WO2022255137A1 - Adhesive composition - Google Patents

Adhesive composition Download PDF

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Publication number
WO2022255137A1
WO2022255137A1 PCT/JP2022/021050 JP2022021050W WO2022255137A1 WO 2022255137 A1 WO2022255137 A1 WO 2022255137A1 JP 2022021050 W JP2022021050 W JP 2022021050W WO 2022255137 A1 WO2022255137 A1 WO 2022255137A1
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WO
WIPO (PCT)
Prior art keywords
styrene
adhesive composition
film
adhesive
adhesive layer
Prior art date
Application number
PCT/JP2022/021050
Other languages
French (fr)
Japanese (ja)
Inventor
栞 門間
航 片桐
一義 吉田
Original Assignee
信越ポリマー株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 信越ポリマー株式会社 filed Critical 信越ポリマー株式会社
Priority to JP2023525733A priority Critical patent/JPWO2022255137A1/ja
Publication of WO2022255137A1 publication Critical patent/WO2022255137A1/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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C09J125/04—Homopolymers or copolymers of styrene
    • C09J125/08—Copolymers of styrene
    • 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
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal

Definitions

  • the present invention relates to adhesive compositions. More particularly, it relates to an adhesive composition that can be used for bonding electronic parts and the like.
  • FPCs flexible printed circuit boards
  • the dielectric of the constituent elements and low dielectric base films and low dielectric adhesives are being developed.
  • low-dielectric adhesives have problems in chemical resistance and heat resistance because the polarity of the base material molecules is low and the crosslink density is also low. From the viewpoint of providing a low-dielectric adhesive layer that adheres even to a low-dielectric base film with poor adhesion and has both chemical resistance and heat resistance, the adhesive described in Patent Document 1 is not satisfactory. However, there was room for improvement.
  • the present invention has good electrical properties (dielectric properties) that are compatible with 5G, exhibits good adhesion even to low-dielectric base films with poor adhesion, and has heat resistance and chemical resistance.
  • An object of the present invention is to provide an adhesive composition for forming a low-dielectric adhesive layer that also has solvent properties.
  • the adhesive composition contains a styrene-based elastomer containing an amino group and a benzoxazine resin. , found that the above problems can be solved, and completed the present invention.
  • the present invention includes the following aspects.
  • the adhesive composition according to [1] which contains 30 to 95 parts by mass of the amino group-containing styrene-based elastomer with respect to 100 parts by mass of the adhesive composition.
  • a coverlay film with an adhesive layer comprising the laminate according to [10] or [11].
  • a copper-clad laminate comprising the laminate according to [10] or [11].
  • a printed wiring board comprising the laminate according to [10] or [11].
  • a shielding film comprising the laminate according to [10] or [11].
  • a printed wiring board with a shielding film comprising the laminate according to [10] or [11].
  • the present invention while having good electrical properties (dielectric properties) compatible with 5G, it exhibits good adhesion even to low-dielectric substrate films with poor adhesion, and has heat resistance and chemical resistance (resistance). It is possible to provide an adhesive composition for forming a low dielectric adhesive layer that also has solvent properties.
  • the adhesive composition of the present invention a laminate containing an adhesive layer made of the adhesive composition, and an electronic component-related constituent member containing the laminate will be described in detail. is an example as one embodiment of the present invention, and is not limited to these contents.
  • the adhesive composition of the present invention contains a styrene-based elastomer and a benzoxazine resin.
  • the styrenic elastomer used in the present invention contains a styrenic elastomer containing an amino group.
  • the styrene elastomer contained in the adhesive composition contains a modified styrene elastomer.
  • the modified styrenic elastomer contains at least a styrenic elastomer containing an amino group.
  • the styrene elastomer used in the present invention may contain a modified styrene elastomer other than the amino group-containing styrene elastomer, or may contain an unmodified styrene elastomer other than the modified styrene elastomer. good.
  • the adhesive composition of the present invention preferably contains at least two types of styrenic elastomers from the viewpoint of satisfying various properties required for the adhesive composition.
  • Styrenic elastomers are copolymers composed mainly of block and random structures of unsaturated hydrocarbons and aromatic vinyl compounds, and hydrogenated products thereof.
  • aromatic vinyl compounds examples include styrene, t-butylstyrene, ⁇ -methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-diethyl-p-aminoethylstyrene and vinyltoluene.
  • unsaturated hydrocarbons include ethylene, propylene, butadiene, isoprene, isobutene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like.
  • the styrene elastomer used in the present invention preferably has a weight average molecular weight of 30,000 or more, more preferably 70,000 or more. If the weight average molecular weight is 30,000 or more, excellent adhesiveness can be exhibited. If the weight-average molecular weight is 70,000 or more, the film-forming property is improved when the polymer is dissolved in a solvent and applied, and thickness unevenness due to pinholes and dripping is less likely to occur. Performance deviation is small, and lack of adhesion and chemical resistance is less likely to occur. In addition, it becomes easy to control the thickness, which is important when manufacturing a printed wiring board.
  • a styrene-based elastomer having a weight average molecular weight of 100,000 or more it is preferable to contain a styrene-based elastomer having a weight average molecular weight of 100,000 or more.
  • a styrene-based elastomer having a weight-average molecular weight of 100,000 or more is contained, excessive resin flow (resin flow) can be suppressed.
  • the styrene elastomer preferably has a weight average molecular weight of 300,000 or less, more preferably 200,000 or less. If the weight average molecular weight is 300,000 or less, the compatibility with the benzoxazine resin is improved, and excellent chemical resistance can be exhibited.
  • the weight-average molecular weight is 200,000 or less, it is possible to suppress an increase in viscosity during coating by dissolving in a solvent, and improve leveling properties, thereby forming a film with a smooth surface. As a result, fluctuations in performance on the coated surface are small, insufficient adhesion and chemical resistance are less likely to occur, and thickness control, which is important in the production of printed wiring boards, becomes easier.
  • the weight average molecular weight is a value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter also referred to as "GPC") into polystyrene.
  • the styrene elastomer used in the present invention preferably has a styrene ratio of 20 or more, more preferably 30 or more. If the styrene ratio is 20 or more, excellent adhesiveness can be exhibited. If the styrene ratio is 30 or more, the heat resistance of the adhesive composition can be expressed. Moreover, it is preferable to contain a styrene-based elastomer having a styrene ratio of 40 or more. When a styrene-based elastomer having a styrene ratio of 40 or more is contained, the compatibility with the benzoxazine resin is improved, and excellent adhesiveness and chemical resistance can be exhibited.
  • the styrene-based elastomer preferably has a styrene ratio of 80 or less, more preferably 60 or less.
  • the styrene ratio is 80 or less, the fluidity at the time of heating can be enhanced, so that the surface of the substrate film can be sufficiently followed and excellent adhesive strength can be exhibited. If the styrene ratio is 60 or less, procurement of the styrene-based elastomer is easy.
  • the styrene ratio of at least one styrene-based elastomer is preferably 40 or more.
  • Types of styrene elastomers include styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-ethylene copolymers, their random copolymers, block copolymers, hydrogenated products thereof, and the like. mentioned.
  • a hydrogenated styrene-butadiene block copolymer is preferable.
  • the block structure mainly composed of styrene can improve compatibility with benzoxazine resin, and the block structure mainly derived from butadiene imparts high flexibility.
  • styrene-based elastomers include styrene-butadiene block copolymers, styrene-ethylenepropylene block copolymers, styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, and styrene-ethylenebutylene.
  • styrene block copolymers and styrene-ethylene propylene-styrene block copolymers may be used alone or in combination of two or more.
  • the styrene-based elastomer of the present invention includes modified styrene-based elastomers in which substituents have been introduced into the above structures, and unmodified styrene-based elastomers in which no substituents have been introduced.
  • the adhesive composition of the present invention contains a modified styrene-based elastomer, it reacts with a benzoxazine resin, a cross-linking agent, etc., which will be described later, and cures, thereby exhibiting excellent adhesiveness and chemical resistance.
  • the introduced substituent since the introduced substituent has a strong interaction with metal, the inclusion of the modified styrene-based elastomer improves the adhesive strength between the adhesive composition and the metal substrate.
  • Modified styrenic elastomers are copolymers mainly composed of block and random structures of unsaturated hydrocarbons and aromatic vinyl compounds, and hydrogenated products thereof containing carboxy groups, amino groups, epoxy groups, isocyanate groups, acryloyl , a hydroxyl group, a mercapto group, an imide group, an alkoxysilyl group, and the like.
  • the adhesive composition of the present invention contains a styrene elastomer containing at least an amino group as the modified styrene elastomer.
  • the adhesive composition of the present invention may contain modified styrene-based elastomers other than the amino group-containing styrene-based elastomer as long as the effects of the present invention are not impaired.
  • the method of amine-modifying the styrene elastomer is not particularly limited, and a known method can be used.
  • a modification method a method of amine-modifying a (hydrogenated) copolymer by using an unsaturated monomer having an amino group as a raw material to be copolymerized, and a styrene-based elastomer containing a carboxy group with two amino groups.
  • a method of modifying the amine by reacting the above amine modifier to form an amide structure or an imide structure, and the like.
  • styrene-based elastomers containing amino groups include those obtained by introducing amino groups into the aforementioned styrene-based elastomers.
  • the total nitrogen content in the amino group-containing styrene elastomer is , preferably 50 to 5000 ppm, more preferably 200 to 3000 ppm. If the total nitrogen content is at least the above lower limit, excellent adhesion can be exhibited. If the total nitrogen content is equal to or less than the above upper limit, the electrical properties are excellent.
  • the total nitrogen content in the styrene-based elastomer containing amino groups can be determined according to JIS-K2609 using a trace nitrogen analyzer ND-100 (manufactured by Mitsubishi Chemical Corporation).
  • the content of the styrene-based elastomer containing an amino group in the adhesive composition is preferably contained in an amount of 30 to 95 parts by mass, more preferably 30 to 80 parts by mass.
  • a styrene-based elastomer containing a carboxy group is effective as a component that imparts electrical properties in addition to adhesiveness and flexibility of a cured product.
  • Carboxy group-containing styrenic elastomers are copolymers mainly composed of block and random structures of unsaturated hydrocarbons and aromatic vinyl compounds, and hydrogenated products thereof modified with unsaturated carboxylic acids. .
  • the types of the aromatic vinyl compound and the unsaturated hydrocarbon and specific examples of the styrene-based elastomer are as described in the section ⁇ Styrene-based elastomer> above.
  • Modification of a styrene-based elastomer containing a carboxy group can be carried out, for example, by copolymerizing an unsaturated carboxylic acid during polymerization of the styrene-based elastomer. It can also be carried out by heating and kneading a styrene-based elastomer and an unsaturated carboxylic acid in the presence of an organic peroxide.
  • unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, maleic anhydride, and itaconic anhydride.
  • the amount of modification with unsaturated carboxylic acid is preferably 0.1 to 10% by mass.
  • the acid value of the styrene-based elastomer containing carboxy groups is preferably 0.1 to 25 mgKOH/g, more preferably 0.5 to 23 mgKOH/g.
  • the acid value is 0.1 mgKOH/g or more, the adhesive composition is sufficiently cured, and good adhesiveness and heat resistance can be obtained.
  • the acid value is 30 mgKOH/g or less, the cohesive force of the adhesive composition is suppressed, resulting in excellent adhesiveness and excellent electrical properties.
  • the adhesive composition of the present invention may contain an unmodified styrene elastomer in addition to the modified styrene elastomer. Only one type of unmodified styrene elastomer may be used, or two or more types may be contained.
  • Unmodified styrene elastomers are copolymers mainly composed of block and random structures of unsaturated hydrocarbons and aromatic vinyl compounds, and hydrogenated products thereof. There are few highly polar bonding groups in the molecule, and good electrical properties (dielectric properties) can be imparted to the composition. Another advantage is that the molecular weight can be easily controlled and the properties of the adhesive composition can be stably produced compared to other types of elastomers.
  • the types of the aromatic vinyl compound and the unsaturated hydrocarbon and specific examples of the styrene-based elastomer are as described in the section ⁇ Styrene-based elastomer> above.
  • the content of the unmodified styrene-based elastomer is preferably 35 to 100 parts by mass with respect to 100 parts by mass of the styrene-based elastomer containing amino groups. If the content of the unmodified styrene elastomer relative to 100 parts by mass of the styrene elastomer containing an amino group is within the above range, the effect of adjusting the elastic modulus and fluidity of the adhesive composition by blending the unmodified styrene elastomer. is likely to occur.
  • the weight average molecular weight (Mw) of the unmodified styrene elastomer is preferably 100,000 or more, more preferably 100,000 to 200,000. Within the above range, it is possible to achieve both fluidity control and adhesion.
  • the unmodified styrene elastomer used in the present invention preferably has a styrene ratio of 40-80.
  • a styrene-based elastomer having a styrene ratio of 40 or more is contained, the compatibility with the benzoxazine resin is improved, and excellent adhesiveness and chemical resistance can be exhibited.
  • the benzoxazine resin increases the cross-linking density of the adhesive composition, thereby making it possible to exhibit high adhesion to adherends and the chemical resistance and heat resistance of the cured adhesive.
  • the benzoxazine resin undergoes a self-polymerization reaction to form a crosslinked structure.
  • the benzoxazine preferably has a structure containing two or more oxazine skeletons in the molecule from the viewpoint of increasing the content of the highly adhesive styrene-based elastomer and improving the crosslink density.
  • Benzoxazine resins include, for example, 6,6-(1-methylethylidene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6-(1-methylethylidene) Examples thereof include bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine) and the like, and two or more of them may be combined.
  • a phenyl group, a methyl group, a cyclohexyl group, or the like may be bonded to the nitrogen of the oxazine ring.
  • Specific examples of benzoxazine resins include "Benzoxazine Fa", "Benzoxazine Pd" and "Benzoxazine ALP-d” manufactured by Shikoku Kasei Co., Ltd., and the like.
  • the melting point or softening point of the benzoxazine resin gives fluidity to the adhesive composition at the temperature of heat lamination or heat press, allowing it to follow the surface of the substrate film or metal substrate sufficiently, resulting in excellent adhesion and curing. It is preferably less than 120° C. from the viewpoint of exhibiting chemical resistance at times.
  • the melting point or softening point of the benzoxazine resin is preferably 40° C. or higher from the viewpoint of increasing the elastic modulus of the adhesive composition at room temperature and improving the adhesion.
  • the content of the benzoxazine resin in the adhesive composition is preferably 5 parts by mass or more with respect to 100 parts by mass of the adhesive composition from the viewpoint of expressing chemical resistance and heat resistance.
  • the content of the benzoxazine resin is preferably 70 parts by mass or less, more preferably 50 parts by mass or less. If the content of the benzoxazine resin is 5 parts by mass or more, excellent chemical resistance to the substrate film can be exhibited. If the content of the benzoxazine resin is 70 parts by mass or less, excellent dielectric properties can be exhibited.
  • the adhesive composition of the present invention may contain, in addition to the styrene elastomer, a resin component other than the styrene elastomer and other components.
  • the adhesive composition of the present invention may contain other resin components in addition to the styrene-based elastomer and benzoxazine resin.
  • the adhesive composition according to the present invention can contain, for example, thermoplastic resins other than the styrene-based elastomer to such an extent that the functions of the adhesive composition are not affected.
  • thermoplastic resins include phenoxy resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene oxide resins, polyurethane resins, polyacetal resins, polyethylene resins, polypropylene resins, polybutadiene resins, and polyvinyl resins. is mentioned. These thermoplastic resins may be used alone or in combination of two or more.
  • the resin composition used in the present invention may contain other components in addition to the resin components such as the styrene-based elastomer, benzoxazine resin, and other resin components described above.
  • Other components include, for example, a cross-linking agent that reacts with the styrene-based elastomer and benzoxazine resin to form a cross-linked structure.
  • a reaction accelerator that accelerates the reaction between the styrene-based elastomer, benzoxazine resin and the cross-linking agent may be included.
  • other components include, for example, fillers, tackifiers, flame retardants, heat anti-aging agents, leveling agents, antifoaming agents, inorganic fillers and pigments. These can be contained to the extent that they do not affect the functions of the adhesive composition.
  • cross-linking agent examples include epoxy resins, isocyanate resins, phenol resins, cyanate resins, polyamides, polyurethanes, organic peroxides, silane coupling agents, and the like. Only one type of cross-linking agent may be used, or two or more types may be contained.
  • the adhesive composition of the present invention preferably contains a filler.
