TW201619292A - Polyimide resin composition, adhesion composition, primer composition, lamination body and resin-adhered copper foil - Google Patents

Abstract

The goal of the present invention is to provide a polyimide resin composition having extremely low dielectric loss tangent and dielectric constant, excellent heat resistance, and high adhesion between a circuit wiring pattern, such as copper wiring, and an insulation layer, such as an insulating film or prepreg material. Another goal of the present invention is to provide an adhesion composition produced by using the polyimide resin composition, and a primer composition produced by using the polyimide resin composition. To achieve the aforementioned goals, a polyimide resin composition is used, which comprises a polyimide resin and a crosslinking component, in which the polyimide resin has repeating structures represented by the general formula (1). In the general formula (1), n represents an integer from 1 to 100.

Description

Polyimine resin composition, adhesive composition, primer composition, laminate, and copper foil with resin

The present invention relates to a polyimide composition, an adhesive composition, a primer composition, a laminate, and a copper foil with a resin attached thereto.

In recent years, in response to the increase in the processing data of high-performance mobile terminals such as smart phones and tablet computers, the high-frequency of digital signals is gradually improving. In order to improve the performance of such high-frequency electronic components, the design of the printed wiring to be transmitted is important, and the quality of the high-speed digital signal including high-order high-frequency signals must be impaired, and the signal propagation speed is improved.

Among them, in order to reduce the transmission loss of the high-frequency digital signal, it is necessary to reduce the dielectric loss tangent and the dielectric constant. Therefore, various materials used for high-frequency electronic components such as high-performance mobile terminals such as printed wiring boards have been seeking extremely low dielectric loss tangent and dielectric constant.

A printed wiring board is obtained by laminating an insulating layer and a copper foil, and etching the copper foil to form an electric circuit. As the insulating layer, generally, a material which is excellent in heat resistance and electrical insulating properties is used. A heat-resistant organic insulating film which is a raw material such as sulfimine or a liquid crystal polymer; or a prepreg obtained by impregnating an epoxy resin, a curing agent, a filler, or the like into a glass cloth. When these materials are laminated with a copper foil, an adhesive layer or a primer layer is used depending on the type of the substrate, the surface state, and the target physical properties of the printed wiring board.

In the case of a printed substrate for a high-frequency electronic component, a low dielectric loss tangent and a low dielectric constant are particularly required for the insulating layer around the copper circuit. Accordingly, a low dielectric loss tangent and a low dielectric constant are particularly required for the adhesive layer and the primer layer. Further, as the line density and the mounting density have increased remarkably in recent years, further improvement in heat resistance, adhesion, and workability of printed wiring boards has been sought. In particular, in the case of a flexible printed circuit board, if the adhesive layer is a rigid substrate, the resin of the copper foil with the resin is required to be a circuit wiring pattern such as a copper wiring or an insulating layer such as an insulating film or a prepreg. They all have high adhesion. Further, in addition to this, heat resistance is also important as a factor for securing the reliability of the electronic component (for example, resistance to warpage after the assembly). This physical property is generally judged by the Tg (glass transition temperature) of the adhesive layer and the primer layer.

The present inventors have proposed "a polyimine-based adhesive composition containing (A) a polyimide resin, (B) a thermosetting resin, and (D), which is required for heat resistance of a printed wiring board. a flammable agent and (D) an organic solvent, wherein the (A) polyimide resin is composed of (a1) an aromatic tetracarboxylic acid and (a2) a specific dimer diamine (dimer diamine) of 30 mol% or more. Diamine The reaction is formed (see Patent Document 1). However, the low dielectric loss tangent and low dielectric constant of the polyimide composition are not discussed, and there is room for improvement in heat resistance.

As described above, although various types of resin compositions used for bonding electronic component materials are various, it is expected to develop a resin composition which has high adhesion and heat resistance and has extremely low dielectric properties. Electrical loss tangent, dielectric constant. In this case, a resin composition characterized by containing (A) a phenoxy resin and (B) a solvent having a weight average molecular weight of 5,000 to 200,000 and having naphthalene has been proposed. A structure in which a hydrogen atom of a skeleton and a hydroxyl group is substituted with a thiol group (see Patent Document 2). However, although it has a low dielectric loss tangent and a low dielectric constant, it is not attached to the circuit wiring pattern such as copper wiring and the insulating layer such as an insulating film or a prepreg. Mentioned. Moreover, regarding the heat resistance, the resin composition is also not perfect.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Patent No. 5534378

Patent Document 2: Japanese Patent No. 5326188

An object of the present invention is to provide a polyimide composition having a very low dielectric loss tangent and dielectric constant, excellent heat resistance, and having a wiring pattern for a copper wiring or the like, and an insulating film or prepreg High adhesion and high processability (compatibility) of both insulating layers such as materials. Moreover, an object of the present invention is to provide an adhesive composition using the composition of the polyimide resin, and a primer composition using the composition of the polyimide resin.

