WO2012029650A1 - Antenne de film, procédé de fabrication de celle-ci et film à utiliser dans celle-ci comme substrat d'antenne - Google Patents

Antenne de film, procédé de fabrication de celle-ci et film à utiliser dans celle-ci comme substrat d'antenne Download PDF

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Publication number
WO2012029650A1
WO2012029650A1 PCT/JP2011/069285 JP2011069285W WO2012029650A1 WO 2012029650 A1 WO2012029650 A1 WO 2012029650A1 JP 2011069285 W JP2011069285 W JP 2011069285W WO 2012029650 A1 WO2012029650 A1 WO 2012029650A1
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Prior art keywords
film
antenna
antenna substrate
substrate film
silane coupling
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PCT/JP2011/069285
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English (en)
Japanese (ja)
Inventor
慎 寺木
吉田　真樹
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ナミックス株式会社
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Publication of WO2012029650A1 publication Critical patent/WO2012029650A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H01Q1/12—Supports; Mounting means
    • H01Q1/1271—Supports; Mounting means for mounting on windscreens
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
    • H01Q1/38—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith formed by a conductive layer on an insulating support
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • the present invention relates to a film antenna and a manufacturing method thereof. Moreover, this invention relates to the film for antenna substrates used for manufacture of a film antenna.
  • a film antenna is a film-like antenna with an antenna circuit on a resin film that forms a substrate. Since it is thin and lightweight, it is widely used in various portable terminals, information terminals such as automobile windows and personal computers, and window glass for houses. (See Patent Documents 1 to 3).
  • film antennas for the above applications it has been demanded that they are suitable for receiving radio waves in a higher frequency band.
  • film antennas used for third-generation mobile phones, PHS, wireless LAN, GPS, VICS, ETC, in-vehicle radars, etc. have a high frequency band in the GHz range, specifically, a high frequency range of 1 to 60 GHz. It must be suitable for receiving radio waves.
  • the material used for the film antenna used for such an application is required to be able to reduce the electric signal loss in the high frequency band, that is, in the high frequency region of the frequency of 1 to 60 GHz. For this reason, the material used for the film antenna is also required to exhibit a low dielectric constant ( ⁇ ) and a low dielectric loss tangent (tan ⁇ ) in a high frequency range of 1 to 60 GHz.
  • Patent Documents 1 to 3 are used for receiving radio waves in a relatively low frequency band from the kHz region to the MHz region, the above-described high frequency band, that is, a high frequency of 1 to 60 GHz.
  • the necessity of reducing the electric signal loss in the region is not recognized, and it is considered that the materials used for the film antenna in these documents have inferior electric characteristics in the high frequency region of 1 to 60 GHz. It is done.
  • an antenna circuit is formed on a resin film by using a photolithography process, a plating method, a vapor deposition method, a screen printing method, or the like.
  • a photolithography process a method using a photolithography process, an unnecessary portion is removed by etching after forming a circuit pattern with a photoresist or the like on a metal foil such as a copper foil or an aluminum foil bonded to a resin film.
  • the plating method has a problem in using dangerous chemicals such as sulfuric acid, hydrochloric acid, and cyanide when forming a circuit pattern on a resin film, and there is a problem in terms of environmental load due to waste liquid.
  • An object of the present invention is to provide a film antenna exhibiting a low dielectric constant ( ⁇ ) and a low dielectric loss tangent (tan ⁇ ) in a high frequency region of a frequency of 1 to 60 GHz, and an antenna substrate film used therefor.
  • the present invention provides a method for manufacturing a film antenna that does not require the use of an expensive device, does not cause a problem of environmental load due to waste liquid, and can form a highly accurate circuit pattern. Objective.
  • the present invention provides a vinyl compound (A) represented by the formula (1), a thermosetting elastomer and / or a thermoplastic elastomer (B), at least two isocyanates in one molecule.
  • the urethane prepolymer (C) containing a group or blocked isocyanate group and the silane coupling agent (D) are contained, and the mass ratio of the component (A) and the component (B) is 3: 7.
  • a film for an antenna substrate which is prepared by using a resin composition of ⁇ 7: 3.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon atom.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6, and R 7 may be the same or different and each represents a halogenated alkyl group or a phenyl group of formula 1-6.
  • — (O—X—O) — is a structure represented by the following formula (2)
  • — (Y—O) — is a repeating unit represented by the following formula (3)
  • Z is an oxygen atom
  • a and b each represent an integer of 0 to 300, at least one of which is not 0, and c and d each independently represents an integer of 0 or 1.
  • R 8 , R 9 , R 10 , R 14 and R 15 each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group
  • R 11 , R 12 and R 15 Each 13 independently represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group
  • R 16 and R 17 each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group
  • R 18 and R 19 each independently represent a hydrogen atom, a halogen atom, or carbon.
  • An alkyl group having 6 or less atoms or a phenyl group is represented.
  • the component (A) — (O—X—O) — is a structure represented by the following formula (4), and the — (YO) — is represented by the following formula ( The repeating unit represented by 5) or (6) is preferred.
  • — (YO) — of the component (A) is a repeating unit represented by the formula (6).
  • the component (B) is preferably a styrene thermoplastic elastomer.
  • the compound containing the raw material isocyanate group of the urethane prepolymer (C) is isophorone diisocyanate or hexamethylene diisocyanate.
  • the component (D) is a vinyl silane silane coupling agent, a (meth) acryloxy silane silane coupling agent, an isocyanate silane silane coupling agent, an epoxy silane silane coupling agent, It is at least one silane coupling agent selected from the group consisting of aminosilane-based silane coupling agents, mercaptosilane-based silane coupling agents, chloropropylsilane-based silane coupling agents, and oligomers of these silane coupling agents. Is preferred.
  • the antenna substrate film of the present invention is preferably formed by impregnating the resin composition with inorganic fibers or organic fibers.
  • the present invention also includes a step of transferring a circuit pattern formed on a support having releasability onto the antenna substrate film of the present invention, and a step of heat-curing the antenna substrate film.
  • An antenna manufacturing method is provided.
  • the circuit pattern formed on the support is formed by firing a conductive paste containing metal fine particles.
  • the conductive paste containing the metal fine particles is obtained by adding a reducing agent to a mixed solution of a silver salt of a carboxylic acid and an aliphatic primary amine to precipitate silver fine particles. It is preferred that
  • the silver salt of the carboxylic acid is at least one selected from the group consisting of silver acetate, silver propionate and silver butyrate.