  • a filler for example, an inorganic filler is preferable from the viewpoint of heat resistance and mechanical property control of the adhesive composition, and as the inorganic filler, a silicon-based inorganic filler and boron nitride are preferable from the viewpoint of electrical properties. preferable.
  • the silicon-based inorganic filler for example, mica and talc are preferable because they can control the mechanical properties of the adhesive composition even in a small amount and have excellent electrical properties.
  • an organic filler is preferable from the viewpoint of dispersibility and brittleness
  • a styrene-based spherical filler is preferable from the viewpoint of electrical properties
  • a styrene-based hollow filler is preferable. more preferred. These may be used alone or in combination of two or more.
  • the content of the filler contained in the adhesive composition of the present invention is preferably 0.5 to 25 parts by volume with respect to 100 parts by volume of the resin composition, and 1 to 15 parts by volume with respect to 100 parts by volume of the resin composition. is more preferable.
  • the shape of the filler is not particularly limited and can be appropriately selected depending on the purpose.
  • the inorganic filler may be a spherical inorganic filler or a non-spherical inorganic filler, but a non-spherical inorganic filler is preferable from the viewpoint of coefficient of thermal expansion (CTE) and film strength.
  • the shape of the non-spherical inorganic filler may be any three-dimensional shape other than a spherical shape (substantially spherical shape), and examples thereof include plate-like, scale-like, columnar, chain-like, and fibrous shapes. Among them, from the viewpoint of coefficient of thermal expansion (CTE) and film strength, plate-like and scale-like inorganic fillers are preferable, and plate-like inorganic fillers are more preferable.
  • tackifiers examples include coumarone-indene resin, terpene resin, terpene-phenol resin, rosin resin, pt-butylphenol-acetylene resin, phenol-formaldehyde resin, xylene-formaldehyde resin, petroleum-based hydrocarbon resin, Examples include hydrogenated hydrocarbon resins and turpentine resins. These tackifiers may be used alone or in combination of two or more.
  • the above flame retardant may be either an organic flame retardant or an inorganic flame retardant.
  • organic flame retardants include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, amide ammonium phosphate, amide ammonium polyphosphate, carbamate phosphate, and carbamate polyphosphate.
  • triazine compounds such as melamine,
  • Inorganic flame retardants include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, and calcium hydroxide; tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, Metal oxides such as molybdenum oxide and nickel oxide; zinc carbonate, magnesium carbonate, barium carbonate, zinc borate, hydrated glass and the like. These flame retardants can be used in combination of two or more.
  • heat antiaging agent examples include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propione.
  • examples of the inorganic filler include powders made of titanium oxide, aluminum oxide, zinc oxide, carbon black, silica, copper, silver, and the like. These may be used alone or in combination of two or more.
  • the adhesive layer according to the present invention is formed using the adhesive composition of the present invention.
  • the adhesive composition that forms the adhesive layer can be cured.
  • the curing method is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include heat curing.
  • the thickness of the adhesive layer is not particularly limited and can be appropriately selected depending on the intended purpose. Also, it is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and even more preferably 30 ⁇ m or less. If the thickness of the adhesive layer is 3 ⁇ m or more, sufficient adhesive strength can be exhibited, and if it is 5 ⁇ m or more, steps such as the pattern of the printed wiring board can be followed. If the thickness of the adhesive layer is 50 ⁇ m or less, the laminate can be made thinner, and if it is 30 ⁇ m or less, the resin flow can be accurately controlled.
  • An adhesive layer can be produced by forming a film from the adhesive composition.
  • the adhesive composition can be produced by mixing the styrene-based elastomer and the benzoxazine resin described above.
  • the mixing method is not particularly limited as long as the adhesive composition becomes uniform.
  • a solvent is also usually used. Examples of solvents include alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol, benzyl alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diacetone alcohol.
  • Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, and isophorone; Aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, and anisole; Methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monomethyl esters such as ether acetate and 3-methoxybutyl acetate; and aliphatic hydrocarbons such as hexane, heptane, cyclohexane and methylcyclohexane.
  • solvents may be used alone or in combination of two or more.
  • the adhesive composition is a solvent-containing solution or dispersion (resin varnish)
  • coating on the substrate film and formation of the adhesive layer can be performed smoothly, and an adhesive layer having a desired thickness can be formed. can be obtained easily.
  • the adhesive composition contains a solvent, the solid content concentration is preferably in the range of 3 to 80% by mass, more preferably 10 to 50% by mass, from the viewpoint of workability including formation of the adhesive layer.
  • a resin varnish containing the adhesive composition and a solvent is applied to the surface of a substrate film to form a resin varnish layer, and then the resin varnish is applied to the surface of the substrate film.
  • a B-staged adhesive layer can be formed by removing the solvent from the layer.
  • the adhesive layer being in a B-stage state means that the adhesive composition is in an uncured state or a semi-cured state in which a part of the adhesive composition has begun to cure, and the curing of the adhesive composition further progresses by heating or the like. It means the state to do.
  • the method for applying the resin varnish on the substrate film is not particularly limited and can be appropriately selected according to the purpose.
  • a blade coating method, a doctor roll method, a doctor blade method, a curtain coating method, a slit coating method, a screen printing method, an inkjet method, a dispensing method, and the like can be mentioned.
  • the B-stage adhesive layer can be further subjected to heating or the like to form a cured adhesive layer.
  • the dielectric constant ( ⁇ r) of the adhesive layer obtained by curing the adhesive composition of the present invention at a frequency of 28 GHz is preferably 3.5 or less, more preferably 2.7 or less.
  • the dielectric loss tangent (tan ⁇ ) of the adhesive layer at a frequency of 28 GHz is preferably 0.005 or less, more preferably 0.0025 or less, and even more preferably 0.0015 or less. If the dielectric constant is 3.5 or less and the dielectric loss tangent is 0.005 or less, it can also be used for high-frequency FPC-related products that require strict electrical characteristics.
  • the dielectric constant is 2.7 or less and the dielectric loss tangent is 0.0025 or less, it is possible to satisfy the electrical characteristics expected for the components of 5G compatible high-frequency FPC related products, LCP ( Liquid crystal polymer) has the same electrical characteristics, and can be suitably used for 5G high-frequency FPC-related products that have strict electrical characteristics requirements.
  • the dielectric loss tangent is 0.0015 or less, it can be suitably used for high-frequency FPC-related products utilizing millimeter waves.
  • the laminate of the present invention comprises a base film and the adhesive layer on at least one surface of the base film.
  • the base film used in the present invention can be selected according to the use of the laminate.
  • the laminate when the laminate is used as a cover lay film or a copper clad laminate (CCL), polyimide film, polyether ether ketone film, polyphenylene sulfide film, aramid film, polyethylene naphthalate film, liquid crystal polymer film, and the like can be used.
  • polyimide film, polyetheretherketone (PEEK) film, polyethylene naphthalate film, and liquid crystal polymer film are preferred from the viewpoint of adhesion and electrical properties.
  • the storage elastic modulus of the base film at 200° C. is 1 ⁇ 10 8 or more. Resin flow is accompanied by deformation of the edges of the base film, and the larger the deformation, the greater the resin flow.
  • the base film when used as a bonding sheet, the base film must be a release film, and examples thereof include polyethylene terephthalate film, polyethylene film, polypropylene film, silicone release treated paper, and polyolefin resin. Coated paper, TPX (polymethylpentene) film, fluorine-based resin film, and the like.
  • the base film When the laminate of the present invention is used as a shielding film, the base film must be a film having electromagnetic wave shielding ability, and examples thereof include a laminate of a protective insulating layer and a metal foil.
  • coverlay film A preferred embodiment of the laminate according to the present invention is a coverlay film.
  • a laminate having an adhesive layer called a "coverlay film” is usually used to protect the wiring portion.
  • This coverlay film comprises an insulating resin layer and an adhesive layer formed on its surface.
  • a coverlay film is a laminate in which the adhesive layer is formed on at least one surface of the base film, and it is generally difficult to separate the base film and the adhesive layer.
  • the thickness of the base film included in the coverlay film is preferably 5 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, even more preferably 5 to 30 ⁇ m. If the thickness of the base film is equal to or less than the above upper limit, the thickness of the coverlay film can be reduced.
  • the printed wiring board can be easily designed and handled well.
  • a method for producing a coverlay film for example, a resin varnish containing the adhesive composition and a solvent is applied to the surface of the base film to form a resin varnish layer, and then the solvent is removed from the resin varnish layer. is removed, a coverlay film having a B-stage adhesive layer formed thereon can be produced.
  • the drying temperature for removing the solvent is preferably 40 to 250°C, more preferably 70 to 170°C. Drying is performed by passing the laminate coated with the adhesive composition through a furnace in which hot air drying, far-infrared heating, high-frequency induction heating, or the like is performed.
  • a release film may be laminated on the surface of the adhesive layer for storage or the like.
  • the releasable film publicly known films such as polyethylene terephthalate film, polyethylene film, polypropylene film, silicone release treated paper, polyolefin resin coated paper, TPX film, and fluororesin film are used. Since the coverlay film according to the present invention uses the low-dielectric adhesive composition of the present invention, it is possible for high-speed transmission of electronic devices, and furthermore, it has excellent adhesive stability with electronic devices. Become.
  • a preferred embodiment of the laminate according to the present invention is a bonding sheet.
  • the bonding sheet is obtained by forming the adhesive layer on the surface of a release film (base film).
  • the bonding sheet may be in a mode in which an adhesive layer is provided between two release films.
  • the release film is peeled off before use.
  • the releasable film the same one as described in the above section (coverlay film) can be used.
  • the thickness of the base film included in the bonding sheet is preferably 5 to 100 ⁇ m, more preferably 25 to 75 ⁇ m, even more preferably 38 to 50 ⁇ m. If the thickness of the base film is within the above range, the bonding sheet can be easily manufactured and handled well.
  • a method for producing a bonding sheet for example, there is a method of applying a resin varnish containing the adhesive composition and a solvent to the surface of a release film and drying in the same manner as in the case of the coverlay film. Since the bonding sheet according to the present invention uses the low-dielectric adhesive composition of the present invention, it is capable of high-speed transmission of electronic devices, and has excellent adhesion stability with electronic devices. .
  • a preferred embodiment of the laminate according to the present invention is a copper-clad laminate obtained by bonding a copper foil to the adhesive layer in the laminate according to the present invention.
  • a copper-clad laminate is obtained by laminating copper foil using the above laminate, and is composed of, for example, a substrate film, an adhesive layer and copper foil in this order.
  • the adhesive layer and the copper foil may be formed on both sides of the base film.
  • the adhesive composition used in the present invention also has excellent adhesion to articles containing copper. Since the copper-clad laminate according to the present invention uses the low-dielectric adhesive composition of the present invention, it enables high-speed transmission of electronic devices and has excellent adhesion stability.
  • the adhesive layer and copper foil of the laminate are brought into surface contact, thermal lamination is performed at 80° C. to 200° C., and the adhesive layer is cured by after-curing.
  • the after-curing conditions can be, for example, 100° C. to 200° C. for 30 minutes to 4 hours in an inert gas atmosphere.
  • the said copper foil is not specifically limited, Electrolytic copper foil, a rolled copper foil, etc. can be used.
  • a preferred embodiment of the laminate according to the present invention is a printed wiring board obtained by laminating copper wiring to the adhesive layer in the laminate according to the present invention.
  • a printed wiring board is obtained by forming an electronic circuit on the copper-clad laminate.
  • a printed wiring board is formed by laminating a substrate film and copper wiring using the laminate, and is composed of a substrate film, an adhesive layer, and copper wiring in this order.
  • the adhesive layer and the copper wiring may be formed on both sides of the base film.
  • a printed wiring board is manufactured by using a hot press or the like to attach a coverlay film to a surface having a wiring portion via an adhesive layer.
  • the printed wiring board according to the present invention uses the low-dielectric adhesive composition of the present invention, it enables high-speed transmission of electronic devices and has excellent adhesion stability.
  • the adhesive layer of the laminate is brought into contact with the copper wiring, thermal lamination is performed at 80 ° C. to 200 ° C., and the adhesive layer is removed by after-curing. There is a way to harden it.
  • the after-cure conditions can be, for example, 100° C. to 200° C. and 30 minutes to 4 hours.
  • the shape of the copper wiring is not particularly limited, and any suitable shape may be selected as desired.
  • a preferred embodiment of the laminate according to the present invention is a shield film.
  • a shield film is a film for shielding various electronic devices in order to cut electromagnetic noise that affects various electronic devices such as computers, mobile phones, and analytical instruments and causes malfunctions. Also called electromagnetic wave shielding film.
  • the electromagnetic wave shielding film is formed by laminating an insulating resin layer, a metal layer, and an adhesive layer according to the present invention in this order, for example. Since the shielding film according to the present invention uses the low dielectric adhesive composition of the present invention, high-speed transmission of electronic devices is possible, and the adhesive stability with electronic devices is also excellent. .
  • a preferred embodiment of the laminate according to the present invention is a printed wiring board with a shield film.
  • a printed wiring board with a shielding film is a printed wiring board having a printed circuit on at least one side of a substrate, and the electromagnetic wave shielding film is attached on the printed wiring board.
  • a printed wiring board with a shield film includes, for example, a printed wiring board, an insulating film adjacent to the surface of the printed wiring board on which the printed circuit is provided, and the electromagnetic wave shielding film. Since the printed wiring board with a shielding film according to the present invention uses the low-dielectric adhesive composition of the present invention, it enables high-speed transmission of electronic devices and has excellent adhesion stability.
  • This copolymer has an acid value of 0 mgKOH/g, a styrene ratio of 30, and a weight average molecular weight of 67,000.
  • Styrene Elastomer Containing Carboxy Group The trade name “Kraton FG1901” (maleic acid-modified hydrogenated styrene-butadiene copolymer (maleic acid-modified styrene-ethylenebutylene-styrene copolymer)) manufactured by Kraton Co., Ltd. was used.
  • This copolymer has an acid value of 19 mgKOH/g, a styrene ratio of 30, and a weight average molecular weight of 81,000.
  • Example 1 Each component constituting the adhesive layer shown in Table 1 was contained in the ratio shown in Table 1, and these components were dissolved in a solvent to prepare a resin varnish, which is an adhesive composition having a solid content concentration of 15% by mass. Each component constituting the resin composition in the adhesive composition is as shown in Table 1.
  • the dielectric constant and dielectric loss tangent at a frequency of 28 GHz were measured for the adhesive layer obtained by curing the resin varnish of Example 1.
  • the relative dielectric constant and dielectric loss tangent of the adhesive layer were determined by the open resonator method using a network analyzer MS46122B (manufactured by Anritsu) and an open resonator Fabry-Perot DPS-03 (manufactured by KEYCOM) at a temperature of 23°C. , and a frequency of 28 GHz.
  • a resin varnish is applied to the release film, then the film with the coating film is left standing in an oven and dried at 110 ° C. for 4 minutes to obtain a B-stage adhesive layer (thickness 50 ⁇ m ) was formed.
  • this adhesive layer was thermally laminated at 150° C.
  • the resin varnish prepared above is applied to the surface of the base film, dried in an oven at 130° C. for 4 minutes, and the solvent is volatilized to form an adhesive layer (15 ⁇ m), and the base film with adhesive (adhesion A laminated body with an agent) was obtained.
  • the adhesive layer of the laminate with adhesive is stacked so that it is in contact with the glossy surface of the electrolytic copper foil, and pressed at 180 ° C. under pressure (3 MPa) and 10 hPa for 3 minutes using a vacuum press, and at 200 for 1 hour. After curing, the adhesive layer was cured to obtain a laminate with an adhesive after curing.
  • the adhesive force (N/cm) between the electrodeposited copper foil and the base film was measured for the laminated body with the adhesive after curing in Example 1.
  • a chemical resistance test was performed on the laminated body with an adhesive after curing in Example 1.
  • Adhesion strength was determined by cutting the laminate with adhesive after curing into a test specimen with a width of 25 mm, and peeling at a peel speed of 0.3 m / min in accordance with JIS Z0237: 2009 (adhesive tape/adhesive sheet test method). Adhesion was measured by measuring the peel strength when the electrolytic copper foil was peeled off from the adhesive-attached substrate film fixed to the support at an angle of 180°.
  • solder heat resistance test In the solder heat resistance test, the laminate with adhesive after curing is cut into a 30 mm ⁇ 30 mm test specimen, and the base film surface is floated in a solder bath at 288 ° C. for 10 seconds ⁇ 3 times, and the adhesive layer Appearance abnormalities such as swelling and peeling were confirmed.
  • the heat resistance of the laminate was evaluated according to the following evaluation criteria. ⁇ No abnormality (no dissolution). x: Partially or completely peeled off.
