resin material having excellent adhesiveness between a metal material (particularly a metal material having a low surface roughness) and a low-dielectric constant resin material. Further, an object of the present invention in another embodiment is to provide a laminate including a metal material layer, an adhesive layer formed of such an adhesive, and a low-dielectric constant resin material layer.

Means for Solving the Problems

[0009] The present invention relates to the following items. [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 [1], wherein the mass ratio of the organic amine compound (A) in the non-volatile content 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 [1] or [2], and a low dielectric constant resin material layer in this order. [4] The laminate according to [3], wherein the ten-point average roughness (Rzjis) of at least the bonding surface of the surface of the metal material layer with the low dielectric constant resin material layer is 2.5 μm or less. [5] The laminate according to [3] or [4], 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 wiring circuit processing of the metal material layer of the laminate according to any one of [3] to [5]. [7] The printed wiring board according to [6], which uses a signal having a frequency of 25 GHz or higher. [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 constant resin material with the adhesive according to [1] or [2] interposed therebetween.

[10] A step of bringing the adhesive according to [1] or [2] into contact with a metal material to form a layer of the adhesive on the metal material; Optionally, a step of drying the layer of the adhesive after the step of bringing into contact; A method for manufacturing a laminate, comprising 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.

[11] The amount of adhesion per unit area of the layer of the adhesive is 0.1 to 4000 mg / m 2 The method for manufacturing a laminate according to

[10] . [Effects of the Invention]

[0010] According to one embodiment of the present invention, it is possible to provide an adhesive excellent in adhesion between a metal material and a low dielectric constant resin material. In particular, it is possible to provide an adhesive excellent in adhesion between a metal material with a low surface roughness and a low dielectric constant resin material excellent in dielectric properties. Furthermore, since the adhesive exhibits excellent adhesion even with an extremely low adhesion amount, the thickness of the adhesive layer can be reduced as much as possible. For the above reasons, by using the adhesive, it is possible to reduce the decrease in the dielectric properties of the laminate due to the provision of the adhesive layer, and thus provide a metal-clad laminate excellent in adhesion between a metal material with a low surface roughness and a low dielectric constant resin material excellent in dielectric properties. The metal-clad laminate can be suitably used for a printed wiring board, particularly a high-frequency printed wiring board.

Embodiments for Carrying Out the Invention

[0011] <1. Adhesive for Low Dielectric Constant Resin Material> The adhesive for a low dielectric constant resin material according to one embodiment of the present invention 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.

[0012] In the present invention, the main component refers to the component having the largest mass ratio among the components contributing to the adhesiveness. The mass ratio of the organic amine compound (A) in the non-volatile content is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and even more preferably 50% by mass or more. Also, the upper limit is not particularly limited, but it may be 100% by mass or less. Therefore, the mass ratio of the organic amine compound (A) in the non-volatile content is preferably 20% by mass to 100% by mass, more preferably 30% by mass to 100% by mass, further preferably 40% by mass to 100% by mass, and even more preferably 50% by mass to 100% by mass.

[0013] In the present invention, the non-volatile 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 non-volatile content are solvents and / or dispersion media. The solvents and / or dispersion media are not particularly limited, and it is preferable that the effect of uniformly dissolving or dispersing the organic amine compound (A) can be obtained, and one or more solvents and / or dispersion media may be used in combination. Typically, water is mentioned.

[0015] In the present invention, the organic amine compound (A) (hereinafter also simply referred to as "amine compound (A)") refers to an organic compound having an amino group and its salts. The amino group referred to herein does not include those derived from nitrogen atoms in the ring structure of the aromatic ring. For example, -NH- in the ring structure of pyrrole is not an amino group. As the acid forming a salt with the amino group, either an inorganic acid or an organic acid may be used. Examples of inorganic acids include hydrohalic acids, oxoacids, hydrocyanic acid, cyanic acid, thiocyanic acid, etc. Examples of hydrohalic acids include hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, etc. 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, dichromic acid, permanganic acid, molybdic acid, and tungstic acid, etc. Examples of organic acids include carboxylic acids, percarboxylic acids, and sulfonic acids, etc. Examples of carboxylic acids include aliphatic carboxylic acids and aromatic carboxylic acids, etc. Examples of sulfonic acids include aliphatic sulfonic acids and aromatic sulfonic acids, etc. 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, etc. Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, and gallic acid, etc. Examples of percarboxylic acids include peracetic acid, etc. Examples of aliphatic sulfonic acids include methanesulfonic acid, etc. Examples of aromatic sulfonic acids include benzenesulfonic acid, etc. The acid forming a salt with the amino group may be used alone or in combination of two or more.