The inventors of the present invention have intensively studied to solve the above problems, and as a result, have found that the above problems can be solved by using a polyimide composition having a specific repeating unit, and the present invention has been completed.

That is, the present invention is a polyimine resin composition (Invention 1) having a polyimine resin and a crosslinking component having a repeating structure represented by the general formula (1) ,

In the general formula (1), n represents an integer of 1 to 100.

Further, the present invention 2 is an adhesive composition comprising the polyimine resin composition of the present invention 1.

The present invention 3 is a primer composition comprising the polyimine resin composition of the present invention 1.

The present invention 4 is a laminate which is formed by using the adhesive composition of the present invention 2.

The present invention 5 is a resin-attached copper foil which is obtained by using the primer composition of the present invention 3.

According to the present invention, there can be provided a polyimide composition having a dielectric loss tangent and a low dielectric constant, high adhesion to a copper circuit wiring pattern (peeling strength), and high heat resistance. Further, the polyimine resin of the present invention has high adhesion to both the circuit wiring pattern and the insulating film, and has excellent workability (compatibility) as an adhesive or a primer, so it is particularly It is suitable as an adhesive composition and a primer composition for a circuit board of an electronic component. Moreover, since the polyimine resin of the present invention has high adhesion to a circuit wiring pattern, an adhesive, or a coating agent, it is particularly suitable for use as a primer for an electronic component circuit substrate. Things.

The present invention is a polyimine resin composition having a polyimine resin and a crosslinking component, the polyimide resin having a repeating structure as shown in the general formula (1),

In the general formula (1), n represents an integer of 1 to 100.

The above polyimine resin has a repeating structure of the formula (1) and has a 2,2-bis[4-(3,4-di) group represented by the following formula (2) in a ratio of 1:1. a portion of 2,2-Bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride) and 1,3 from the following formula (3) a moiety of bis(aminomethyl)cyclohexane. Moreover, the repeating unit n is 1 to 100. When n exceeds 100, the compatibility with the crosslinking component deteriorates.

The above polyimine resin can be produced by various conventional methods. For example, first, usually around 60~120 °C, Preferably, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride and 1,3-bis(aminomethyl) ring are at a temperature of about 80 to 100 ° C. The hexane is subjected to a polyaddition reaction, which is usually about 0.1 to 5 hours, preferably about 0.1 to 3 hours. Then, the obtained addition polymer is further subjected to a ruthenium imidization reaction, that is, a dehydration ring closure reaction at a temperature of about 80 to 250 ° C, preferably about 100 to 200 ° C, for about 0.5 to 50 hours, preferably The above polyimine resin is obtained in about 1 to 20 hours.

In the above hydrazine imidization reaction, various conventional reaction catalysts, dehydrating agents, and organic solvents described later can be used. Examples of the reaction catalyst include aliphatic tertiary amines such as triethylamine; aromatic tertiary amines such as dimethylaniline; and heterocyclic tertiary amines such as pyridine, pyridyl and isoquinoline. Further, examples of the dehydrating agent include an aliphatic acid anhydride such as acetic anhydride or an aromatic acid anhydride such as benzoic anhydride.

The feed ratio of the above 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride to 1,3-bis(aminomethyl)cyclohexane is not particularly limited, and From the viewpoint of the solubility of the cross-linking component of the above polyimine resin or the ability to obtain sufficient flatness at the time of film formation, [the former using the molar number / the latter using the molar number] is usually 0.6 to 1.4. Left and right, preferably in the range of about 0.9 to 1.2. Further preferably, it is 1.02 to 1.18.

The dielectric loss tangent of the polyimine resin contained in the polyimide composition of the present invention is preferably 0.015 or less. Enter It is preferably 0.01 or less. If it is within this range, it can be used for high-frequency electronic parts that have been seeking high performance in recent years.

The glass transition temperature (Tg) of the polyimine resin composition contained in the polyimide composition of the present invention is preferably 130 ° C or higher. Further preferably, it is 150 ° C to 200 ° C. More preferably, it is 150~180 °C. Thereby, the polyimine resin composition of the present invention has high heat resistance and can be used for high-frequency electronic parts which have been sought for high performance in recent years.

The number average molecular weight of the polyimine resin composition of the present invention is preferably from 3,000 to 50,000. Further preferably, it is 4000 to 20000. More preferably, it is 5000~15000.

The crosslinking component is not particularly limited, and various conventional examples can be mentioned. Specific examples thereof include oligophenylene ether, bismaleimide resin, epoxy resin, cyanate ester, and benzo. Wait. Among them, epoxy resins, cyanate esters, and oligomeric phenylene ethers are preferred from the viewpoint of generally good adhesion.