  • Table 1 shows each measurement result.
  • Example 2 to 4 Laminates of Examples 2 to 4 were produced in the same manner as in Example 1, except that the types and amounts of the components constituting the adhesive layer were changed as shown in Table 1. . Evaluation similar to Example 1 was performed with respect to the produced laminated body. Table 1 shows the results.
  • Comparative Examples 1 to 4 Laminates of Comparative Examples 1 to 4 were produced in the same manner as in Example 1, except that the types and amounts of the components constituting the adhesive layer were changed as shown in Table 1. . Evaluation similar to Example 1 was performed with respect to the produced laminated body. Table 1 shows the results.
  • the adhesive layer made of the adhesive composition of the present invention exhibits good electrical properties (dielectric properties) compatible with 5G, and adhesion, heat resistance, and chemical resistance (solvent resistance). It is also excellent in sex.
  • a laminate having an adhesive layer comprising the adhesive composition of the present invention is suitable for manufacturing FPC-related products for electronic devices such as smartphones, mobile phones, optical modules, digital cameras, game machines, laptop computers, and medical instruments. can be used for

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  • Organic Chemistry (AREA)
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Abstract

The present invention provides an adhesive composition for forming a low-dielectric adhesive layer that has both heat resistance and chemical resistance (solvent resistance), the adhesive composition exhibiting favorable adhesion to a low-dielectric base material film having poor adhesion properties, while having favorable electrical properties (dielectric properties) compatible with 5G.　The adhesive composition contains a styrene elastomer and a benzoxazine resin, and the styrene elastomer includes a styrene elastomer containing an amino group.

Description

接着剤組成物adhesive composition
　本発明は、接着剤組成物に関する。詳しくは、電子部品等の接着用途に使用することができる接着剤組成物に関する。 The present invention relates to adhesive compositions. More particularly, it relates to an adhesive composition that can be used for bonding electronic parts and the like.
　電子機器の小型化、軽量化等に伴い、電子部品等の接着用途は多様化し、接着剤層付き積層体の需要は増大している。
　また、電子部品の１つであるフレキシブルプリント配線板（以下、ＦＰＣともいう）では、大量のデータを高速で伝送する必要があり、高周波数への対応が進んでいる。ＦＰＣの高周波数化には構成要素の低誘電化が必要であり、低誘電の基材フィルムや低誘電の接着剤の開発が行われている。特に、第５世代移動通信システム（以下、５Ｇともいう）で使われる６ＧＨｚ及び２８ＧＨｚ帯域の周波数を有する信号を効率的に伝送するためには、２８ＧＨｚのミリ波帯域でも損失が小さい基材フィルムや接着剤の重要性が大きくなっている。 With the miniaturization and weight reduction of electronic devices, the applications for bonding electronic parts and the like are diversifying, and the demand for laminates with adhesive layers is increasing.
In addition, flexible printed circuit boards (hereinafter also referred to as FPCs), which are one type of electronic component, need to transmit a large amount of data at high speed, and are becoming increasingly compatible with high frequencies. In order to increase the frequency of the FPC, it is necessary to reduce the dielectric of the constituent elements, and low dielectric base films and low dielectric adhesives are being developed. In particular, in order to efficiently transmit signals having frequencies in the 6 GHz and 28 GHz bands used in the 5th generation mobile communication system (hereinafter also referred to as 5G), a base film with low loss even in the 28 GHz millimeter wave band, Adhesives are becoming more and more important.
　しかし、低誘電の接着剤は、主剤分子の極性が低いため基材フィルムや電子部品関連の他の構成要素との密着性が発現しづらく、また低誘電の基材フィルムも同様に接着剤との密着性が悪いことがあり、密着性の向上が求められている。
　そこで、良好な電気特性（低比誘電率、及び低誘電正接）を有しつつ、高い密着性に応えるため、カルボキシ基含有スチレン系エラストマー（Ａ）と、エポキシ樹脂（Ｂ）とを含有する接着剤組成物を用い、該接着剤組成物からなる接着剤層と基材フィルムとからなる積層体についての提案がなされている（例えば、特許文献１参照）。 However, low-dielectric adhesives have a low polarity of the base molecules, making it difficult to develop adhesion to base films and other components related to electronic components. In some cases, the adhesiveness of the adhesive is poor, and improvement of the adhesiveness is required.
Therefore, in order to respond to high adhesion while having good electrical properties (low dielectric constant and low dielectric loss tangent), an adhesive containing a carboxy group-containing styrene elastomer (A) and an epoxy resin (B) Using an adhesive composition, a laminate comprising an adhesive layer made of the adhesive composition and a base film has been proposed (see, for example, Patent Document 1).
国際公開第２０１６／０１７４７３号WO2016/017473
　ところで、低誘電の接着剤は、主剤分子の極性が低く、架橋密度も低いことから、耐薬品性や耐熱性にも課題がある。
　密着性が悪い低誘電基材フィルムでも密着し、耐薬品性や耐熱性を兼ね備える低誘電接着層を提供するという観点からは、上記特許文献１に記載の接着剤は満足のいくものとはいえず、改良の余地があった。 By the way, low-dielectric adhesives have problems in chemical resistance and heat resistance because the polarity of the base material molecules is low and the crosslink density is also low.
From the viewpoint of providing a low-dielectric adhesive layer that adheres even to a low-dielectric base film with poor adhesion and has both chemical resistance and heat resistance, the adhesive described in Patent Document 1 is not satisfactory. However, there was room for improvement.
　そこで、本発明は、５Ｇ対応可能な良好な電気特性（誘電特性）を有しつつ、密着性の悪い低誘電基材フィルムに対しても良好な密着性を示し、耐熱性、耐薬品（耐溶剤）性を兼ね備えた低誘電接着剤層を形成するための接着剤組成物を提供することを目的とする。 Therefore, the present invention has good electrical properties (dielectric properties) that are compatible with 5G, exhibits good adhesion even to low-dielectric base films with poor adhesion, and has heat resistance and chemical resistance. An object of the present invention is to provide an adhesive composition for forming a low-dielectric adhesive layer that also has solvent properties.
　本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、接着剤組成物にアミノ基を含有するスチレン系エラストマーとベンゾオキサジン樹脂とを含有させることで、該接着剤組成物が、上記課題を解決できることを見出し、本発明を完成するに至った。 The present inventors have made intensive studies to solve the above problems, and found that the adhesive composition contains a styrene-based elastomer containing an amino group and a benzoxazine resin. , found that the above problems can be solved, and completed the present invention.
　本発明は、以下の態様を包含するものである。
［１］　スチレン系エラストマーと、ベンゾオキサジン樹脂とを含有する接着剤組成物であって、
　前記スチレン系エラストマーが、アミノ基を含有するスチレン系エラストマーを含有する、接着剤組成物。
［２］　前記接着剤組成物１００質量部に対し、前記アミノ基を含有するスチレン系エラストマーを３０～９５質量部含有する、［１］に記載の接着剤組成物。
［３］　前記接着剤組成物１００質量部に対し、前記ベンゾオキサジン樹脂を５～７０質量部含有する、［１］～［２］のいずれかに記載の接着剤組成物。
［４］　前記接着剤組成物が、少なくとも２種類以上のスチレン系エラストマーを含有する、［１］～［３］のいずれかに記載の接着剤組成物。
［５］　前記スチレン系エラストマーは、重量平均分子量が３０，０００～３００，０００であるスチレン系エラストマーを含有する、［１］～［４］のいずれかに記載の接着剤組成物。
［６］　前記スチレン系エラストマーは、スチレン比が２０～６０であるスチレン系エラストマーを含有する、［１］～［５］のいずれかに記載の接着剤組成物。
［７］　前記ベンゾオキサジン樹脂の融点、又は軟化点が１２０℃未満である、［１］～［６］のいずれかに記載の接着剤組成物。
［８］　［１］～［７］のいずれかに記載の接着剤組成物を硬化させてなる接着剤層。
［９］　前記接着剤層に対し、周波数２８ＧＨｚで測定した前記接着剤層の比誘電率が３．５以下であり、かつ誘電正接が０．００５以下である、［８］に記載の接着剤層。
［１０］　基材フィルムと、
　［８］または［９］に記載の接着剤層と、を有する積層体。
［１１］　前記基材フィルムが、ポリエーテルエーテルケトン（ＰＥＥＫ）樹脂を含有する、［１０］に記載の積層体。
［１２］　［１０］又は［１１］に記載の積層体を含む接着剤層付きカバーレイフィルム。
［１３］　［１０］又は［１１］に記載の積層体を含む銅張積層板。
［１４］　［１０］又は［１１］に記載の積層体を含むプリント配線板。
［１５］　［１０］又は［１１］に記載の積層体を含むシールドフィルム。
［１６］　［１０］又は［１１］に記載の積層体を含むシールドフィルム付きプリント配線板。 The present invention includes the following aspects.
[1] An adhesive composition containing a styrene-based elastomer and a benzoxazine resin,
The adhesive composition, wherein the styrene-based elastomer contains a styrene-based elastomer containing an amino group.
[2] The adhesive composition according to [1], which contains 30 to 95 parts by mass of the amino group-containing styrene-based elastomer with respect to 100 parts by mass of the adhesive composition.
[3] The adhesive composition according to any one of [1] to [2], which contains 5 to 70 parts by mass of the benzoxazine resin with respect to 100 parts by mass of the adhesive composition.
[4] The adhesive composition according to any one of [1] to [3], which contains at least two types of styrenic elastomers.
[5] The adhesive composition according to any one of [1] to [4], wherein the styrene elastomer contains a styrene elastomer having a weight average molecular weight of 30,000 to 300,000.
[6] The adhesive composition according to any one of [1] to [5], wherein the styrene elastomer contains a styrene elastomer having a styrene ratio of 20-60.
[7] The adhesive composition according to any one of [1] to [6], wherein the benzoxazine resin has a melting point or softening point of less than 120°C.
[8] An adhesive layer obtained by curing the adhesive composition according to any one of [1] to [7].
[9] The adhesive according to [8], wherein the adhesive layer has a dielectric constant of 3.5 or less and a dielectric loss tangent of 0.005 or less when measured at a frequency of 28 GHz. layer.
[10] a substrate film;
[8] or the adhesive layer according to [9], and a laminate having.
[11] The laminate according to [10], wherein the base film contains a polyetheretherketone (PEEK) resin.
[12] A coverlay film with an adhesive layer comprising the laminate according to [10] or [11].
[13] A copper-clad laminate comprising the laminate according to [10] or [11].
[14] A printed wiring board comprising the laminate according to [10] or [11].
[15] A shielding film comprising the laminate according to [10] or [11].
[16] A printed wiring board with a shielding film comprising the laminate according to [10] or [11].
　本発明によれば、５Ｇ対応可能な良好な電気特性（誘電特性）を有しつつ、密着性の悪い低誘電基材フィルムに対しても良好な密着性を示し、耐熱性、耐薬品（耐溶剤）性を兼ね備えた低誘電接着剤層を形成するための接着剤組成物を提供することができる。 According to the present invention, while having good electrical properties (dielectric properties) compatible with 5G, it exhibits good adhesion even to low-dielectric substrate films with poor adhesion, and has heat resistance and chemical resistance (resistance). It is possible to provide an adhesive composition for forming a low dielectric adhesive layer that also has solvent properties.
　以下、本発明の接着剤組成物、該接着剤組成物からなる接着剤層を含む積層体、及び該積層体を含む電子部品関連の構成部材について詳細に説明するが、以下に記載する構成要件の説明は、本発明の一実施態様としての一例であり、これらの内容に特定されるものではない。 Hereinafter, the adhesive composition of the present invention, a laminate containing an adhesive layer made of the adhesive composition, and an electronic component-related constituent member containing the laminate will be described in detail. is an example as one embodiment of the present invention, and is not limited to these contents.
（接着剤組成物）
　本発明の接着剤組成物は、スチレン系エラストマーと、ベンゾオキサジン樹脂とを含有する。
　本発明で使用するスチレン系エラストマーは、アミノ基を含有するスチレン系エラストマーを含有する。 (Adhesive composition)
The adhesive composition of the present invention contains a styrene-based elastomer and a benzoxazine resin.
The styrenic elastomer used in the present invention contains a styrenic elastomer containing an amino group.
＜スチレン系エラストマー＞
　接着剤組成物に含有されるスチレン系エラストマーは、変性スチレン系エラストマーを含有する。変性スチレン系エラストマーは少なくとも、アミノ基を含有するスチレン系エラストマーを含有する。
　本発明で使用するスチレン系エラストマーは、アミノ基を含有するスチレン系エラストマー以外の他の変性スチレン系エラストマーを含有してもよく、また変性スチレン系エラストマー以外の無変性スチレン系エラストマーを含有してもよい。
　本発明の接着剤組成物は、接着剤組成物に要求される様々な特性を満足させるという観点から、少なくとも２種類以上のスチレン系エラストマーを含有することが好ましい。
　スチレン系エラストマーとは、不飽和炭化水素と芳香族ビニル化合物とのブロック及びランダム構造を主体とする共重合体、並びにその水素添加物である。 <Styrene-based elastomer>
The styrene elastomer contained in the adhesive composition contains a modified styrene elastomer. The modified styrenic elastomer contains at least a styrenic elastomer containing an amino group.
The styrene elastomer used in the present invention may contain a modified styrene elastomer other than the amino group-containing styrene elastomer, or may contain an unmodified styrene elastomer other than the modified styrene elastomer. good.
The adhesive composition of the present invention preferably contains at least two types of styrenic elastomers from the viewpoint of satisfying various properties required for the adhesive composition.
Styrenic elastomers are copolymers composed mainly of block and random structures of unsaturated hydrocarbons and aromatic vinyl compounds, and hydrogenated products thereof.
　芳香族ビニル化合物としては、例えばスチレン、ｔ－ブチルスチレン、α－メチルスチレン、ジビニルベンゼン、１，１－ジフェニルエチレン、Ｎ，Ｎ－ジエチル－ｐ－アミノエチルスチレン、ビニルトルエン等が挙げられる。
　不飽和炭化水素としては、例えば、エチレン、プロピレン、ブタジエン、イソプレン、イソブテン、１，３－ペンタジエン、２，３－ジメチル－１，３－ブタジエン等を挙げることができる。 Examples of aromatic vinyl compounds include styrene, t-butylstyrene, α-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-diethyl-p-aminoethylstyrene and vinyltoluene.
Examples of unsaturated hydrocarbons include ethylene, propylene, butadiene, isoprene, isobutene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like.
　本発明で使用するスチレン系エラストマーは、重量平均分子量が、３０，０００以上であることが好ましく、７０，０００以上であることがより好ましい。重量平均分子量が３０，０００以上であれば、優れた接着性を発現できる。重量平均分子量が７０，０００以上であれば、溶媒に溶解させて塗工する際の成膜性が向上し、ピンホールや液だれによる厚みムラが発生しづらくなるため、塗工した面での性能のブレが小さく、密着力や耐薬品性の不足が起こりづらくなる。また、プリント配線板作製時に重要になる厚さの制御も容易になる。また、重量平均分子量が１００，０００以上のスチレン系エラストマーを含有することが好ましい。重量平均分子量が１００，０００以上のスチレン系エラストマーを含有する場合、プリント配線板作製時の熱圧着で応力がかかっても、設計サイズから逸脱するような接着剤組成物の過度な樹脂流れ（レジンフロー）を抑制できる。スチレン系エラストマーは、重量平均分子量が、３００，０００以下であることが好ましく、２００，０００以下であることがより好ましい。重量平均分子量が３００，０００以下であれば、ベンゾオキサジン樹脂との相溶性が向上し、優れた耐薬品性が発現できる。重量平均分子量が２００，０００以下であれば、溶媒に溶解させて塗工する際の粘度上昇を抑えることができ、レベリング性が向上することで平滑な面状態で製膜できる。その結果、塗工した面での性能のブレが小さく、密着力や耐薬品性の不足が起こりづらくなり、プリント配線板作製時に重要になる厚さの制御も容易になる。
　重量平均分子量は、ゲル・パーミエーションクロマトグラフィー（以下、「ＧＰＣ」ともいう）により測定した分子量をポリスチレン換算した値である。
　また、本発明で使用するスチレン系エラストマーは、スチレン比が２０以上であることが好ましく、３０以上であることがより好ましい。スチレン比が２０以上であれば、優れた接着性を発現できる。スチレン比が３０以上であれば、接着剤組成物の耐熱性を発現できる。また、スチレン比が４０以上であるスチレン系エラストマーを含有することが好ましい。スチレン比が４０以上であるスチレン系エラストマーを含有する場合、ベンゾオキサジン樹脂との相溶性が向上して、優れた接着性と耐薬品性を発現できる。スチレン系エラストマーは、スチレン比が８０以下であることが好ましく、６０以下であることがより好ましい。スチレン比が８０以下であることで、加熱時の流動性を高められることで、基材フィルムの表面に十分に追従して優れた接着力を発現できる。スチレン比が６０以下であれば、スチレン系エラストマーの調達が容易である。
　２種以上のスチレン系エラストマーを含有する場合、少なくとも一つのスチレン系エラストマーのスチレン比が、４０以上であるとよい。 The styrene elastomer used in the present invention preferably has a weight average molecular weight of 30,000 or more, more preferably 70,000 or more. If the weight average molecular weight is 30,000 or more, excellent adhesiveness can be exhibited. If the weight-average molecular weight is 70,000 or more, the film-forming property is improved when the polymer is dissolved in a solvent and applied, and thickness unevenness due to pinholes and dripping is less likely to occur. Performance deviation is small, and lack of adhesion and chemical resistance is less likely to occur. In addition, it becomes easy to control the thickness, which is important when manufacturing a printed wiring board. Moreover, it is preferable to contain a styrene-based elastomer having a weight average molecular weight of 100,000 or more. When a styrene-based elastomer having a weight-average molecular weight of 100,000 or more is contained, excessive resin flow (resin flow) can be suppressed. The styrene elastomer preferably has a weight average molecular weight of 300,000 or less, more preferably 200,000 or less. If the weight average molecular weight is 300,000 or less, the compatibility with the benzoxazine resin is improved, and excellent chemical resistance can be exhibited. If the weight-average molecular weight is 200,000 or less, it is possible to suppress an increase in viscosity during coating by dissolving in a solvent, and improve leveling properties, thereby forming a film with a smooth surface. As a result, fluctuations in performance on the coated surface are small, insufficient adhesion and chemical resistance are less likely to occur, and thickness control, which is important in the production of printed wiring boards, becomes easier.
