WO2024048444A1 - Coating agent, coating film, and laminate - Google Patents

Coating agent, coating film, and laminate Download PDF

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Publication number
WO2024048444A1
WO2024048444A1 PCT/JP2023/030701 JP2023030701W WO2024048444A1 WO 2024048444 A1 WO2024048444 A1 WO 2024048444A1 JP 2023030701 W JP2023030701 W JP 2023030701W WO 2024048444 A1 WO2024048444 A1 WO 2024048444A1
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WIPO (PCT)
Prior art keywords
acid
mass
coating agent
resin
coating
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Application number
PCT/JP2023/030701
Other languages
French (fr)
Japanese (ja)
Inventor
和史 山本
晴樹 大藤
宗紀 山田
剛正 吉野
雄一郎 伏井
Original Assignee
ユニチカ株式会社
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Publication of WO2024048444A1 publication Critical patent/WO2024048444A1/en

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Classifications

    • 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
    • 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
    • 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
    • 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

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.

Abstract

A coating agent which comprises an acid-modified polyolefin resin (A), an epoxy compound (B), and an aqueous medium, and is characterized in that the acid-modified polyolefin resin (A) contains 0.1-10 mass% unsaturated carboxylic acid component and the epoxy compound (B) has an epoxy equivalent of 500 or less and is contained in an amount of 0.2-5 parts by mass, excluding 5 parts by mass, per 100 parts by mass of the acid-modified polyolefin resin (A).

Description

塗工剤、塗膜および積層体Coating agents, coatings and laminates
　本発明は、塗工剤、塗膜および積層体に関する。 The present invention relates to a coating agent, a coating film, and a laminate.
　近年、プリント配線板においては、伝送信号の高速化が進んでおり、高周波領域で優れた誘電特性（低誘電率、低誘電正接）を有する材料が要求されている。このような要求に対して、プリント配線板を構成する基材の樹脂として、ポリイミド樹脂や誘電特性に優れた液晶樹脂（ＬＣＰ）が提案されている。 In recent years, the speed of transmission signals has been increasing in printed wiring boards, and materials with excellent dielectric properties (low dielectric constant, low dielectric loss tangent) in the high frequency region are required. In response to such demands, polyimide resins and liquid crystal resins (LCP) with excellent dielectric properties have been proposed as base resins constituting printed wiring boards.
　特許文献１には、液晶樹脂基材と熱可塑性樹脂基材との接着に優れる水性接着剤が開示されている（特許文献１）。 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).
特開２００９－２３５２９０号公報JP2009-235290A
　特許文献１に開示された水性接着剤を使用して基材と銅箔とを接着して得られる積層体においては、接着性や繰り返しハンダ耐熱性がさらに向上するとともに、接着剤層の誘電特性が向上して、伝送損失が抑制されることが求められている。 In the laminate obtained by bonding a base material and copper foil using the water-based adhesive disclosed in Patent Document 1, the adhesiveness and repeated soldering heat resistance are further improved, and the dielectric properties of the adhesive layer are improved. There is a need for improvement in transmission loss and suppression of transmission loss.
　本発明は、上記のような従来技術の問題に鑑みて、液晶樹脂やポリイミド樹脂からなる基材と金属箔との接着性に優れ、誘電特性に優れる塗膜を形成することができ、得られる積層体の伝送損失を低く抑制することができる塗工剤を提供することを技術的課題とするものである。 In view of the problems of the prior art as described above, 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.
　本発明者らは、上記課題を解決するために鋭意検討した結果、特定の酸変性ポリオレフィン樹脂と、特定のエポキシ化合物とを特定割合で含有し、さらに水性媒体を含有する塗工剤が、上記課題を解決することを見出し、本発明に到達した。
　すなわち、本発明の要旨は、下記の通りである。 As a result of intensive studies to solve the above problems, 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. We have found a solution to the problem and have arrived at the present invention.
That is, the gist of the present invention is as follows.
　本発明の塗工剤は、酸変性ポリオレフィン樹脂（Ａ）と、エポキシ化合物（Ｂ）と、水性媒体とを含有し、
酸変性ポリオレフィン樹脂（Ａ）が、不飽和カルボン酸成分を０．１～１０質量％含有し、
エポキシ化合物（Ｂ）は、エポキシ当量が５００以下であり、含有量が酸変性ポリオレフィン樹脂（Ａ）１００質量部に対して０．２質量部以上、５質量部未満であることを特徴とする。
　本発明の塗工剤によれば、エポキシ樹脂（Ｂ）が、１分子中にエポキシ基を３個以上有するエポキシ化合物を含むことが好ましい。
　本発明の塗工剤によれば、エポキシ樹脂（Ｂ）が、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテルおよびグリセロールポリグリシジルエーテルから選択される１種以上であることが好ましい。
　本発明の塗工剤によれば、酸変性ポリオレフィン樹脂（Ａ）が、（メタ）アクリル酸エステル成分を３～２５質量％含有することが好ましい。
　本発明の塗工剤によれば、液晶樹脂またはポリイミド樹脂からなる基材と、塗工剤から得られる塗膜と、銅箔とを貼り合わせてヒートシール加工を行って得られる積層体において、基材と銅箔とを引張速度５０ｍｍ/分で９０°の方向に剥離した際の接着強度が、０．８ｋＮ／ｍ以上であることが好ましい。
　本発明の塗膜は、上記の塗工剤から得られるものである。
　本発明の塗膜によれば、周波数１０ＧＨｚで測定した比誘電率が３．０以下であり、誘電正接が０．０１以下であることが好ましい。
　本発明の積層体は、液晶樹脂またはポリイミド樹脂からなる基材と、上記の塗膜と、金属箔とがこの順に積層されたものである。
　本発明のプリント配線板は、上記の積層体を含むものである。 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).
According to the coating agent of the present invention, the epoxy resin (B) preferably contains an epoxy compound having three or more epoxy groups in one molecule.
According to the coating agent of the present invention, the epoxy resin (B) is preferably one or more selected from sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, and glycerol polyglycidyl ether.
According to the coating agent of the present invention, the acid-modified polyolefin resin (A) preferably contains 3 to 25% by mass of a (meth)acrylic acid ester component.
According to 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.
　本発明の塗工剤から得られる塗膜は、液晶樹脂やポリイミド樹脂からなる基材と金属箔との接着性に優れ、さらには、繰り返しのハンダ処理に対する耐熱性に優れ、また誘電特性に優れていることから、積層体においては、伝送損失を低く抑えることができる。そのため、本発明の塗工剤は、従来では適用できなかった高周波対応のプリント配線板の積層に適用できる。さらに一般的に販売されているポリエステル樹脂基材などと金属箔との接着にも適用できるため、基材汎用性にも優れる塗工剤である。 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.
　以下、本発明を詳細に説明する。
　本発明の塗工剤は、酸変性ポリオレフィン樹脂（Ａ）と、エポキシ化合物（Ｂ）と、水性媒体とを含有する。本発明の塗工剤において、酸変性ポリオレフィン樹脂（Ａ）は、水性媒体中に分散されていることが好ましい。 The present invention will be explained in detail below.