The oligophenylene oxide is not particularly limited, and specific examples thereof include a commercially available bifunctional core having a poly(phenylene ether) bonded to both ends of the core (oligophenylene oxide, OPE, Mitsubishi Gas Chemical Co., Ltd.) Manufactured by the company, epoxy derivative of OPE (manufactured by Mitsubishi Gas Chemical Co., Ltd.), styrene derivative of OPE (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like. These compounds can also be used in combination of 2 or more types.

The bismaleimide resin is not particularly limited, and specific examples thereof include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, and double Phenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl Benzyl-1,3-phenylene bismaleimide, 1,6'-bismaleimido-(2,2,4-trimethyl)hexane, 4,4'-diphenyl Ethyl ether bismaleimide, 4,4'-diphenylfluorene bismaleimide, and the like. In addition, as a commercial item, "BAF-BMI" manufactured by JFE Chemical Corporation, etc. are mentioned, and these compounds can also be used in combination of 2 or more types.

Examples of the epoxy resin include a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol S type epoxy resin. Resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, stilbene epoxy resin, containing three Skeleton epoxy resin, epoxy resin containing ruthenium skeleton, linear aliphatic epoxy resin, alicyclic epoxy resin, glycidylamine epoxy resin, trisphenol phenol methane epoxy resin, alkane Base modified trisphenol methane type epoxy resin, biphenyl type epoxy resin, epoxy resin containing dicyclopentadiene skeleton, epoxy resin containing naphthalene skeleton, arylalkylene type epoxy resin, Some of the epoxy resins modified with dimer acid are modified epoxy resins, dimerized diglycidyl esters, etc., and from the viewpoint of adhesion of the adhesive composition and resin compatibility, it is preferred to select At least one selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, and alicyclic epoxy resin. In addition, as a commercial item, "jER828", "jER834", or "jER807" manufactured by Mitsubishi Chemical Corporation, "ST-3000" manufactured by Nippon Steel Chemical Co., Ltd.; Daicel Chemical Industry "Celloxide 2021P" manufactured by the company, "YD172-X75" manufactured by Nippon Steel Chemical Co., Ltd., etc., may be used in combination of two or more kinds.

The cyanate ester is not particularly limited, and specific examples thereof include 2-allylphenyl cyanate, 4-methoxyphenyl cyanate, and 2,2-bis(4-cyanooxybenzene). -1,1,1,3,3,3-hexafluoropropane, bisphenol A cyanate, diallyl bisphenol A cyanate, 4-phenylphenol cyanate, 1,1, 1-gin(4-cyanooxyphenyl)ethane, 4-cumylphenol cyanate, 1,1-bis(4-cyanooxyphenyl)ethane, 4,4'-bisphenol cyanate, For example, a commercially available product such as "PRIMASET BTP-6020S (manufactured by LONZA Japan Ltd.)" can be used as the 2,2-bis(4-cyanooxyphenyl)propane. These compounds can also be used in combination of 2 or more types.

As the above benzo The resin may, for example, be 6,6-(1-methylethylidene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoene ,6,6-(1-methylethylidene)bis(3,4-dihydro-3-methyl-2H-1,3-benzoene) )Wait. In addition, The nitrogen of the ring may also be bonded to a phenyl group, a methyl group, a cyclohexyl group or the like. In addition, as a commercial item, "Fa type Benzoxazine" or "Pd type Benzoxazine" manufactured by Shikoku Chemicals Co., Ltd., "RLV-100" manufactured by AIR WATER INC., etc. may be mentioned, and these compounds may be combined. Use two or more.

Further, when an epoxy resin is used as the thermosetting resin, various conventional hardeners for epoxy resins can be used in combination. Specific examples thereof include succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic acid, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, and 4 -methyl-hexahydrophthalic anhydride, a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, Nadic acid anhydride, methyl An acid anhydride hardener such as nadic anhydride, norbornyl-2,3-dicarboxylic anhydride, methylnorbornyl-2,3-dicarboxylic anhydride or methylcyclohexanedicarboxylic anhydride; dicyandiamide (DICY), amine-based curing agent such as aromatic diamine; phenol novolak resin, cresol novolak resin, bisphenol A novolac resin, three A modified phenol novolac resin, a phenolic curing agent such as phosphatidyl phosphazene (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd.), and a cyclic phosphazene compound Wait. Among them, a phenolic curing agent, particularly a phosphazene-based curing agent containing a phenolic hydroxyl group, is preferred because it is easy to impart flame retardancy to the laminate of the present invention. The amount of the curing agent to be used is not particularly limited, and the curing agent is used when the solid content of the polyimine resin composition of the present invention is 100% by weight from the viewpoint of the balance between the use period and the reactivity. The amount is usually about 0.01 to 5% by weight.