The weight average molecular weight is a value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter also referred to as "GPC") into polystyrene.
The styrene elastomer used in the present invention preferably has a styrene ratio of 20 or more, more preferably 30 or more. If the styrene ratio is 20 or more, excellent adhesiveness can be exhibited. If the styrene ratio is 30 or more, the heat resistance of the adhesive composition can be expressed. Moreover, it is preferable to contain a styrene-based elastomer having a styrene ratio of 40 or more. When a styrene-based elastomer having a styrene ratio of 40 or more is contained, the compatibility with the benzoxazine resin is improved, and excellent adhesiveness and chemical resistance can be exhibited. The styrene-based elastomer preferably has a styrene ratio of 80 or less, more preferably 60 or less. When the styrene ratio is 80 or less, the fluidity at the time of heating can be enhanced, so that the surface of the substrate film can be sufficiently followed and excellent adhesive strength can be exhibited. If the styrene ratio is 60 or less, procurement of the styrene-based elastomer is easy.
When two or more styrene-based elastomers are contained, the styrene ratio of at least one styrene-based elastomer is preferably 40 or more.
　スチレン系エラストマーの種類としては、スチレン－ブタジエン共重合体、スチレン－イソプレン共重合体、スチレン－エチレン共重合体、それらのランダム共重合体、ブロック共重合体、さらに、それらの水素添加物等が挙げられる。スチレン系エラストマーとしては、スチレン－ブタジエンのブロック共重合体の水素添加物が好ましい。スチレン－ブタジエンのブロック共重合体の水素添加物は、スチレンを主とするブロック構造がベンゾオキサジン樹脂との相溶性を向上でき、主にブタジエンに由来するブロック構造が高い可撓性を付与することで、優れた接着性を発現できる。
　スチレン系エラストマーの具体例としては、スチレン－ブタジエンブロック共重合体、スチレン－エチレンプロピレンブロック共重合体、スチレン－ブタジエン－スチレンブロック共重合体、スチレン－イソプレン－スチレンブロック共重合体、スチレン－エチレンブチレン－スチレンブロック共重合体及びスチレン－エチレンプロピレン－スチレンブロック共重合体等が挙げられる。
　これらのスチレン系エラストマーは１種のみを用いてもよく、２種以上を併用してもよい。
　上記共重合体の中でも、上記の理由に加え、接着剤組成物に電気特性（誘電特性）を付与でき、分子構造の制御が比較的簡易で接着剤組成物の特性を調整しやすい観点から、スチレン－エチレンブチレン－スチレンブロック共重合体及びスチレン－エチレンプロピレン－スチレンブロック共重合体が好ましい。
　本発明のスチレン系エラストマーには、上記の構造に置換基を導入した変性スチレン系エラストマーと、置換基を導入していない無変性スチレン系エラストマーとが含まれる。 Types of styrene elastomers include styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-ethylene copolymers, their random copolymers, block copolymers, hydrogenated products thereof, and the like. mentioned. As the styrene-based elastomer, a hydrogenated styrene-butadiene block copolymer is preferable. In the hydrogenated styrene-butadiene block copolymer, the block structure mainly composed of styrene can improve compatibility with benzoxazine resin, and the block structure mainly derived from butadiene imparts high flexibility. , excellent adhesiveness can be expressed.
Specific examples of styrene-based elastomers include styrene-butadiene block copolymers, styrene-ethylenepropylene block copolymers, styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, and styrene-ethylenebutylene. -styrene block copolymers and styrene-ethylene propylene-styrene block copolymers.
These styrene-based elastomers may be used alone or in combination of two or more.
Among the above copolymers, in addition to the above reasons, from the viewpoint that they can impart electrical properties (dielectric properties) to the adhesive composition, control the molecular structure is relatively easy, and the properties of the adhesive composition can be easily adjusted. Styrene-ethylenebutylene-styrene block copolymers and styrene-ethylenepropylene-styrene block copolymers are preferred.
The styrene-based elastomer of the present invention includes modified styrene-based elastomers in which substituents have been introduced into the above structures, and unmodified styrene-based elastomers in which no substituents have been introduced.
＜＜変性スチレン系エラストマー＞＞
　本発明の接着剤組成物は、変性スチレン系エラストマーを含有することで、後述のベンゾオキサジン樹脂、架橋剤等と反応し、硬化することで、優れた接着性と耐薬品性を発現する。また、導入された置換基は金属と相互作用が強いため、変性スチレン系エラストマーを含有することで、接着剤組成物と金属基材との接着力が向上する。
　変性スチレン系エラストマーとは、不飽和炭化水素と芳香族ビニル化合物とのブロック及びランダム構造を主体とする共重合体、並びにその水素添加物に、カルボキシ基、アミノ基、エポキシ基、イソシアネート基、アクリロイル基、ヒドロキシ基、メルカプト基、イミド基、アルコキシシリル基等の置換基を導入したものである。
　本発明の接着剤組成物は、変性スチレン系エラストマーとして、少なくともアミノ基を含有するスチレン系エラストマーを含有する。
　本発明の接着剤組成物は、本発明の効果を損なわない限り、アミノ基を含有するスチレン系エラストマー以外の他の変性スチレン系エラストマーを含有してもよい。 <<Modified Styrene Elastomer>>
Since the adhesive composition of the present invention contains a modified styrene-based elastomer, it reacts with a benzoxazine resin, a cross-linking agent, etc., which will be described later, and cures, thereby exhibiting excellent adhesiveness and chemical resistance. In addition, since the introduced substituent has a strong interaction with metal, the inclusion of the modified styrene-based elastomer improves the adhesive strength between the adhesive composition and the metal substrate.
Modified styrenic elastomers are copolymers mainly composed of block and random structures of unsaturated hydrocarbons and aromatic vinyl compounds, and hydrogenated products thereof containing carboxy groups, amino groups, epoxy groups, isocyanate groups, acryloyl , a hydroxyl group, a mercapto group, an imide group, an alkoxysilyl group, and the like.
The adhesive composition of the present invention contains a styrene elastomer containing at least an amino group as the modified styrene elastomer.
The adhesive composition of the present invention may contain modified styrene-based elastomers other than the amino group-containing styrene-based elastomer as long as the effects of the present invention are not impaired.
＜＜＜アミノ基を含有するスチレン系エラストマー＞＞＞
　接着剤組成物中にアミノ基を含有するスチレン系エラストマーが含有されていることで、アミノ基が低誘電基材フィルムとの強い相互作用を発現し、接着剤組成物の密着性が向上する。また、アミノ基を含有するため金属との密着性が向上する。
　アミノ基を含有するスチレン系エラストマーとは、不飽和炭化水素と芳香族ビニル化合物とのブロック及びランダム構造を主体とする共重合体、並びにその水素添加物を、アミン変性したものである。 <<<Styrene Elastomer Containing Amino Group>>>
When the adhesive composition contains a styrene-based elastomer containing amino groups, the amino groups exhibit a strong interaction with the low-dielectric substrate film, improving the adhesion of the adhesive composition. Moreover, since it contains an amino group, the adhesion to metals is improved.
Styrenic elastomers containing amino groups are copolymers mainly composed of block and random structures of unsaturated hydrocarbons and aromatic vinyl compounds, and hydrogenated products thereof modified with amines.
　スチレン系エラストマーをアミン変性する方法は、特に限定されず、公知の方法を用いることができ、例えば、アミノ基を有する重合開始剤を用いて（水添）ブロック共重合体を重合することによりアミン変性する方法、アミノ基を有する不飽和単量体を、共重合する原料と用いることにより（水添）共重合体をアミン変性する方法、カルボキシ基を含有するスチレン系エラストマーにアミノ基を２つ以上有するアミン変性剤を反応させ、アミド構造、あるいは、またはイミド構造を形成することでアミン変性する方法等が挙げられる。 The method of amine-modifying the styrene elastomer is not particularly limited, and a known method can be used. A modification method, a method of amine-modifying a (hydrogenated) copolymer by using an unsaturated monomer having an amino group as a raw material to be copolymerized, and a styrene-based elastomer containing a carboxy group with two amino groups. A method of modifying the amine by reacting the above amine modifier to form an amide structure or an imide structure, and the like.
　アミノ基を含有するスチレン系エラストマーの具体例としては、前述のスチレン系エラストマーにアミノ基を導入したものが挙げられる。 Specific examples of styrene-based elastomers containing amino groups include those obtained by introducing amino groups into the aforementioned styrene-based elastomers.
　接着剤組成物の良好な電気特性(低比誘電率、低誘電損失)と、密着性（接着性）とを担保するという観点からすると、アミノ基を含有するスチレン系エラストマー中の全窒素量は、５０～５０００ｐｐｍであることが好ましく、２００～３０００ｐｐｍであることがより好ましい。全窒素量が上記下限以上であれば、優れた密着性を発現できる。全窒素量が上記上限以下であれば、電気特性が優れる。
　アミノ基を含有するスチレン系エラストマー中の全窒素量は、微量窒素分析装置ＮＤ―１００型（三菱化学株式会社製）を使用して、ＪＩＳ－Ｋ２６０９に従い求めることができる。 From the viewpoint of securing good electrical properties (low dielectric constant, low dielectric loss) and adhesion (adhesiveness) of the adhesive composition, the total nitrogen content in the amino group-containing styrene elastomer is , preferably 50 to 5000 ppm, more preferably 200 to 3000 ppm. If the total nitrogen content is at least the above lower limit, excellent adhesion can be exhibited. If the total nitrogen content is equal to or less than the above upper limit, the electrical properties are excellent.
The total nitrogen content in the styrene-based elastomer containing amino groups can be determined according to JIS-K2609 using a trace nitrogen analyzer ND-100 (manufactured by Mitsubishi Chemical Corporation).
　接着剤組成物におけるアミノ基を含有するスチレン系エラストマーの含有量としては、耐薬品性と耐熱性との両立という観点から、本発明の接着剤組成物１００質量部に対し、アミノ基を含有するスチレン系エラストマーは、３０～９５質量部含有することが好ましく、３０～８０質量部含有することがより好ましい。 From the viewpoint of achieving both chemical resistance and heat resistance, the content of the styrene-based elastomer containing an amino group in the adhesive composition is The styrene-based elastomer is preferably contained in an amount of 30 to 95 parts by mass, more preferably 30 to 80 parts by mass.
＜＜＜カルボキシ基を含有するスチレン系エラストマー＞＞＞
　カルボキシ基を含有するスチレン系エラストマーは、接着性や硬化物の柔軟性に加えて、電気特性を与える成分として有効である。
　カルボキシ基を含有するスチレン系エラストマーは、不飽和炭化水素と芳香族ビニル化合物とのブロック及びランダム構造を主体とする共重合体、並びにその水素添加物を、不飽和カルボン酸で変性したものである。
　芳香族ビニル化合物及び不飽和炭化水素の種類やスチレン系エラストマーの具体例としては、上記＜スチレン系エラストマー＞の欄で述べたとおりである。 <<<Styrene Elastomer Containing Carboxy Group>>>
A styrene-based elastomer containing a carboxy group is effective as a component that imparts electrical properties in addition to adhesiveness and flexibility of a cured product.
Carboxy group-containing styrenic elastomers are copolymers mainly composed of block and random structures of unsaturated hydrocarbons and aromatic vinyl compounds, and hydrogenated products thereof modified with unsaturated carboxylic acids. .
The types of the aromatic vinyl compound and the unsaturated hydrocarbon and specific examples of the styrene-based elastomer are as described in the section <Styrene-based elastomer> above.
　カルボキシ基を含有するスチレン系エラストマーの変性は、例えば、スチレン系エラストマーの重合時に、不飽和カルボン酸を共重合させることにより行うことができる。また、スチレン系エラストマーと不飽和カルボン酸を有機パーオキサイドの存在下に加熱、混練することにより行うこともできる。
　不飽和カルボン酸としては、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、フマル酸、無水マレイン酸、無水イタコン酸等を挙げることができる。
　不飽和カルボン酸による変性量は、０．１～１０質量％であることが好ましい。
　カルボキシ基を含有するスチレン系エラストマーの酸価は、０．１～２５ｍｇＫＯＨ／ｇであることが好ましく、０．５～２３ｍｇＫＯＨ／ｇであることがより好ましい。この酸価が０．１ｍｇＫＯＨ／ｇ以上であると、接着剤組成物の硬化が十分であり、良好な接着性、及び耐熱性が得られる。一方、前記酸価が３０ｍｇＫＯＨ／ｇ以下であると、接着剤組成物の凝集力が抑えられるため粘着性に優れ、電気特性にも優れる。 Modification of a styrene-based elastomer containing a carboxy group can be carried out, for example, by copolymerizing an unsaturated carboxylic acid during polymerization of the styrene-based elastomer. It can also be carried out by heating and kneading a styrene-based elastomer and an unsaturated carboxylic acid in the presence of an organic peroxide.
Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, maleic anhydride, and itaconic anhydride.
The amount of modification with unsaturated carboxylic acid is preferably 0.1 to 10% by mass.
The acid value of the styrene-based elastomer containing carboxy groups is preferably 0.1 to 25 mgKOH/g, more preferably 0.5 to 23 mgKOH/g. When the acid value is 0.1 mgKOH/g or more, the adhesive composition is sufficiently cured, and good adhesiveness and heat resistance can be obtained. On the other hand, when the acid value is 30 mgKOH/g or less, the cohesive force of the adhesive composition is suppressed, resulting in excellent adhesiveness and excellent electrical properties.
＜＜無変性スチレン系エラストマー＞＞
　本発明の接着剤組成物は、上記変性スチレン系エラストマー以外に、無変性スチレン系エラストマーを含有してもよい。
　無変性スチレン系エラストマーは、１種のみ用いてもよく、２種以上含有させてもよい。 <<Non-modified styrene elastomer>>
The adhesive composition of the present invention may contain an unmodified styrene elastomer in addition to the modified styrene elastomer.
Only one type of unmodified styrene elastomer may be used, or two or more types may be contained.
　無変性スチレン系エラストマーとは、不飽和炭化水素と芳香族ビニル化合物とのブロック及びランダム構造を主体とする共重合体、並びにその水素添加物である。
　分子内に極性の高い結合基が少なく、組成物に良好な電気特性（誘電特性）を付与できる。また、他の種類のエラストマーと比較して、分子量の制御が容易で、接着剤組成物の特性を安定して生産できることも利点である。
　芳香族ビニル化合物及び不飽和炭化水素の種類やスチレン系エラストマーの具体例としては、上記＜スチレン系エラストマー＞の欄で述べたとおりである。 Unmodified styrene elastomers are copolymers mainly composed of block and random structures of unsaturated hydrocarbons and aromatic vinyl compounds, and hydrogenated products thereof.