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

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

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

[0019] In the present invention, the amino group in the compound (B) in which an amino group is directly bonded to a nitrogen-containing aromatic ring (hereinafter, also simply referred to as "compound (B)") is preferably a primary to tertiary amino group, more preferably a primary to secondary amino group. Further, the amino group may be in the form of a salt, but it 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 for the same ring structure, it is preferable that two or more amino groups are bonded to one nitrogen-containing aromatic ring. The element that constitutes the nitrogen-containing aromatic ring and to which the amino group is directly bonded is preferably carbon or nitrogen. Examples of the compound (B) include, but are not limited to, aminoazole and aminoazine. Examples of aminoazole include aminoazole having a primary amino group such as aminopyrrole, diaminopyrrole, amino-diazole, diaminodiazole, aminotriazole, diaminotriazole, triaminotriazole, aminotetrazole, diaminotetrazole, aminooxazole, diaminooxazole, aminoisoxazole, diaminoisoxazole, aminothiazole, diaminothiazole, aminoisothiazole, diaminoisothiazole, aminooxadiazole, diaminooxadiazole, aminothiadiazole, diaminothiadiazole; aminoazole having a secondary amino group such as N-methylaminopyrrole, N,N'-dimethyl-diaminopyrrole, N-methylamino-diazole, N,N'-dimethyl-diaminodiazole, N-methylaminotriazole, N,N'-dimethyl-diaminotriazole, N,N',N''-trimethyl-triaminotriazole, N-methylaminotetrazole, N,N'-dimethyl-diaminotetrazole, N-methylaminooxazole, N,N'-dimethyl-diaminooxazole, N-methylaminoisoxazole, N,N'-dimethyl-diaminoisoxazole, N-methylaminothiazole, N,N'-dimethyl-diaminothiazole, N-methylaminoisothiazole, N,N'-dimethyl-diaminoisothiazole, N-methylaminooxadiazole, N,N'-dimethyl-diaminooxadiazole, N-methylaminothiadiazole, N,N'-dimethyl-diaminothiadiazole;Aminoazoles having a tertiary amino group such as 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-dimethylaminoisoxazole, N,N,N´,N´-tetramethyldiaminoisoxazole, N,N-dimethylaminothiazole, N,N,N´,N´-tetramethyldiaminothiazole, N,N-dimethylaminoisothiazole, N,N,N´,N´-tetramethyldiaminoisothiazole, N,N-dimethylaminoxadiazole, N,N,N´,N´-tetramethyldiaminoxadiazole, N,N-dimethylaminothiadiazole or N,N,N´,N´-tetramethyldiaminothiadiazole, etc. are included, but not limited thereto. As aminoazines, aminoazines having a primary amino group such as aminopyridine, diaminopyridine, triaminopyridine, aminodiazine, diaminodiazine, triaminodiazine, aminotriazine, diaminotriazine, 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, N,N´,N´´-trimethyltriaminotriazine;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, N,N,N',N',N'',N''-hexamethyltriaminotriazine; are exemplified, but not limited thereto. Compound (B) may be used alone or in combination of two or more, and those having an amino group in the form of a salt and those not in the form of a salt may be used in combination. In the above examples, 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) are also included.;

[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 by an alkyl group, hydroxyalkyl group, carboxyalkyl group, phenyl group, etc. Further, hydroxyalkylation (e.g., hydroxyethylation) by reacting with an epoxy compound is also exemplified. 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 by an alkyl group, hydroxyalkyl group, carboxyalkyl group, phenyl group, etc. It is preferable that the nitrogen atom constituting the nitrogen-containing aromatic ring is not chemically modified by a functional group containing Si, and it is preferable that no chemical modification involving N-C bond formation is carried out.

[0022] In the present invention, the compound (C) having a polyalkylamine skeleton (hereinafter also simply referred to as compound (C)) refers to a compound having two or more repeating units having an alkylamine structure. The number average molecular weight of the compound (C) is preferably 150 or more, more preferably 185 or more, and particularly preferably 250 or more. Also, 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 the 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. Also, the repeating unit constituting the compound (C) may be linear or branched. Specific examples of the compound (C) include, but are not limited to, ethylenediamines, polyallylamine, and polydiallylamine. The ethylenediamines in the present invention are those having two or more ethylene groups (-CH2-CH2-) connecting amino groups, and specifically include polyethyleneimine, aminoethylpiperazine, tris(2-aminoethyl)amine, N,N'-bis-(2-aminoethyl)piperazine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and the like. As the compound (C), polyethyleneimine is preferred, and branched polyethyleneimine is more preferred than linear polyethyleneimine. Also, the number of ethylene groups connecting amino groups in the ethylenediamines is preferably 2 or more, preferably 3 or more, more preferably 4 or more, even more preferably 5 or more, and particularly preferably 6 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, still more preferably 0.13 or more, particularly preferably 0.23 or more, and most preferably 0.30 or more. Also, 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 from 0.08 to 0.4, more preferably from 0.10 to 0.4, still more preferably from 0.13 to 0.4, particularly preferably from 0.23 to 0.4, and most preferably from 0.30 to 0.35.

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

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

[0026] The amino group in compound (C) may be appropriately chemically modified. For example, the hydrogen atom of the amino group may be substituted by an alkyl group, a hydroxyalkyl group, a carboxyalkyl group, a phenyl group, etc. Further, hydroxyalkylation (e.g., hydroxyethylation) by reacting with an epoxy compound can also be mentioned. Note that it is preferable that the amino group is not chemically modified by a Si-containing functional group, more preferably that compound (C) itself does not contain Si, and even more preferably that the amino group is not chemically modified.

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

[0028] The method for measuring the strong heat residue in this embodiment is shown below. (1) Dilute the measurement sample with a solvent or dispersion medium to prepare a solution or dispersion of 1% by mass of the measurement sample. As the solvent or dispersion medium to be used, use the solvent or dispersion medium used in the adhesive. When no solvent or dispersion medium is used in the adhesive, use water. Usually, water is preferable as the solvent or dispersion medium. (2) Measure the weight m of a petri dish made of fluororesin with an electronic balance capable of weighing up to four decimal places in grams. Before measurement, heat the petri dish to be used at 265°C for 1 hour to confirm that there is no weight loss before use. (3) Drop the solution or dispersion diluted in (1) onto the petri dish and measure the weight n of the dropped solution or dispersion. (4) Place the petri dish in a stainless-steel tray, cover the opening with aluminum foil, make a plurality of holes with a diameter of about 1 cm as vent holes for volatile components, place it in a hot-air circulation drying oven, and heat at 265°C for 1 hour. (5) After (4), take out the petri dish, allow it to cool until the sample temperature reaches 30°C, and after cooling, measure the weight M of the compound A after heating and the petri dish. (6) Calculate the ignition residue by the following formula (i). Ignition residue (%) = { (M - m) / (n × 0.01)} × 100 ··· Formula (i) (7) Conduct the above measurement four times and use the arithmetic mean value as the evaluation value.

[0029] Also, 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 a functional group that can easily undergo an addition reaction with the active hydrogen of the amino group in a 1:1 ratio is y, y / x is preferably 1.50 or less, more preferably 1.20 or less, further preferably 1.00 or less, particularly preferably 0.80 or less, and most preferably 0.67 or less. The lower limit is not particularly limited, but usually, the closer to 0, the more preferable. As the 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) It is not particularly limited as long as it is a functional group that undergoes a nucleophilic attack by the lone pair of electrons of the amino group and forms a covalent bond. Examples include isocyanate groups, blocked isocyanate groups, epoxy groups, and the like. The blocking agent for the blocked isocyanate is not particularly limited, and examples include acetoxime, phenol, ε-caprolactam, active methylene compounds, triazoles, pyrazoles, and the like.

