Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
  • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
  • C09D123/30—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by oxidation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1515—Three-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/65—Additives macromolecular
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/08—Macromolecular additives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
  • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
  • C09J123/30—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by oxidation
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
  • H05K1/056—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an organic insulating layer

Definitions

• the present invention relates to a coating agent, a coating film, and a laminate.
• Patent Document 1 discloses a water-based adhesive that has excellent adhesion between a liquid crystal resin base material and a thermoplastic resin base material (Patent Document 1).
• the present invention is capable of forming and obtaining a coating film that has excellent adhesion between a base material made of liquid crystal resin or polyimide resin and metal foil, and has excellent dielectric properties.
• the technical object is to provide a coating agent that can suppress the transmission loss of a laminate to a low level.
• the present inventors have found that a coating agent containing a specific acid-modified polyolefin resin and a specific epoxy compound in a specific ratio, and further containing an aqueous medium has been developed as described above.
• a solution to the problem and have arrived at the present invention is as follows.
• the coating agent of the present invention contains an acid-modified polyolefin resin (A), an epoxy compound (B), and an aqueous medium
• the acid-modified polyolefin resin (A) contains 0.1 to 10% by mass of an unsaturated carboxylic acid component
• the epoxy compound (B) is characterized by having an epoxy equivalent of 500 or less and a content of 0.2 parts by mass or more and less than 5 parts by mass based on 100 parts by mass of the acid-modified polyolefin resin (A).
• the epoxy resin (B) preferably contains an epoxy compound having three or more epoxy groups in one molecule.
• the epoxy resin (B) is preferably one or more selected from sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, and glycerol polyglycidyl ether.
• the acid-modified polyolefin resin (A) preferably contains 3 to 25% by mass of a (meth)acrylic acid ester component.
• the coating agent of the present invention in a laminate obtained by heat-sealing a base material made of a liquid crystal resin or a polyimide resin, a coating film obtained from the coating agent, and a copper foil, it is preferable that the adhesive strength is 0.8 kN/m or more when the base material and the copper foil are peeled in a 90° direction at a tensile speed of 50 mm/min.
• the coating film of the present invention is obtained from the above-mentioned coating agent. According to the coating film of the present invention, it is preferable that the dielectric constant measured at a frequency of 10 GHz is 3.0 or less, and the dielectric loss tangent is 0.01 or less.
• the laminate of the present invention has a base material made of a liquid crystal resin or a polyimide resin, the above coating film, and a metal foil laminated in this order.
• the printed wiring board of the present invention includes the above-mentioned laminate.
• the coating film obtained from the coating agent of the present invention has excellent adhesion between the base material made of liquid crystal resin or polyimide resin and metal foil, has excellent heat resistance against repeated soldering, and has excellent dielectric properties. Therefore, transmission loss can be kept low in the laminate. Therefore, the coating agent of the present invention can be applied to the lamination of printed wiring boards compatible with high frequencies, which could not be applied conventionally. Furthermore, it is a coating agent with excellent versatility for substrates, as it can be applied to bond metal foils to commonly sold polyester resin substrates.
• the coating agent of the present invention contains an acid-modified polyolefin resin (A), an epoxy compound (B), and an aqueous medium.
• the acid-modified polyolefin resin (A) is preferably dispersed in an aqueous medium.
• the acid-modified polyolefin resin (A) is a copolymer containing an unsaturated carboxylic acid component and an olefin component as copolymerization components.
• the coating agent of the present invention improves coating properties on a substrate and film-forming properties by containing an acid-modified polyolefin resin (A) in which the polyolefin resin is acid-modified with an unsaturated carboxylic acid component.
• the unsaturated carboxylic acid component is composed of unsaturated carboxylic acids and their anhydrides.
• the unsaturated carboxylic acid components include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride.
• acids such as fumaric acid and crotonic acid
• examples include half esters and half amides of unsaturated dicarboxylic acids.
• acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferred, and acrylic acid and maleic anhydride are particularly preferred.
• the content of the unsaturated carboxylic acid component in the acid-modified polyolefin resin (A) is 0.1 to 10% by mass, preferably 0.2 to 8% by mass, and 0.5 to 6% by mass. It is more preferable. If the content of the unsaturated carboxylic acid component is less than 0.1% by mass, the acid-modified polyolefin resin (A) cannot be stably dispersed in an aqueous medium, and if it exceeds 10% by mass, the coating formed The film has poor adhesion and dielectric properties, and furthermore, the resulting laminate has high transmission loss.
• Examples of the olefin component constituting the acid-modified polyolefin resin (A) include alkenes having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 1-butene, 1-pentene, and 1-hexene, and mixtures thereof. You can also use Among these, alkenes having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene, and 1-butene are preferred, and ethylene is more preferred.
• the content of the olefin component in the acid-modified polyolefin resin (A) is preferably 60% by mass or more, more preferably 80% by mass or more, from the viewpoint of the dielectric properties of the resulting coating film.
• the acid-modified polyolefin resin (A) preferably contains a (meth)acrylic ester component in order to improve the adhesion between the base material made of liquid crystal resin or polyimide resin and the metal foil.
• the content of the (meth)acrylic acid ester component in the acid-modified polyolefin resin (A) is preferably 3 to 25% by mass, more preferably 4 to 22% by mass, and 5 to 20% by mass. It is even more preferable that the amount is 6 to 18% by mass.
• Examples of (meth)acrylic acid ester components include esterified products of (meth)acrylic acid and alcohols having 1 to 30 carbon atoms. -20 esters with alcohols are preferred. Specific examples of such compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, and (meth)acrylate. Examples include octyl, decyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate. Mixtures of these may also be used.
• (meth)acrylic acid means "acrylic acid or methacrylic acid”.
• the acid-modified polyolefin resin (A) may contain other components other than the above-mentioned components in an amount of about 10% by mass or less of the acid-modified polyolefin resin (A).
• Other components include alkenes and dienes having more than 6 carbon atoms such as 1-octene and norbornenes, maleic acid esters such as dimethyl maleate, diethyl maleate, and dibutyl maleate, and (meth)acrylic acid amides.
• alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether
• vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, and vinyl versatate
• vinyl esters obtained by saponifying them with a basic compound etc.
• Examples include vinyl alcohol, 2-hydroxyethyl acrylate, glycidyl (meth)acrylate, (meth)acrylonitrile, styrene, substituted styrene, carbon monoxide, sulfur dioxide, and mixtures thereof can also be used.
• the acid-modified polyolefin resin (A) may contain an N-substituted amide structure in which the hydroxyl group of the carboxyl group is substituted with an N,N-dimethylamino group, an N,N-diethylamino group, or the like.
• the melting point of the polyolefin resin is preferably 50 to 150°C, more preferably 60 to 130°C, even more preferably 70 to 110°C. If the melting point is less than the above range, the cohesive force may be weak and the adhesiveness may be poor. Moreover, when the above range is exceeded, the fluidity decreases, so that the adhesion between the base material made of liquid crystal resin or polyimide resin and the metal foil may decrease.
• Examples of the acid-modified polyolefin resin (A) include ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid-maleic anhydride copolymer, acid-modified polyethylene, acid-modified polypropylene, and acid-modified ethylene- Propylene resin, acid-modified ethylene-butene resin, acid-modified propylene-butene resin, acid-modified ethylene-propylene-butene resin, or ethylene-(meth) which is further acrylic-modified with (meth)acrylic acid ester etc. to these acid-modified resins.
• Examples include acrylic ester-unsaturated carboxylic acid copolymers. Among these, ethylene-(meth)acrylic acid-maleic anhydride copolymer is preferred.