There are few highly polar bonding groups in the molecule, and good electrical properties (dielectric properties) can be imparted to the composition. Another advantage is that the molecular weight can be easily controlled and the properties of the adhesive composition can be stably produced compared to other types of elastomers.
The types of the aromatic vinyl compound and the unsaturated hydrocarbon and specific examples of the styrene-based elastomer are as described in the section <Styrene-based elastomer> above.
　アミノ基を含有するスチレン系エラストマー１００質量部に対する無変性スチレン系エラストマーの含有量は、３５～１００質量部であると好ましい。アミノ基を含有するスチレン系エラストマー１００質量部に対する無変性スチレン系エラストマーの含有量が上記範囲内であれば、無変性スチレン系エラストマーの配合により接着剤組成物の弾性率や流動性の調整する効果が発現しやすい。 The content of the unmodified styrene-based elastomer is preferably 35 to 100 parts by mass with respect to 100 parts by mass of the styrene-based elastomer containing amino groups. If the content of the unmodified styrene elastomer relative to 100 parts by mass of the styrene elastomer containing an amino group is within the above range, the effect of adjusting the elastic modulus and fluidity of the adhesive composition by blending the unmodified styrene elastomer. is likely to occur.
　無変性スチレン系エラストマーの重量平均分子量（Ｍｗ）としては、１００,０００以上であることが好ましく、１００，０００～２００,０００であることがより好ましい。上記範囲内であれば、流動性の制御と密着力の両立が可能である。 The weight average molecular weight (Mw) of the unmodified styrene elastomer is preferably 100,000 or more, more preferably 100,000 to 200,000. Within the above range, it is possible to achieve both fluidity control and adhesion.
　本発明で使用する無変性スチレン系エラストマーは、スチレン比が４０～８０であることが好ましい。スチレン比が４０以上であるスチレン系エラストマーを含有する場合、ベンゾオキサジン樹脂との相溶性が向上して、優れた接着性と耐薬品性を発現できる。 The unmodified styrene elastomer used in the present invention preferably has a styrene ratio of 40-80. When a styrene-based elastomer having a styrene ratio of 40 or more is contained, the compatibility with the benzoxazine resin is improved, and excellent adhesiveness and chemical resistance can be exhibited.
＜ベンゾオキサジン樹脂＞
　ベンゾオキサジン樹脂は、接着剤組成物の架橋密度を高めることで、被着体に対する高い接着性や、接着剤硬化物の耐薬品性、耐熱性を発現させることができる。ベンゾオキサジン樹脂は、自己重合反応し、架橋構造を形成する。
　ベンゾオキサジンとしては、密着性が高いスチレン系エラストマーの含有量を高めつつ、架橋密度を向上できる観点から分子中にオキサジン骨格を２個以上含む構造であることが好ましい。 <Benzoxazine resin>
The benzoxazine resin increases the cross-linking density of the adhesive composition, thereby making it possible to exhibit high adhesion to adherends and the chemical resistance and heat resistance of the cured adhesive. The benzoxazine resin undergoes a self-polymerization reaction to form a crosslinked structure.
The benzoxazine preferably has a structure containing two or more oxazine skeletons in the molecule from the viewpoint of increasing the content of the highly adhesive styrene-based elastomer and improving the crosslink density.
　ベンゾオキサジン樹脂としては、例えば、６，６－（１－メチルエチリデン）ビス（３，４－ジヒドロ－３－フェニル－２Ｈ－１，３－ベンゾオキサジン）、６，６－（１－メチルエチリデン）ビス（３，４－ジヒドロ－３－メチル－２Ｈ－１，３－ベンゾオキサジン）等が挙げられ、二種以上組み合わせてもよい。なお、オキサジン環の窒素にはフェニル基、メチル基、シクロヘキシル基等が結合していてもよい。また、ベンゾオキサジン樹脂の具体例としては、四国化成工業（株）社製の「ベンゾオキサジンＦ－ａ」や「ベンゾオキサジンＰ－ｄ」、「ベンゾオキサジンＡＬＰ－ｄ」等が挙げられる。 Benzoxazine resins include, for example, 6,6-(1-methylethylidene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6-(1-methylethylidene) Examples thereof include bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine) and the like, and two or more of them may be combined. A phenyl group, a methyl group, a cyclohexyl group, or the like may be bonded to the nitrogen of the oxazine ring. Specific examples of benzoxazine resins include "Benzoxazine Fa", "Benzoxazine Pd" and "Benzoxazine ALP-d" manufactured by Shikoku Kasei Co., Ltd., and the like.
　ベンゾオキサジン樹脂の融点、又は軟化点は、熱ラミネートや熱プレスの温度で接着剤組成物に流動性を与え、基材フィルムや金属基材の表面に十分に追従させ、優れた密着性と硬化時の耐薬品性を発現させる等の観点から、１２０℃未満であることが好ましい。
　ベンゾオキサジン樹脂の融点、又は軟化点は、常温での接着剤組成物の弾性率を高め、密着力を向上できる観点から、４０℃以上であることが好ましい。
　また、接着剤組成物におけるベンゾオキサジン樹脂の含有量としては、耐薬品性と耐熱性とを発現させるという観点から、接着剤組成物１００質量部に対し、５質量部以上であることが好ましく、１０質量部以上であることがより好ましい。また、ベンゾオキサジン樹脂の含有量は７０質量部以下であることが好ましく、５０質量部以下であることがより好ましい。ベンゾオキサジン樹脂の含有量が５質量部以上であれば、基材フィルムへの優れた耐薬品性が発現できる。ベンゾオキサジン樹脂の含有量が７０質量部以下であれば、優れた誘電特性を発現できる。 The melting point or softening point of the benzoxazine resin gives fluidity to the adhesive composition at the temperature of heat lamination or heat press, allowing it to follow the surface of the substrate film or metal substrate sufficiently, resulting in excellent adhesion and curing. It is preferably less than 120° C. from the viewpoint of exhibiting chemical resistance at times.
The melting point or softening point of the benzoxazine resin is preferably 40° C. or higher from the viewpoint of increasing the elastic modulus of the adhesive composition at room temperature and improving the adhesion.
In addition, the content of the benzoxazine resin in the adhesive composition is preferably 5 parts by mass or more with respect to 100 parts by mass of the adhesive composition from the viewpoint of expressing chemical resistance and heat resistance. It is more preferably 10 parts by mass or more. Also, the content of the benzoxazine resin is preferably 70 parts by mass or less, more preferably 50 parts by mass or less. If the content of the benzoxazine resin is 5 parts by mass or more, excellent chemical resistance to the substrate film can be exhibited. If the content of the benzoxazine resin is 70 parts by mass or less, excellent dielectric properties can be exhibited.
　本発明の接着剤組成物は、スチレン系エラストマーの他、スチレン系エラストマー以外の樹脂成分やその他の成分を含有してもよい。 The adhesive composition of the present invention may contain, in addition to the styrene elastomer, a resin component other than the styrene elastomer and other components.
＜その他の樹脂成分＞
　本発明の接着剤組成物は、上記スチレン系エラストマー、ベンゾオキサジン樹脂以外にその他の樹脂成分を含有してもよい。
　本発明に係る接着剤組成物は、例えば、スチレン系エラストマー以外の他の熱可塑性樹脂を、接着剤組成物の機能に影響を与えない程度に含有することができる。
　上記他の熱可塑性樹脂としては、例えば、フェノキシ樹脂、ポリアミド樹脂、ポリエステル樹脂、ポリカーボネート樹脂、ポリフェニレンオキシド樹脂、ポリウレタン樹脂、ポリアセタール樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリブタジエン系樹脂、及びポリビニル系樹脂等が挙げられる。これらの熱可塑性樹脂は、単独で用いてもよいし、２種以上を併用してもよい。 <Other resin components>
The adhesive composition of the present invention may contain other resin components in addition to the styrene-based elastomer and benzoxazine resin.
The adhesive composition according to the present invention can contain, for example, thermoplastic resins other than the styrene-based elastomer to such an extent that the functions of the adhesive composition are not affected.
Examples of other thermoplastic resins include phenoxy resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene oxide resins, polyurethane resins, polyacetal resins, polyethylene resins, polypropylene resins, polybutadiene resins, and polyvinyl resins. is mentioned. These thermoplastic resins may be used alone or in combination of two or more.
＜その他の成分＞
　本発明で使用する樹脂組成物は、スチレン系エラストマー、ベンゾオキサジン樹脂や上記その他の樹脂成分等の樹脂成分以外に、その他の成分を含有することができる。
　その他の成分としては、例えば、上記スチレン系エラストマー、ベンゾオキサジン樹脂と反応し、架橋構造を形成する架橋剤が挙げられる。必要に応じて、上記スチレン系エラストマー、ベンゾオキサジン樹脂と架橋剤との反応を促進する反応促進剤を含んでよい。
　また、上記以外に、その他の成分として、例えば、フィラー、粘着付与剤、難燃剤、熱老化防止剤、レベリング剤、消泡剤、無機充填剤及び顔料が挙げられる。これらを、接着剤組成物の機能に影響を与えない程度に含有することができる。 <Other ingredients>
The resin composition used in the present invention may contain other components in addition to the resin components such as the styrene-based elastomer, benzoxazine resin, and other resin components described above.
Other components include, for example, a cross-linking agent that reacts with the styrene-based elastomer and benzoxazine resin to form a cross-linked structure. If necessary, a reaction accelerator that accelerates the reaction between the styrene-based elastomer, benzoxazine resin and the cross-linking agent may be included.
In addition to the above, other components include, for example, fillers, tackifiers, flame retardants, heat anti-aging agents, leveling agents, antifoaming agents, inorganic fillers and pigments. These can be contained to the extent that they do not affect the functions of the adhesive composition.
＜＜架橋剤＞＞
　架橋剤としては、エポキシ樹脂、イソシアネート樹脂、フェノール樹脂、シアネート樹脂、ポリアミド、ポリウレタン、有機過酸化物、シランカップリング剤等が挙げられる。架橋剤は１種のみ用いてもよく、２種以上含有させてもよい。 <<crosslinking agent>>
Examples of cross-linking agents include epoxy resins, isocyanate resins, phenol resins, cyanate resins, polyamides, polyurethanes, organic peroxides, silane coupling agents, and the like. Only one type of cross-linking agent may be used, or two or more types may be contained.
＜＜フィラー＞＞
　本発明の接着剤組成物は、フィラーを含有することが好ましい。
　本発明に係るフィラーとしては、例えば、耐熱性や接着剤組成物の機械的特性制御の観点から、無機フィラーが好ましく、無機フィラーとしては、電気特性の観点から、ケイ素系無機フィラーおよび窒化ホウ素が好ましい。また、ケイ素系無機フィラーとしては、例えば、少量でも接着剤組成物の機械的物性の制御が可能で、電気特性にも優れるマイカおよびタルクが好ましい。
　また、本発明に係るフィラーとしては、例えば、分散性や脆性の観点から、有機フィラーが好ましく、有機フィラーとしては、電気特性の観点から、スチレン系の真球状フィラーが好ましく、スチレン系中空フィラーがより好ましい。
　これらは、単独で使用してもよいし、２種以上を組み合わせて使用してもよい。
　本発明の接着剤組成物に含有されるフィラーの含有量は、樹脂組成物１００体積部に対して０．５～２５体積部が好ましく、樹脂組成物１００体積部に対して１～１５体積部であるとより好ましい。
　フィラーの形状としては、特に限定されず、目的に応じて適宜選択することができる。例えば、無機フィラーは、球状無機フィラーでも非球状無機フィラーでもよいが、熱膨張率（ＣＴＥ）、フィルム強度の観点からは、非球状無機フィラーが好ましい。非球状無機フィラーの形状は、球状（略真円球状）以外の三次元形状であればよく、例えば、板状、鱗片状、柱状、鎖状、繊維状等が挙げられる。中でも、熱膨張率（ＣＴＥ）、フィルム強度の観点から、板状、鱗片状の無機フィラーが好ましく、板状の無機フィラーがより好ましい。 <<Filler>>
The adhesive composition of the present invention preferably contains a filler.
As the filler according to the present invention, for example, an inorganic filler is preferable from the viewpoint of heat resistance and mechanical property control of the adhesive composition, and as the inorganic filler, a silicon-based inorganic filler and boron nitride are preferable from the viewpoint of electrical properties. preferable. Moreover, as the silicon-based inorganic filler, for example, mica and talc are preferable because they can control the mechanical properties of the adhesive composition even in a small amount and have excellent electrical properties.
Further, as the filler according to the present invention, for example, an organic filler is preferable from the viewpoint of dispersibility and brittleness, and as the organic filler, a styrene-based spherical filler is preferable from the viewpoint of electrical properties, and a styrene-based hollow filler is preferable. more preferred.
These may be used alone or in combination of two or more.
The content of the filler contained in the adhesive composition of the present invention is preferably 0.5 to 25 parts by volume with respect to 100 parts by volume of the resin composition, and 1 to 15 parts by volume with respect to 100 parts by volume of the resin composition. is more preferable.
The shape of the filler is not particularly limited and can be appropriately selected depending on the purpose. For example, the inorganic filler may be a spherical inorganic filler or a non-spherical inorganic filler, but a non-spherical inorganic filler is preferable from the viewpoint of coefficient of thermal expansion (CTE) and film strength. The shape of the non-spherical inorganic filler may be any three-dimensional shape other than a spherical shape (substantially spherical shape), and examples thereof include plate-like, scale-like, columnar, chain-like, and fibrous shapes. Among them, from the viewpoint of coefficient of thermal expansion (CTE) and film strength, plate-like and scale-like inorganic fillers are preferable, and plate-like inorganic fillers are more preferable.
　上記粘着付与剤としては、例えば、クマロン－インデン樹脂、テルペン樹脂、テルペン－フェノール樹脂、ロジン樹脂、ｐ－ｔ－ブチルフェノール－アセチレン樹脂、フェノール－ホルムアルデヒド樹脂、キシレン－ホルムアルデヒド樹脂、石油系炭化水素樹脂、水素添加炭化水素樹脂、テレピン系樹脂等を挙げることができる。これらの粘着付与剤は、単独で用いてもよいし、２種以上を併用してもよい。 Examples of the tackifier include coumarone-indene resin, terpene resin, terpene-phenol resin, rosin resin, pt-butylphenol-acetylene resin, phenol-formaldehyde resin, xylene-formaldehyde resin, petroleum-based hydrocarbon resin, Examples include hydrogenated hydrocarbon resins and turpentine resins. These tackifiers may be used alone or in combination of two or more.
　上記難燃剤は、有機系難燃剤及び無機系難燃剤のいずれでもよい。有機系難燃剤としては、例えば、リン酸メラミン、ポリリン酸メラミン、リン酸グアニジン、ポリリン酸グアニジン、リン酸アンモニウム、ポリリン酸アンモニウム、リン酸アミドアンモニウム、ポリリン酸アミドアンモニウム、リン酸カルバメート、ポリリン酸カルバメート、トリスジエチルホスフィン酸アルミニウム、トリスメチルエチルホスフィン酸アルミニウム、トリスジフェニルホスフィン酸アルミニウム、ビスジエチルホスフィン酸亜鉛、ビスメチルエチルホスフィン酸亜鉛、ビスジフェニルホスフィン酸亜鉛、ビスジエチルホスフィン酸チタニル、テトラキスジエチルホスフィン酸チタン、ビスメチルエチルホスフィン酸チタニル、テトラキスメチルエチルホスフィン酸チタン、ビスジフェニルホスフィン酸チタニル、テトラキスジフェニルホスフィン酸チタン等のリン系難燃剤； メラミン、メラム、メラミンシアヌレート等のトリアジン系化合物や、シアヌル酸化合物、イソシアヌル酸化合物、トリアゾール系化合物、テトラゾール化合物、ジアゾ化合物、尿素等の窒素系難燃剤；シリコーン化合物、シラン化合物等のケイ素系難燃剤等が挙げられる。また、無機系難燃剤としては、水酸化アルミニウム、水酸化マグネシウム、水酸化ジルコニウム、水酸化バリウム、水酸化カルシウム等の金属水酸化物；酸化スズ、酸化アルミニウム、酸化マグネシウム、酸化ジルコニウム、酸化亜鉛、酸化モリブデン、酸化ニッケル等の金属酸化物；炭酸亜鉛、炭酸マグネシウム、炭酸バリウム、ホウ酸亜鉛、水和ガラス等が挙げられる。これらの難燃剤は、２種以上を併用することができる。 The above flame retardant may be either an organic flame retardant or an inorganic flame retardant. Examples of organic flame retardants include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, amide ammonium phosphate, amide ammonium polyphosphate, carbamate phosphate, and carbamate polyphosphate. , aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate , titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, and titanium tetrakisdiphenylphosphinate; triazine compounds such as melamine, melam, and melamine cyanurate; , isocyanuric acid compounds, triazole compounds, tetrazole compounds, diazo compounds, urea, and other nitrogen-based flame retardants; silicone compounds, silane compounds, and other silicon-based flame retardants. Inorganic flame retardants include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, and calcium hydroxide; tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, Metal oxides such as molybdenum oxide and nickel oxide; zinc carbonate, magnesium carbonate, barium carbonate, zinc borate, hydrated glass and the like. These flame retardants can be used in combination of two or more.