  • the aliphatic primary amine is at least one selected from the group consisting of 3-methoxypropylamine, 3-aminopropanol, and 1,2-diaminocyclohexane. preferable.
  • the reducing agent is at least one selected from the group consisting of formic acid, formaldehyde, ascorbic acid and hydrazine.
  • the present invention also provides a film antenna produced by the film antenna manufacturing method of the present invention.
  • the film antenna of the present invention exhibits a low dielectric constant ( ⁇ ) and a low dielectric loss tangent (tan ⁇ ) in a high frequency range of 1 to 60 GHz, and thus is suitable as a film antenna used for receiving radio waves in the frequency range. .
  • the antenna substrate is heated and cured. Unlike conventional methods that use a photolithographic process, plating method, or vapor deposition method when forming a circuit pattern on a resin film, there is no need to use expensive equipment, and the environment can be exposed to waste liquids. Load is not a problem.
  • the antenna substrate film of the present invention does not change in shape or size during heat curing. Further, the antenna substrate film of the present invention is excellent in adhesiveness in a temperature range when transferring a circuit pattern, and the film does not initiate a curing reaction in the temperature range. It is suitable as a film for an antenna substrate used in a method for manufacturing a film antenna. Since the antenna substrate film of the present invention obtained by impregnating the resin composition with inorganic fibers or carbon fibers is excellent in mechanical strength, it is particularly suitable as an antenna substrate film used in the method for producing a film antenna of the present invention. It is.
  • FIGS. 1A to 1C are schematic views showing an example of a manufacturing procedure of a film antenna according to the manufacturing method of the present invention.
  • FIG. 2 is a perspective view showing an example of a circuit pattern formed on a support having releasability.
  • FIGS. 3A to 3J are schematic views showing another example of the manufacturing procedure of the film antenna according to the manufacturing method of the present invention.
  • FIG. 4 is a perspective view showing another example of a circuit pattern formed on a support having releasability.
  • the antenna substrate film of the present invention is produced using a resin composition containing the following components (A) to (D) as essential components.
  • (A) Component Vinyl Compound Represented by Formula (1)
  • the resin composition used for producing the film for an antenna substrate is an ether bond and a benzene nucleus represented by the following formula (1) as the component (A).
  • a vinyl compound having In the resin composition used for the production of the antenna substrate film, the component (A) is an electric characteristic in the high frequency region after the heat curing of the antenna substrate film produced using the film composition, specifically, Mainly contributes to lowering the dielectric constant ( ⁇ ) and lowering the dielectric loss tangent (tan ⁇ ) in the high frequency region of 1 to 60 GHz.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or the number of carbon atoms 1 to 6 halogenated alkyl groups or phenyl groups, and a plurality of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may be the same or different.
  • — (O—X—O) — is a structure represented by the following formula (2)
  • — (Y—O) — is a repeating unit represented by the following formula (3).
  • R 8 , R 9 , R 10 , R 14 and R 15 each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group
  • R 11 , R 12 and R 13 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group
  • R 16 and R 17 each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group
  • R 18 and R 19 each independently represent a hydrogen atom, a halogen atom, or carbon.
  • An alkyl group having 6 or less atoms or a phenyl group is represented.
  • Z represents an organic group having 1 to 3 carbon atoms which may contain an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom.
  • a and b each represent an integer of 0 to 300, at least one of which is not 0, and c and d each independently represents an integer of 0 or 1.
  • — (O—X—O) — in the formula (1) is a structure represented by the following formula (4), and — (Y—O) — is a formula (5) or ( The repeating unit represented by 6) is preferred.
  • Z in the formula (1) is preferably an alkylene group having 1 to 3 carbon atoms.
  • the number average molecular weight of the (A) component vinyl compound is preferably 500 to 5000, and more preferably 1000 to 3000.
  • the vinyl compound (A) has a vinyl group as a functional group at both ends.
  • the equivalent per functional group is preferably 250 to 2500, more preferably 500 to 1500 corresponding to half the number average molecular weight.
  • the equivalent weight per functional group indicates the degree of cross-linking density of the cured product of the resin composition, and when it is 250 or more, the antenna substrate film produced using the resin composition is bent-resistant after being heat-cured. It is excellent in properties, and cracks and the like do not occur in the film after heat curing.
  • the compatibility with the component (B) is good, and the transparency of the antenna substrate film produced using the resin composition is excellent.
  • the melting temperature of the resin composition is lowered and the reactivity is improved, so that the curing temperature is lowered.
  • the number average molecular weight is a value determined by GPC using a standard polystyrene calibration curve.
  • vinyl compound as component (A) include those in formula (1), wherein R 1 to R 7 are hydrogen, — (O—X—O) — is structural formula (4), and — (Y A compound in which —O) — is the structural formula (6), Z is a methylene group, a to d are 1, and the number average molecular weight is 2200 or 1200, 2,2 ′, 3,3 ′, 5
  • R 1 to R 7 are hydrogen
  • — (O—X—O) — is structural formula (4)
  • — (Y—O) — is structural formula (5)
  • Z is a methylene group A compound in which a to d are 1 and 2,2 ′, 3,3 ′, 5,5′-hexamethyl having
  • Thermosetting elastomer, thermoplastic elastomer Thermosetting elastomer, thermoplastic elastomer
  • the resin composition used for the production of the antenna substrate film contains a thermosetting elastomer and / or a thermoplastic elastomer as the component (B). That is, it contains at least one of a thermosetting elastomer and a thermoplastic elastomer.
  • the resin composition may contain both a thermosetting elastomer and a thermoplastic elastomer.
  • the component (B) contributes to the compatibility of the resin composition, improves the film forming property of the resin composition, and uses the resin composition. The adhesiveness at the time of heat curing of the antenna substrate film to be produced is improved.
  • (B) component contributes to the softness
  • thermosetting elastomer examples include rubbers such as styrene-butadiene rubber, butyl rubber, butadiene rubber, and acrylic rubber. These rubbers may be used alone or in combination of two or more.
  • thermoplastic elastomer examples include a styrene thermoplastic elastomer, an olefin thermoplastic elastomer, and a polyester thermoplastic elastomer.
  • a thermoplastic elastomer may be used individually by 1 type, and may use 2 or more types together.
  • the compatibility with component (A) is good, the film-forming property when creating a film for an antenna substrate using the resin composition, and the resin composition is used.
  • the antenna substrate film to be used is preferably a thermoplastic elastomer, and a styrene-based thermoplastic elastomer is particularly preferable because the film for an antenna substrate is excellent in adhesiveness at the time of heat curing and the antenna substrate film is excellent in flexibility.