The coating agent of the present invention contains an acid-modified polyolefin resin (A), an epoxy compound (B), and an aqueous medium. In the coating agent of the present invention, the acid-modified polyolefin resin (A) is preferably dispersed in an aqueous medium.
＜酸変性ポリオレフィン樹脂（Ａ）＞
　酸変性ポリオレフィン樹脂（Ａ）は、不飽和カルボン酸成分とオレフィン成分とを共重合成分として含有する共重合体である。本発明の塗工剤は、ポリオレフィン樹脂が不飽和カルボン酸成分で酸変性されている酸変性ポリオレフィン樹脂（Ａ）を含有することにより基材への塗工性、造膜性が向上する。 <Acid-modified polyolefin resin (A)>
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.
　不飽和カルボン酸成分は、不飽和カルボン酸やその無水物で構成され、不飽和カルボン酸成分としては、具体的には、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸、フマル酸、クロトン酸等のほか、不飽和ジカルボン酸のハーフエステル、ハーフアミド等が挙げられる。中でもアクリル酸、メタクリル酸、マレイン酸、無水マレイン酸が好ましく、特にアクリル酸、無水マレイン酸が好ましい。 The unsaturated carboxylic acid component is composed of unsaturated carboxylic acids and their anhydrides. Specifically, the unsaturated carboxylic acid components include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride. In addition to acids such as fumaric acid and crotonic acid, examples include half esters and half amides of unsaturated dicarboxylic acids. Among them, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferred, and acrylic acid and maleic anhydride are particularly preferred.
　酸変性ポリオレフィン樹脂（Ａ）における不飽和カルボン酸成分の含有量は、０．１～１０質量％であり、０．２～８質量％であることが好ましく、０．５～６質量％であることがより好ましい。酸変性ポリオレフィン樹脂（Ａ）は、不飽和カルボン酸成分の含有量が０．１質量％未満であると、水性媒体中に安定して分散できず、１０質量％を超えると、形成される塗膜は、接着性や誘電特性に劣り、さらに、得られる積層体は、伝送損失が大きくなる。 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.
　酸変性ポリオレフィン樹脂（Ａ）を構成するオレフィン成分としては、例えば、エチレン、プロピレン、イソブチレン、１－ブテン、１－ペンテン、１－ヘキセン等の炭素数２～６のアルケンが挙げられ、これらの混合物を用いることもできる。中でも、エチレン、プロピレン、イソブチレン、１－ブテン等の炭素数２～４のアルケンが好ましく、エチレンがより好ましい。 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.
　酸変性ポリオレフィン樹脂（Ａ）におけるオレフィン成分の含有量は、得られる塗膜の誘電特性の観点から、６０質量％以上であることが好ましく、８０質量％以上であることがより好ましい。 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.
　酸変性ポリオレフィン樹脂（Ａ）は、液晶樹脂やポリイミド樹脂からなる基材と、金属箔との接着性を向上させる理由から、（メタ）アクリル酸エステル成分を含有することが好ましい。酸変性ポリオレフィン樹脂（Ａ）における（メタ）アクリル酸エステル成分の含有量は、３～２５質量％であることが好ましく、４～２２質量％であることがより好ましく、５～２０質量％であることがさらに好ましく、６～１８質量％であることが特に好ましい。 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.
　（メタ）アクリル酸エステル成分としては、（メタ）アクリル酸と炭素数１～３０のアルコールとのエステル化物が挙げられ、中でも入手のし易さの点から、（メタ）アクリル酸と炭素数１～２０のアルコールとのエステル化物が好ましい。そのような化合物の具体例としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸デシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸ステアリル等が挙げられる。これらの混合物を用いてもよい。これらの中で、液晶樹脂やポリイミド樹脂からなる基材と、金属箔との接着性を向上させる観点から、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、アクリル酸ヘキシル、アクリル酸オクチルがより好ましく、アクリル酸エチル、アクリル酸ブチルがより好ましく、アクリル酸エチルが特に好ましい。なお、「（メタ）アクリル酸～」とは、「アクリル酸～またはメタクリル酸～」を意味する。 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. Among these, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, acrylic Hexyl acrylate and octyl acrylate are more preferred, ethyl acrylate and butyl acrylate are more preferred, and ethyl acrylate is particularly preferred. Note that "(meth)acrylic acid" means "acrylic acid or methacrylic acid".
　また、酸変性ポリオレフィン樹脂（Ａ）は、上記成分以外に他の成分を酸変性ポリオレフィン樹脂（Ａ）の１０質量％以下程度、含有してもよい。他の成分としては、１－オクテン、ノルボルネン類等の炭素数６を超えるアルケン類やジエン類、マレイン酸ジメチル、マレイン酸ジエチル、マレイン酸ジブチル等のマレイン酸エステル類、（メタ）アクリル酸アミド類、メチルビニルエーテル、エチルビニルエーテルなどのアルキルビニルエーテル類、ぎ酸ビニル、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、バーサチック酸ビニル等のビニルエステル類ならびにビニルエステル類を塩基性化合物等でケン化して得られるビニルアルコール、２－ヒドロキシエチルアクリレート、グリシジル（メタ）アクリレート、（メタ）アクリロニトリル、スチレン、置換スチレン、一酸化炭素、二酸化硫黄などが挙げられ、これらの混合物を用いることもできる。 In addition, 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, and 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.
　また、酸変性ポリオレフィン樹脂（Ａ）は、カルボキシル基の水酸基が、Ｎ，Ｎ－ジメチルアミノ基、Ｎ，Ｎ－ジエチルアミノ基等で置換されたＮ－置換アミド構造を含有していてもよい。 Further, 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.
　ポリオレフィン樹脂の融点は、５０～１５０℃が好ましく、６０～１３０℃がさらに好ましく、７０～１１０℃がさらに好ましい。融点が上記の範囲未満であると、凝集力が弱くなり、接着性に劣る場合がある。また、上記の範囲を超えると、流動性が低下するため、液晶樹脂やポリイミド樹脂からなる基材と、金属箔との接着性が低下する場合がある。 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.
　酸変性ポリオレフィン樹脂（Ａ）としては、例えば、エチレン－（メタ）アクリル酸共重合体、エチレン－（メタ）アクリル酸－無水マレイン酸共重合体、酸変性ポリエチレン、酸変性ポリプロピレン、酸変性エチレン－プロピレン樹脂、酸変性エチレン－ブテン樹脂、酸変性プロピレン－ブテン樹脂、酸変性エチレン－プロピレン－ブテン樹脂、あるいはこれらの酸変性樹脂にさらに（メタ）アクリル酸エステル等でアクリル変性したエチレン－（メタ）アクリル酸エステル－不飽和カルボン酸共重合体等が挙げられる。中でも、エチレン－（メタ）アクリル酸－無水マレイン酸共重合体が好ましい。さらに、酸変性ポリオレフィン樹脂は５～４０質量％の範囲で塩素化されていてもよい。 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. Furthermore, the acid-modified polyolefin resin may be chlorinated in a range of 5 to 40% by mass.