• the acid-modified polyolefin resin may be chlorinated in a range of 5 to 40% by mass.
• the acid-modified polyolefin resin (A) As the acid-modified polyolefin resin (A), the Bondine series manufactured by Arkema, the Bestplast series manufactured by Evonik Japan, the Primacol series manufactured by Dow Chemical, the Umex series manufactured by Sanyo Chemical, and the Admer manufactured by Mitsui Chemicals.
• Commercially available products such as Toyobo series and Toyo Tack series can be used.
• commercially available water-based products can be used, including the Super Chron series manufactured by Nippon Paper Chemicals, the Zaixen series manufactured by Sumitomo Seika, the Chemipearl series manufactured by Mitsui Chemicals, and the Hardren series manufactured by Toyobo. etc. can be used.
• the coating agent of the present invention contains an epoxy compound (B) for the purpose of improving adhesiveness and heat resistance.
• the epoxy compound (B) preferably has two or more epoxy groups in its molecule, and more preferably contains three or more epoxy groups.
• the epoxy compound (B) include bisphenol A epoxy resin, bisphenol F epoxy resin, novolak epoxy resin, alicyclic epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, and ethylene glycol.
• diglycidyl ether propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, glycerol poly Examples include glycidyl ether, polyglycerol polyglycidyl ether, etc., and it is preferably one or more selected from sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, and glycerol polyglycidyl ether because high adhesiveness can be obtained. .
• the epoxy equivalent (g/eq.) of the epoxy compound (B) is 500 or less, preferably 400 or less, more preferably 300 or less, even more preferably 200 or less, and particularly preferably 150 or less. If the epoxy equivalent of the epoxy compound (B) exceeds 500, the resulting coating film will have poor adhesion between the base material made of liquid crystal resin or polyimide resin and the metal foil, as well as dielectric properties, and the resulting laminate will have poor dielectric properties. transmission loss increases.
• the lower limit of the epoxy equivalent is not particularly limited, but is, for example, 80.
• the content of the epoxy compound (B) is 0.2 parts by mass or more and less than 5 parts by mass, preferably 0.5 to 4.5 parts by mass, based on 100 parts by mass of the acid-modified polyolefin resin. More preferably, it is 1.0 to 4.0 parts by mass.
• the content of the epoxy compound (B) in the coating agent is less than 0.2 parts by mass, the adhesion between the base material made of liquid crystal resin or polyimide resin and the metal foil, the heat resistance, and the durability of the heat resistance will deteriorate. If the amount is 5 parts by mass or more, the adhesion between the base material and the metal foil will decrease, the dielectric properties of the resulting coating will decrease, and furthermore, the resulting laminate will have low transmission loss. growing.
• the aqueous medium constituting the coating agent of the present invention is water or a liquid containing water as a main component. It is preferable from an environmental point of view to use an aqueous medium.
• the aqueous medium may contain a basic compound or a hydrophilic organic solvent. When the aqueous medium contains a hydrophilic organic solvent, the coating agent exhibits the effects of improved wettability to the substrate and improved coating properties and film-forming properties.
• the content of the hydrophilic organic solvent is preferably 1 to 50% by mass, more preferably 3 to 30% by mass based on the total amount of the coating agent, in order to impart appropriate wettability to the substrate. It is preferably 5 to 25% by mass, and more preferably 5 to 25% by mass.
• hydrophilic organic solvent examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, and tert-amyl alcohol.
• Alcohol such as 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone, tetrahydrofuran, dioxane, etc.
• Ethers ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, diethyl carbonate, dimethyl carbonate esters such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, glycol derivatives such as ethylene glycol ethyl ether acetate, and furthermore, 1-methoxy-2-propanol, 1- Ethoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate, 1,2-dimethylglycer
• Examples of basic compounds include ammonia, triethylamine, N,N-dimethylethanolamine, isopropylamine, aminoethanol, dimethylaminoethanol, diethylaminoethanol, ethylamine, diethylamine, isobutylamine, dipropylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, n-butylamine, 2-methoxyethylamine, 3-methoxypropylamine, 2,2-dimethoxyethylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine , pyrrole, or pyridine.