  • the styrenic thermoplastic elastomer examples include a styrene-butadiene block copolymer, a styrene-isoprene-styrene block copolymer, or a copolymer obtained by hydrogenating a part of these double bonds. More specifically, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene.
  • SBS styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • SEBS styrene-ethylene-butylene-styrene block copolymer
  • SEEPS -Propylene-styrene block copolymer
  • SBS and SEBS are easy to control the glass transition point of the cured product of the resin composition within an appropriate range, and the adhesive strength of the antenna substrate film produced using the resin composition is good even at high temperatures. This is preferable.
  • the mass average molecular weight is preferably 20,000 to 250,000. Also, since the compatibility with the component (A) is good and the film for an antenna substrate prepared using the resin composition is excellent in transparency, the styrene content in the styrene-based thermoplastic elastomer is 25 to 60% by mass. Preferably, the content is 30 to 50% by mass.
  • the mass average molecular weight is a value determined by GPC using a standard polystyrene calibration curve.
  • styrene thermoplastic elastomer examples include a styrene-butadiene block copolymer “JSR TR” series and a styrene-isoprene block copolymer “JSR SIS” series manufactured by JSR Corporation.
  • Component (C) Urethane prepolymer
  • the resin composition used for the production of the antenna substrate film is composed of a urethane prepolymer having two or more isocyanate groups or blocked isocyanate groups in one molecule as the component (C). contains.
  • a urethane prepolymer includes a polyol and a compound having two or more isocyanate groups or blocked isocyanate groups in at least one molecule.
  • the component (C) contributes to the adhesiveness of the antenna substrate film produced using the resin composition, and in the temperature range when the circuit pattern is transferred. Improves the adhesiveness of the antenna substrate film.
  • the reactivity at the time of heat-curing of the film for antenna substrates produced using this resin composition is improved, and heat-curing at a lower temperature is enabled.
  • the resin composition used for the production of the antenna substrate film may contain other urethane prepolymers as long as the effect of the use of the urethane prepolymer of the component (C) is not impaired.
  • polyol used as a raw material for the urethane prepolymer of component (C) include a polyolefin-based polyol obtained by hydrogenating polybutadiene polyol, polyisoprene polyol, polyisoprene polyol, etc., dimer acid using dimer acid as a carboxylic acid component A polyester polyol etc. are mentioned.
  • Other specific examples of the polyol used as a raw material for the urethane prepolymer of component (C) include bifunctional alcohols such as 1,4-butanediol, 1,6-hexanediol, and ethylene glycol, trimethylolpropane, and the like. A trifunctional alcohol is mentioned. Two or more of these polyols may be used in combination.
  • the compound having an isocyanate group used as a raw material for the urethane prepolymer of component (C) is not particularly limited as long as it has two or more isocyanate groups or blocked isocyanate groups in total in one molecule.
  • Specific examples of the compound having two or more isocyanate groups in one molecule include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and the like.
  • tolylene diisocyanate and isophorone diisocyanate are particularly suitable.
  • the compound which blocked the compound which has the isocyanate group illustrated here with blocking agents, such as alcohol, phenols, and oximes is mentioned.
  • the urethane prepolymer of component (C) is produced using an organic solvent having no active hydrogen that reacts with an isocyanate group.
  • organic solvents include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone and the like. Of these, toluene is particularly preferred.
  • the urethane prepolymer of component (C) contains a total of two or more isocyanate groups or blocked isocyanate groups in one molecule.
  • a resin composition used for producing a film for an antenna substrate it is usually desirable to have a highly active isocyanate group as it is in a urethane prepolymer.
  • a blocked diisocyanate in which an isocyanate group is blocked with a blocking agent can also be used.
  • the blocking agent that can be used is not particularly limited, but methyl ethyl ketone oxime is preferred from the viewpoint of drying temperature.
  • a preferred urethane prepolymer as the component (C) is a urethane prepolymer containing 50 parts by mass or more of a urethane prepolymer obtained from polybutadiene polyol and 1,4-butanediol and tolylene diisocyanate, isophorone diisocyanate or hexamethylene diisocyanate. is there.
  • (D) component Silane coupling agent
  • the resin composition used for preparation of the film for antenna substrates contains a silane coupling agent as (D) component.
  • the component (D) contributes to adhesion to the antenna pattern formed on the support having releasability when the film antenna is manufactured.
  • silane coupling agent used as the component (D) include vinyl silane silane coupling agents, (meth) acryloxy silane silane coupling agents, isocyanate silane silane coupling agents, and epoxy silane silane coupling agents. , Aminosilane-based silane coupling agents, mercaptosilane-based silane coupling agents, chloropropylsilane-based silane coupling agents, and oligomers of these silane coupling agents. Among these, (meth) acryloxysilane-based silane coupling agents and aminosilane-based silane coupling agents are preferable.
  • vinyl silane coupling agents include vinyl triethoxysilane, vinyl trimethoxylane, vinyl tris (2-methoxyethoxy) silane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, etc. Is mentioned.
  • examples of the (meth) acryloxysilane-based silane coupling agent include ⁇ -acryloxypropyltrimethoxysilane, 3- (trimethoxysilyl) propyl acrylate, ⁇ -methacryloxypropyltrimethoxysilane, and the like.
  • Examples of the isocyanate silane coupling agent include 3- (triethoxysilyl) propyl isocyanate.
  • Examples of the epoxysilane-based silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.
  • aminosilane-based silane coupling agents include N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Aminopropyltrimethoxysilane, 3-aminopropyldiethoxymethylsilane and the like.
  • chloropropylsilane-based silane coupling agent include 3-chloropropyltrichlorosilane.
  • Examples of the mercaptosilane-based silane coupling agent include (3-mercaptopropyl) triethoxysilane, (3-mercaptopropyl) trimethoxysilane, and the like.
  • the oligomer of these silane coupling agents can also be used as (D) component.
  • (meth) acryloxysilane-based silane coupling agents such as ⁇ -acryloxypropyltrimethoxysilane, 3- (trimethoxysilyl) propyl acrylate, ⁇ -methacryloxypropyltrimethoxysilane, and the like are preferable.
  • N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, etc.
  • An aminosilane-based silane coupling agent An aminosilane-based silane coupling agent.
  • the mass ratio of the component (A) and the component (B) is from 3: 7 to 7: 3.
  • the compatibility of the resin composition is good, and the antenna substrate film is produced using the resin composition.
  • the film properties are excellent, and the antenna substrate film produced using the resin composition is excellent in adhesiveness during heat curing.