Further, as a catalyst for promoting the reaction of the epoxy resin with the hardener, for example, 1,8-diazabicyclo[5.4.0]11 carbon-7-ene, triethylenediamine, benzyl group can be used. Tertiary amines such as dimethylamine, triethanolamine, dimethylaminoethanol, ginseng (dimethylaminomethyl)ethanol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl Imidazoles such as imidazole and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine; tetraphenylphosphonium tetrakis Boronate, 2-ethyl-4-methylimidazolium tetraphenylborate, N-methyl Tetraphenylborate such as phenanthrene/tetraphenylborate may be used in combination of two or more kinds. In addition, the amount of the catalyst used is not particularly limited. When the solid content of the polyimine resin composition of the present invention is 100% by weight, the amount of the catalyst used is usually about 0.01 to 5% by weight.

In the polyimine resin composition of the present invention, the ratio of the polyimine resin to the crosslinking component is preferably a polyimide resin: crosslinking component = 60 to 90% by weight: 10 to 40 weight %. Further preferably, it is 70 to 90% by weight: 10 to 30% by weight. More preferably, it is 80 to 90% by weight: 10 to 20% by weight. By setting this ratio, it is possible to obtain a polyimide composition having a balance between adhesion, heat resistance, dielectric properties, and workability (compatibility).

The polyimine resin composition can be obtained by mixing a polyimide resin and a crosslinking component at normal temperature. Order and mix The temperature at the time is not particularly limited. Further, in order to improve the compatibility and workability between the crosslinking component and the polyimide resin, a diluent solvent can be used. The type of the diluent solvent is not limited, and from the viewpoints of solubility and drying property, toluene, a ketone solvent, DMAc (dimethylacetamide), or the like is preferable.

The polyimine resin composition of the present invention may have other reaction components added thereto within a range not detracting from the effects of the present invention. Further, various additives such as an organic or inorganic filler, an antifoaming agent, a leveling agent, a stabilizer, and an antioxidant may be added as needed.

As the above other monomer, for example, an acid anhydride, various conventional aromatic tetracarboxylic anhydrides can be used. Specific examples thereof include pyromellitic dianhydride, 4,4′-oxybiphthalic anhydride, 3,3′, 4,4′-benzophenonetetracarboxylic dianhydride, and 3,3'. , 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic anhydride, 1 , 4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3 , 3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic acid Anhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2-bis (3, 3',4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)ruthenic anhydride, 2,2-bis (3, 4-dicarboxyphenyl)propane dianhydride, cyclopentane tetracarboxylic anhydride, butane-1,2,3,4-tetracarboxylic acid, 2,3,5-tricarboxycyclopentyl acetic anhydride, and 4, 4'-[propane-2,2- Di-bis(1,4-phenyleneoxy)]dicarboxylic acid dianhydride, etc., and, as the diamine, may be exemplified by α,ω-bis(2-aminoethyl)polydimethyloxane. , α,ω-bis(3-aminopropyl)polydimethyloxane, α,ω-bis(4-aminobutyl)polydimethyloxane, α,ω-bis(5-amine Pentyl)polydimethyloxane, α,ω-bis[3-(2-aminophenyl)propyl]polydimethyloxane, α,ω-bis[3-(4-amine Anthracene resin diamine such as phenylphenyl)propyl]polydimethyloxane; aliphatic diamine such as dimer diamine; diaminocyclohexane, diaminocyclohexylmethane, dimethyl- Diaminodicyclohexylmethane, tetramethyl-diaminodicyclohexylmethane, diaminodicyclohexylpropane, diaminobicyclo[2.2.1]heptane, bis(aminomethyl)-bicyclo[2.2 .1] heptane, 3(4), 8(9)-bis(aminomethyl)tricyclo[5.2.1.02,6]decane, 1,3-diaminemethylcyclohexane, isophorone Diamine and the like. Among them, diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, diaminobicyclo[2.2.1]heptane, bis(aminomethyl) )-bicyclo[2.2.1]heptane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.02,6]decane, isophoronediamine, 4,4' An alicyclic diamine such as diaminodicyclohexylmethane or 1,3-diaminemethylcyclohexane, or the like, and these compounds may be used in combination of two or more.

The dielectric loss tangent of the cured product of the polyimine resin composition of the present invention is not particularly limited, but is preferably 0.015 or less. If it is in this range, it can be suitably used for high-frequency electronic parts which seek high performance in recent years. The dielectric loss tangent is further preferably 0.01 or less.

The above method for measuring the dielectric loss tangent is preferably carried out by using an open resonator method, a stripline resonator method, and a microstrip line resonator method (micro) -stripline resonator method), resonant cavity perturbation method.

An adhesive composition comprising the above polyimine resin composition is also one of the present inventions. In addition to the above polyimine resin composition, the adhesive composition may further contain a flame retardant, a filler, an ion scavenger, and the like.