• the coating agent of the present invention may contain additives other than the epoxy compound (B), such as a crosslinking agent and a curing accelerator, in order to further improve performance depending on the purpose.
• the crosslinking agent is not particularly limited, and includes, for example, a crosslinking agent having self-crosslinking properties, a compound having a plurality of functional groups in the molecule that reacts with a carboxyl group, a metal having a polyvalent coordination site, and the like. Specifically, isocyanate compounds, melamine compounds, urea compounds, carbodiimide compounds, oxazoline group-containing compounds, zirconium salt compounds, silane coupling agents, etc. are preferred. Further, a plurality of these crosslinking agents may be used simultaneously.
• the content of the crosslinking agent is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and 0.5 parts by mass based on 100 parts by mass of the acid-modified polyolefin resin (A). More preferably, the amount is 10 parts by mass. If the content of the crosslinking agent is less than 0.01 parts by mass, the coating film formed tends to have no improvement in performance, and if it exceeds 30 parts by mass, the coating film formed will Dielectric properties may deteriorate.
• the coating agent of the present invention may contain a curing accelerator.
• the curing accelerator is not particularly limited, and examples thereof include tertiary amine curing agents, tertiary amine salt curing agents, imidazole curing agents, phosphate curing accelerators, and the like.
• the content of the curing accelerator is preferably 1 to 100 parts by weight, more preferably 3 to 70 parts by weight, based on 100 parts by weight of the epoxy compound (B).
• the coating agent of the present invention further contains various additives such as a surfactant, a leveling agent, an antifoaming agent, an anti-wrinkle agent, a pigment dispersant, an ultraviolet absorber, a weathering agent, and a flame retardant, as necessary. It's okay.
• the coating agent of the present invention preferably does not substantially contain a nonvolatile aqueous forming aid.
• a nonvolatile aqueous forming aid is a chemical or compound that is added for the purpose of promoting aqueous dispersion or stabilizing an aqueous dispersion. It means that there is no boiling point or that it has a high boiling point (for example, 300°C or higher) at normal pressure.
• substantially free of non-volatile aqueous dispersion aids means that such aids are not used during production (during aqueous dispersion of acid-modified polyolefin resin (A)), and the resulting aqueous dispersion is This means that it does not contain this auxiliary agent.
• the amount of the non-volatile aqueous forming aid is preferably 5% by mass or less, more preferably 2% by mass or less, even more preferably less than 0.5% by mass, and 0% by mass based on the acid-modified polyolefin resin (A). % is particularly preferred.
• nonvolatile aqueous dispersion aids include emulsifiers, compounds with protective colloid action, modified waxes, acid-modified compounds with high acid values, and water-soluble polymers.
• the coating agent of the present invention contains an acid-modified polyolefin resin (A), an epoxy compound (B), and an aqueous medium, and the acid-modified polyolefin resin (A) containing a carboxyl group contains an aqueous medium. It is preferable that it is dispersed in
• the content of non-volatile components in the coating agent of the present invention can be appropriately selected depending on the coating conditions, the desired thickness and performance of the coating film, etc., and is not particularly limited. In terms of expressing properties, the content is preferably 1 to 60% by mass, more preferably 3 to 55% by mass, even more preferably 5 to 50% by mass, and even more preferably 10 to 45% by mass. is particularly preferred.
• the viscosity of the coating agent of the present invention is preferably from 1 to 2000 mPa ⁇ s, more preferably from 3 to 1000 mPa ⁇ s, and from 5 to 500 mPa ⁇ s from the viewpoint of coatability to the substrate. It is even more preferable.