　酸変性ポリオレフィン樹脂（Ａ）として、アルケマ社製のボンダインシリーズ、エボニックジャパン社製のベストプラストシリーズ、ダウ・ケミカル社製のプリマコールシリーズ、三洋化成社製のユーメックスシリーズ、三井化学社製のアドマーシリーズ、東洋紡社製のトーヨータックシリーズなどの市販品を使用することができる。また、市販の水系のものも使用することができ、日本製紙ケミカル社製のスーパークロンシリーズ、住友精化社製のザイクセンシリーズ、三井化学社製のケミパールシリーズ、東洋紡社製のハードレンシリーズ等を使用することができる。 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. In addition, 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.
＜エポキシ化合物（Ｂ）＞
　本発明の塗工剤は、接着性および耐熱性向上を目的として、エポキシ化合物（Ｂ）を含有するものである。 <Epoxy compound (B)>
The coating agent of the present invention contains an epoxy compound (B) for the purpose of improving adhesiveness and heat resistance.
　エポキシ化合物（Ｂ）は、接着性および耐熱性向上の点から、分子中に２個以上のエポキシ基を有するものが好ましく、３個以上のエポキシ基を有するものを含むことがより好ましい。エポキシ化合物（Ｂ）としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ノボラック型エポキシ樹脂、脂環式エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル、１,６－ヘキサンジオールジグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテル、ソルビトールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル等が挙げられ、高い接着性が得られることから、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、およびグリセロールポリグリシジルエーテルから選択される１種以上であることが好ましい。 From the viewpoint of improving adhesion 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. Examples of 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. .
　エポキシ化合物（Ｂ）のエポキシ当量（ｇ／ｅｑ．）は、５００以下であり、４００以下が好ましく、３００以下がより好ましく、２００以下がさらに好ましく、１５０以下が特に好ましい。エポキシ化合物（Ｂ）のエポキシ当量が５００を超えると、得られる塗膜は、液晶樹脂やポリイミド樹脂からなる基材と金属箔との接着性や、誘電特性が低下し、さらに、得られる積層体は伝送損失が大きくなる。エポキシ当量の下限値は特に限定されないが、例えば、８０である。 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.
　エポキシ化合物（Ｂ）の含有量は、酸変性ポリオレフィン樹脂１００質量部に対して、０．２質量部以上、５質量部未満であり、０．５～４．５質量部であることが好ましく、１．０～４．０質量部であることがより好ましい。塗工剤は、エポキシ化合物（Ｂ）の含有量が０．２質量部未満であると、液晶樹脂やポリイミド樹脂からなる基材と金属箔との接着性や、耐熱性、耐熱性の耐久性に劣るものとなり、５質量部以上であると、上記基材と金属箔との接着性が低下し、得られる塗膜は、誘電特性が低下し、さらに、得られる積層体は、伝送損失が大きくなる。 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. When 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.
＜水性媒体＞
　本発明の塗工剤を構成する水性媒体は、水または、水を主成分とする液体である。水性媒体を用いることは環境面から好ましい。
　水性媒体は、塩基性化合物や親水性有機溶媒を含有してもよい。水性媒体が親水性有機溶媒を含有することで、塗工剤は、基材への濡れ性が向上し、塗工性および造膜性が向上するという効果が奏される。 <Aqueous medium>
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.
　親水性有機溶媒の含有量は、基材への適度な濡れ性付与のために、塗工剤全量に対して１～５０質量％であることが好ましく、３～３０質量％であることがより好ましく、５～２５質量％であることがさらに好ましい。 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.
　親水性有機溶剤としては、例えば、メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、イソブタノール、ｓｅｃ－ブタノール、ｔｅｒｔ－ブタノール、ｎ－アミルアルコール、イソアミルアルコール、ｓｅｃ－アミルアルコール、ｔｅｒｔ－アミルアルコール、１－エチル－１－プロパノール、２－メチル－１－ブタノール、ｎ－ヘキサノール、シクロヘキサノール等のアルコール類、メチルエチルケトン、メチルイソブチルケトン、エチルブチルケトン、シクロヘキサノン等のケトン類、テトラヒドロフラン、ジオキサン等のエーテル類、酢酸エチル、酢酸－ｎ－プロピル、酢酸イソプロピル、酢酸－ｎ－ブチル、酢酸イソブチル、酢酸－ｓｅｃ－ブチル、酢酸－３－メトキシブチル、プロピオン酸メチル、プロピオン酸エチル、炭酸ジエチル、炭酸ジメチル等のエステル類、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールエチルエーテルアセテート等のグリコール誘導体、さらには、１－メトキシ－２－プロパノール、１－エトキシ－２－プロパノール、３－メトキシ－３－メチル－１－ブタノール、メトキシブタノール、アセトニトリル、ジメチルホルムアミド、ジメチルアセトアミド、ジアセトンアルコール、アセト酢酸エチル、１，２－ジメチルグリセリン、１，３－ジメチルグリセリン、またはトリメチルグリセリン等が挙げられる。 Examples of the hydrophilic organic solvent 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, alcohols 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-dimethylglycerin, 1,3-dimethylglycerin , or trimethylglycerin.
　塩基性化合物としては、例えば、アンモニア、トリエチルアミン、Ｎ，Ｎ－ジメチルエタノールアミン、イソプロピルアミン、アミノエタノール、ジメチルアミノエタノール、ジエチルアミノエタノール、エチルアミン、ジエチルアミン、イソブチルアミン、ジプロピルアミン、３－エトキシプロピルアミン、３－ジエチルアミノプロピルアミン、ｓｅｃ－ブチルアミン、プロピルアミン、ｎ－ブチルアミン、２－メトキシエチルアミン、３－メトキシプロピルアミン、２，２－ジメトキシエチルアミン、モノエタノールアミン、モルホリン、Ｎ－メチルモルホリン、Ｎ－エチルモルホリン、ピロール、またはピリジン等が挙げられる。 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.
＜添加剤＞
　本発明の塗工剤は、目的に応じて性能をさらに向上させるために、エポキシ化合物（Ｂ）以外の架橋剤や硬化促進剤等の添加剤を含有してもよい。 <Additives>
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.
　架橋剤としては、特に限定されず、例えば、自己架橋性を有する架橋剤、カルボキシル基と反応する官能基を分子内に複数個有する化合物、多価の配位座を有する金属等が挙げられる。具体的には、イソシアネート化合物、メラミン化合物、尿素化合物、カルボジイミド化合物、オキサゾリン基含有化合物、ジルコニウム塩化合物、シランカップリング剤等が好ましい。また、これらの架橋剤も複数同時に使用してもよい。 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.
　架橋剤の含有量は、酸変性ポリオレフィン樹脂（Ａ）１００質量部に対し、０．０１～３０質量部であることが好ましく、０．１～２０質量部であることがより好ましく、０．５～１０質量部であることがさらに好ましい。架橋剤の含有量が０．０１質量部未満の場合には、形成される塗膜は、性能の向上が見込めなくなる傾向にあり、３０質量部を超える場合には、形成される塗膜は、誘電特性が低下することがある。 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.