Examples of the flame retardant include phenoxyphosphazene and melamine polyphosphate. Examples of the filler include a cerium oxide filler and a silver powder. Examples of the ion scavenger include an organic ion exchange resin and zeolite. .

The above-mentioned adhesive composition has extremely low dielectric loss tangent, excellent heat resistance, and high adhesion to an insulating layer and an insulating layer of a circuit wiring pattern, and thus can be used in a printed wiring board for electronic parts. The insulating film is adhered to the circuit wiring pattern.

Examples of the insulating film include polyimine, polyimine-ceria mixed material, polyethylene (PE), polypropylene (PP), and polyethylene terephthalate (PET). Polyethylene naphthalate (PEN), polymethyl methacrylate resin (PMMA), polystyrene resin (PSt), polycarbonate resin (PC), acrylonitrile-butadiene-styrene resin (ABS), ethylene terephthalate or phenol, citric acid, hydroxynaphthalene An organic substrate such as an aromatic polyester resin (so-called liquid crystal polymer, manufactured by KURARAY CO., LTD., "VECSTAR") obtained from p-hydroxybenzoic acid or the like.

A primer composition comprising the above polyimine resin composition is also one of the present inventions. In addition to the above polyimine resin composition, the primer composition may further contain other components such as a flame retardant, a filler, an ion scavenger, and the like.

Examples of the flame retardant include phenoxyphosphazene and melamine polyphosphate. Examples of the filler include a cerium oxide filler and a silver powder. Examples of the ion scavenger include an organic ion exchange resin, zeolite, and the like.

The blending ratio of the above polyimine resin composition to other components such as a flame retardant, a conductive filler, and an ion scavenger is 100 parts by weight: 1 to 42 parts by weight.

The primer composition has extremely low dielectric loss tangent, excellent heat resistance, and has high adhesion to a metal conductive layer such as a copper wiring or an insulating layer such as an insulating film or a prepreg, and thus is suitable for a host. A resin composition of a resin-coated copper foil (RCC) used for a plate or a package substrate.

A laminate body using the adhesive composition of the present invention is also one of the present inventions. The laminate of the present invention can be obtained by subjecting a sheet substrate to a sheet-like uncured material of the adhesive composition of the present invention by thermocompression bonding. Such a laminate (adhesive sheet) is suitable for use in a high-frequency substrate because of its excellent heat resistance, adhesion, and electrical properties.

As the sheet base material, an inorganic substrate such as glass, iron, aluminum, 42 alloy (42 Alloy), copper or the like, or ITO (indium tin oxide), tantalum or tantalum carbide is preferably used, and the thickness thereof can be appropriately set depending on the use. . Further, the laminate may be formed by further heat treatment.

A resin-attached copper foil using the primer composition of the present invention is also one of the present inventions. The resin-attached copper foil can be produced by forming a primer composition on a copper foil by brushing, drying, or the like. The resin-attached copper foil of the present invention is suitable for use in a motherboard or a package substrate for a high-frequency substrate because of its excellent heat resistance, adhesion, and electrical characteristics.

The copper foil may, for example, be an electrolytic copper foil, a rolled copper foil, an aluminum foil or a stainless steel foil. Among them, the electrolytic copper foil and the rolled copper foil are preferable because they are excellent in electrical conductivity, heat resistance, mechanical strength, and surface smoothness. When used for FPC (Flexible Printed Circuit) or TAB (Tape Automated Bonding), it is generally used to adhere copper foil based on the purpose of obtaining adhesion to an adhesive. surface The surface-treated copper foil having a high surface roughness is obtained. However, the cured product obtained from the primer composition of the present invention is excellent in adhesion to the copper foil even without using an adhesive, and therefore it is not particularly necessary. The surface is roughened, and even if it is an untreated copper foil, or a low-thickness copper foil with a fine pitch and high frequency, sufficient adhesion can be obtained. Therefore, as the copper foil, it is preferable to use a copper foil having a small surface roughness, and particularly a metal foil laminate, the surface roughness (Rz) is preferably 7 μm or less, and particularly preferably a copper foil having an Rz of 2.2 μm or less. . The thickness of the metal foil is not particularly limited, and is preferably 70 μm or less, and particularly preferably 20 μm or less, for the fine pitch of the substrate.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited thereto. In addition, in the examples, "parts" or "%" are weight basis.

[Manufacturing Example 1]

Feeding 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (trade name "BisDA" in a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen inlet tube -1000", manufactured by SABIC Innovative Plastics Japan Ltd., hereinafter referred to as dibasic bis-phenyloxy dicarboxylic acid dianhydride 455.00 g, methylcyclohexane 130.43 g, dimethyl acetamide 782.60 g, The solution was heated to 100 °C. Then, slowly add 1,3-bis(amine methyl) After 113.15 g of cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd.), the mixture was heated to 130 ° C, and the oxime imidization reaction was carried out for 36 hours, after which dimethylacetamide was added to adjust the nonvolatile component to 30.0%. And a solution of the polyimide resin is obtained. Further, the molar ratio of the acid component/amine component was 1.10. The number average molecular weight is about 8,000.