• the method for producing the coating agent of the present invention is not particularly limited, and includes a method of mixing the above-mentioned raw materials, and the order of mixing them is arbitrary.
• the acid-modified polyolefin resin (A) may be mixed in the form of an aqueous dispersion dispersed in an aqueous medium.
• the coating agent of the present invention can be applied to a base material such as a film or a nonwoven fabric using a known coating method to form a coating film of the present invention.
• the coating is applied uniformly to the surface of the substrate by gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating, etc., and then dried.
• a uniform coating film can be formed in close contact with the surface of the substrate.
• an ordinary hot air circulation type oven, an infrared heater, or the like may be used. Further, the heating temperature and heating time are appropriately selected in consideration of economical efficiency and the like.
• the coating film of the present invention preferably has a thickness of 1 to 30 ⁇ m, more preferably 2 to 20 ⁇ m, and even more preferably 3 to 15 ⁇ m. By setting the thickness within the above range, the formed coating film has high adhesiveness.
• a coating agent with a concentration suitable for the desired thickness.
• concentration of the coating agent can be adjusted by changing the charge composition at the time of preparation, and may also be adjusted by suitably diluting or concentrating the coating agent once prepared.
• the coating film of the present invention has excellent dielectric properties, and preferably has a dielectric constant of 3.0 or less when measured at a frequency of 10 GHz, a dielectric loss tangent of 0.01 or less, and a dielectric constant of 2.0 or less. It is more preferable that the dielectric constant is 8 or less and the dielectric loss tangent is 0.008 or less, and it is even more preferable that the dielectric constant is 2.6 or less and the dielectric loss tangent is 0.006 or less.
• the laminate of the present invention includes the coating film of the present invention, and includes, for example, a laminate containing the coating film of the present invention on the surface of various substrates, adhesive layers, or primer layers.
• the coating agent of the present invention has excellent adhesion between the base material made of liquid crystal resin or polyimide resin and the metal foil. It is preferable that the coating film formed from the agent and the metal foil be contained in this order.
• the liquid crystal resin that makes up the base material is a polymer whose molecular chains are almost regularly arranged (liquid crystallinity) when the resin becomes fluid by melting at high temperatures or dissolving in a solvent. refers to For example, it is known that some resins such as wholly aromatic polyester, aromatic polyazomethine, aromatic aliphatic polyester, aromatic polyester carbonate, wholly aromatic or non-wholly aromatic polyesteramide, etc. exhibit liquid crystallinity. ing.
• polyesters known as liquid crystal resins include those obtained by linear polycondensation of parahydroxybenzoic acid and other components. Specifically, polyesters produced by polycondensing ethylene terephthalate and para-hydroxybenzoic acid, polyesters produced by polycondensing phenol and phthalic acid with para-hydroxybenzoic acid, and polyesters produced by polycondensing 2,6-hydroxynaphthoic acid and para-hydroxybenzoic acid. Examples include condensed polyester.
• liquid crystal resins are available. Examples include the Vectra series “A950, E951SX” manufactured by Polyplastics, the Sumika Super series “E5204L, E6807LHF” manufactured by Sumitomo Chemical, and the Rod Run series “LC5030G, LC5030MF” manufactured by Unitika. These may be ones in which the elasticity and strength are improved by mixing fillers, or may be ones in which the elastic modulus is improved by converting them into ester amides. Commercial products are also available for substrates made of liquid crystal resins, such as the Vector series manufactured by Kuraray Co., Ltd., and the like.
• Examples of the base material made of polyimide resin include those in the form of a film.
• a polyamic acid (polyimide precursor) solution obtained by reacting diamines and tetracarboxylic acids is applied to a substrate for producing a polyimide film, dried to form a precursor film, and then peeled off from the substrate or as it is.
• Examples include polyimide films obtained by performing a dehydration ring-closing reaction through high-temperature heat treatment.