  • the mass ratio of the component (A) and the component (B) is preferably 4: 6 to 6: 4.
  • the mass ratio of the component (C) to the total amount of the components (A) and (B) is preferably 99: 1 to 40:60.
  • the mass ratio of the component (C) to the total amount of the components (A) and (B) is more preferably 97.5: 2.5 to 50:50, still more preferably 95: 5 to 60:40. .
  • the mass ratio of the component (D) to the total amount of the components (A) to (C) is preferably 99.99: 0.01 to 90:10. .
  • the mass ratio of the component (D) to the total amount of the components (A) to (C) is more preferably 99.9: 0.1 to 95: 5, still more preferably 99.7: 0.3 to 98. : 2.
  • the resin composition used for the production of the antenna substrate film may contain any component other than the above-described components (A) to (D) as long as the original physical properties and characteristics are not impaired.
  • an optional component include a filler used for the purpose of improving the mechanical strength of an antenna substrate film produced using a resin composition.
  • a filler include metals such as silver powder, gold powder and copper powder, metal compounds such as silica, alumina, titania, boron nitride and iron oxide, and organic fillers such as carbon.
  • the content can be appropriately selected within the range where the intended effect can be exhibited by the inclusion and the original physical properties and characteristics of the resin composition are not impaired. can do.
  • the mass ratio of the filler to the total amount of components (A) to (D) is preferably 9: 1 to 1: 9, more preferably 8: 2 to 2: 8, more preferably 7: 3 to 3: 7.
  • the resin composition used for the production of the antenna substrate film contains the components (A) to (D) described above, and when the resin composition contains the optional components described above, these optional components are further converted into known methods. For example, it can prepare by stirring and mixing using the mixer provided with the vertical stirrer.
  • the antenna substrate film of the present invention can be obtained from the above resin composition by a known method.
  • a film for an antenna substrate can be obtained by diluting the above resin composition with an organic solvent to form a varnish, applying the varnish to a support, drying, and cooling.
  • the antenna substrate film of the present invention can be provided as a film with a support or a film peeled from the support.
  • the thickness of the antenna substrate film is determined by the amount of varnish applied, but the thickness of the antenna substrate film is preferably 5 to 100 ⁇ m.
  • the organic solvent used to create the varnish is uniform for each component of the resin composition (the above components (A) to (D), and if the resin composition contains the above optional components, these optional components).
  • it may be any one that can be dissolved or dispersed in water, specifically, ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); ethers such as ethylene glycol monomethyl ether and propylene glycol dimethyl ether; toluene, xylene and the like An aromatic hydrocarbon etc. are mentioned.
  • MEK, MIBK, toluene, xylene and the like are examples of MEK, MIBK, toluene, xylene and the like.
  • the application of the varnish is carried out by a usual method, but it is preferable to use a gravure method.
  • the drying of the varnish is performed under conditions where the organic solvent is sufficiently volatilized, for example, when the mass loss rate before and after heating at 200 ° C. for 2 hours is 2% by mass or less, ie, at 60 to 200 ° C., 0.1 to Heat for 90 minutes.
  • the antenna substrate film is preferably cooled by an ordinary method, that is, standing at room temperature.
  • the support on which the varnish is applied is not particularly limited as long as it can withstand the heating and drying during the film formation of the resin composition.
  • Specific examples include films of polyethylene terephthalate, polypropylene, polyimide, polyetherimide, and the like. Two or more of these films may be combined to form a multilayer film. These films may be surface-treated with a silicone release agent.
  • the film for an antenna substrate of the present invention can also be obtained by impregnating the above resin composition with inorganic fibers such as glass fibers and carbon fibers, or organic fibers such as aramid fibers.
  • inorganic fibers such as glass fibers and carbon fibers, or organic fibers such as aramid fibers.
  • organic fibers such as aramid fibers.
  • the antenna substrate film obtained by impregnating the above resin composition into inorganic fibers or organic fibers is excellent in mechanical strength, so that it is a film antenna for use where mechanical strength is required, such as a third generation mobile phone.
  • the inorganic fiber and organic fiber impregnated with the above resin composition are not particularly limited, but glass fiber is preferable from the viewpoint of both mechanical strength and cost.
  • a resin composition can be prepared as a varnish obtained by adding the above components (A) to (D) (and optionally the optional components described above) to an organic solvent and mixing them.
  • the above-described components (A) to (D) (and optionally the optional components described above) can be dissolved in an organic solvent in any order and mixed to prepare a varnish.
  • a well-known method is employable.
  • the above-described components (A) to (D) (optionally further optional components described above) and an organic solvent are placed in a metal container or glass container, and the mixture is heated and stirred.
  • the heating temperature is preferably 0 to 100 ° C., more preferably 20 to 80 ° C., which is a temperature at which the polymerization of component (A) does not proceed.
  • the antenna substrate film of the present invention obtained by the above procedure is excellent in electrical characteristics in a high frequency region of 1 to 60 GHz after heat curing, and has a low dielectric constant ( ⁇ ) and low in the high frequency region.
  • the dielectric loss tangent (tan ⁇ ) is shown. More specifically, the antenna substrate film after heat curing preferably has a dielectric constant ( ⁇ ) of 5 or less, more preferably 4 or less, in a high frequency region of 1 to 60 GHz, and 3 or less. More preferably it is.
  • the dielectric loss tangent (tan ⁇ ) is preferably 0.01 or less, more preferably 0.005 or less, and further preferably 0.003 or less in a high frequency region of 1 to 60 GHz.
  • the antenna substrate film of the present invention is excellent in adhesiveness in a temperature range when transferring a circuit pattern.
  • a support having a circuit pattern formed on the surface is heated and pressure-bonded to the antenna substrate film of the present invention.
  • the circuit pattern formed on the support is transferred to the antenna substrate film.
  • the antenna substrate film is heated to a temperature of 100 to 150 ° C.
  • the antenna substrate film of the present invention is excellent in adhesiveness.
  • the tackiness index is 30 to 500 gf when the tack test is used.
  • the curing reaction of the film for antenna substrate of the present invention starts when heated at a temperature of 180 ° C. or higher, it can be cured by heating at a temperature of 180 ° C. or higher for 60 to 90 minutes. If the heating temperature of the antenna substrate film of the present invention is too high, the film may change in shape or dimensions, so the heating temperature of the film is preferably 300 ° C. or less, and preferably 250 ° C. or less. More preferably, it is 220 degrees C or less. When heat curing is performed in the above temperature range, that is, a temperature range of 180 ° C. or higher and 220 ° C. or lower, the antenna substrate film of the present invention has little shape change and dimensional change during heat curing.