[Manufacturing Example 2]

In a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen inlet tube, 455.00 g of diradyl phenyloxydiphthalic acid dianhydride, 130.43 g of methylcyclohexane, and dimethylacetamide were fed. 782.60g, the solution was heated to 100 °C. Then, 108.23 g of 1,3-bis(aminomethyl)cyclohexane was gradually added, and then heated to 130 ° C, and the oxime imidization reaction was carried out for 36 hours, and then dimethylacetamide was added to obtain a poly A solution of a quinone imine resin (non-volatile component is 30.0%). Further, the molar ratio of the acid component/amine component was 1.15. The number average molecular weight is about 9000.

[Manufacturing Example 3]

In a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen inlet tube, 455.00 g of diradyl phenyloxydiphthalic acid dianhydride, 130.43 g of methylcyclohexane, and dimethylacetamide were fed. 782.60g, the solution was heated to 100 °C. Then, after slowly adding 118.53g of 1,3-bis(aminomethyl)cyclohexane, it is heated to 130. °C, the hydrazine imidization reaction was carried out for 36 hours, and then dimethylacetamide was added to obtain a solution of a polyimine resin (non-volatile component was 30.0%). Further, the molar ratio of the acid component/amine component was 1.05. The number average molecular weight is about 12,000.

[Comparative Manufacturing Example 1]

In a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen inlet tube, 455.00 g of diradyl phenyloxydiphthalic acid dianhydride, 130.43 g of methylcyclohexane, and dimethylacetamide were fed. 782.60g, the solution was heated to 100 °C. Then, 118.53 g of 1,3-bis(aminomethyl)cyclohexane was gradually added, and then heated to 130 ° C, and the oxime imidization reaction was carried out for 36 hours, followed by the addition of dimethylacetamide to obtain a poly A solution of a quinone imine resin (non-volatile component is 30.0%). Further, the molar ratio of the acid component/amine component was 1.20. The number average molecular weight is about 6,000.

[Comparative Manufacturing Example 2]

In a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen inlet tube, 455.00 g of diradyl phenyloxydiphthalic acid dianhydride, 130.43 g of methylcyclohexane, and dimethylacetamide were fed. 782.60g, the solution was heated to 100 °C. Then, 118.53 g of 1,4-bis(aminomethyl)cyclohexane was gradually added, and then heated to 130 ° C to try to carry out oxime imidization, but the inside of the reaction vessel became cloudy and faint. Aggregation, unable to obtain a transparent liquid. Further, the molar ratio of the acid component/amine component was 1.05.

[Comparative Manufacturing Example 3]

Feeding 3,3',4,4'-benzophenone tetracarboxylic dianhydride (trade name "BTDA", Daicel Chemical Industry, Japan) in a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen inlet tube Manufactured by the company, hereinafter referred to as benzophenone tetracarboxylic dianhydride, 53.00 g, cyclohexanone 185.50 g, methylcyclohexane 37.10 g, and the solution was heated to 60 °C. Then, 85.40 g of a dimer diamine (trade name "PRIAMINE 1075", manufactured by Croda International Plc, hereinafter referred to as dimer diamine) was added dropwise, and then the oxime imidization reaction was carried out at 140 ° C for 1 hour. A solution of a polyamidene resin (nonvolatile component 38.0%) was obtained. Further, the molar ratio of the acid component/amine component was 1.04.

[Example 1]

6.00 g of a solution of the polyimine resin of the production example 1 was added as a polyamidene resin, and 0.45 g of a phenol novolac type epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name "YDPN638") was added. In the combined component, 1.04 g of toluene was added as an organic solvent, and the mixture was thoroughly stirred, whereby an adhesive composition of 30.0% of a nonvolatile component was obtained.

[Embodiment 2]

6.00 g of a solution of the polyimine resin of the production example 2 was added as a polyamidene resin, and 0.45 g of a phenol novolac type epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name "YDPN638") was added as a cross. In the combined component, 1.04 g of toluene was added as an organic solvent, and the mixture was thoroughly stirred, whereby an adhesive composition of 30.0% of a nonvolatile component was obtained.

[Example 3]

6.00 g of a solution of the polyimine resin of the production example 3 was added as a polyamidene resin, and 0.45 g of a phenol novolac type epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name "YDPN638") was added. In the combined component, 1.04 g of toluene was added as an organic solvent, and the mixture was thoroughly stirred, whereby an adhesive composition of 30.0% of a nonvolatile component was obtained.