[0030] <2. Laminated body> The laminated body according to an embodiment of the present invention includes a metal material layer, an adhesive layer formed from the above-described adhesive for a low dielectric constant resin material, and a low dielectric constant resin material layer, in this order. Typically, the laminated body is provided as a metal-clad laminate including a copper-based material sheet or an aluminum-based material sheet, an adhesive layer formed from the above-described adhesive for a low dielectric constant resin material, and a low dielectric constant resin sheet, in this order.

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

[0032] An adhesive layer formed from an adhesive for a resin material with low dielectric characteristics (hereinafter referred to as "adhesive layer") is usually formed on the entire bonding surface of a metal material sheet with a resin sheet, but may also be formed on a part of the bonding surface of the metal material sheet with the resin sheet. Similarly, the adhesive layer may be formed on the entire bonding surface of the resin sheet with the metal material sheet, or may be formed on a part of the bonding surface. In the case where the metal material sheet is laminated on both sides of the resin sheet, at least one of the metal material sheets may be laminated on the resin sheet via the adhesive layer according to an embodiment of the present invention, but it is preferable that both metal material sheets are laminated on the resin sheet via the adhesive layer according to an 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 the metal material sheet is laminated on one side of the 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 the other layer include a release film layer for protecting the resin sheet, but are not limited thereto. Further, the metal-clad laminate may have 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 an adhesive layer for a resin material with low dielectric characteristics, that is, an adhesive layer formed from an adhesive containing an organic amine compound (A) as a main component.

[0033] [2-1. Metal Material] The metal material is not particularly limited, but may be a material mainly composed of copper, a copper alloy, aluminum or an aluminum alloy (the total concentration of copper, copper alloy, aluminum or aluminum alloy is 50% by mass or more, preferably 60% by mass or more, more preferably 75% by mass or more, still more preferably 85% by mass or more, for example, 50 to 100% by mass), and a material mainly composed of copper and a copper alloy is preferred (the total concentration of copper and a copper alloy is 50% by mass or more, preferably 60% by mass or more, more preferably 75% by mass or more, still more preferably 85% by mass or more, for example, 50 to 100% by mass). The metal material is typically provided in the form of a sheet such as a plate or a foil. The sheet may be composed of a single layer or may be composed of two or more layers laminated. The content ratio of aluminum in the aluminum alloy is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 75% by mass or more, and particularly preferably 85% by mass or more. Specific examples of the aluminum alloy include, but are not limited to, known alloys such as those defined by JIS H4000:2014 and JIS H4160:1994. The content ratio of copper in the copper alloy is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 75% by mass or more, and particularly preferably 85% by mass or more. Specific examples of the copper alloy include, but are not limited to, those defined by JIS H3100:2012 or CDA (Copper Development Association) standards, such as copper-zinc alloy systems, copper-iron-phosphorus alloy systems, copper-tin alloy systems, copper-zirconium alloy systems, copper-nickel alloy systems, copper-silver alloy systems, etc. The metal material may be subjected to a surface treatment generally applied to the copper foil or copper alloy foil of a metal-clad laminate used for a printed wiring board. Examples of the surface treatment include plating treatments such as single metal plating treatment or alloy plating treatment, and chromate treatment, etc.As the plating treatment, any known plating treatment may be used. For example, single-metal plating treatment or alloy plating treatment 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 can be mentioned. The plating treatment may be single-layer plating or multi-layer plating of two or more layers. Further, the metal material may be one subjected to surface treatment with a coupling agent such as a silane coupling agent. However, according to the present invention, usually, excellent adhesiveness between the metal material and the low dielectric constant resin material can be obtained without performing surface treatment of the metal material with a coupling agent. Such surface treatment can be performed according to a known method.

[0034] The form of the metal material is not particularly limited, and examples include plates, foils, strips, blocks, etc. For example, rolled plates can be used as plates, and electrolytic metal foils can be used as foils. Further, those obtained by subjecting these surfaces to the above-described surface treatment can be used. As the foil, a metal foil with a carrier and a foil obtained by subjecting its surface to the above-described surface treatment can be used. In this case, the metal foil that is not the carrier of the metal foil with a carrier can be used as the metal material according to an embodiment of the present invention. The carrier of the metal foil with a carrier is not particularly limited, and those generally used as carriers such as metal foils such as electrolytic copper foil and electrolytic aluminum foil, and resin films can be used. The thickness of the carrier is also not particularly limited and can be appropriately selected. As the metal foil with a carrier, carrier-attached electrolytic copper foil and carrier-attached electrolytic copper alloy foil are common, but are not limited thereto. In the present invention, plates, foils, strips, and blocks of copper, copper alloy, aluminum, or aluminum alloy are preferred. In addition, laminates having metal materials such as plating materials and clad materials on the surface, and those obtained by subjecting the surfaces of these metal materials to the above-described surface treatment can also be preferably used. In this case, the metal material contained in the laminate becomes the metal material of the laminate according to an embodiment of the present invention. In the present invention, plating materials and clad materials of copper, copper alloy, aluminum, or aluminum alloy are preferred. Further, a low dielectric constant resin material can be laminated on the metal material contained in an existing method or a metal-clad laminate produced in this embodiment via the adhesive for the low dielectric constant resin material, and the laminate thus obtained is also a laminate according to an embodiment of the present invention.