• the diamine components constituting the polyimide resin include p-phenylenediamine (PDA), 4,4'-diaminodiphenyl ether (ODA), 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl (PFMB), 2,2'-dimethyl- 4,4'-diaminodiphenyl (DMDB), 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylmethane, 3,4' -Diamino diphenyl ether, 3,3'-di
• tetracarboxylic acid component constituting the polyimide resin examples include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic dianhydride (ODPA), 3,3' , 4,4'-diphenylsulfonetetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA), 2,2-bis[4-(3,4-dicarboxylic acid)
• polyimide resin base material commercially available polyimide films may be used, such as "Kapton” (trade name manufactured by DuPont-Toray), "Upilex” (trade name manufactured by Ube Industries, Ltd.), etc. Can be done. It is also possible to use a substrate coated with a modified polyimide (MPI) film or a modified polyimide (MPI) varnish.
• MPI modified polyimide
• MPI modified polyimide
• These polyimide films may be subjected to chemical or physical surface treatment.
• chemical surface treatments include surface treatments using silane coupling agents, aluminum alcoholates, and the like.
• physical surface treatments include surface roughening treatment, plasma treatment, and the like.
• the coating agent of the present invention has excellent adhesion even to substrates that are not subjected to surface treatment.
• the coating agent of the present invention also has excellent adhesion between other general-purpose resin base materials and metal foil.
• general-purpose resin base materials include polyester resin base materials, polycarbonate resin base materials, polyphenylene sulfide resin base materials, cycloolefin resin base materials, polyethylene resin base materials, polypropylene resin base materials, semi-aromatic polyamide resin base materials, etc. .
• metal foil examples include, but are not limited to, those made of copper, nickel, aluminum, etc.
• the laminate of the present invention can be used for, for example, bonding sheets, resin-coated copper foils, coverlay films, printed wiring boards, copper-clad laminates, flat cables, circuit boards for tape automated bonding, electromagnetic shielding materials, etc. .
• Adhesive strength After coating each coating agent on the liquid crystal resin base material, polyimide resin base material, or polyester resin base material using a bar coater so that the dried coating film thickness is 10 ⁇ m, drying with hot air. It was dried at 100° C. for 1 minute using a machine. Thereafter, copper foil was bonded to the coated surface, and heat sealing was performed at a temperature of 200° C. and a pressure of 0.2 MPa for 60 seconds. Thereafter, the bonded laminate was cut into a 10 mm width, and the base material and the copper foil were peeled off in a 90 degree direction at a pulling speed of 50 mm/min in an atmosphere of 23°C. Adhesion was evaluated based on the following criteria.
• the dielectric loss tangent was evaluated based on the following criteria. ⁇ : 0.0060 or less ⁇ : More than 0.0060, 0.0080 or less ⁇ : More than 0.0080, 0.0100 or less ⁇ : More than 0.0100
• Transmission loss (S21) A coating agent was applied to both sides of the liquid crystal resin base material using a bar coater so that the coating film thickness after drying was 10 ⁇ m, and then dried at 100° C. for 1 minute using a hot air dryer. Thereafter, both coated surfaces and copper foil were bonded together, and heat sealing was performed under vacuum at a temperature of 200° C. and a pressure of 3.0 MPa for 30 minutes. Thereafter, a microstrip line was formed using the bonded laminate to have a characteristic impedance of 50 ⁇ , and transmission loss was measured between 10 MHz and 40 GHz (using Keysight Technologies' network analyzer E5227B). Transmission loss was evaluated using the following criteria. ⁇ : Absolute value of transmission loss at 30 GHz is less than 5.0 dB/100 mm ⁇ : Absolute value of transmission loss at 30 GHz is 5.0 dB/100 mm or more
• solder heat resistance (heat resistance) A laminate using a liquid crystal resin base material as a base material was prepared by the method described in "1. Adhesive strength" above, and a sample piece of 2.5 cm x 2.5 cm was dried at 120 ° C. for 30 minutes. The solder was flowed into a solder bath melted at 260° C. for 1 minute, and the solder heat resistance was visually evaluated according to the following criteria. ⁇ : No bulge ⁇ : Slight bulge ⁇ : Large bulge
• E-2 Production of aqueous dispersion (E-2) of acid-modified polyolefin resin (A-2) Acid-modified polyolefin resin (A-2) [ethylene-ethyl acrylate-maleic anhydride copolymer, ethylene 80 mass %, ethyl acrylate 18% by mass, maleic anhydride 2% by mass, melting point 83°C]. Other than that, an aqueous dispersion (E-2) was obtained in the same manner as in the case of the aqueous dispersion (E-1).