[Example 4]

6.00 g of a solution of the polyimine resin of the production example 1 was added as a polyimine resin, and 0.20 g of a phenol novolac type epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name "YDPN638") was added as a cross. In the combined component, 0.47 g of toluene was added as an organic solvent, and the mixture was thoroughly stirred, whereby an adhesive composition of 30.0% of a nonvolatile component was obtained.

[Example 5]

6.00 g of a solution of the polyimine resin of the production example 1 was added as a polyimine resin, and 0.77 g of a phenol novolac type epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name "YDPN638") was added as a cross. In the combined component, 0.47 g of toluene was added as an organic solvent, and the mixture was thoroughly stirred, whereby an adhesive composition of 30.0% of a nonvolatile component was obtained.

[Embodiment 6]

6.00 g of a solution of the polyimine resin of the production example 1 was added as a polyimine resin, and 1.20 g of a phenol novolac type epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name "YDPN638") was added as a cross. As a component, 2.80 g of toluene was added as an organic solvent, and the mixture was sufficiently stirred to obtain an adhesive composition of 30.0% of a nonvolatile component.

[Embodiment 7]

6.00 g of a solution of the polyimine resin of the production example 1 was added as a polyimine resin, and 0.45 g of a polyfunctional epoxy resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TetradX") was added as a crosslinking component. 1.04 g of toluene was used as an organic solvent and stirred well, whereby an adhesive composition of 30.0% of a nonvolatile component was obtained.

[Embodiment 8]

6.00 g of a solution of the polyimine resin of the production example 1 was added as a polyimine resin, and 0.45 g of a polyfunctional epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "jER630") was added as a crosslinking component, and toluene was added. 1.04 g was used as an organic solvent and stirred well, whereby an adhesive composition of 30.0% of a nonvolatile component was obtained.

[Embodiment 9]

6.00 g of a solution of the polyimine resin of the production example 1 was added as a polyimine resin, and 0.20 g of a liquid bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "jER828") was added. 0.25 g of phenoxyphosphazene (manufactured by Otsuka Chemical Co., Ltd., trade name "SPH-100"), 0.002 g of imidazole (manufactured by Shikoku Chemicals Co., Ltd., trade name "C11Z-CN") as a crosslinking component , adding 0.50 g of toluene and 0.56 g of methyl ethyl ketone As an organic solvent, it was sufficiently stirred, whereby an adhesive composition of 30.0% of a nonvolatile component was obtained.

[Comparative Example 1]

6.00 g of a solution of the polyimine resin of Comparative Production Example 1 was added as a polyimine resin, and 0.45 g of a phenol novolac type epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name "YDPN638") was added as 0.45 g. As a crosslinking component, 1.04 g of toluene was added as an organic solvent, and the mixture was thoroughly stirred, whereby an adhesive composition of 30.0% of a nonvolatile component was obtained.

[Comparative Example 2]

6.00 g of a solution of the polyimine resin of Comparative Production Example 3 was added as a polyimine resin, and 0.57 g of a phenol novolac type epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name "YDPN638") was added. As a crosslinking component, 2.94 g of toluene was added as an organic solvent, and the mixture was thoroughly stirred, whereby an adhesive composition of 30.0% of a nonvolatile component was obtained.

[Comparative Example 3]

6.00 g of a solution of the polyimine resin of the production example 1 was added as a polyimine resin, and 1.80 g of a phenol novolac type epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name "YDPN638") was added as a cross. Combined component, adding toluene 4.20 g was sufficiently stirred as an organic solvent to obtain an adhesive composition of 30.0% of a nonvolatile component.

<Production of cured adhesive (for viscoelasticity measurement and dielectric constant measurement)>

The adhesive composition solution prepared in the examples and the comparative examples was applied to a PET film, dried at 80 ° C for 3 hours, peeled off from PET, fixed to a metal frame, and hardened at 180 ° C for 6 hours. An adhesive cured product having a film thickness of about 100 μm was obtained.

<Production of laminate 1 (sample for evaluation of adhesive composition)>

The adhesive composition of Example 1 was applied to a block copolymerized polyimide-ceria composite film by a gap coater so as to have a thickness of 10 μm after drying (product name " Pomiran N25", manufactured by Arakawa Chemical Industries Co., Ltd.; thermal expansion coefficient = 18 ppm, tensile modulus of elasticity = 5.9 GPa, film thickness of 25 μm), and then dried at 200 ° C for 3 minutes, thereby obtaining an adhesive sheet. The adhesive composition of the comparative example was also carried out in the same manner to obtain an adhesive sheet. Then, the treated surface of an 18 μm thick electrolytic copper foil (trade name "F2-WS", manufactured by Furukawa Circuit Foil Co., Ltd.) was laminated on the adhesive surface of the adhesive sheet at a pressure of 4.5 MPa, 200 ° C, and 30 The laminated body 1 was produced by heating and pressing in a minute condition. The adhesive composition of Comparative Example 1 was also carried out in the same manner to obtain a laminated body 1.