[0035] A metal material preferably has a smooth surface in general. In particular, when the metal material is provided in the form of a sheet such as a plate and a foil, it is preferable that at least the bonding surface with the low dielectric constant resin material layer is smooth, and it is more preferable that both surfaces are smooth. Specifically, among the surfaces of the metal material, at least the bonding surface with the low dielectric constant resin material layer, preferably the ten-point mean roughness (Rzjis) of both surfaces is preferably 10 μm or less, more preferably 5 μm or less, further preferably 2.5 μm or less, particularly preferably 1.8 μm or less, and most preferably 1.0 μm or less. Also, the metal material preferably has its surface not roughened in general. The lower limit value of the ten-point mean roughness (Rzjis) of the metal material surface is not particularly limited, and it is usually preferably as close to 0 μm as possible. The ten-point mean 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 mean roughness (Rzjis) can be measured in accordance with JIS B0601:2001 using a laser microscope (VK-X1000 manufactured by KEYENCE CORPORATION), etc.

[0036] When the metal material is in the form of a sheet, its thickness is not particularly limited and can be appropriately selected according to the application, etc., but usually, it is preferably 0.5 μm to 1000 μm, more preferably 1 μm to 100 μm. Also, the bonding area of the metal material with the low dielectric constant resin material is not particularly limited and can be appropriately selected according to the application.

[0037] [2-2. Low dielectric constant resin material] The low dielectric constant resin material may be a material containing a low dielectric constant resin, which may be composed of only resin or may contain components other than resin. When the low dielectric constant resin material contains components other than resin, the resin may be the main component (the resin concentration is 50% by mass or more), or the resin may not be the main component. Examples of the components other than resin include inorganic fibers, specifically carbon fibers, glass fibers, etc. Examples of the low dielectric constant resin material containing components other than resin include materials in which inorganic fibers (which may be in the form of woven fabric or non-woven fabric) are impregnated with resin or a resin composition, typically prepregs. The low dielectric constant resin material is typically provided in the form of a sheet such as a film or a prepreg. The sheet may be composed of a single layer or may be composed of two or more layers laminated. Also, the sheet may be soft (flexible) or hard (rigid). The resin contained in the low dielectric constant resin material may be one type or a mixture of two or more resins. Further, the low dielectric constant resin material can contain inorganic particles (fillers), various other additives, etc. as required. Note that the components other than resin that the low dielectric constant resin material can contain are not particularly limited, and those other than the above can also be used.

[0038] The low dielectric constant resin material in the present invention refers to a resin material having a relative dielectric constant of 4.0 or less and a dielectric loss tangent of 0.01 or less at a temperature of 23°C and a frequency of 10 GHz. The low dielectric constant resin material can be appropriately selected according to the application and the like, and a thermoplastic resin can be preferably used. Further, a resin having a relative dielectric constant of 4.0 or less at a temperature of 23°C and a frequency of 10 GHz is preferable, a resin having a relative dielectric constant of 3.4 or less is more preferable, and a resin having a relative dielectric constant of 3.1 or less is particularly preferable. Typically, a resin having a relative dielectric constant of more than 1.0 to 4.0 at a temperature of 23°C and a frequency of 10 GHz, more typically 1.1 to 4.0, can be used. The relative dielectric constant of the resin can be measured by the cavity resonator method in accordance with IEC 62810. Further, the dielectric loss tangent at a temperature of 23°C and a frequency of 10 GHz is preferably 0.01 or less, more preferably 0.008 or less, further 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 at a temperature of 23°C and a frequency of 10 GHz, more typically 0.0003 to 0.01, and even more typically 0.0005 to 0.01 can be used. The dielectric loss tangent of the resin can be measured by the cavity resonator method in accordance with IEC 62810.

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

[0040] As the resin material with low dielectric characteristics, commercially available resin films and prepregs can also be used as the resin material with low dielectric characteristics of the printed wiring board.

[0041] When the resin material with low dielectric characteristics is in the form of a sheet, its thickness is not particularly limited and can be appropriately selected according to the application, etc., but 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 an embodiment of the present invention, typically a metal-clad laminate, can be manufactured by bonding a metal material and a resin material with low dielectric constant characteristics with the above-described adhesive for the resin material with low dielectric constant characteristics interposed therebetween. The method of interposing an adhesive between the metal material and the resin material with low dielectric constant characteristics is not particularly limited, but preferably, after forming a layer of the adhesive for the resin material with low dielectric constant characteristics (adhesive layer) on the surface of the metal material, the resin material with low dielectric constant characteristics is bonded onto the adhesive layer. When forming an adhesive layer on the surface of the resin material with low dielectric constant characteristics, in order to improve the coatability of the adhesive with respect to the resin material with low dielectric constant characteristics, an appropriate leveling agent may be added to the adhesive, or an activation treatment may be performed on the surface of the resin material with low dielectric constant characteristics in advance. Specific examples of the activation treatment include corona treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, plasma treatment, primer treatment, and the like. The adhesive for the resin material with low dielectric constant characteristics may be provided in a liquid form, or may be provided in a sheet form (e.g., sheet-like hot melt adhesive). When the adhesive for the resin material with low dielectric constant characteristics is in a liquid form, a method of bonding the resin material with low dielectric constant characteristics onto the adhesive layer after forming the adhesive layer on the surface of the metal material, as described later, can be mentioned. When the adhesive for the resin material with low dielectric constant characteristics is in a sheet form, a method of sandwiching the sheet-like adhesive between the metal material and the resin material with low dielectric constant characteristics and bonding them can be mentioned. Hereinafter, a preferred manufacturing method of the laminate according to an embodiment of the present invention will be exemplarily described, but the manufacturing method of the laminate is not limited to the following method.

[0043] First, on a metal material, typically a copper foil, copper plate, copper alloy foil, or copper alloy plate (which may be subjected to the surface treatment as described above) or an aluminum-based material sheet, or when using a laminate having a metal material on its surface, an adhesive layer is formed on the metal material (which may be subjected to the surface treatment as described above).

[0044] The adhesive layer can be formed, for example, by dissolving or dispersing an adhesive for a resin material with low dielectric constant characteristics 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 appropriately selected.

[0046] The solvent or dispersion medium used in the adhesive is not particularly limited and can be appropriately selected from those commonly used. Organic solvents can also be used, but usually water is preferred. The solvent or dispersion medium may be used in combination of two or more.