• A-3 acid-modified polyolefin resin
• This resin was further washed several times with acetone to remove unreacted maleic anhydride, and then dried under reduced pressure in a vacuum dryer to obtain acid-modified polyolefin resin (A-3) [mass ratio: propylene 75.4/ Ethylene 16.8/maleic anhydride 7.8, melting point 70°C] was obtained.
• A-3 acid-modified polyolefin resin
• a milky white aqueous dispersion (E-3) of acid-modified polyolefin resin (A-3) was obtained in the same manner as described in Japanese Patent Application No. 2005-506371.
• E-4 Production of aqueous dispersion (E-4) of acid-modified polyolefin resin (A-4) Acid-modified polyolefin resin (A-4) [ethylene-acrylic acid copolymer, 80% by mass of ethylene, 20% by mass of acrylic acid % by mass, melting point 79°C]. Other than that, an aqueous dispersion (E-4) was obtained in the same manner as in the case of the aqueous dispersion (E-1).
• Epoxy compound (B) B-1 Sorbitol polyglycidyl ether (manufactured by Nagase ChemteX, Denacol EX-614, tetrafunctional epoxy compound (having 4 epoxy groups), epoxy equivalent 167)
• Base material Aromatic polyester liquid crystal resin obtained from hydroxynaphthoic acid, etc. and para-hydroxybenzoic acid
• Base material Manufactured by Kuraray Co., Ltd., Vector CTQ-50, thickness 50 ⁇ m
• Polyimide resin base material Manufactured by Ube Industries, Upilex-S, thickness 50 ⁇ m
• Polyester resin base material Manufactured by Unitika, Emblet S-50, thickness 50 ⁇ m
• Example 1 Aqueous dispersion (E-1) of acid-modified polyolefin resin (A-1) and epoxy compound (B-1) are mixed so that the solid content mass ratio is 100/1, and for 100 parts by mass of the mixed liquid.
• a coating agent was prepared by adding 20 parts by mass of isopropanol.
• Table 1 shows the compositions and evaluation results of various properties of the coating agents produced in Examples and Comparative Examples.
• the coating agents of Examples 1 to 9 had excellent adhesion between the liquid crystal resin base material, the polyimide resin base material, and the copper foil.
• the obtained coating film has excellent dielectric properties with low relative dielectric constant and dielectric loss tangent values, and the obtained laminate has low transmission loss and high heat resistance (soldering heat resistance). It was also excellent.
• the coating agent also had excellent adhesiveness between the polyester resin base material and the copper foil.
• the coating agent of Comparative Example 1 had poor adhesion and heat resistance because the content of the epoxy compound was less than the range defined by the present invention.
• the content of the epoxy compound exceeded the range specified by the present invention, the coating film had poor dielectric properties, and the laminate had large transmission loss.
• the coating agent of Comparative Example 3 used an epoxy compound with an epoxy equivalent of more than 500, and therefore had poor adhesiveness. Furthermore, the obtained laminate had a large transmission loss.
• the content of the unsaturated carboxylic acid component in the acid-modified polyolefin resin exceeded the range specified in the present invention, so high adhesion could not be obtained, and the coating film had poor dielectric properties.
• the laminate also had a large transmission loss.

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