　上記熱老化防止剤としては、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノ－ル、ｎ－オクタデシル－３－（３’，５’－ジ－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネ－ト、テトラキス〔メチレン－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネ－ト〕メタン、ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェノール、トリエチレングリコール－ビス〔３－（３－ｔ－ブチル－５－メチル－４－ヒドロキシフェニル）プロピオネート等のフェノ－ル系酸化防止剤；ジラウリル－３，３’－チオジプロピオネ－ト、ジミリスチル－３，３’－ジチオプロピオネ－ト等のイオウ系酸化防止剤；トリスノニルフェニルホスファイト、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト等のリン系酸化防止剤等が挙げられる。これらは、単独で用いてよいし、２種以上を組み合わせて用いてもよい。 Examples of the heat antiaging agent include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propione. -tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, pentaerythritoltetrakis[3-(3,5-di-t-butyl-4- Phenolic antioxidants such as hydroxyphenol, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate; dilauryl-3,3'-thiodipropionate, dimyristyl sulfur-based antioxidants such as -3,3'-dithiopropionate; phosphorus-based antioxidants such as trisnonylphenyl phosphite and tris(2,4-di-tert-butylphenyl)phosphite; These may be used alone or in combination of two or more.
　上記無機充填剤としては、酸化チタン、酸化アルミニウム、酸化亜鉛、カ－ボンブラック、シリカ、銅、及び銀等からなる粉体が挙げられる。これらは、単独で用いてよいし、２種以上を組み合わせて用いてもよい。 Examples of the inorganic filler include powders made of titanium oxide, aluminum oxide, zinc oxide, carbon black, silica, copper, silver, and the like. These may be used alone or in combination of two or more.
（接着剤層）
　本発明に係る接着剤層は、上記本発明の接着剤組成物を用いて形成される。
　接着剤層を形成する接着剤組成物は、硬化させることができる。
　硬化方法としては、特に限定はなく、目的に応じて適宜選択することができ、例えば、熱硬化等が挙げられる。
　接着剤層の厚みは、特に制限はなく、目的に応じて適宜選択することができるが、例えば、３μｍ以上であることが好ましく、５μｍ以上であることがより好ましい。また、１００μｍ以下であることが好ましく、５０μｍ以下であることがより好ましく、３０μｍ以下であることが更に好ましい。接着剤層の厚みが３μｍ以上であれば、十分な密着力を発現することができ、５μｍ以上であれば、プリント配線板のパターン等の段差に追従することができる。接着剤層の厚みが５０μｍ以下であれば、積層板の薄膜化が可能であり、３０μｍ以下であれば、レジンフローを正確に制御できる。 (adhesive layer)
The adhesive layer according to the present invention is formed using the adhesive composition of the present invention.
The adhesive composition that forms the adhesive layer can be cured.
The curing method is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include heat curing.
The thickness of the adhesive layer is not particularly limited and can be appropriately selected depending on the intended purpose. Also, it is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. If the thickness of the adhesive layer is 3 μm or more, sufficient adhesive strength can be exhibited, and if it is 5 μm or more, steps such as the pattern of the printed wiring board can be followed. If the thickness of the adhesive layer is 50 μm or less, the laminate can be made thinner, and if it is 30 μm or less, the resin flow can be accurately controlled.
＜接着剤層の製造方法＞
　上記接着剤組成物を成膜することで接着剤層を製造することができる。
　上記接着剤組成物は、上述したスチレン系エラストマー、及びベンゾオキサジン樹脂を混合することにより製造することができる。混合方法は特に限定されず、接着剤組成物が均一になればよい。接着剤組成物は、溶液又は分散液の状態で好ましく用いられることから、通常は、溶媒も使用される。
　溶媒としては、例えば、メタノール、エタノール、イソプロピルアルコール、ｎ－プロピルアルコール、イソブチルアルコール、ｎ－ブチルアルコール、ベンジルアルコール、エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、ジアセトンアルコール等のアルコール類；アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルアミルケトン、シクロヘキサノン、イソホロン等のケトン類；トルエン、キシレン、エチルベンゼン、メシチレン、アニソール等の芳香族炭化水素類；酢酸メチル、酢酸エチル、酢酸ブチル、エチレングリコールモノメチルエーテルアセテ－ト、３－メトキシブチルアセテート等のエステル類；ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等の脂肪族炭化水素類等が挙げられる。これらの溶媒は、単独で用いてよいし、２種以上を組み合わせて用いてもよい。特に極性の低い樹脂を溶解できるトルエンに、少量のシクロヘキサノンを添加することで、硬化剤等との相溶性が良くなり、接着剤層を均一にすることができる。
　接着剤組成物が溶媒を含む溶液又は分散液（樹脂ワニス）であると、基材フィルムへの塗工及び接着剤層の形成を円滑に行うことができ、所望の厚さの接着剤層を容易に得ることができる。
　接着剤組成物が溶媒を含む場合、接着剤層の形成を含む作業性等の観点から、固形分濃度は、好ましくは３～８０質量％、より好ましくは１０～５０質量％の範囲である。固形分濃度が８０質量％以下であると、溶液の粘度が適度であり、均一に塗工し易い。
　接着剤層の製造方法のより具体的な実施態様としては、上記接着剤組成物及び溶媒を含有する樹脂ワニスを、基材フィルムの表面に塗布して樹脂ワニス層を形成した後、該樹脂ワニス層から溶媒を除去することにより、Ｂステージ状の接着剤層を形成することができる。ここで、接着剤層がＢステージ状であるとは、接着剤組成物が未硬化状態あるいは一部が硬化し始めた半硬化状態をいい、加熱等により、接着剤組成物の硬化が更に進行する状態をいう。
　ここで、基材フィルム上に樹脂ワニスを塗布する方法としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、スプレー法、スピンコート法、ディップ法、ロールコート法、ブレードコート法、ドクターロール法、ドクターブレード法、カーテンコート法、スリットコート法、スクリーン印刷法、インクジェット法、ディスペンス法等が挙げられる。
　上記Ｂステージ状の接着剤層は、さらに加熱等を施し、硬化した接着剤層を形成することができる。 <Method for producing adhesive layer>
An adhesive layer can be produced by forming a film from the adhesive composition.
The adhesive composition can be produced by mixing the styrene-based elastomer and the benzoxazine resin described above. The mixing method is not particularly limited as long as the adhesive composition becomes uniform. Since the adhesive composition is preferably used in the form of a solution or dispersion, a solvent is also usually used.
Examples of solvents include alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol, benzyl alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diacetone alcohol. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, and isophorone; Aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, and anisole; Methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monomethyl esters such as ether acetate and 3-methoxybutyl acetate; and aliphatic hydrocarbons such as hexane, heptane, cyclohexane and methylcyclohexane. These solvents may be used alone or in combination of two or more. By adding a small amount of cyclohexanone to toluene, which can dissolve particularly low-polarity resins, the compatibility with the curing agent and the like is improved, and the adhesive layer can be made uniform.
When the adhesive composition is a solvent-containing solution or dispersion (resin varnish), coating on the substrate film and formation of the adhesive layer can be performed smoothly, and an adhesive layer having a desired thickness can be formed. can be obtained easily.
When the adhesive composition contains a solvent, the solid content concentration is preferably in the range of 3 to 80% by mass, more preferably 10 to 50% by mass, from the viewpoint of workability including formation of the adhesive layer. When the solid content concentration is 80% by mass or less, the viscosity of the solution is moderate, and it is easy to apply uniformly.
As a more specific embodiment of the method for producing an adhesive layer, a resin varnish containing the adhesive composition and a solvent is applied to the surface of a substrate film to form a resin varnish layer, and then the resin varnish is applied to the surface of the substrate film. A B-staged adhesive layer can be formed by removing the solvent from the layer. Here, the adhesive layer being in a B-stage state means that the adhesive composition is in an uncured state or a semi-cured state in which a part of the adhesive composition has begun to cure, and the curing of the adhesive composition further progresses by heating or the like. It means the state to do.
Here, the method for applying the resin varnish on the substrate film is not particularly limited and can be appropriately selected according to the purpose. A blade coating method, a doctor roll method, a doctor blade method, a curtain coating method, a slit coating method, a screen printing method, an inkjet method, a dispensing method, and the like can be mentioned.
The B-stage adhesive layer can be further subjected to heating or the like to form a cured adhesive layer.
＜接着剤層の特性＞
　本発明の接着剤組成物を硬化させてなる接着剤層の周波数２８ＧＨｚにおける比誘電率（εｒ）は３．５以下が好ましく、２．７以下がより好ましい。該接着剤層の周波数２８ＧＨｚにおける誘電正接（ｔａｎδ）は０．００５以下が好ましく、０．００２５以下がより好ましく、０．００１５以下がさらに好ましい。
　比誘電率が３．５以下であり、かつ、誘電正接が０．００５以下であれば、電気特性の要求が厳しい高周波ＦＰＣ関連製品にも用いることができる。また、比誘電率が２．７以下であり、かつ、誘電正接が０．００２５以下であれば、５Ｇ対応高周波ＦＰＣ関連製品の構成要素に期待される電気特性を満足することができ、ＬＣＰ（液晶ポリマー）同等の電気特性となり、電気特性の要求が厳しい５Ｇ高周波ＦＰＣ関連製品にも好適に用いることができる。さらに、誘電正接が０．００１５以下であれば、ミリ波を活用した高周波ＦＰＣ関連製品にも好適に用いることができる。 <Characteristics of Adhesive Layer>
The dielectric constant (εr) of the adhesive layer obtained by curing the adhesive composition of the present invention at a frequency of 28 GHz is preferably 3.5 or less, more preferably 2.7 or less. The dielectric loss tangent (tan δ) of the adhesive layer at a frequency of 28 GHz is preferably 0.005 or less, more preferably 0.0025 or less, and even more preferably 0.0015 or less.
If the dielectric constant is 3.5 or less and the dielectric loss tangent is 0.005 or less, it can also be used for high-frequency FPC-related products that require strict electrical characteristics. In addition, if the dielectric constant is 2.7 or less and the dielectric loss tangent is 0.0025 or less, it is possible to satisfy the electrical characteristics expected for the components of 5G compatible high-frequency FPC related products, LCP ( Liquid crystal polymer) has the same electrical characteristics, and can be suitably used for 5G high-frequency FPC-related products that have strict electrical characteristics requirements. Furthermore, if the dielectric loss tangent is 0.0015 or less, it can be suitably used for high-frequency FPC-related products utilizing millimeter waves.
［比誘電率及び誘電正接］
　接着剤層の比誘電率及び誘電正接は、ネットワークアナライザーＭＳ４６１２２Ｂ（Ａｎｒｉｔｓｕ社製）と開放型共振器ファブリペローＤＰＳ－０３（ＫＥＹＣＯＭ社製）とを使用し、開放型共振器法で、温度２３℃、周波数２８ＧＨｚの条件で測定することができる。 [Relative permittivity and dielectric loss tangent]
The relative dielectric constant and dielectric loss tangent of the adhesive layer were determined by the open resonator method using a network analyzer MS46122B (manufactured by Anritsu) and an open resonator Fabry-Perot DPS-03 (manufactured by KEYCOM) at a temperature of 23°C. , and a frequency of 28 GHz.
（積層体）
　本発明の積層体は、基材フィルムと、該基材フィルムの少なくとも一方の表面に上記接着剤層とを備える。 (Laminate)
The laminate of the present invention comprises a base film and the adhesive layer on at least one surface of the base film.
＜基材フィルム＞
　本発明に用いる基材フィルムは、積層体の用途により選択することができる。例えば、積層体をカバーレイフィルムや銅張積層板（ＣＣＬ）として用いる場合は、ポリイミドフィルム、ポリエーテルエーテルケトンフィルム、ポリフェニレンサルファイドフィルム、アラミドフィルム、ポリエチレンナフタレートフィルム、及び液晶ポリマーフィルム等が挙げられる。これらの中でも、接着性及び電気特性の観点から、ポリイミドフィルム、ポリエーテルエーテルケトン（ＰＥＥＫ）フィルム、ポリエチレンナフタレートフィルム、及び液晶ポリマーフィルムが好ましい。
　基材フィルムの２００℃の貯蔵弾性率が１×１０８以上であることが好ましい。レジンフローは、基材フィルムの端部の変形を伴い、変形が大きいほどレジンフローが大きくなるため、圧着温度での貯蔵弾性率が高いほど、接着剤組成物のレジンフローが抑制できる。 <Base film>
The base film used in the present invention can be selected according to the use of the laminate. For example, when the laminate is used as a cover lay film or a copper clad laminate (CCL), polyimide film, polyether ether ketone film, polyphenylene sulfide film, aramid film, polyethylene naphthalate film, liquid crystal polymer film, and the like can be used. . Among these, polyimide film, polyetheretherketone (PEEK) film, polyethylene naphthalate film, and liquid crystal polymer film are preferred from the viewpoint of adhesion and electrical properties.
It is preferable that the storage elastic modulus of the base film at 200° C. is 1×10 8 or more. Resin flow is accompanied by deformation of the edges of the base film, and the larger the deformation, the greater the resin flow.
　また、本発明の積層体をボンディングシートとして用いる場合には、基材フィルムは離型性フィルムである必要があり、例えば、ポリエチレンテレフタレートフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、シリコーン離型処理紙、ポリオレフィン樹脂コート紙、ＴＰＸ（ポリメチルペンテン）フィルム、及びフッ素系樹脂フィルム等が挙げられる。 Further, when the laminate of the present invention is used as a bonding sheet, the base film must be a release film, and examples thereof include polyethylene terephthalate film, polyethylene film, polypropylene film, silicone release treated paper, and polyolefin resin. Coated paper, TPX (polymethylpentene) film, fluorine-based resin film, and the like.
　本発明の積層体をシールドフィルムとして用いる場合には、基材フィルムは電磁波遮蔽能を有するフィルムである必要があり、例えば、保護絶縁層と金属箔の積層体等が挙げられる。 When the laminate of the present invention is used as a shielding film, the base film must be a film having electromagnetic wave shielding ability, and examples thereof include a laminate of a protective insulating layer and a metal foil.
（カバーレイフィルム）
　本発明に係る積層体の好ましい一実施態様として、カバーレイフィルムが挙げられる。
　ＦＰＣを製造する場合、配線部分を保護するために、通常、「カバーレイフィルム」と呼ばれる接着剤層を有する積層体が用いられる。このカバーレイフィルムは、絶縁樹脂層と、その表面に形成された接着剤層とを備えている。
　例えば、カバーレイフィルムは、上記基材フィルムの少なくとも一方の表面に上記接着剤層が形成されており、基材フィルムと接着剤層の剥離が一般に困難な積層体である。
　カバーレイフィルムに含まれる基材フィルムの厚さは、５～１００μｍであることが好ましく、５～５０μｍであることがより好ましく、５～３０μｍであることが更に好ましい。基材フィルムの厚さが上記上限以下であれば、カバーレイフィルムを薄膜化することができる。基材フィルムの厚さが上記下限以上であれば、プリント配線板の設計が容易にでき、ハンドリングもよい。
　カバーレイフィルムを製造する方法としては、例えば、上記接着剤組成物及び溶媒を含有する樹脂ワニスを、上記基材フィルムの表面に塗布して樹脂ワニス層を形成した後、該樹脂ワニス層から溶媒を除去することにより、Ｂステージ状の接着剤層が形成されたカバーレイフィルムを製造することができる。
　溶媒を除去するときの乾燥温度は、４０～２５０℃であることが好ましく、７０～１７０℃であることがより好ましい。
　乾燥は、接着剤組成物が塗布された積層体を、熱風乾燥、遠赤外線加熱、及び高周波誘導加熱等がなされる炉の中を通過させることにより行われる。
　なお、必要に応じて、接着剤層の表面には、保管等のため、離型性フィルムを積層してもよい。離型性フィルムとしては、ポリエチレンテレフタレートフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、シリコーン離型処理紙、ポリオレフィン樹脂コート紙、ＴＰＸフィルム、フッ素系樹脂フィルム等の公知のものが用いられる。
　本発明に係るカバーレイフィルムは、低誘電な本発明の接着剤組成物を使用しているため、電子機器の高速伝送が可能であり、さらに電子機器との接着安定性にも優れたものとなる。 (coverlay film)
A preferred embodiment of the laminate according to the present invention is a coverlay film.