[0047] If necessary, various commonly used additives can be added to the adhesive, such as inorganic compounds and organic compounds such as resins (for example, acrylic resins, epoxy resins, urethane resins, ether resins, amide resins, alkylene vinyl acetate copolymers, polyvinyl alcohol, polyalkylene glycols, styrene maleic anhydride copolymers, oxidation-modified polyalkylene resins, thickening polysaccharides, and cellulose nanofibers, etc.), surfactants, defoamers, leveling agents, antibacterial agents, antifungal agents, dyes, pigments, fragrances, antiblocking agents, release agents, rust inhibitors, etc. It may or may not be added.

[0048] The application of the adhesive is not particularly limited and can be carried out by known methods, for example, by bar coating method, spray method, spin coating method, roll coating method, curtain coating method, electrostatic powder coating method, fluid dipping coating method, dipping method, etc.

[0049] The drying conditions after the adhesive application are not particularly limited and can be appropriately selected. Usually, it is preferable to perform heat drying so that the maximum temperature reached (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 it is more preferable that the maximum temperature reached (PMT) of the metal material is within the range of 60°C to 250°C, and particularly preferably within 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. For example, it may be 0.5 minutes or more, 1 minute or more, 5 minutes or more, 10 minutes or more, and may also be within 120 minutes, within 60 minutes, or within 20 minutes.

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

[0051] The adhesion amount per unit area of the adhesive layer is not particularly limited. However, from the viewpoints of adhesiveness and making use of the characteristics of the low dielectric constant resin material, 0.1 to 4000 mg / m 2 is preferable, 0.3 to 2000 mg / m 2 is more preferable, 0.3 to 1500 mg / m 2 is further preferable, 0.3 to 1000 mg / m 2 is further preferable, 0.3 to 700 mg / m 2 is further preferable, 0.3 to 600 mg / m 2 is further preferable, 0.3 to 500 mg / m 2 is further preferable, 0.3 to 250 mg / m 2 is further preferable, 0.3 to 125 mg / m 2 is particularly preferable.

[0052] Note that the coating amount of the adhesive layer is the coating amount per side (one layer). The coating amount of the adhesive layer is calculated by burning all the organic substances in the adhesive with a total organic carbon meter (TOC meter) and quantifying them as the amount of carbon. The specific calculation method is shown below. The solid content concentration a (%) of the measurement sample (e.g., diluted 5000 times) obtained by diluting the adhesive (e.g., solid content 3 mass%, 10 mass%, or 30 mass%), the measured carbon amount value b (mg / L) per unit volume of the measurement sample by the TOC meter, and the density c (g / L) of the measurement sample are applied to the following formula 1 to calculate the carbon amount ratio d (%) in the solid content of the adhesive. d = [b / {c×(a / 100)×1000}]×100 ··· Formula 1 Subsequently, the carbon amount of the adhesive layer of the measurement sample on which the adhesive layer is formed is measured by a TOC meter, and the carbon amount measurement value e (mg) and the area f (m 2 ) where the adhesive layer is formed on the measurement sample are applied to the following formula 2 to calculate the film amount g (mg / m 2 ). g = {e / (d / 100)} / f ··· Formula 2 Also, when the film amount is 2000 mg / m 2 or more according to the above calculation method, the coating amount is calculated by the gravimetric method using the following formula 3. Let the weight h (mg) of the copper foil before treatment, the weight i (mg) of the copper foil after forming the adhesive layer, the area j (m 2 ) of the part where the adhesive layer is formed on the measured copper foil, and the coating amount k (mg / m 2 ). k = (i - h) / j ··· Formula 3

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

[0054] Next, a resin sheet such as a low dielectric constant resin material, typically a resin film or prepreg, is overlaid on the layer of the adhesive thus formed on the surface of the metal material, and heated and pressed to adhere, whereby the laminate according to the present embodiment can be manufactured. Since the layer of the adhesive is altered by volatilization or polymerization of volatile components during heating and pressing, the layer of the adhesive after heating and pressing is referred to as an adhesive layer. When manufacturing a laminate in which the metal material is laminated on both sides of the low dielectric constant resin material, the metal material may be simultaneously adhered to both sides of the low dielectric constant resin material such as a resin film or prepreg through the layer of the adhesive, or may be adhered one side at a time in order.

[0055] The method of adhering the metal material having the layer of the adhesive formed on the surface to the resin film or prepreg is not particularly limited, and can be performed using a known heating and pressing apparatus. The pressing conditions (pressing pressure) are not particularly limited, and can be appropriately selected according to the materials used, the type of resin, etc., and may be 1 to 1000 kgf / cm 2 and preferably 5 to 100 kgf / cm 2 The heating conditions are not particularly limited, and can be appropriately selected according to the materials used, the type of resin, etc., and may be 80°C to 600°C, preferably 150°C to 450°C, but a temperature equal to or higher than the temperature at which the resin becomes fluid due to heating is desirable. After the resin temporarily becomes fluid, it may become a state where it does not show fluidity due to heat curing or the like. Further, from the viewpoint of causing the amine compound to undergo a polymerization and / or condensation reaction during adhesion, the temperature is preferably 150°C or higher, more preferably 180°C or higher, further preferably 200°C or higher, particularly preferably 230°C or higher, and most preferably 260°C or higher. Further, from the viewpoint of thermal decomposition of the resin base material and the adhesive, 800°C or lower is preferable, 700°C or lower is more preferable, and 600°C or lower is particularly preferable. The adhesion time is not particularly limited, but may be 0.1 minute to 1440 minutes, preferably 0.5 minute to 600 minutes.

[0056] During the above heating and pressing, the pressure may be reduced from normal pressure and then heated and pressed, or heating and pressing may be performed in a state where air is blocked, or heating and pressing may be performed in an inert gas (for example, nitrogen gas, helium gas or argon gas) atmosphere.

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

Examples

[0058] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Note that the present invention is not limited to the following Examples.

[0059] The raw materials used in the Examples and Comparative Examples are shown below. Unless otherwise specified, compounds manufactured by FUJIFILM Wako Pure Chemical Corporation were used.