　本発明の塗工剤は、硬化促進剤を含有してもよい。硬化促進剤としては、特に限定されず、例えば、第三級アミン系硬化剤、第三級アミン塩系硬化剤、イミダゾール系硬化剤、リン酸塩系硬化促進剤等が挙げられる。 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.
　硬化促進剤の含有量は、エポキシ化合物（Ｂ）１００質量部に対して、１～１００質量部であることが好ましく、３～７０質量部であることがより好ましい。 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).
　本発明の塗工剤は、さらに必要に応じて、界面活性剤、レベリング剤、消泡剤、ワキ防止剤、顔料分散剤、紫外線吸収剤、耐候剤、難燃剤等の各種添加剤を含有してもよい。 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.
　本発明の塗工剤は、不揮発性の水性化助剤を実質的に含有しないことが好ましい。本発明は、不揮発性水性化助剤の使用を排除するものではないが、水性化助剤を用いずとも、酸変性ポリオレフィン樹脂（Ａ）を水性媒体中に微細かつ安定的に分散することができる。
　不揮発性水性分散化助剤とは、水性分散化促進や水性分散体の安定化の目的で添加される薬剤や化合物のことであり、「不揮発性」とは、常圧での沸点を有さないか、または常圧で高沸点（例えば３００℃以上）であることを指す。 The coating agent of the present invention preferably does not substantially contain a nonvolatile aqueous forming aid. Although the present invention does not exclude the use of a nonvolatile aqueous forming aid, it is possible to finely and stably disperse the acid-modified polyolefin resin (A) in an aqueous medium without using a water forming aid. can.
A nonvolatile aqueous dispersion 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.
　「不揮発性水性分散化助剤を実質的に含有しない」とは、こうした助剤を製造時（酸変性ポリオレフィン樹脂（Ａ）の水性分散化時）に用いず、得られる水性分散体が結果的にこの助剤を含有しないことを意味する。不揮発性水性化助剤は、酸変性ポリオレフィン樹脂（Ａ）に対して５質量％以下であることが好ましく、より好ましくは２質量％以下、さらに好ましくは０．５質量％未満であり、０質量％であることが特に好ましい。 "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.
　不揮発性水性分散化助剤としては、例えば、乳化剤、保護コロイド作用を有する化合物、変性ワックス類、高酸価の酸変性化合物、水溶性高分子等が挙げられる。 Examples of nonvolatile aqueous dispersion aids include emulsifiers, compounds with protective colloid action, modified waxes, acid-modified compounds with high acid values, and water-soluble polymers.
＜塗工剤＞
　本発明の塗工剤は、酸変性ポリオレフィン樹脂（Ａ）と、エポキシ化合物（Ｂ）と、水性媒体とを含有するものであり、カルボキシル基を含有する酸変性ポリオレフィン樹脂（Ａ）は、水性媒体に分散していることが好ましい。 <Coating agent>
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
　本発明の塗工剤における、不揮発成分の含有率は、塗工条件、目的とする塗膜の厚みや性能等により適宜選択でき、特に限定されないが、粘度を適度に保ち、かつ良好な造膜性を発現させる点で、１～６０質量％であることが好ましく、３～５５質量％であることがより好ましく、５～５０質量％であることがさらに好ましく、１０～４５質量％であることが特に好ましい。
　本発明の塗工剤の粘度は、基材へ塗工性の観点から、１～２０００ｍＰａ・ｓであることが好ましく、３～１０００ｍＰａ・ｓであることがより好ましく、５～５００ｍＰａ・ｓであることがさらに好ましい。 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.
　本発明の塗工剤を製造する方法は、特に限定されず、上記の原料を混合する方法が挙げられ、それらの混合順序は任意である。酸変性ポリオレフィン樹脂（Ａ）は、水性媒体に分散した水性分散体の状態で混合してもよい。 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.
＜塗膜＞
　本発明の塗工剤は、フィルムや不織布等の基材に対して、公知の塗工方法を用いて塗工し、本発明の塗膜とすることができる。例えば、グラビアロールコーティング、リバースロールコーティング、ワイヤーバーコーティング、リップコーティング、エアナイフコーティング、カーテンフローコーティング、スプレーコーティング、浸漬コーティング、はけ塗り法等により、基材表面に均一に塗工し、乾燥のための加熱処理に供することにより、均一な塗膜を基材表面に密着させて形成することができる。加熱装置としては、通常の熱風循環型のオーブンや赤外線ヒーター等を使用すればよい。また、加熱温度や加熱時間は、経済性等を考慮して、適宜に選択される。 <Coating film>
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. For example, 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. By subjecting the substrate to the heat treatment, a uniform coating film can be formed in close contact with the surface of the substrate. As the heating device, 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.
　本発明の塗膜は、厚みが１～３０μｍであることが好ましく、２～２０μｍであることがより好ましく、３～１５μｍであることがさらに好ましい。厚みが上記範囲となるようにすることで、形成された塗膜は高い接着性を有する。 The coating film of the present invention preferably has a thickness of 1 to 30 μm, more preferably 2 to 20 μm, and even more preferably 3 to 15 μm. By setting the thickness within the above range, the formed coating film has high adhesiveness.
　塗膜の厚みを調節するためには、塗工に用いる装置やその使用条件を適宜選択することに加えて、目的とする厚みに適した濃度の塗工剤を使用することが好ましい。塗工剤の濃度は、調製時の仕込み組成により調節することができ、また、一旦調製した塗工剤を適宜希釈あるいは濃縮して調節してもよい。 In order to adjust the thickness of the coating film, in addition to appropriately selecting the equipment used for coating and its usage conditions, it is preferable to use a coating agent with a concentration suitable for the desired thickness. The 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.
　本発明の塗膜は、誘電特性に優れるものであり、周波数１０ＧＨｚで測定した比誘電率が３．０以下であり、誘電正接が０．０１以下であることが好ましく、比誘電率が２．８以下であり、誘電正接が０．００８以下であることがより好ましく、比誘電率が２．６以下であり、誘電正接が０．００６以下であることがさらに好ましい。 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.
＜積層体＞
　本発明の積層体は、本発明の塗膜を含むものであり、例えば、各種基材表面、接着層またはプライマー層に、本発明の塗膜を含む積層体が挙げられる。
　本発明の塗工剤は、液晶樹脂やポリイミド樹脂からなる基材と金属箔との接着性に優れることから、積層体は、液晶樹脂やポリイミド樹脂からなる基材上に、本発明の塗工剤から形成される塗膜、および金属箔をこの順に含有するものが好ましい。 <Laminated body>
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.
（基材）
　基材を構成する液晶樹脂とは、樹脂が高温での溶融や溶媒への溶解により流動状態となった際に、分子鎖がほぼ規則的に整列している状態（液晶性）を示す高分子を指す。たとえば、全芳香族ポリエステル、芳香族ポリアゾメチン、芳香族脂肪族ポリエステル、芳香族ポリエステルカーボネート、全芳香族又は非全芳香族ポリエステルアミドなどのうちの一部の樹脂が液晶性を示すことが知られている。 (Base material)
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.