  • the shape change and dimensional change of the film during heat curing are within 0.075 mm, preferably within 0.05 mm, and more preferably within 0.01 mm.
  • the curing reaction starts when the film for antenna substrate of the present invention is heated at a temperature of 180 ° C. or higher, the curing reaction does not start in the temperature range when transferring the circuit pattern described above.
  • the method for producing a film antenna of the present invention includes a step of transferring a circuit pattern formed on a support having releasability onto a film for an antenna substrate of the present invention, and a step of heat-curing the film for an antenna substrate.
  • FIGS. 1A to 1C are schematic views showing an example of a manufacturing procedure of a film antenna according to the manufacturing method of the present invention.
  • the film for an antenna substrate of the present invention and a support having releasability on which a circuit pattern is formed are prepared.
  • the antenna substrate film 10 of the present invention is shown as a film with a support 20.
  • a circuit pattern 40 having a predetermined shape corresponding to the film antenna to be manufactured is formed on the support 30 having releasability.
  • FIG. 2 is a perspective view showing an example of a circuit pattern 40 formed on the support 30 having releasability.
  • the antenna substrate film 10 of the present invention (the film 10 with the support 20) and the support 30 on which the circuit pattern 40 is formed are heated at a predetermined temperature.
  • Crimp For example, thermocompression bonding is performed at 150 ° C. for 30 seconds by a vacuum press (1 MPa).
  • the circuit pattern 40 is transferred to the antenna substrate film 10 of the present invention having excellent adhesiveness by peeling the support 30 having releasability as shown in FIG. Is done.
  • the antenna substrate film 10 of the present invention is heated to a temperature of 100 to 150 ° C. during thermocompression bonding.
  • the film antenna can be obtained by heat-curing the antenna substrate film 10 of the present invention to which the circuit pattern 40 is transferred at a predetermined temperature.
  • the film 10 for antenna substrates of this invention is heat-hardened by heating to the temperature of 180 degreeC or more.
  • the antenna substrate film 10 and the support 30 on which the circuit pattern 40 is formed are provided. The thermocompression bonding and the heat curing of the antenna substrate film 10 may be performed simultaneously.
  • the antenna substrate film 10 and the support 30 on which the circuit pattern 40 is formed in a temperature range of 100 to 150 ° C.
  • the antenna substrate is obtained by thermocompression bonding both at a temperature of 180 ° C. or higher.
  • the transfer of the circuit pattern 40 to the film 10 for use and the heat curing of the film 10 for the antenna substrate can be performed simultaneously.
  • FIGS. 3A and 3B are schematic views showing another example of the manufacturing procedure of the film antenna according to the manufacturing method of the present invention, in which the film antenna having circuit patterns formed on both sides of the antenna substrate film is shown.
  • the manufacturing procedure is shown.
  • the procedure shown in FIGS. 3A and 3B is the same as the procedure shown in FIGS. That is, the antenna substrate film 10 of the present invention (the film 10 with the support body 20) and the support 30 having releasability on which the circuit pattern 40 is formed are prepared, and the antenna substrate film 10 of the present invention ( The film 10) with the support 20 and the support 30 on which the circuit pattern 40 is formed are heat-bonded at a predetermined temperature.
  • a hole 50 for forming a jumper is formed.
  • a jumper 60 for ensuring the continuity of circuit patterns formed on both surfaces of the antenna substrate film is formed.
  • the procedure of filling the holes 50 with the conductive paste can be performed using a known method, for example, a screen printing method.
  • a known conductive paste can be used.
  • a conductive paste used to form a circuit pattern having releasability can also be used.
  • a jumper is used as a means for ensuring the continuity of the circuit pattern formed on both sides of the antenna substrate film, but the continuity of the circuit pattern formed on both sides of the antenna substrate film is ensured.
  • a means is not limited to this, For example, you may use plating.
  • FIGS. 3E and 3F the antenna substrate film 10 of the present invention is transferred to the surface of the antenna substrate film 10 exposed by peeling off the support 20.
  • a support 70 having a releasability on which a circuit pattern 80 is formed is prepared.
  • a circuit pattern 80 having a predetermined shape corresponding to the film antenna to be manufactured is formed on the support 70 having releasability.
  • FIG. 4 is a perspective view showing an example of a circuit pattern 80 formed on the support 70 having releasability.
  • the antenna substrate film 10 of the present invention and the support 70 on which the circuit pattern 80 is formed are heat-bonded at a predetermined temperature.
  • the conditions at the time of thermocompression bonding both the conditions at the time of thermocompression bonding the film 10 for antenna substrates mentioned above and the support body 30 in which the circuit pattern 40 was formed are the same.
  • the circuit pattern 80 is transferred to the antenna substrate film 10 of the present invention having excellent adhesiveness, as shown in FIG. Is done.
  • the support 30 is peeled off at the stage shown in FIG. 3 (h).
  • the support 30 heat-pressed on the antenna substrate film 10 is peeled off at the stage shown in FIG. 3 (b).
  • the stage of performing is not limited to this. That is, after the circuit pattern 40 is transferred to the antenna substrate film 10 by thermocompression bonding, the support 30 may be peeled off immediately, or the support 20 of the antenna substrate film 10 is peeled off in FIG. When doing so, the support 30 may be peeled off. However, from the viewpoint of protecting the circuit pattern 40 transferred to the antenna substrate film 10, the circuit patterns 40 and 80 transferred to both surfaces of the antenna substrate film 10 were transferred as shown in FIG. It is preferable to peel the support 30 later.
  • a film antenna can be obtained by heat-curing the antenna substrate film 10 of the present invention having the circuit patterns 40 and 80 transferred on both sides at a predetermined temperature.
  • the film 10 for antenna substrates of this invention is heat-hardened by heating to the temperature of 180 degreeC or more.
  • the thermocompression bonding between the antenna substrate film 10 and the support 70 on which the circuit pattern 80 is formed and the heat curing of the antenna substrate film 10 may be performed simultaneously. That is, instead of thermocompression bonding the antenna substrate film 10 and the support 70 on which the circuit pattern 80 is formed in a temperature range of 100 to 150 ° C., the antenna substrate is obtained by thermocompression bonding both at a temperature of 180 ° C. or higher.