[0060] [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 (manufactured by Tokyo Chemical Industry Co., Ltd.) (B-2) 3-Amino-1,2,4-triazole (B-3) 5-Aminotetrazole (B-4) Na salt of 5-aminotetrazole (neutralization of 5-aminotetrazole 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 (Trademark Registered) - 1 (Polyallylamine) (manufactured by Nitto Boehringer Medical Co., Ltd.) (C-5) PAS (Trademark Registered) - 21 (Polydiallylamine) (manufactured by Nitto Boehringer Medical Co., Ltd.) (C-6) Epomin (Trademark Registered) SP-003 (Polyethyleneimine, number average molecular weight 300) (manufactured by Nippon Shokubai Co., Ltd.) (C-7) Epomin (Trademark Registered) SP-006 (Polyethyleneimine, number average molecular weight 600) (manufactured by Nippon Shokubai Co., Ltd.) (C-8) Epomin (Trademark Registered) P-1000 (Polyethyleneimine, number average molecular weight 70,000) (manufactured by Nippon Shokubai Co., Ltd.) (C-9) Lupasol (Trademark Registered) FG (Polyethyleneimine, weight average molecular weight 800) (manufactured by BASF SE) [Metal Material] (D-1) Electrolytic copper foil having on its surface, from the outside to the inside, a heat-resistant plating layer and an electrolytic chromate layer in this order (thickness 18μm, Rzjis 0.15μm, Ra 0.04μm) (D-2) Electrolytic copper foil (thickness 18μm, Rzjis 0.09μm, Ra 0.02μm) (D-3) Pure aluminum plate (thickness 0.8mm, Rzjis 0.14μm, Ra 0.01μm) (D-4) Electrolytic copper foil having on its surface, from the outside to the inside, a silane coupling agent layer, a heat-resistant plating layer and an electrolytic chromate layer in this order (thickness 18μm, Rzjis 0.16μm, Ra 0.04μm) [Low Dielectric Constant Resin Material] (E-1) PTFE prepreg (manufactured by Rogers Corporation, product name "RO3003 Bondply", thickness 0.1mm) (Catalog value: relative permittivity 3.0 ± 0.04, dielectric tangent 0.0010 at 23°C, 10GHz) (Measured value: relative permittivity: 2.44, dielectric tangent: 0.00063 at 23°C, 10GHz) (E-2) PEEK-based prepreg (thickness 0.05mm) (Catalog value: relative permittivity 3.1, dielectric tangent 0.0033 at 23°C, 10GHz) (Measured value: relative permittivity: 2.88, dielectric tangent: 0.00337 at 23°C, 10GHz) [Compound (F)] (F-1) Imidazole (F-2) 1,2,4-Triazole (F-3) Tetrazole (F-4) Oxalate of aniline (neutralized aniline with oxalic acid) (F-5) Bismarck Brown [Water-based resin (G)] (G-1) Modipics (registered trademark) 302 (manufactured by Arakawa Chemical Industries, Ltd.) (epoxy resin) (G-2) Gosenex (registered trademark) LW-100 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) (sulfonate group-modified PVOH) (G-3) Aron Base (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) Eter (registered trademark) KT-507 (manufactured by Unitika Ltd.) (ester resin) [Epoxy adhesive (H)] (H-1) ThreeBond (trademark registration) 2086M main agent (epoxy resin) / hardener (polythiol) (H-2) jER (trademark registration) 828EL (Mitsubishi Chemical Corporation) (epoxy compound (bisphenol A type epoxy resin)) / pentaethylenehexamine (used as an amine hardener) (H-3) jER (trademark registration) 828EL (Mitsubishi Chemical Corporation) (epoxy compound (bisphenol A type epoxy resin)) / Epomin SP-006 (used as an amine hardener) (H-4) Denacol (trademark registration) EX313 (Mitsubishi Chemical Corporation) (epoxy compound (glycerol polyglycidyl ether)) / pentaethylenehexamine (used as an amine hardener) [High dielectric constant resin material (I)] (I-1) Epoxy resin prepreg (manufactured by Showa Denko Materials Co., Ltd., trade name "GEA-679N") (measured value: relative permittivity 3.20, dielectric tangent 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) The glass fiber cloth of (J-1) was put into chloroform heated to 60°C, which was an epoxy resin prepreg (manufactured by Showa Denko Materials Co., Ltd., trade name "GEA-679N"), to completely dissolve the epoxy resin, and only the glass fiber cloth was taken out. It was immersed again in another chloroform heated to 60°C to remove the remaining epoxy resin, and then dried in a circulating drying oven at 80°C for 1 minute before use.

[0061] <Manufacture of metal-clad laminate [Formation of adhesive layer for low dielectric constant resin material] [Example 1] As a 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 amount of adhesion of the adhesive layer formed on the copper foil surface was 12 mg / m 2 The solid content concentration of the compound (B-1) in which an amino group was directly bonded to the nitrogen-containing aromatic ring with ion-exchanged water was adjusted so as to have an adhesion amount of, and it was used as an aqueous adhesive and applied (bar coating method) to the surface provided with the plating layer and the electrolytic chromate layer of the copper foil. The mass ratio of the compound (B-1) excluding water in the adhesive is shown in Table 1. Then, it was dried at 100°C for 1 minute in a hot air circulation drying oven to form an adhesive layer on the copper foil surface.

[0062] [Adhesion between metal material with adhesive layer formed and low dielectric constant resin material] A PTFE prepreg (manufactured by Rogers Corporation, trade name "RO3003 Bondply", thickness 0.1 mm) (E-1) was laminated on the surface of the adhesive layer formed on the metal material, and a matte surface of an electrolytic copper foil with a thickness of 35 μm was laminated as a ground layer on the back surface of the lamination surface of the above (E-1). The metal material, the adhesive layer, (E-1), and the ground layer were laminated in this order. The ground layer was provided because it is necessary for the adhesion evaluation described later. Then, the metal-clad laminate was manufactured by wrapping it with an aluminum foil and bonding it in a state where the air was blocked. The bonding conditions were a press pressure of 30 kgf / cm 2 , a press time of 45 minutes, and a press temperature of 370°C.