　液晶樹脂として知られるポリエステルとして、パラヒドロキシ安息香酸とその他の成分とを直鎖状に重縮合したものが挙げられる。具体的には、エチレンテレフタレートとパラヒドロキシ安息香酸とを重縮合したポリエステル、フェノールおよびフタル酸とパラヒドロキシ安息香酸とを重縮合したポリエステル、２，６－ヒドロキシナフトエ酸とパラヒドロキシ安息香酸とを重縮合したポリエステルなどが挙げられる。 Examples of 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.
　液晶樹脂は市販品が入手可能である。例えば、ポリプラスチック社製ベクトラシリーズ「Ａ９５０、Ｅ９５１ＳＸ」や、住友化学社製スミカスーパーシリーズ「Ｅ５２０４Ｌ、Ｅ６８０７ＬＨＦ」や、ユニチカ社製ロッドランシリーズ「ＬＣ５０３０Ｇ、ＬＣ５０３０ＭＦ」などが挙げられる。これらは、フィラーを混合して弾性や強度を向上させたものであってもよいし、エステルアミド化させて弾性率を向上させたものであってもよい。
　液晶樹脂からなる基材についても市販品が入手可能であり、例えば、クラレ社製ベクスターシリーズなどが挙げられる。 Commercially available 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.
　ポリイミド樹脂からなる基材としては、フィルム形態のものが挙げられる。例えば、ジアミン類とテトラカルボン酸類とを反応させて得られるポリアミド酸（ポリイミド前駆体）溶液を、ポリイミドフィルム作製用基材に塗布、乾燥して前駆体フィルムとした後に、基材から剥がす又はそのまま高温熱処理して脱水閉環反応を行わせることによって得られるポリイミドフィルムなどが挙げられる。 Examples of the base material made of polyimide resin include those in the form of a film. For example, 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.
　ポリイミド樹脂を構成するジアミン成分としては、ｐ－フェニレンジアミン（ＰＤＡ）、４，４′－ジアミノジフェニルエーテル（ＯＤＡ）、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン（ＢＡＰＰ）、ｍ－フェニレンジアミン、２，４－ジアミノトルエン、４，４′－ジアミノビフェニル、４，４′－ジアミノ－２，２′－ビス（トリフルオロメチル）ビフェニル（ＰＦＭＢ）、２，２′－ジメチル‐４，４′－ジアミノビフェニル（ＤＭＤＢ）、３，３′－ジアミノジフェニルスルフォン、４，４′－ジアミノジフェニルスルフォン、４，４′－ジアミノジフェニルスルフィド、４，４′－ジアミノジフェニルメタン、３，４′－ジアミノジフェニルエーテル、３，３′－ジアミノジフェニルエーテル、１，４－ビス（４－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，３－ビス（３－アミノフェノキシ）ベンゼン、４，４′－ビス（４－アミノフェノキシ）ビフェニル、ビス［４－（４－アミノフェノキシ）フェニル］スルフォン、ビス［４－（３－アミノフェノキシ）フェニル］スルフォン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、１，３－ビス（アミノメチル）シクロヘキサン、１，４－ビス（アミノメチル）シクロヘキサン、ビス（アミノメチル）ノルボルナン、３（４），８（９）－ビス（アミノメチル）トリシクロ［５．２．１．０２，６］デカン、１，３－シクロヘキサンジアミン、１，４－シクロヘキサンジアミン、イソホロンジアミン、４，４′－メチレンビス（シクロヘキシルアミン）、４，４′－メチレンビス（２－メチルシクロヘキシルアミン）、１，４－ジアミノブタン、１，１０－ジアミノデカン、１，１２－ジアミノドデカン、１，７－ジアミノヘプタン、１，６－ジアミノヘキサン、１，５－ジアミノペンタン、１，８－ジアミノオクタン、１，３－ジアミノプロパン、１，１１－ジアミノウンデカン、２－メチル－１，５－ジアミノペンタン、ダイマージアミン等のジアミンを挙げることができる。
　これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。 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'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene , 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4 -(4-aminophenoxy)phenyl]hexafluoropropane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(aminomethyl)norbornane, 3(4), 8(9) )-bis(aminomethyl)tricyclo[5.2.1.0 2,6 ]decane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, isophoronediamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), 1,4-diaminobutane, 1,10-diaminodecane, 1,12-diaminododecane, 1,7-diaminoheptane, 1,6-diaminohexane, 1 , 5-diaminopentane, 1,8-diaminooctane, 1,3-diaminopropane, 1,11-diaminoundecane, 2-methyl-1,5-diaminopentane, and dimer diamine.
These may be used alone or in combination of two or more.
　ポリイミド樹脂を構成するテトラカルボン酸成分としては、ピロメリット酸二無水物（ＰＭＤＡ）、３，３′，４，４′－ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）、２，３，３′，４′－ビフェニルテトラカルボン酸二無水物、３，３′，４，４′－ベンゾフェノンテトラカルボン酸二無水物（ＢＴＤＡ）、４，４′－オキシジフタル酸二無水物（ＯＤＰＡ）、３，３′，４，４′－ジフェニルスルホンテトラカルボン酸二無水物、４，４′－（ヘキサフルオロイソプロピリデン）ジフタル酸二無水物（６ＦＤＡ）、２，２－ビス〔４－（３，４－ジカルボキシフェノキシ）フェニル〕プロパン二無水物（ＢＰＡＤＡ）等のテトラカルボン酸二無水物を挙げることができる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the tetracarboxylic acid component constituting the polyimide resin 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) Examples include tetracarboxylic dianhydrides such as phenoxy)phenyl]propane dianhydride (BPADA). These may be used alone or in combination of two or more.
　ポリイミド樹脂基材としては、市販のポリイミドフィルムを用いてもよく、例えば、「カプトン」（東レ・デュポン社製の商品名）、「ユーピレックス」（宇部興産社製の商品名）等を使用することができる。また、変性ポリイミド（ＭＰＩ）フィルムまたは変性ポリイミド（ＭＰＩ）ワニスを塗布した基材も使用することができる。 As the 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.
　これらのポリイミドフィルムは、化学的あるいは物理的な表面処理が施されていてもよい。化学的な表面処理としては、シランカップリング剤、アルミニウムアルコラート等による表面処理を挙げることができる。一方、物理的な表面処理としては、粗面化処理、プラズマ処理等を挙げることができる。但し、本発明の塗工剤は、表面処理を行わない基材に対しても、接着性に優れる。 These polyimide films may be subjected to chemical or physical surface treatment. Examples of chemical surface treatments include surface treatments using silane coupling agents, aluminum alcoholates, and the like. On the other hand, physical surface treatments include surface roughening treatment, plasma treatment, and the like. However, the coating agent of the present invention has excellent adhesion even to substrates that are not subjected to surface treatment.