When manufacturing an FPC, a laminate having an adhesive layer called a "coverlay film" is usually used to protect the wiring portion. This coverlay film comprises an insulating resin layer and an adhesive layer formed on its surface.
For example, a coverlay film is a laminate in which the adhesive layer is formed on at least one surface of the base film, and it is generally difficult to separate the base film and the adhesive layer.
The thickness of the base film included in the coverlay film is preferably 5 to 100 μm, more preferably 5 to 50 μm, even more preferably 5 to 30 μm. If the thickness of the base film is equal to or less than the above upper limit, the thickness of the coverlay film can be reduced. When the thickness of the substrate film is at least the above lower limit, the printed wiring board can be easily designed and handled well.
As a method for producing a coverlay film, for example, a resin varnish containing the adhesive composition and a solvent is applied to the surface of the base film to form a resin varnish layer, and then the solvent is removed from the resin varnish layer. is removed, a coverlay film having a B-stage adhesive layer formed thereon can be produced.
The drying temperature for removing the solvent is preferably 40 to 250°C, more preferably 70 to 170°C.
Drying is performed by passing the laminate coated with the adhesive composition through a furnace in which hot air drying, far-infrared heating, high-frequency induction heating, or the like is performed.
If necessary, a release film may be laminated on the surface of the adhesive layer for storage or the like. As the releasable film, publicly known films such as polyethylene terephthalate film, polyethylene film, polypropylene film, silicone release treated paper, polyolefin resin coated paper, TPX film, and fluororesin film are used.
Since the coverlay film according to the present invention uses the low-dielectric adhesive composition of the present invention, it is possible for high-speed transmission of electronic devices, and furthermore, it has excellent adhesive stability with electronic devices. Become.
（ボンディングシート）
　本発明に係る積層体の好ましい一実施態様として、ボンディングシートが挙げられる。
　ボンディングシートは、離型性フィルム（基材フィルム）の表面に上記接着剤層が形成されているものである。また、ボンディングシートは、２枚の離型性フィルムの間に接着剤層を備える態様であってもよい。ボンディングシートを使用するときに、離型性フィルムを剥離して使用する。離型性フィルムは、上記（カバーレイフィルム）の欄で記載したものと同様なものを用いることができる。
　ボンディングシートに含まれる基材フィルムの厚さは、５～１００μｍであることが好ましく、２５～７５μｍであることがより好ましく、３８～５０μｍであることが更に好ましい。基材フィルムの厚さが上記範囲内であれば、ボンディングシートの製造が容易であり、ハンドリングもよい。
　ボンディングシートを製造する方法としては、例えば、離型性フィルムの表面に上記接着剤組成物及び溶媒を含有する樹脂ワニスを塗布し、上記カバーレイフィルムの場合と同様にして乾燥する方法がある。
　本発明に係るボンディングシートは、低誘電な本発明の接着剤組成物を使用しているため、電子機器の高速伝送が可能であり、さらに電子機器との接着安定性にも優れたものとなる。 (bonding sheet)
A preferred embodiment of the laminate according to the present invention is a bonding sheet.
The bonding sheet is obtained by forming the adhesive layer on the surface of a release film (base film). Also, the bonding sheet may be in a mode in which an adhesive layer is provided between two release films. When using the bonding sheet, the release film is peeled off before use. As the releasable film, the same one as described in the above section (coverlay film) can be used.
The thickness of the base film included in the bonding sheet is preferably 5 to 100 μm, more preferably 25 to 75 μm, even more preferably 38 to 50 μm. If the thickness of the base film is within the above range, the bonding sheet can be easily manufactured and handled well.
As a method for producing a bonding sheet, for example, there is a method of applying a resin varnish containing the adhesive composition and a solvent to the surface of a release film and drying in the same manner as in the case of the coverlay film.
Since the bonding sheet according to the present invention uses the low-dielectric adhesive composition of the present invention, it is capable of high-speed transmission of electronic devices, and has excellent adhesion stability with electronic devices. .
（銅張積層板（ＣＣＬ））
　本発明に係る積層体の好ましい一実施態様として、本発明の積層体中の接着剤層に、銅箔を貼り合せてなる銅張積層板が挙げられる。
　銅張積層板は、上記積層体を用いて、銅箔が貼り合わされており、例えば、基材フィルム、接着剤層及び銅箔の順に構成されている。なお、接着剤層及び銅箔は、基材フィルムの両面に形成されていてもよい。
　本発明で用いる接着剤組成物は、銅を含む物品との接着性にも優れている。
　本発明に係る銅張積層板は、低誘電な本発明の接着剤組成物を使用しているため、電子機器の高速伝送を可能とし、かつ接着安定性に優れたものとなる。 (Copper clad laminate (CCL))
A preferred embodiment of the laminate according to the present invention is a copper-clad laminate obtained by bonding a copper foil to the adhesive layer in the laminate according to the present invention.
A copper-clad laminate is obtained by laminating copper foil using the above laminate, and is composed of, for example, a substrate film, an adhesive layer and copper foil in this order. In addition, the adhesive layer and the copper foil may be formed on both sides of the base film.
The adhesive composition used in the present invention also has excellent adhesion to articles containing copper.
Since the copper-clad laminate according to the present invention uses the low-dielectric adhesive composition of the present invention, it enables high-speed transmission of electronic devices and has excellent adhesion stability.
　銅張積層板を製造する方法としては、例えば、上記積層体の接着剤層と銅箔とを面接触させ、８０℃～２００℃で熱ラミネートを行い、更にアフターキュアにより接着剤層を硬化する方法がある。アフターキュアの条件は、例えば、不活性ガスの雰囲気下で１００℃～２００℃、３０分～４時間とすることができる。なお、上記銅箔は、特に限定されず、電解銅箔、圧延銅箔等を用いることができる。 As a method for producing a copper-clad laminate, for example, the adhesive layer and copper foil of the laminate are brought into surface contact, thermal lamination is performed at 80° C. to 200° C., and the adhesive layer is cured by after-curing. There is a way. The after-curing conditions can be, for example, 100° C. to 200° C. for 30 minutes to 4 hours in an inert gas atmosphere. In addition, the said copper foil is not specifically limited, Electrolytic copper foil, a rolled copper foil, etc. can be used.
（プリント配線板）
　本発明に係る積層体の好ましい一実施態様として、本発明の積層体中の接着剤層に、銅配線を貼り合せてなるプリント配線板が挙げられる。
　プリント配線板は、上記銅張積層板に電子回路を形成することにより得られる。
　プリント配線板は、上記積層体を用いて、基材フィルムと銅配線とが貼り合わされており、基材フィルム、接着層及び銅配線の順に構成されている。なお、接着層及び銅配線は、基材フィルムの両面に形成されていてもよい。
　例えば、熱プレス等を利用して、配線部分を有する面に、接着剤層を介してカバーレイフィルムを貼り付けることにより、プリント配線板が製造される。
　本発明に係るプリント配線板は、低誘電な本発明の接着剤組成物を使用しているため、電子機器の高速伝送を可能とし、かつ接着安定性に優れたものとなる。
　本発明に係るプリント配線板を製造する方法としては、例えば、上記積層体の接着剤層と銅配線とを接触させ、８０℃～２００℃で熱ラミネートを行い、更にアフターキュアにより接着剤層を硬化する方法がある。アフターキュアの条件は、例えば、１００℃～２００℃、３０分～４時間とすることができる。上記銅配線の形状は、特に限定されず、所望に応じ、適宜形状等を選択すればよい。 (Printed wiring board)
A preferred embodiment of the laminate according to the present invention is a printed wiring board obtained by laminating copper wiring to the adhesive layer in the laminate according to the present invention.
A printed wiring board is obtained by forming an electronic circuit on the copper-clad laminate.
A printed wiring board is formed by laminating a substrate film and copper wiring using the laminate, and is composed of a substrate film, an adhesive layer, and copper wiring in this order. In addition, the adhesive layer and the copper wiring may be formed on both sides of the base film.
For example, a printed wiring board is manufactured by using a hot press or the like to attach a coverlay film to a surface having a wiring portion via an adhesive layer.
Since the printed wiring board according to the present invention uses the low-dielectric adhesive composition of the present invention, it enables high-speed transmission of electronic devices and has excellent adhesion stability.
As a method for producing the printed wiring board according to the present invention, for example, the adhesive layer of the laminate is brought into contact with the copper wiring, thermal lamination is performed at 80 ° C. to 200 ° C., and the adhesive layer is removed by after-curing. There is a way to harden it. The after-cure conditions can be, for example, 100° C. to 200° C. and 30 minutes to 4 hours. The shape of the copper wiring is not particularly limited, and any suitable shape may be selected as desired.
（シールドフィルム）
　本発明に係る積層体の好ましい一実施態様として、シールドフィルムが挙げられる。
　シールドフィルムは、コンピュータや携帯電話や分析機器等の各種電子機器に影響し誤作動の原因となる電磁波ノイズをカットするために、各種電子機器にシールドするためのフィルムである。電磁波シールドフィルムともいう。
　電磁波シールドフィルムは、例えば、絶縁樹脂層、金属層、及び本発明に係る接着層をこの順で積層してなる。
　本発明に係るシールドフィルムは、低誘電な本発明の接着剤組成物を使用しているため、電子機器の高速伝送が可能であり、さらに電子機器との接着安定性にも優れたものとなる。 (shield film)
A preferred embodiment of the laminate according to the present invention is a shield film.
A shield film is a film for shielding various electronic devices in order to cut electromagnetic noise that affects various electronic devices such as computers, mobile phones, and analytical instruments and causes malfunctions. Also called electromagnetic wave shielding film.
The electromagnetic wave shielding film is formed by laminating an insulating resin layer, a metal layer, and an adhesive layer according to the present invention in this order, for example.
Since the shielding film according to the present invention uses the low dielectric adhesive composition of the present invention, high-speed transmission of electronic devices is possible, and the adhesive stability with electronic devices is also excellent. .
（シールドフィルム付プリント配線板）
　本発明に係る積層体の好ましい一実施態様として、シールドフィルム付プリント配線板が挙げられる。
　シールドフィルム付プリント配線板は、基板の少なくとも片面にプリント回路が設けられたプリント配線板上に、上記電磁波シールドフィルムが貼付されたものである。
　シールドフィルム付プリント配線板は、例えば、プリント配線板と、プリント配線板のプリント回路が設けられた側の面に隣接する絶縁フィルムと、上記電磁波シールドフィルムとを有する。
　本発明に係るシールドフィルム付プリント配線板は、低誘電な本発明の接着剤組成物を使用しているため、電子機器の高速伝送を可能とし、かつ接着安定性に優れたものとなる。 (Printed wiring board with shield film)
A preferred embodiment of the laminate according to the present invention is a printed wiring board with a shield film.
A printed wiring board with a shielding film is a printed wiring board having a printed circuit on at least one side of a substrate, and the electromagnetic wave shielding film is attached on the printed wiring board.
A printed wiring board with a shield film includes, for example, a printed wiring board, an insulating film adjacent to the surface of the printed wiring board on which the printed circuit is provided, and the electromagnetic wave shielding film.
Since the printed wiring board with a shielding film according to the present invention uses the low-dielectric adhesive composition of the present invention, it enables high-speed transmission of electronic devices and has excellent adhesion stability.
　以下に実施例を挙げて本発明を更に詳述するが、本発明の範囲はこれらの実施例に限定されるものではない。なお、下記において、部及び％は、特に断らない限り、質量基準である。 Although the present invention will be described in more detail with examples below, the scope of the present invention is not limited to these examples. In the following, parts and % are based on mass unless otherwise specified.
（アミノ基を含有するスチレン系エラストマー）
　旭化成株式会社製の商品名「タフテックＭＰ１０」（アミン変性水添スチレン-ブタジエン共重合体（アミン変性スチレン－エチレンブチレン－スチレン共重合体））を用いた。この共重合体のスチレン比は３０であり、重量平均分子量は７８，０００である。この共重合体に含有されている全窒素量は、４３０ｐｐｍ（μｇ／ｇ）であった。
（無変性スチレン系エラストマー）
　クレイトン社製の商品名「Ａ１５３５」（水添スチレン－ブタジエン共重合体）を用いた。この共重合体の酸価は０ｍｇＫＯＨ／ｇであり、重量平均分子量は１３５，７００である。この共重合体のスチレン比は、５８である。
（無変性スチレン系エラストマー）
　旭化成株式会社製の商品名「タフテックＰ１５００」（水添スチレン系エラストマー）を用いた。この共重合体の酸価は０ｍｇＫＯＨ／ｇであり、スチレン比は３０であり、重量平均分子量は６７，０００である。
（カルボキシ基を含有するスチレン系エラストマー）
　クレイトン社製の商品名「クレイトンＦＧ１９０１」（マレイン酸変性水添スチレン－ブタジエン共重合体（マレイン酸変性スチレン－エチレンブチレン－スチレン共重合体））を用いた。この共重合体の酸価は１９ｍｇＫＯＨ／ｇであり、スチレン比は３０であり、重量平均分子量は８１，０００である。
（ベンゾオキサジン樹脂）
　四国化成工業株式会社製の商品名「ＡＬＰ－ｄ」（液体）を用いた。
（溶剤）
　トルエン及びシクロヘキサノンからなる混合溶媒（質量比＝９７：３）を用いた。
（基材フィルム）
　基材フィルムとして、信越ポリマー社製の「Ｓｈｉｎ－Ｅｔｓｕ　Ｓｅｐｌａ　Ｆｉｌｍ　ＰＥＥＫ」（ポリエーテルエーテルケトン、厚さ５０μｍ）を用いた。基材フィルムの２００℃の貯蔵弾性率は５×１０８であった。
（電解銅箔）
　電解銅箔として、三井金属鉱業製の「ＴＱ－Ｍ７－ＶＳＰ」（電解銅箔、厚さ１２μｍ、光沢面Ｒｚ１．２７μｍ、光沢面Ｒａ０．１９７μｍ、光沢面Ｒｓｍ１２．９５μｍ）を用いた。光沢面の表面粗さは、レーザー顕微鏡を用いて粗さ曲線を測定し、この粗さ曲線から、ＪＩＳ　Ｂ　０６０１：２０１３（ＩＳＯ　４２８７：１９９７　Ａｍｄ．１：２００９）に基づいて求めた値である。
（離型フィルム）
　離型フィルムとして、パナック社製ＮＰ７５ＳＡ(シリコーン離型ＰＥＴフィルム、７５μｍ)を用いた。 (Styrenic elastomer containing amino group)
Asahi Kasei Co., Ltd. trade name “Tuftec MP10” (amine-modified hydrogenated styrene-butadiene copolymer (amine-modified styrene-ethylenebutylene-styrene copolymer)) was used. This copolymer has a styrene ratio of 30 and a weight average molecular weight of 78,000. The total nitrogen content in this copolymer was 430 ppm (μg/g).
(Unmodified styrene elastomer)
A product name "A1535" (hydrogenated styrene-butadiene copolymer) manufactured by Kraton was used. This copolymer has an acid value of 0 mgKOH/g and a weight average molecular weight of 135,700. The styrene ratio of this copolymer is 58.
(Unmodified styrene elastomer)
Asahi Kasei Co., Ltd. trade name "Tuftec P1500" (hydrogenated styrene elastomer) was used. This copolymer has an acid value of 0 mgKOH/g, a styrene ratio of 30, and a weight average molecular weight of 67,000.
(Styrene Elastomer Containing Carboxy Group)
The trade name “Kraton FG1901” (maleic acid-modified hydrogenated styrene-butadiene copolymer (maleic acid-modified styrene-ethylenebutylene-styrene copolymer)) manufactured by Kraton Co., Ltd. was used. This copolymer has an acid value of 19 mgKOH/g, a styrene ratio of 30, and a weight average molecular weight of 81,000.
(benzoxazine resin)
A product name “ALP-d” (liquid) manufactured by Shikoku Kasei Co., Ltd. was used.
(solvent)
A mixed solvent of toluene and cyclohexanone (mass ratio=97:3) was used.