  • the circuit pattern 80 can be transferred to the film 10 and the antenna substrate film 10 can be cured by heating at the same time. Further, in the procedure shown in FIG. 3, the transfer of the circuit pattern 40 and the transfer of the circuit pattern 80 are performed as separate procedures, but these procedures may be performed simultaneously as a single procedure. That is, the support body 30 and the support body 70 may be simultaneously heat-bonded to the antenna substrate film 10.
  • the film antenna obtained by the above procedure can be covered with a cover film as necessary.
  • both the surfaces of the antenna substrate film 10 are covered with cover films by performing the procedure shown in FIGS.
  • the cover films 100 and 120 with the supports 110 and 130 are thermocompression bonded to both surfaces of the antenna substrate film 10.
  • thermocompression bonding is performed at 200 ° C. for 60 seconds by a vacuum press (1 MPa).
  • both the surfaces of the antenna substrate film 10 are covered with the cover films 100 and 120 by peeling off the supports 110 and 130 of the cover films 100 and 120.
  • some film antennas have a structure in which a plurality of antenna substrate films on which circuit patterns are formed are laminated.
  • a predetermined number of antenna substrate films having a circuit pattern transferred thereon may be laminated by the above-described procedure, and then the antenna substrate film laminate may be heat-cured.
  • the circuit pattern formed on the support having releasability is obtained by firing a conductive paste containing metal fine particles.
  • the method of forming an antenna circuit by screen-printing a conductive paste containing metal fine particles on a resin film and then baking it at a predetermined temperature is a burden on the environment due to the use of expensive equipment or waste liquid etc.
  • This method is superior to other methods used for forming an antenna circuit, that is, a photolithography process, a plating method, a vapor deposition method, and the like, in that the above problem does not occur.
  • the problem with the above method is that, depending on the material of the resin film used, the shape and dimensions of the resin film change when the conductive paste is baked, resulting in a decrease in the accuracy of the antenna circuit.
  • a conductive paste containing metal fine particles is screen-printed, and then the conductive pattern is formed.
  • silver fine particles are preferably used because of excellent conductivity and oxidation resistance.
  • a conductive paste containing silver fine particles a paste obtained by adding a reducing agent to a mixed solution of a silver salt of a carboxylic acid and an aliphatic primary amine to precipitate silver fine particles has a firing temperature of 200 ° C. or lower. It is preferable because the circuit pattern obtained by firing has a sufficient conductivity (for example, a specific resistance value of 1 to 10 ⁇ ). Since the average particle diameter of the silver fine particles contained in the conductive paste is small, it can meet the demand for circuit pattern formation to be further refined.
  • the above conductive paste can be obtained by adding a reducing agent to a mixed solution of a silver salt of a carboxylic acid and an aliphatic primary amine and precipitating silver fine particles at a reaction temperature of 20 to 80 ° C.
  • the silver salt of a carboxylic acid may be a silver salt of any aliphatic or aromatic carboxylic acid. Further, it may be a silver salt of monocarboxylic acid or a silver salt of polycarboxylic acid such as dicarboxylic acid.
  • the silver salt of an aliphatic carboxylic acid may be a silver salt of a chain aliphatic carboxylic acid or a silver salt of a cyclic aliphatic carboxylic acid.
  • the aliphatic primary amine may be a chain aliphatic primary amine or a cyclic aliphatic primary amine. Moreover, even if it is a monoamine compound, polyamine compounds, such as a diamine compound, may be sufficient.
  • Aliphatic primary amines include those in which an aliphatic hydrocarbon group is substituted with an alkoxy group such as a hydroxyl group, a methoxy group, an ethoxy group, or a propyl group. More preferred are 3-methoxypropylamine, 3-aminopropanol and 1,2-diaminocyclohexane. These can be used alone or in combination of two or more.
  • the amount of the aliphatic primary amine used is determined by process requirements and equipment such as post-treatment of the silver fine particles to be produced, but it will be described later that it is 1 equivalent or more per 1 equivalent of the silver salt of carboxylic acid. It is preferable because a conductive paste containing silver fine particles with a controlled particle diameter can be obtained.
  • Excessive aliphatic primary amine is preferably 1.0 to 3.0 equivalents, more preferably 1.0 because it may affect the environment and the like by evaporation from the conductive paste by heating. To 1.5 equivalents, particularly preferably 1.0 to 1.1 equivalents.
  • the silver salt of carboxylic acid and the aliphatic primary amine can be mixed in the absence or presence of an organic solvent. Mixing can be facilitated by the use of organic solvents.
  • organic solvents include alcohols such as ethanol, propanol and butanol, ethers such as propylene glycol dibutyl ether, and aromatic hydrocarbons such as toluene. These can be used alone or in combination of two or more.
  • the amount of the organic solvent used can be set to an arbitrary amount from the viewpoint of convenience of mixing and precipitation of silver fine particles in the subsequent step.
  • the mixing of the silver salt of the carboxylate and the aliphatic primary amine is performed, for example, by stirring the silver salt of the carboxylic acid while stirring the primary aliphatic amine or the mixture of the primary aliphatic amine and the organic solvent. Add and do. Stirring can be continued as appropriate even after the end of the addition. Meanwhile, the temperature is preferably maintained at 20 to 80 ° C., more preferably 20 to 60 ° C.
  • a reducing agent is added to precipitate silver fine particles.
  • a reducing agent formic acid, formaldehyde, ascorbic acid or hydrazine is preferable from the viewpoint of controlling the reaction, and formic acid is more preferable. These may be used alone or in combination of two or more.
  • the amount of the reducing agent used is usually not less than the redox equivalent relative to the silver salt of the carboxylic acid, and the redox equivalent is preferably 0.5 to 5 times, more preferably 1 to 3 times.
  • the amount of formic acid used in terms of mole is 0.5 to 1 with respect to 1 mol of the silver salt of carboxylic acid.
  • the amount is preferably 0.5 mol, more preferably 0.5 to 1.0 mol, still more preferably 0.5 to 0.75 mol.
  • the temperature is maintained at 20 ° C to 80 ° C.
  • the temperature is preferably 20 to 70 ° C, more preferably 20 to 60 ° C.
  • the time required for the addition of the reducing agent and the subsequent reaction depends on the scale of the reaction apparatus, but is usually 10 minutes to 10 hours.
  • an organic solvent such as an alcohol such as ethanol, propanol or butanol, an ether such as propylene glycol dibutyl ether, or an aromatic hydrocarbon such as toluene is added as necessary. Can be added.
  • the silver of the carboxylic acid with respect to the total volume (L) of the mixed solution of the silver salt of the carboxylic acid and the aliphatic primary amine, the reducing agent, and any organic solvent.