　また、本発明の塗工剤は、その他の汎用樹脂基材と金属箔との接着性にも優れる。汎用樹脂基材としては、ポリエステル樹脂基材、ポリカーボネート樹脂基材、ポリフェニレンサルファイド樹脂基材、シクロオレフィン樹脂基材、ポリエチレン樹脂基材、ポリプロピレン樹脂基材、半芳香族ポリアミド樹脂基材などが挙げられる。 Furthermore, the coating agent of the present invention also has excellent adhesion between other general-purpose resin base materials and metal foil. Examples of 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. .
（金属箔）
　金属箔としては、特に限定されないが、銅、ニッケル、アルミニウム等からなるものが挙げられる。 (metal foil)
Examples of the metal foil include, but are not limited to, those made of copper, nickel, aluminum, etc.
　本発明の積層体は、例えば、ボンディングシート、樹脂付き銅箔、カバーレイフィルム、プリント配線板、銅張積層板、フラットケーブル、テープオートメイテッドボンディング用回路板、電磁波シールド材等に用いることができる。 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. .
　以下、実施例によって本発明を具体的に説明する。ただし、本発明はこれらによって限定されるものではない。
　各種の特性について、以下の方法で測定または評価した。 Hereinafter, the present invention will be specifically explained with reference to Examples. However, the present invention is not limited to these.
Various properties were measured or evaluated using the following methods.
１．接着強度
　液晶樹脂基材、ポリイミド樹脂基材、またはポリエステル樹脂基材上に、それぞれ塗工剤を、バーコーターを用いて乾燥後の塗膜厚みが１０μｍになるように塗工した後、熱風乾燥機を用いて、１００℃×１分間乾燥した。その後、塗工面に銅箔を貼り合わせ、温度２００℃、圧力０．２ＭＰａで６０秒間のヒートシール加工を行った。その後、貼り合わせた積層体を１０ｍｍ幅に切り出し、２３℃の雰囲気下で、基材と銅箔とを引っ張り速度５０ｍｍ／分で９０度の方向に剥離した。接着性を次の基準で評価した。
◎：１．２０ｋＮ／ｍ以上
○：１．００ｋＮ／ｍ以上、１．２０ｋＮ／ｍ未満
△：０．８０ｋＮ／ｍ以上、１．００ｋＮ／ｍ未満
×：０．８０ｋＮ／ｍ未満 1. 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 μm, 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.
◎: 1.20 kN/m or more ○: 1.00 kN/m or more, less than 1.20 kN/m △: 0.80 kN/m or more, less than 1.00 kN/m ×: Less than 0.80 kN/m
２．比誘電率、誘電正接
　離型フィルム（ＴＯＭＢＯ社製、ナフロンＰＴＦＥテープ、厚み２００μｍ）上に、塗工剤を乾燥後の塗膜厚みが３０μｍになるように塗工し、１００℃／１０分の条件で乾燥して塗膜を形成した。その後、離型フィルムから塗膜を引きはがし、測定用シートを作製した。得られたシートを、スプリットポスト誘電体共振器法で、２３℃雰囲気下、周波数１０ＧＨｚの条件で測定した。
　比誘電率は、次の基準で評価した。
◎：２．６０以下
○：２．６０を超え、２．８０以下
△：２．８０を超え、３．００以下
×：３．００を超える
　誘電正接は、次の基準で評価した。
◎：０．００６０以下
○：０．００６０を超え、０．００８０以下
△：０．００８０を超え、０．０１００以下
×：０．０１００を超える 2. Relative dielectric constant, dielectric loss tangent A coating agent was applied on a release film (manufactured by TOMBO, NAFLON PTFE tape, thickness 200 μm) so that the coating thickness after drying was 30 μm, and the coating was heated at 100°C for 10 minutes. A coating film was formed by drying under the following conditions. Thereafter, the coating film was peeled off from the release film to prepare a measurement sheet. The obtained sheet was measured using a split post dielectric resonator method in an atmosphere of 23° C. and at a frequency of 10 GHz.
The relative dielectric constant was evaluated based on the following criteria.
◎: 2.60 or less ○: More than 2.60, 2.80 or less Δ: More than 2.80, 3.00 or less ×: More than 3.00 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
３．伝送損失（Ｓ２１）
　液晶樹脂基材の両面に、塗工剤を、バーコーターを用いて乾燥後の塗膜厚みが１０μｍになるように塗工した後、熱風乾燥機を用いて、１００℃×１分間乾燥した。その後、両方の塗工面と銅箔を貼り合わせ、真空下、温度２００℃、圧力３．０ＭＰａで３０分間のヒートシール加工を行った。その後、貼り合わせた積層体を特性インピーダンスが５０Ωになるようにマイクロストリップ線路を形成し、１０ＭＨｚ～４０ＧＨｚの間で伝送損失を測定した（キーサイトテクノロジー社、ネットワークアナライザＥ５２２７Ｂを使用）。伝送損失を次の基準で評価した。
○：３０ＧＨｚにおける伝送損失の絶対値が５．０ｄＢ／１００ｍｍ未満
×：３０ＧＨｚにおける伝送損失の絶対値が５．０ｄＢ／１００ｍｍ以上 3. 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 μm, 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 50Ω, 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
４．ハンダ耐熱性（耐熱性）
　上記「１．接着強度」に記載の方法で、基材として液晶樹脂基材を用いた積層体を作製し、２．５ｃｍ×２．５ｃｍのサンプル片を１２０℃で３０分乾燥処理を行い、２６０℃で溶融したハンダ浴に１分間フローし、次の基準により、目視にてハンダ耐熱性を評価した。
○：膨れなし
△：やや膨れあり
×：大きな膨れあり 4. 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
５．繰り返しハンダ耐熱性（耐熱性の耐久性）
　上記「４．ハンダ耐熱性（耐熱性）」に記載の方法でサンプルを作製し、２６０℃で溶融したハンダ浴に１分間フローを１０回繰り返し、次の基準により、目視にて繰り返しハンダ耐熱性を評価した。
○：膨れなし
△：やや膨れあり
×：大きな膨れあり 5. Repeated soldering heat resistance (durability of heat resistance)
A sample was prepared by the method described in "4. Solder heat resistance (heat resistance)" above, and the flow was repeated 10 times for 1 minute in a solder bath melted at 260°C, and the solder heat resistance was repeatedly checked visually according to the following criteria. was evaluated.
○: No bulge △: Slight bulge ×: Large bulge
６．総合評価
○：上記「１．接着強度」、「２．比誘電率、誘電正接」、「３．伝送損失」、「４．ハンダ耐熱性（耐熱性）」、「５．繰り返しハンダ耐熱性（耐熱性の耐久性）」の何れにおいても、「△」以上の評価である。
×：上記「１．接着強度」、「２．比誘電率、誘電正接」、「３．伝送損失」、「４．ハンダ耐熱性（耐熱性）」、「５．繰り返しハンダ耐熱性（耐熱性の耐久性）」の何れかにおいて、「×」の評価がある。 6. Overall evaluation ○: Above "1. Adhesive strength", "2. Relative permittivity, dielectric loss tangent", "3. Transmission loss", "4. Soldering heat resistance (heat resistance)", "5. Repeated soldering heat resistance ( The evaluation was ``△'' or higher in both ``durability of heat resistance''.