(Base film)
As a base film, “Shin-Etsu Sepla Film PEEK” (polyetheretherketone, thickness 50 μm) manufactured by Shin-Etsu Polymer Co., Ltd. was used. The storage elastic modulus of the base film at 200°C was 5×10 8 .
(electrolytic copper foil)
As the electrolytic copper foil, “TQ-M7-VSP” manufactured by Mitsui Kinzoku Mining Co., Ltd. (electrolytic copper foil, thickness 12 μm, glossy surface Rz 1.27 μm, glossy surface Ra 0.197 μm, glossy surface Rsm 12.95 μm) was used. The surface roughness of the glossy surface is a value determined based on JIS B 0601:2013 (ISO 4287:1997 Amd.1:2009) from the roughness curve measured using a laser microscope. .
(release film)
As the release film, NP75SA (silicone release PET film, 75 μm) manufactured by Panac was used.
（実施例１）
　表１に示す接着剤層を構成する各成分を表１に示す割合で含有し、これら成分を溶剤に溶かし、固形分濃度が１５質量％の接着剤組成物である樹脂ワニスを作製した。
　接着剤組成物における樹脂組成物を構成する各成分は表１に示すとおりである。 (Example 1)
Each component constituting the adhesive layer shown in Table 1 was contained in the ratio shown in Table 1, and these components were dissolved in a solvent to prepare a resin varnish, which is an adhesive composition having a solid content concentration of 15% by mass.
Each component constituting the resin composition in the adhesive composition is as shown in Table 1.
　実施例１の樹脂ワニスを用いて硬化させて得られた接着剤層について、周波数２８ＧＨｚにおける比誘電率、及び誘電正接を測定した。 The dielectric constant and dielectric loss tangent at a frequency of 28 GHz were measured for the adhesive layer obtained by curing the resin varnish of Example 1.
［比誘電率及び誘電正接］
　接着剤層の比誘電率及び誘電正接は、ネットワークアナライザーＭＳ４６１２２Ｂ（Ａｎｒｉｔｓｕ社製）と開放型共振器ファブリペローＤＰＳ－０３（ＫＥＹＣＯＭ社製）とを使用し、開放型共振器法で、温度２３℃、周波数２８ＧＨｚの条件で測定した。測定試料は、離型フィルム上に樹脂ワニスを塗布し、次いで、この塗膜付きフィルムをオーブン内に静置して、１１０℃で４分間乾燥させてＢステージ状の接着剤層（厚さ５０μｍ）を形成した。次に、この接着剤層を接着面同士が接する様に１５０℃で熱ラミネートして硬化前接着剤フィルム（厚さ１００μｍ）を形成した。この硬化前接着剤フィルム（厚さ１００μｍ）をオーブン内に静置して、１５０℃で６０分間加熱硬化処理をして、硬化後接着剤フィルム（１００ｍｍ×１００ｍｍ）を作製した。硬化後接着剤フィルムから離型フィルムを剥離して接着剤層の比誘電率及び誘電正接を測定した。 [Relative permittivity and dielectric loss tangent]
The relative dielectric constant and dielectric loss tangent of the adhesive layer were determined by the open resonator method using a network analyzer MS46122B (manufactured by Anritsu) and an open resonator Fabry-Perot DPS-03 (manufactured by KEYCOM) at a temperature of 23°C. , and a frequency of 28 GHz. For the measurement sample, a resin varnish is applied to the release film, then the film with the coating film is left standing in an oven and dried at 110 ° C. for 4 minutes to obtain a B-stage adhesive layer (thickness 50 μm ) was formed. Next, this adhesive layer was thermally laminated at 150° C. so that the adhesive surfaces were in contact with each other to form an uncured adhesive film (thickness: 100 μm). This pre-curing adhesive film (thickness: 100 μm) was placed in an oven and heat-cured at 150° C. for 60 minutes to prepare a post-curing adhesive film (100 mm×100 mm). After curing, the release film was peeled off from the adhesive film, and the dielectric constant and dielectric loss tangent of the adhesive layer were measured.
　実施例１の樹脂ワニスを用いて、以下の方法により硬化後の接着剤付き積層体を作製した。 Using the resin varnish of Example 1, a laminate with an adhesive after curing was produced by the following method.
＜硬化後の接着剤付き積層体＞
　基材フィルムの表面にコロナ処理を行った。
　上記で作製した樹脂ワニスを基材フィルムの表面に塗布し、１３０℃のオーブンで４分間乾燥させ、溶剤を揮発させることで接着剤層（１５μｍ）を形成し、接着剤付き基材フィルム（接着剤付き積層体）を得た。接着剤付き積層体の接着剤層が電解銅箔の光沢面と接する様に重ね、真空プレス機を用いて、１８０℃、加圧（３ＭＰａ）、１０ｈＰａ下で３分間プレスし、２００で１時間、アフターキュアを行うことにより接着剤層を硬化し、硬化後の接着剤付き積層体を得た。 <Laminate with adhesive after curing>
Corona treatment was performed on the surface of the base film.
The resin varnish prepared above is applied to the surface of the base film, dried in an oven at 130° C. for 4 minutes, and the solvent is volatilized to form an adhesive layer (15 μm), and the base film with adhesive (adhesion A laminated body with an agent) was obtained. The adhesive layer of the laminate with adhesive is stacked so that it is in contact with the glossy surface of the electrolytic copper foil, and pressed at 180 ° C. under pressure (3 MPa) and 10 hPa for 3 minutes using a vacuum press, and at 200 for 1 hour. After curing, the adhesive layer was cured to obtain a laminate with an adhesive after curing.
　実施例１の硬化後の接着剤付き積層体について、電解銅箔と基材フィルムとの密着力（Ｎ／ｃｍ）を測定した。
　実施例１の硬化後の接着剤付き積層体に対して、耐薬品試験を行った。 The adhesive force (N/cm) between the electrodeposited copper foil and the base film was measured for the laminated body with the adhesive after curing in Example 1.
A chemical resistance test was performed on the laminated body with an adhesive after curing in Example 1.
［密着力（Ｎ／ｃｍ）］
　密着力は、硬化後の接着剤付き積層体をカットして幅２５ｍｍの試験体とし、ＪＩＳ　Ｚ０２３７：２００９（粘着テープ・粘着シート試験方法）に準拠して、剥離速度０．３ｍ／分、剥離角１８０°にて支持体に固定した接着剤付き基材フィルムから電解銅箔を剥がす際の剥離強度を測定することにより、密着力を測定した。 [Adhesion (N/cm)]
Adhesion strength was determined by cutting the laminate with adhesive after curing into a test specimen with a width of 25 mm, and peeling at a peel speed of 0.3 m / min in accordance with JIS Z0237: 2009 (adhesive tape/adhesive sheet test method). Adhesion was measured by measuring the peel strength when the electrolytic copper foil was peeled off from the adhesive-attached substrate film fixed to the support at an angle of 180°.
［耐薬品試験］
　耐薬品性試験は、硬化後の接着剤付き積層体をカットして３０ｍｍ×３０ｍｍの試験体とし、２％ＨＣｌ溶液に１時間浸漬後、さらに２％ＮａＯＨ溶液に１時間浸漬後、続いて２％Ｈ２ＳＯ４溶液に１時間浸漬し、以下の基準により耐薬品性を評価した。
　　〇　　剥離は生じない。
　　×　　部分的もしくは完全に剥離している。 [Chemical resistance test]
In the chemical resistance test, the cured laminate with adhesive was cut into a 30 mm × 30 mm test piece, immersed in a 2% HCl solution for 1 hour, further immersed in a 2% NaOH solution for 1 hour, and then tested for 2 hours. % H 2 SO 4 solution for 1 hour, and chemical resistance was evaluated according to the following criteria.
〇 Peeling does not occur.
x: Partially or completely peeled off.
[レジンフロー（樹脂流れ出し性）（ｍｍ）]
　接着剤付き積層体をカットして３０ｍｍ×９０ｍｍの試験体として、ベルトポンチを使用して５ｍｍ径の穴を３か所空けた。
　電解銅箔の光沢面と接するように重ね、真空プレス機を用いて、１８０℃、加圧（３ＭＰａ）、１０ｈＰａ下で３分間プレスし、２００で１時間、アフターキュアを行うことにより接着剤層を硬化し、銅箔にはみ出た樹脂の長さを顕微鏡で（４点×３か所）１２点測定し、平均値を記載した。
　　顕微鏡（ＫＥＹＥＮＣＥ社製　ＤＩＧＩＴＡＬ　ＭＩＣＲＯＳＣＯＰＥ　ＶＨＸ－５００）：レンズ倍率　３００倍 [Resin flow (resin outflow property) (mm)]
The adhesive-attached laminate was cut into a 30 mm×90 mm test piece, and three holes of 5 mm diameter were punched using a belt punch.
The adhesive layer is laminated so as to be in contact with the glossy surface of the electrolytic copper foil, pressed at 180 ° C. under pressure (3 MPa) and 10 hPa for 3 minutes using a vacuum press, and after-cured at 200 for 1 hour. was cured, and the length of the resin protruding onto the copper foil was measured at 12 points (4 points x 3 points) with a microscope, and the average value was recorded.
Microscope (DIGITAL MICROSCOPE VHX-500 manufactured by KEYENCE): lens magnification 300 times
［はんだ耐熱試験］
　はんだ耐熱試験は、硬化後の接着剤付き積層体をカットして３０ｍｍ×３０ｍｍの試験体とし、基材フィルム面を上にして、２８８℃のはんだ浴に１０秒間×３回浮かべ、接着剤層の膨れ、剥がれ等の外観異常を確認した。
　以下の評価基準により、積層体の耐熱性を評価した。
　　〇　異常なし（溶解もなし）。
　　×　　部分的もしくは完全に剥離している。 [Solder heat resistance test]
In the solder heat resistance test, the laminate with adhesive after curing is cut into a 30 mm × 30 mm test specimen, and the base film surface is floated in a solder bath at 288 ° C. for 10 seconds × 3 times, and the adhesive layer Appearance abnormalities such as swelling and peeling were confirmed.
The heat resistance of the laminate was evaluated according to the following evaluation criteria.
〇 No abnormality (no dissolution).
x: Partially or completely peeled off.
　各測定結果を表１に示す。 Table 1 shows each measurement result.
（実施例２～実施例４）
　実施例１において、接着剤層を構成する成分の種類及び配合量を表１に示すように変更した以外は、実施例１と同様にして、実施例２～実施例４の積層体を作製した。
　作製した積層体に対して、実施例１と同様の評価を行った。
　結果を表１に示す。 (Examples 2 to 4)
Laminates of Examples 2 to 4 were produced in the same manner as in Example 1, except that the types and amounts of the components constituting the adhesive layer were changed as shown in Table 1. .
Evaluation similar to Example 1 was performed with respect to the produced laminated body.
Table 1 shows the results.
（比較例１～比較例４）
　実施例１において、接着剤層を構成する成分の種類及び配合量を表１に示すように変更した以外は、実施例１と同様にして、比較例１～比較例４の積層体を作製した。
　作製した積層体に対して、実施例１と同様の評価を行った。
　結果を表１に示す。 (Comparative Examples 1 to 4)
Laminates of Comparative Examples 1 to 4 were produced in the same manner as in Example 1, except that the types and amounts of the components constituting the adhesive layer were changed as shown in Table 1. .
Evaluation similar to Example 1 was performed with respect to the produced laminated body.
Table 1 shows the results.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例で示されるように、本発明の接着剤組成物からなる接着剤層は、５Ｇ対応可能な良好な電気特性（誘電特性）を示し、かつ密着性、耐熱性、耐薬品（耐溶剤）性にも優れている。 As shown in the examples, the adhesive layer made of the adhesive composition of the present invention exhibits good electrical properties (dielectric properties) compatible with 5G, and adhesion, heat resistance, and chemical resistance (solvent resistance). It is also excellent in sex.
　本発明の接着剤組成物からなる接着剤層を有する積層体は、スマートフォン、携帯電話、光モジュール、デジタルカメラ、ゲーム機、ノートパソコン、医療器具等の電子機器用のＦＰＣ関連製品の製造に好適に用いられ得る。 A laminate having an adhesive layer comprising the adhesive composition of the present invention is suitable for manufacturing FPC-related products for electronic devices such as smartphones, mobile phones, optical modules, digital cameras, game machines, laptop computers, and medical instruments. can be used for

Claims (9)

  1. 　スチレン系エラストマーと、ベンゾオキサジン樹脂とを含有する接着剤組成物であって、
    　前記スチレン系エラストマーが、アミノ基を含有するスチレン系エラストマーを含有する、接着剤組成物。     An adhesive composition containing a styrene-based elastomer and a benzoxazine resin,
    The adhesive composition, wherein the styrene-based elastomer contains a styrene-based elastomer containing an amino group.
  2. 　前記接着剤組成物１００質量部に対し、前記アミノ基を含有するスチレン系エラストマーを３０～９５質量部含有する、請求項１に記載の接着剤組成物。 The adhesive composition according to claim 1, which contains 30 to 95 parts by mass of the amino group-containing styrene-based elastomer with respect to 100 parts by mass of the adhesive composition.
  3. 　前記接着剤組成物１００質量部に対し、前記ベンゾオキサジン樹脂を５～７０質量部含有する、請求項１に記載の接着剤組成物。 The adhesive composition according to claim 1, which contains 5 to 70 parts by mass of the benzoxazine resin with respect to 100 parts by mass of the adhesive composition.
  4. 　前記接着剤組成物が、少なくとも２種類以上のスチレン系エラストマーを含有する、請求項１に記載の接着剤組成物。 The adhesive composition according to claim 1, wherein the adhesive composition contains at least two types of styrene-based elastomers.
  5. 　請求項１～４のいずれか一項に記載の接着剤組成物を硬化させてなる接着剤層。 An adhesive layer obtained by curing the adhesive composition according to any one of claims 1 to 4.
  6. 　前記接着剤層に対し、周波数２８ＧＨｚで測定した前記接着剤層の比誘電率が３．５以下であり、かつ誘電正接が０．００５以下である、請求項５に記載の接着剤層。 The adhesive layer according to claim 5, wherein the adhesive layer has a dielectric constant of 3.5 or less and a dielectric loss tangent of 0.005 or less when measured at a frequency of 28 GHz.
  7. 　基材フィルムと、
    　請求項５に記載の接着剤層と、を有する積層体。     a base film;
    A laminate comprising the adhesive layer according to claim 5 .
  8. 　前記基材フィルムが、ポリエーテルエーテルケトン（ＰＥＥＫ）樹脂を含有する、請求項７に記載の積層体。 The laminate according to claim 7, wherein the base film contains polyetheretherketone (PEEK) resin.
  9. 　請求項７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 7 .
PCT/JP2022/021050 2021-06-02 2022-05-23 Adhesive composition WO2022255137A1 (en)

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JP2007051226A (en) * 2005-08-18 2007-03-01 Ajinomoto Co Inc Resin composition with low dielectric constant
WO2020017412A1 (en) * 2018-07-20 2020-01-23 三菱瓦斯化学株式会社 Resin composition, prepreg, metal foil-clad laminated plate, resin sheet, and printed-wiring board
JP2020015859A (en) * 2018-07-26 2020-01-30 味の素株式会社 Resin composition
WO2020090634A1 (en) * 2018-10-31 2020-05-07 三井化学株式会社 Bendable circuit board, expandable circuit board, and electronic device made therefrom
WO2020130008A1 (en) * 2018-12-18 2020-06-25 日立化成株式会社 Composite material, method of manufacturing same, prepreg, laminated board, printed wiring board, and semiconductor package
JP2020128501A (en) * 2019-02-08 2020-08-27 味の素株式会社 Resin composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007051226A (en) * 2005-08-18 2007-03-01 Ajinomoto Co Inc Resin composition with low dielectric constant
WO2020017412A1 (en) * 2018-07-20 2020-01-23 三菱瓦斯化学株式会社 Resin composition, prepreg, metal foil-clad laminated plate, resin sheet, and printed-wiring board
JP2020015859A (en) * 2018-07-26 2020-01-30 味の素株式会社 Resin composition
WO2020090634A1 (en) * 2018-10-31 2020-05-07 三井化学株式会社 Bendable circuit board, expandable circuit board, and electronic device made therefrom
WO2020130008A1 (en) * 2018-12-18 2020-06-25 日立化成株式会社 Composite material, method of manufacturing same, prepreg, laminated board, printed wiring board, and semiconductor package
JP2020128501A (en) * 2019-02-08 2020-08-27 味の素株式会社 Resin composition

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