[0063] [Examples 2 to 30] An adhesive layer was formed on one surface of the metal materials (D-1, 2) shown in Table 1 in the same manner as in Example 1, except that aqueous solutions of the compounds (B-1 to 6) and compounds (C-1 to 9) shown in Table 1 were used as the adhesive. When the solubility of compound (B) and compound (C) is low and the compound concentration in the aqueous solution cannot be increased, the adhesion amount shown in Table 1 was obtained by, for example, making the mesh of the bar used for bar coating coarser or overcoating the dried adhesive layer. Then, a metal-clad laminate was manufactured in the same manner as in Example 1, except that it was bonded under the conditions of the press time and press temperature shown in Table 1. [Examples 31 to 36] A metal-clad laminate was manufactured in the same manner as in Example 1, except that an adhesive layer was formed using the aqueous solutions of the compounds (B-1, C-8) shown in Table 1 as the adhesive and bonded under the conditions of the press time and press pressure shown in Table 1. [Examples 37, 38] A metal-clad laminate was manufactured in the same manner as in Example 1, except that an adhesive layer was formed using the aqueous solutions of the compounds (B-1, C-8) shown in Table 1 as the adhesive, the resin material (E-2) shown in Table 1 was used, and it was bonded under the conditions of the press time, press temperature, and press pressure shown in Table 1. [Examples 39, 40] An aqueous solution of the compounds (B-1, C-8) shown in Table 1 was used as an adhesive to form an adhesive layer, and a metal-clad laminate was produced in the same manner as in Example 1 except that it was adhered using the metal material (D-3) shown in Table 1.

[0064] [Comparative Examples 1 to 3, 9, 16, 28] A metal-clad laminate was produced in the same manner as in Example 1 except that no adhesive layer was formed and it was adhered using the metal materials (D-1 to 4), low dielectric constant resin materials (E-1, 2) or resin material I-1 shown in Table 2 under the press time and press temperature conditions shown in Table 2. [Comparative Examples 4 to 8] An aqueous solution of the compounds (F-1 to 5) shown in Table 2 was used as an adhesive to form an adhesive layer, and a metal-clad laminate was produced in the same manner as in Example 1. [Comparative Examples 10 to 15] An aqueous solution of the aqueous resins (G-1 to 6) shown in Table 2 was used as an adhesive to form an adhesive layer, and a metal-clad laminate was produced in the same manner as in Example 1. [Comparative Examples 17, 18] An aqueous solution of the compounds (B-1, C-8) shown in Table 2 was used as an adhesive to form an adhesive layer, and a metal-clad laminate was produced in the same manner as in Example 1 except that it was adhered using resin material I-1 under the press time and press temperature conditions shown in Table 2. [Comparative Example 19] Epoxy adhesive H-1 (ThreeBond (registered trademark) 2086M main agent (epoxy resin) / hardener (polythiol)) was used as an adhesive to form an adhesive layer of 10 g / m 2 and without drying, it was laminated with the resin material and adhered under the press time and press temperature conditions shown in Table 2, and a metal-clad laminate was produced in the same manner as in Example 1. [Comparative Example 20] jER828EL (epoxy compound) was diluted with toluene, and pentaethylenehexamine (amine curing agent) was stirred until homogeneous so that the molar ratio was epoxy group: number of active hydrogens of amino group = 1.2:1.0. The toluene solution thus prepared was used as an adhesive and applied to one surface of the copper foil (bar coating method). Thereafter, except that it was dried at 40 °C for 3 minutes in a hot air circulation drying furnace to form an adhesive layer on the copper foil surface, a metal-clad laminate was manufactured in the same manner as in Example 1. The concentration during dilution was adjusted so that the adhesion amount of the adhesive layer formed on the copper foil surface was 106 mg / m 2 . Only the adhesion amount of pentaethylenehexamine in the total adhesion amount of the adhesive layer at this time was 12 mg / m 2 . [Comparative Example 21] A metal-clad laminate was manufactured in the same manner as in Comparative Example 20, except that the concentration was adjusted so that the adhesion amount of the adhesive layer formed on the copper foil surface was 1762 mg / m 2 . Only the adhesion amount of pentaethylenehexamine in the total adhesion amount of the adhesive layer at this time was 200 mg / m 2 . [Comparative Example 22] A metal-clad laminate was manufactured 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. Only the adhesion amount of Epomin SP-006 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 manufactured 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. Only the adhesion amount of pentaethylenehexamine in the total adhesion amount of the adhesive layer at this time was 12 mg / m 2 . [Comparative Examples 24 to 27] Using the aqueous solutions of the compounds (B-1, C-8) shown in Table 2 as adhesives to form an adhesive layer, a metal-clad laminate was manufactured in the same manner as in Example 1, except that materials other than resins (J-1, 2) were used.

[0065] [Ten-point mean roughness (Rzjis) of the metal material surface] The ten-point mean roughness (Rzjis) and arithmetic mean roughness (Ra) of the bonding surface of the metal materials (D-1 to 4) used above with the resin were measured in accordance with JIS B0601:2001 using a laser microscope (VK-X1000 manufactured by Keyence Corporation). The detailed measurement method is shown below. The measurement environmental temperature by the laser microscope was set to 23 to 25°C. (1) Place the measurement sample on the stage with the roughness measurement surface of the metal material facing upward. (2) Adjust the focus with a 50x objective lens and take a photograph in the shape measurement mode. For the photograph, select [Basic Settings], and perform it with [Scan Mode: Laser Confocal], [Measurement Size: Standard], and [Measurement Quality: High Precision]. (3) The measurement target area shall be 202 μm × 270 μm (magnification on the monitor is 1200 times) that has been imaged, and the surface roughness shall be measured within this range. (4) Start [Multi-File Analysis Application VK-X], select [Image Processing], and correct the surface. (5) For the surface roughness, select [Line Roughness], display five horizontal lines and five vertical lines each at five different arbitrary locations within the surface image, and obtain the numerical values of the respective ten-point mean roughness Rzjis and arithmetic mean roughness Ra. At this time, the cut-off value of each contour curve filter was set to λc = 0.25 μm. (6) Calculate the average value of the obtained 10 numerical values respectively to obtain the ten-point mean roughness Rzjis and arithmetic mean roughness Ra.