×: Above "1. Adhesive strength", "2. Relative permittivity, dielectric loss tangent", "3. Transmission loss", "4. Soldering heat resistance (heat resistance)", "5. Repeated soldering heat resistance (heat resistance)" There is a rating of "x" for any of the following:
　塗工剤の原料および基材として、下記のものを使用した。
Ｉ．酸変性ポリオレフィン樹脂（Ａ）の水性分散体（Ｅ）
Ｅ－１：酸変性ポリオレフィン樹脂（Ａ－１）の水性分散体（Ｅ－１）の製造
　ヒーター付きの密閉できる耐圧１Ｌ容ガラス容器を備えた撹拌機を用いて、１００ｇの酸変性ポリオレフィン樹脂（Ａ－１）［エチレン－アクリル酸エチル－無水マレイン酸共重合体、エチレン９２質量％、アクリル酸エチル６質量％、無水マレイン酸２質量％、融点１０５℃］、８０ｇのイソプロパノール、４．０ｇのＮ，Ｎ－ジメチルエタノールアミン、および２２０ｇの水をガラス容器内に仕込み、１３０℃で６０分間加熱撹拌をおこなった。その後、撹拌しつつ室温まで冷却したのち、１５０ｇの水を加え、エバポレータを用いて水およびイソプロパノールを減圧留去することによって、酸変性ポリオレフィン樹脂（Ａ－１）粒子の水性分散体（Ｅ－１）を得た。 The following materials were used as raw materials and base materials for the coating agent.
I. Aqueous dispersion (E) of acid-modified polyolefin resin (A)
E-1: Production of aqueous dispersion (E-1) of acid-modified polyolefin resin (A-1) 100 g of acid-modified polyolefin resin ( A-1) [Ethylene-ethyl acrylate-maleic anhydride copolymer, 92% by mass of ethylene, 6% by mass of ethyl acrylate, 2% by mass of maleic anhydride, melting point 105°C], 80g of isopropanol, 4.0g of N,N-dimethylethanolamine and 220 g of water were placed in a glass container, and heated and stirred at 130° C. for 60 minutes. Thereafter, after cooling to room temperature while stirring, 150 g of water was added, and water and isopropanol were distilled off under reduced pressure using an evaporator to obtain an aqueous dispersion (E-1) of acid-modified polyolefin resin (A-1) particles. ) was obtained.
Ｅ－２：酸変性ポリオレフィン樹脂（Ａ－２）の水性分散体（Ｅ－２）の製造
　酸変性ポリオレフィン樹脂（Ａ－２）［エチレン－アクリル酸エチル－無水マレイン酸共重合体、エチレン８０質量％、アクリル酸エチル１８質量％、無水マレイン酸２質量％、融点８３℃］を用いた。それ以外は、水性分散体（Ｅ－１）の場合と同様の操作で、水性分散体（Ｅ－２）を得た。 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).
Ｅ－３：酸変性ポリオレフィン樹脂（Ａ－３）の水性分散体（Ｅ－３）の製造
　プロピレン－エチレン共重合体（プロピレン／エチレン＝８１．８／１８．２（質量比）、重量平均分子量８５，０００）２８０ｇを、４つ口フラスコ中において、窒素雰囲気下で加熱溶融させた。
　その後、系内温度を１８０℃に保って、撹拌下、不飽和カルボン酸としての無水マレイン酸３５．０ｇとラジカル発生剤としてのジ－ｔ－ブチルパーオキサイド６．０ｇとをそれぞれ２時間かけて加え、その後１時間反応させた。反応終了後、得られた反応物を多量のアセトン中に投入し、樹脂を析出させた。この樹脂をさらにアセトンで数回洗浄し、未反応の無水マレイン酸を除去した後、減圧乾燥機中で減圧乾燥して、酸変性ポリオレフィン樹脂（Ａ－３）［質量比：プロピレン７５．４／エチレン１６．８／無水マレイン酸７．８、融点７０℃］を得た。
　得られた樹脂を用いて、特願２００５－５０６３７１記載の方法と同様にして、乳白色の酸変性ポリオレフィン樹脂（Ａ－３）の水性分散体（Ｅ－３）を得た。 E-3: Production of aqueous dispersion (E-3) of acid-modified polyolefin resin (A-3) Propylene-ethylene copolymer (propylene/ethylene = 81.8/18.2 (mass ratio), weight average molecular weight 85,000) was heated and melted in a four-necked flask under a nitrogen atmosphere.
Thereafter, while maintaining the system temperature at 180°C, 35.0 g of maleic anhydride as an unsaturated carboxylic acid and 6.0 g of di-t-butyl peroxide as a radical generator were each added over 2 hours while stirring. After that, the mixture was reacted for 1 hour. After the reaction was completed, the obtained reaction product was poured into a large amount of acetone to precipitate the 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.
Using the obtained 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：酸変性ポリオレフィン樹脂（Ａ－４）の水性分散体（Ｅ－４）の製造
　酸変性ポリオレフィン樹脂（Ａ－４）［エチレン－アクリル酸共重合体、エチレン８０質量％、アクリル酸２０質量％、融点７９℃］を用いた。それ以外は、水性分散体（Ｅ－１）の場合と同様の操作で、水性分散体（Ｅ－４）を得た。 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).