  • the amount (mol) of salt is preferably in the range of 1.0 to 6.0 mol / L, more preferably 2.0 to 5.0 mol / L, still more preferably 2.0 to 4 0.0 mol / L. If the concentration is within this range, the reaction solution can be sufficiently stirred and the heat of reaction can be removed, so that the average particle size of the precipitated silver fine particles becomes appropriate. As a result, precipitation decantation, solvent replacement, etc. in subsequent steps It will not interfere with the operation.
  • the silver fine particles thus precipitated have a narrow particle size distribution and a geometric standard deviation of 2.0 or less.
  • the geometric standard deviation is the ratio (D84) of the 84.3% particle diameter (D84.3 value) to the 50% particle diameter (D50 value) based on the number measured by the laser diffraction scattering type particle size distribution measurement. .3 value / D50 value).
  • the silver fine particles thus precipitated are usually substantially spherical, and the average particle size of the primary particles is preferably 40 to 350 nm, more preferably 40 to 100 nm, still more preferably 50 to 80 nm. It is. When the average particle diameter of the silver fine particles is within the above range, the aggregation of the silver fine particles is suppressed, so that the storage stability of the conductive paste is good. Moreover, it is suitable as a conductive paste for printing a fine circuit pattern.
  • the silver fine particles thus precipitated preferably have a crystallite diameter of 20 to 70 nm, more preferably 20 to 50 nm.
  • the crystallite diameter of the silver fine particles is in the above range, volume shrinkage during firing is suppressed, and the denseness and surface smoothness of the circuit pattern formed by firing are ensured, so that precision electronic circuit applications It is suitable as a conductive paste.
  • an average particle diameter means the average particle diameter based on a number standard by laser diffraction scattering type particle size distribution measurement.
  • the crystallite diameter is obtained by measuring the half width of the plane index (1,1,1) plane peak from the measurement by the powder X-ray diffraction method using Cu K ⁇ ray as the source, and the Scherrer equation. This is the result of more calculations.
  • the silver fine particles thus precipitated have a ratio of the average particle diameter to the crystallite diameter of the primary silver fine particles (average particle diameter / crystallite diameter) of 1 to 5, preferably 1 to 4. A range of 1 to 3 is more preferable. When the above ratio is within this range, the circuit pattern obtained by firing the conductive paste exhibits sufficient conductivity at a firing temperature of 200 ° C. or less.
  • the silver fine particles precipitated by the reaction can be allowed to settle and the supernatant can be removed by decantation or the like, or a solvent such as alcohol such as methanol, ethanol, terpineol, etc. can be added and fractionated.
  • the layer containing silver fine particles can be used as a conductive paste as it is.
  • the conductive paste preferably has a silver content in the conductive paste of 40 to 90% by mass, more preferably 45 to 80% by mass.
  • the firing temperature of the conductive paste obtained by the above procedure is preferably 60 to 200 ° C., more preferably 60 to 150 ° C.
  • the support to be used is required not to have a releasability but to change in shape and dimensions when the conductive paste is baked.
  • the firing temperature is 60 to 200 ° C., more preferably 60 to 150 ° C.
  • Specific examples of such a support include those obtained by subjecting a resin film such as polyethylene terephthalate, polypropylene, polyimide, and polyetherimide to a surface treatment with a silicone release agent.
  • Example 1 For the production of the antenna substrate film, a resin composition containing the following components was used.
  • Component (A) Vinyl compound 2,2 ′, 3,3 ′, 5,5′-hexamethylbiphenyl-4,4′-diol-2,6-dimethylphenol and a reaction product of chloromethylstyrene (Mitsubishi) Gas Chemical Co., Ltd .; “OPE-2st”; number average molecular weight 1200) 54.3 parts
  • the above components were dry-mixed at a peripheral speed of 400 rpm using a three-one motor (manufactured by Shinto Kagaku Co., Ltd., BLW1200) to prepare a resin composition.
  • the resin composition was added to the solvent methyl ethyl ketone and heated and stirred to prepare a varnish (solid content concentration of about 30% by mass).
  • the varnish was applied to a PET film (thickness 50 ⁇ m) as a support with a gravure coater, dried at 80 to 120 ° C. for 10 minutes, and allowed to cool to obtain an antenna substrate film with a support.
  • the film thickness for the antenna substrate film was uniform at 30 m.
  • Dielectric constant ( ⁇ ), dielectric loss tangent (tan ⁇ ) After the film for antenna substrate obtained by the above procedure was cured by heating at 200 ° C. for 60 minutes, a test piece (40 ⁇ 0.5 mm ⁇ 100 ⁇ 2 mm) was formed from the film. Cut out and measured for thickness. The test piece was rolled into a cylinder having a length of 100 mm and a diameter of 2 mm or less, and the dielectric constant ( ⁇ ) and the dielectric loss tangent (tan ⁇ ) were measured by a cavity resonator perturbation method (20 GHz). As a result, the dielectric constant ( ⁇ ) was 2.4, and the dielectric loss tangent (tan ⁇ ) was 0.0025.
  • Adhesiveness Using a tackiness tester (Resca Co., Ltd., Tack-II), the push speed of the probe was 1.0 mm / min, the test speed was 600 mm / min, the initial load was 100 gf, the pressurization time was 1.0 sec, and the temperature was 20 to The change in tack load of the antenna substrate film was measured at 200 ° C. As a result, it was confirmed that the adhesiveness was excellent (adhesiveness was in the range of 30 to 500 gf) in the temperature range (100 to 150 ° C.) when transferring the circuit pattern.
  • the conductive paste used for forming the circuit pattern 40 was prepared by the following procedure.
  • a 10 L glass reaction vessel 3.0 kg (30.9 mol) of 3-methoxypropylamine was placed. While stirring, the reaction temperature was kept at 45 ° C. or lower, and 5.0 kg (30.0 mol) of silver acetate was added. Immediately after the addition, the solution became a transparent solution and dissolved, but as the addition proceeded, the solution gradually became turbid, and when the entire amount was added, it became an ash brown cloudy viscous solution. Thereto was slowly added dropwise 1.0 kg (21.0 mol) of 95% by mass of formic acid. Vigorous exotherm was observed immediately after the addition, and during that time, the reaction temperature was maintained at 30-45 ° C.
  • the turbid viscous solution changed from brown to black.
  • the reaction was terminated after the entire amount was added dropwise.
  • the reaction mixture was allowed to stand at 40 ° C. and separated into two layers.
  • the upper layer is a yellow transparent liquid, and black silver fine particles settled in the lower layer.