[0066] The adhesion amount of the adhesive layer was determined by the following method. The carbon amount in the liquid adhesive was measured using a TOC meter (total organic carbon analyzer ON-LINE TOC-VCSH (manufactured by Shimadzu Corporation)), and the ratio of carbon in the solid content was calculated by the method described above. Using the adhesive aqueous solution, a coating film was formed on the metal materials used in each example and comparative example by the bar coating method, and then dried at 100 °C for 1 minute in a hot air circulation drying furnace to form a dried coating film. The copper foil on which the above dried coating film was formed was cut into two pieces with a width of 1 cm and a length of 3 cm to be used as measurement samples, and analyzed with a total organic carbon analyzer TOC-5000A (manufactured by Shimadzu Corporation) to measure the carbon amount per unit area. Since the adhesion amount per unit area can be calculated from the carbon amount per unit area by the method described above, the solid content concentration of the adhesive that gives the adhesion amount shown in Table 1 was determined, and an adhesive evaluation metal-clad laminate having an adhesive layer was produced. In addition, when the solubility of the adhesive component is low and the target adhesion amount cannot be obtained by forming a coating film by the bar coating method once, the formation of the coating film by the bar coating method is repeated, and the adhesion amount is calculated using the same TOC meter as above. After confirming that it is the target adhesion amount, an adhesive evaluation metal-clad laminate was produced. In the same manner as the above method, for each of the other adhesives, the solid content 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 amounts shown in Tables 1 and 2. The solid content concentration was determined for each combination of the compound and the metal material used for forming the adhesive layer shown in Tables 1 and 2.

[0067] [Evaluation of Ignition Residue] For the compound (B) and the compound (C) used in the above examples, the ignition residue was measured by the following procedure. (1) The measurement sample was prepared as a 1 mass% solution with deionized water. (2) The weight m (about 25 g) of a PFA petri dish was measured using an electronic balance capable of weighing up to 4 decimal places in grams. (3) The solution diluted in (1) was dropped onto the petri dish, and the weight n (about 5 g) of the dropped solution was measured. (4) Place the petri dish in a stainless-steel tray, cover the opening with aluminum foil, make a plurality of holes with a diameter of about 1 cm as vent holes for volatile components, place it in a hot-air circulation drying oven, and heat it at 265 °C for 1 hour. (5) After (4), take out the petri dish, allow it to cool until the sample temperature reaches 30 °C, and measure the weight M of the petri dish after cooling. (6) Measure the ignition residue by the above formula (i). (7) Conduct the above measurement 4 times, and use the arithmetic mean value as the evaluation value. (8) Rate the evaluation value calculated in (7) according to the following criteria. The results are shown in Table 1. D: The ignition residue is 0% or more and less than 10% C: The ignition residue is 10% or more and less than 20% B: The ignition residue is 20% or more and less than 30% A: The ignition residue is 30% or more

[0068] <Adhesion evaluation> Regarding the metal-clad laminates using the metal materials (D-1), (D-2), and (D-4) produced in the above examples and comparative examples, they were cut into pieces with 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 grasped with the jig of a tensile testing machine and peeled off. Specifically, among the peel lengths (the lengths in the direction orthogonal to the width of the cut metal-clad laminate), starting from 2.75 mm and ending at 15.25 mm, at intervals of 0.1 mm for that length (12.5 mm), the peel strength (peeling strength) was plotted, and except that the arithmetic mean was taken as the evaluation value, in accordance with JIS C5012:1993, the peel strength (peeling strength) of the metal material in the 90° direction was measured, and the adhesiveness was evaluated according to the following evaluation criteria. Regarding the metal-clad laminate using the metal material (D-3), except that the tip of the laminated part of the resin material layer and the ground layer was grasped with the jig of a tensile testing machine, the peel strength was measured and the adhesiveness was evaluated in the same manner as the above method. In this evaluation, in view of the adhesiveness when no adhesive was used, for the metal materials (D-1), (D-2), and (D-4), those with a score of 2 or less were evaluated as having poor adhesiveness, and for the metal material (D-3), those with a score of 4 or less were evaluated as having poor adhesiveness. Also, since the resin material layer underwent cohesive failure at 10.0 N or more in the tensile testing machine and measurement was difficult, for the metal materials (D-1), (D-2), and (D-4), a test was further carried out to peel off the metal material in the 90° direction with fingers at a speed of about 600 mm / min, and for the metal material (D-3), a test was carried out to peel off the layer where the resin material and the ground layer were bonded together at a speed of about 600 mm / min, and the degree of spreading of the resin material on the surface of the metal material after peeling was rated. The results are shown in Tables 1 and 2. [Evaluation Criteria: Peel Strength and Appearance of the 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: above 10.0 N / cm and the spreading area of the resin material with cohesive failure on the surface of the metal material after peeling is more than 20% and less than 40% of the surface area of the metal material. 7 points: above 10.0 N / cm and the spreading area of the resin material with cohesive failure on the surface of the metal material after peeling is more than 40% and less than 70% of the surface area of the metal material. 8 points: above 10.0 N / cm and the spreading area of the resin material with cohesive failure on the surface of the metal material after peeling is 70% or more of the surface area of the metal material.

[0069]

Table 1

[0070]

Table 2

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) is a compound (B) in which an amino group is directly bonded to a nitrogen-containing aromatic ring and at least one selected from compounds (C) having a polyalkylamine skeleton. An adhesive.

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 of the metal material layer with the low dielectric constant resin 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 wiring and processing the metal material layer of the laminate according to claim 3.

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 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; After the contacting step, optionally a step of drying the layer of the adhesive; A method for manufacturing a laminate, which includes 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 formed by laminating a first substrate and a second substrate with an adhesive layer therebetween.

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