ＩＩ．エポキシ化合物（Ｂ）
Ｂ－１：ソルビトールポリグリシジルエーテル（ナガセケムテックス社製、デナコールＥＸ－６１４、４官能エポキシ化合物（エポキシ基を４個有する）、エポキシ当量１６７） II. 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)
Ｂ－２：ポリエチレングリコールジグリシジルエーテル（ナガセケムテックス社製、デナコールＥＸ－８３２、２官能エポキシ化合物（エポキシ基を２個有する）、エポキシ当量２８４） B-2: Polyethylene glycol diglycidyl ether (manufactured by Nagase ChemteX, Denacol EX-832, bifunctional epoxy compound (having two epoxy groups), epoxy equivalent 284)
Ｂ－３：ジグリセロールポリグリシジルエーテル（ナガセケムテックス社製、デナコールＥＸ－４２１、３官能エポキシ化合物、エポキシ当量１５９） B-3: Diglycerol polyglycidyl ether (manufactured by Nagase ChemteX, Denacol EX-421, trifunctional epoxy compound, epoxy equivalent 159)
Ｂ－４：グリセロールポリグリシジルエーテル（ナガセケムテックス社製、デナコールＥＸ－３１３、２官能エポキシ化合物と３官能エポキシ化合物の複合体、エポキシ当量１４１） B-4: Glycerol polyglycidyl ether (manufactured by Nagase ChemteX, Denacol EX-313, complex of bifunctional epoxy compound and trifunctional epoxy compound, epoxy equivalent 141)
Ｂ－５：ポリエチレングリコールジグリシジルエーテル（ナガセケムテックス社製、デナコールＥＸ－８６１、２官能エポキシ化合物、エポキシ当量５５１） B-5: Polyethylene glycol diglycidyl ether (manufactured by Nagase ChemteX, Denacol EX-861, bifunctional epoxy compound, epoxy equivalent 551)
ＩＩＩ．銅箔
接着強度測定用：日立金属ネオマテリアル社製、厚み３０μｍ
伝送損失測定用：福田金属箔粉工業社製、電解銅箔、厚み１２μｍ III. For copper foil adhesive strength measurement: Manufactured by Hitachi Metals Neomaterials, thickness 30μm
For transmission loss measurement: Manufactured by Fukuda Metal Foil and Powder Industries Co., Ltd., electrolytic copper foil, thickness 12 μm
ＩＶ．基材
ヒドロキシナフトエ酸等とパラヒドロキシ安息香酸とから得られる芳香族系ポリエステル液晶樹脂基材：クラレ社製、ベクスター　ＣＴＱ―５０、厚み５０μｍ
ポリイミド樹脂基材：宇部興産社製、ユーピレックス－Ｓ、厚み５０μｍ
ポリエステル樹脂基材：ユニチカ社製、エンブレットＳ－５０、厚み５０μｍ IV. 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 μm
Polyimide resin base material: Manufactured by Ube Industries, Upilex-S, thickness 50 μm
Polyester resin base material: Manufactured by Unitika, Emblet S-50, thickness 50 μm
実施例１
　酸変性ポリオレフィン樹脂（Ａ－１）の水性分散体（Ｅ－１）とエポキシ化合物（Ｂ－１）を固形分質量比が１００／１になるように混合し、その混合液１００質量部に対して、イソプロパノールを２０質量部添加することにより塗工剤を作製した。 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.
実施例２～９、比較例１～４
　表１に記載のように、酸変性ポリオレフィン樹脂（Ａ）、エポキシ化合物（Ｂ）の種類、または固形分質量比（含有量）を変更して、塗工剤を作製した。 Examples 2 to 9, Comparative Examples 1 to 4
As shown in Table 1, coating agents were prepared by changing the types of acid-modified polyolefin resin (A) and epoxy compound (B), or the solid content mass ratio (content).
　実施例、比較例で作製した塗工剤の構成、各種特性の評価結果を表１に示す。 Table 1 shows the compositions and evaluation results of various properties of the coating agents produced in Examples and Comparative Examples.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例１～９の塗工剤は、液晶樹脂基材やポリイミド樹脂基材と、銅箔との接着性に優れていた。得られた塗膜は、比誘電率や誘電正接の値も低く優れた誘電特性を有しており、得られた積層体は、伝送損失が低く抑えられており、耐熱性（ハンダ耐熱性）にも優れていた。塗工剤は、さらにポリエステル樹脂基材と銅箔との接着性にも優れるものであった。 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.
　比較例１の塗工剤は、エポキシ化合物の含有量が本発明で規定する範囲より少なかったことから、接着性に劣り、また、耐熱性にも劣っていた。
　比較例２の塗工剤は、エポキシ化合物の含有量が本発明で規定する範囲を超えており、塗膜は誘電特性に劣り、積層体は伝送損失が大きいものであった。
　比較例３の塗工剤は、エポキシ当量が５００を超えるエポキシ化合物を用いたため、接着性に劣っていた。また、得られた積層体は伝送損失も大きいものであった。
　比較例４の塗工剤は、酸変性ポリオレフィン樹脂における不飽和カルボン酸成分の含有量が本発明で規定する範囲を超えていたため、高い接着性を得ることができず、塗膜は誘電特性にも劣っており、積層体は伝送損失も大きいものであった。 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.
In the coating agent of Comparative Example 2, 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.
In the coating agent of Comparative Example 4, 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.

Claims (9)

  1. 　酸変性ポリオレフィン樹脂（Ａ）と、エポキシ化合物（Ｂ）と、水性媒体とを含有する塗工剤であって、
    酸変性ポリオレフィン樹脂（Ａ）が、不飽和カルボン酸成分を０．１～１０質量％含有し、
    エポキシ化合物（Ｂ）は、エポキシ当量が５００以下であり、含有量が酸変性ポリオレフィン樹脂（Ａ）１００質量部に対して０．２質量部以上、５質量部未満であることを特徴とする塗工剤。     A coating agent containing 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) has 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). Engineering agent.
  2. 　エポキシ化合物（Ｂ）が、１分子中にエポキシ基を３個以上有するエポキシ化合物を含むことを特徴とする請求項１に記載の塗工剤。 The coating agent according to claim 1, wherein the epoxy compound (B) contains an epoxy compound having three or more epoxy groups in one molecule.
  3. 　エポキシ化合物（Ｂ）が、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテルおよびグリセロールポリグリシジルエーテルから選択される１種以上であることを特徴とする請求項１に記載の塗工剤。 The coating agent according to claim 1, wherein the epoxy compound (B) is one or more selected from sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, and glycerol polyglycidyl ether.
  4. 　酸変性ポリオレフィン樹脂（Ａ）が、（メタ）アクリル酸エステル成分を３～２５質量％含有することを特徴とする請求項１～３のいずれかに記載の塗工剤。 The coating agent according to any one of claims 1 to 3, wherein the acid-modified polyolefin resin (A) contains 3 to 25% by mass of a (meth)acrylic acid ester component.
  5. 　液晶樹脂またはポリイミド樹脂からなる基材と、塗工剤から得られる塗膜と、銅箔とを貼り合わせてヒートシール加工を行って得られる積層体において、基材と銅箔とを引張速度５０ｍｍ／分で９０°の方向に剥離した際の接着強度が、０．８ｋＮ／ｍ以上であることを特徴とする請求項１～４のいずれかに記載の塗工剤。 In a laminate obtained by heat-sealing a base material made of liquid crystal resin or polyimide resin, a coating film obtained from a coating agent, and copper foil, the base material and copper foil are pulled at a tensile speed of 50 mm. The coating agent according to any one of claims 1 to 4, wherein the coating agent has an adhesive strength of 0.8 kN/m or more when peeled in a direction of 90° at a rate of 0.8 kN/m or more.
  6. 　請求項１～４のいずれかに記載の塗工剤から得られることを特徴とする塗膜。 A coating film obtained from the coating agent according to any one of claims 1 to 4.
  7. 　周波数１０ＧＨｚで測定した比誘電率が３．０以下であり、誘電正接が０．０１以下であることを特徴とする請求項６に記載の塗膜。 The coating film according to claim 6, wherein 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.
  8. 　液晶樹脂またはポリイミド樹脂からなる基材と、請求項６に記載の塗膜と、金属箔とがこの順に積層された積層体。 A laminate in which a base material made of liquid crystal resin or polyimide resin, the coating film according to claim 6, and metal foil are laminated in this order.
  9. 　請求項８に記載の積層体を含むプリント配線板。 A printed wiring board comprising the laminate according to claim 8.
PCT/JP2023/030701 2022-08-30 2023-08-25 Coating agent, coating film, and laminate WO2024048444A1 (en)

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