<Production of laminate 2 (sample for evaluation of primer composition)>

The adhesive composition of Example 1 was applied to a 18 μm-thick electrolytic copper foil mirror surface by a gap setting coater so as to have a thickness of 5 μm after drying, and then dried at 200 ° C for 3 minutes to obtain an attached film. Primed copper foil. Then, an 80 μm-thick epoxy prepreg (trade name "5100", manufactured by Teraoka Manufacturing Co., Ltd.) was laminated on the primer surface of the primer-attached copper foil at a pressure of 4.5 MPa, 200 ° C, and 30 minutes. The condition is heated and pressed, whereby the laminated body 2 is produced. The adhesive composition of Comparative Example 1 was also carried out in the same manner to obtain a laminated body 2.

<Adhesion test>

The peel strength was measured in accordance with JIS C-6481 for each of the laminates of the examples and the comparative examples. The results are shown in Table 1.

<Viscoelasticity test>

The viscoelasticity of the cured product of the examples and the comparative examples was measured using a dynamic viscoelasticity measuring apparatus (product name "EXTAR6000 DMS6100", manufactured by Seiko Instruments Inc.) (temperature rising rate was 5 ° C / min). The peak of the loss modulus tan δ (the ratio of the storage elastic modulus to the loss elastic modulus) was set to Tg, and it was confirmed. The results are shown in Table 2.

<Dielectric coefficient measurement test>

For the adhesive cured product, the relative permittivity and dielectric loss tangent were measured using a Vector Network Analyzer Wiltron 37169A (manufactured by Wiltron) at a measurement frequency of 10 GHz. The results are shown in Table 2.

<Solder heat resistance test>

The samples for evaluation of the adhesive composition of the examples and the comparative examples were respectively heated at 120 ° C for 5 minutes, and then the plastic substrate was faced upward, and floated in a solder bath at 300 ° C for 1 minute, and then the adhesion layer was confirmed. Peeling of the foam or metal substrate. The results are shown in Table 2.

<Painting test>

The adhesive composition of each of the examples and the comparative examples was applied to a block copolymerized polyimide-ceria composite film by a gap setting coater so as to have a thickness of 10 μm after drying (product name " Pomiran N25", manufactured by Arakawa Chemical Industries Co., Ltd.; thermal expansion coefficient = 18 ppm, tensile modulus of elasticity = 5.9 GPa, film thickness: 25 μm), and the state of the coating film was visually confirmed. When the coating film is flat and inelastic, it is set to ○, and if it is uneven, it is "elastic". The results are shown in Table 2.

[Table 2]

<Production of Flexible Printed Circuit Board>

The adhesive composition of the example was applied to Pomiran N25 with a gap setting coater so as to have a thickness of 30 μm after drying, and then dried at 200 ° C for 3 minutes to obtain an adhesive sheet. Then, the treated surface of the electrodeposited copper foil (F2-WS) was superposed on the adhesive surface of the adhesive sheet, and was pressure-bonded by a 200 ° C lamination roll, and then treated at 200 ° C for 2 hours. Flexible copper clad laminate. The copper surface of the copper clad laminate is subjected to a soft etching treatment to form a copper circuit, and the laminate 1 obtained by the above method (using the adhesive composition of the present invention in the embodiment) is further laminated on the copper circuit to be pressurized The film was heated and pressed at 10 MPa, 200 ° C, and 1 minute, and further heated at 200 ° C for 1 hour to prepare a flexible printed wiring board.

<Production of rigid printed circuit board>

The adhesive composition of the example was applied to the treated surface of the electrodeposited copper foil (F2-WS) by a gap setting coater so as to have a thickness of 5 μm after drying, and then dried at 200 ° C for 3 minutes. This results in a copper foil with a primer. Then, the epoxy prepreg (5100) is laminated on the primer surface of the primer-attached copper foil, and is heated and pressed at a pressure of 10 MPa, 200 ° C, and 30 minutes, thereby obtaining single-sided and double-sided. Copper clad laminate. The copper of the double-sided copper-clad laminate is etched to form a copper circuit to form an inner substrate. Using the prepreg described above, the inner layer substrate and the outer layer substrate are covered by one side The copper laminate is laminated. The outer layer is electrically connected to the inner layer by drilling and through-hole plating. Thereafter, the outer layer of copper is etched to form a copper circuit to form a multilayer printed wiring board.

Claims (5)

A polyimine resin composition having a polyimine resin and a crosslinking component, the polyimine resin having a repeating structure as shown in the general formula (1), In the general formula (1), n represents an integer of 1 to 100. An adhesive composition comprising the polyimine resin composition according to claim 1. A primer composition comprising the polyimine resin composition according to claim 1. A laminate comprising the adhesive composition of claim 2. A copper foil with a resin obtained by using the primer composition as claimed in claim 3.