  • the upper layer liquid did not contain a silver component.
  • the upper layer liquid was removed by decantation, and the layers were separated using methanol to obtain a conductive paste having a silver content of 65% by mass.
  • the time required from the start of formic acid dropping to the end of the reaction was 6 hours.
  • the amount of silver fine particles deposited per reaction volume was 0.57 mol / h / L.
  • the silver content is calculated by collecting about 3 g of conductive paste in a crucible and weighing it accurately, then using an electric furnace and baking at 800 ° C. for 0.5 hours to remove organic products and measure the mass. It is the value.
  • the dispersion sample was measured by 3 (LS230) manufactured by Beckman Coulter and based on the number standard, the average particle size, 10% particle size (D10 value), 25% particle size (D25 value), 50% particle size ( D50 value), 75% particle diameter (D75 value), 90% particle diameter (D90 value), 84.3% particle diameter (D84.3 value), and geometric standard deviation (50% particle diameter (D50 value)). ) Ratio of 84.3% particle diameter (D84.3 value) to). The results are shown below.
  • Average particle size 61 nm
  • D10 46 D25: 51 D50: 61 D75: 69
  • the half width of the surface index (1,1,1) plane peak using Cu K ⁇ ray as the radiation source is obtained by measurement with an X-ray diffractometer (M18XHF22) manufactured by Mac Science, and the crystallite diameter is calculated from the Scherrer equation. Calculated. As a result, the crystallite diameter was 40 nm. Further, from this result and the measurement result of the above average particle diameter, the average particle diameter / crystallite diameter is 1.5.
  • the conductive paste obtained by the above procedure was screen-printed on the support 30 so as to have a predetermined circuit pattern shape, and then baked at 200 ° C. for 10 minutes to form the circuit pattern 40 on the support 30. .
  • the support body 70 which has the circuit pattern 80 used in the procedure shown in FIG.3 (f) was created in the same procedure.
  • the antenna substrate film 10 with the support 20 obtained by the above procedure and the support 30 having the circuit pattern 40 formed by the above procedure are vacuum-pressed.
  • the circuit pattern 40 was transferred to the antenna substrate film 10 by thermocompression bonding at 150 ° C. for 30 seconds (1 MPa).
  • a hole 50 for forming a jumper was formed by punching.
  • the antenna substrate film 10 and the circuit pattern are formed.
  • the substrate 70 on which 80 is formed is heat-pressed at 200 ° C. for 60 minutes by a vacuum press (1 MPa) to transfer the circuit pattern 80 to the antenna substrate film 10 and the antenna substrate film 10 is heat-cured. I let you.
  • the support bodies 30 and 70 were peeled off to obtain a film antenna in which circuit patterns 40 and 80 were formed on both surfaces of the antenna substrate film 10.
  • the displacement of the circuit patterns 40 and 80 was not recognized by the microscope.
  • Example 2 A film for an antenna substrate with a support is prepared in the same procedure as in Example 1. However, the glass fiber is impregnated with the varnish by applying the varnish in a state in which the glass fiber (1000TF, manufactured by Asahi Kasei E-Materials Co., Ltd.) is arranged on the surface of the PET film varnish to which the support is applied. After applying the varnish, the film is dried at 80 to 120 ° C. for 10 minutes and allowed to cool to obtain an antenna substrate film with a support, in which the glass fiber is impregnated with the resin composition. The resulting antenna substrate film has the same physical properties (dielectric constant ( ⁇ ), dielectric loss tangent (tan ⁇ ), adhesiveness) as the antenna substrate film of Example 1. Similarly to Example 1, a film antenna can be produced by carrying out the procedures of FIGS. 3A to 3F using the obtained antenna substrate film.
  • the glass fiber 1000TF, manufactured by Asahi Kasei E-Materials Co., Ltd.
  • the film antenna of the present invention exhibits a low dielectric constant ( ⁇ ) and a low dielectric loss tangent (tan ⁇ ) in a high frequency range of 1 to 60 GHz. Therefore, a film antenna used for receiving radio waves in the frequency range, for example, It is suitable as a film antenna used for 3rd generation mobile phones, PHS, wireless LAN, GPS, VICS, ETC, in-vehicle radar, and the like.

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Abstract

La présente invention concerne : une antenne de film qui montre d'excellentes caractéristiques électriques dans une région de haute fréquence ; et un film de résine à utiliser dans l'antenne de film comme substrat. Spécifiquement, la présente invention concerne un film qui est destiné à l'utilisation comme substrat d'antenne et qui est fabriqué en utilisant une composition de résine qui comprend (A) un composé de vinyle représenté par la formule (1), (B) un élastomère, (C) un prépolymère d'uréthanne qui contient deux ou plus de deux groupes isocyanate ou groupes isocyanate bloqués dans une molécule, et (D) un agent de couplage de silane et dans lequel la teneur en masse du composant (B) est de 10 à 90% par rapport à 100% du composant (A). Dans la formule (1), R1 à R7 sont chacun hydrogène, alkyle, ou similaire ; X dans la partie -(O-X-O)- est un squelette de diphénylène ; Y dans chaque partie -(Y-O)- est un squelette de phénylène ; Z est un groupe organique ; a et b sont chacun un entier de 0 à 300, avec la condition qu'un cas où les deux sont 0 est excepté ; et c et d sont chacun un entier de 0 ou 1.
PCT/JP2011/069285 2010-09-03 2011-08-26 Antenne de film, procédé de fabrication de celle-ci et film à utiliser dans celle-ci comme substrat d'antenne WO2012029650A1 (fr)

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JP2010197683A JP5731148B2 (ja) 2010-09-03 2010-09-03 フィルムアンテナおよびその製造方法、ならびに、それに用いるアンテナ基板用フィルム

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CN107464995A (zh) * 2017-08-01 2017-12-12 全普光电科技(上海)有限公司 一种薄膜天线及其制备方法
CN111448713A (zh) * 2017-12-11 2020-07-24 株式会社村田制作所 带天线的基板、以及天线模块

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JP6207064B2 (ja) * 2013-09-05 2017-10-04 住友電工プリントサーキット株式会社 アンテナ基板の製造方法
JP6140095B2 (ja) * 2014-03-28 2017-05-31 富士フイルム株式会社 積層体及びその製造方法、並びに反射板、ミラーフィルム、抗菌コート、導電膜、熱伝導体
KR101841686B1 (ko) 2016-09-29 2018-03-27 한국생산기술연구원 곡면형 내장 안테나 제조방법

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