US20110272185A1 - Pregreg, film with resin, metal foil with resin, metal-clad laminate, and printed wiring board - Google Patents

Pregreg, film with resin, metal foil with resin, metal-clad laminate, and printed wiring board Download PDF

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Publication number
US20110272185A1
US20110272185A1 US13/145,840 US201013145840A US2011272185A1 US 20110272185 A1 US20110272185 A1 US 20110272185A1 US 201013145840 A US201013145840 A US 201013145840A US 2011272185 A1 US2011272185 A1 US 2011272185A1
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Prior art keywords
resin
weight
parts
acrylic resin
resin composition
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US13/145,840
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English (en)
Inventor
Akiko Kawaguchi
Nozomu Takano
Yasuyuki Mizuno
Kazumasa Takeuchi
Shigeru Haeno
Yoshinori Nagai
Masato Fukui
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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Assigned to HITACHI CHEMICAL COMPANY, LTD. reassignment HITACHI CHEMICAL COMPANY, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FUKUI, MASATO, TAKEUCHI, KAZUMASA, HAENO, SHIGERU, NAGAI, YOSHINORI, MIZUNO, YASUYUKI, TAKANO, NOZOMU, KAWAGUCHI, AKIKO
Publication of US20110272185A1 publication Critical patent/US20110272185A1/en
Priority to US15/831,667 priority Critical patent/US10251265B2/en
Abandoned legal-status Critical Current

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/145—Organic substrates, e.g. plastic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • 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
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/425—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern
    • H05K3/427—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern initial plating of through-holes in metal-clad substrates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

  • the present invention relates to a prepreg, to a film with a resin, to a metal foil with a resin, to a metal-clad laminate and to a printed wiring board.
  • Such connecting materials i.e flexible wiring board materials
  • resin compositions comprising curing agents added to acrylic-based resins such as acrylonitrile-butadiene-based resins or carboxy-containing acrylonitrile-butadiene resins (see Patent document 1, for example).
  • Acrylic-based resins have excellent features compared to other flexible resins, including (1) suitable tack strength, (2) easy introduction of functional groups and (3) transparency.
  • Ion migration is a phenomenon in which a metal composing the wiring or circuit pattern on an insulating material or inside an insulating material, or an electrode, migrates onto the insulating material or into the insulating material by differences in potential during electrification in a high humidity environment.
  • Patent document 2 a method of adding an inorganic ion exchanger is proposed as a countermeasure.
  • the invention provides a prepreg formed by impregnating a fiber base material with a resin composition, wherein the resin composition comprises an acrylic resin, and the ratio of the peak height near 2240 cm ⁇ 1 due to nitrile groups (P CN ) to the peak height near 1730 cm ⁇ 1 due to carbonyl groups (P CO ) in the IR spectrum of the cured resin composition (P CN /P CO ) is no greater than 0.001 (first invention of prepreg).
  • the invention further provides a prepreg formed by impregnating a fiber base material with a resin composition, wherein the resin composition comprises an acrylic resin, the acrylic resin being an acrylic resin obtained by polymerizing a monomer mixture containing 5-30 parts by weight of a compound represented by the following formula (1), 0.5-30 parts by weight of a functional group-containing monomer, and 40-94.5 parts by weight of another monomer (monomer(s) other than the aforementioned two components) that is copolymerizable with these components and has no nitrile groups in the structure, combined to a total amount of 100 parts by weight (second invention of prepreg).
  • the resin composition comprises an acrylic resin, the acrylic resin being an acrylic resin obtained by polymerizing a monomer mixture containing 5-30 parts by weight of a compound represented by the following formula (1), 0.5-30 parts by weight of a functional group-containing monomer, and 40-94.5 parts by weight of another monomer (monomer(s) other than the aforementioned two components) that is copolymerizable with these
  • R 1 represents a hydrogen atom or a methyl group and R 2 represents a C5-10 cycloalkyl, C6-13 cycloalkylalkyl, C6-10 aryl or C7-13 aralkyl group.
  • a cycloalkylalkyl group is an alkyl group having one hydrogen atom replaced with a cycloalkyl group.
  • the invention further provides a metal foil with a resin, comprising a B-stage resin layer formed using a resin composition and a metal foil formed on at least one side of the resin layer, wherein the resin composition is a resin composition according to the first invention of prepreg.
  • the invention still further provides a film with a resin, comprising a B-stage resin film formed using a resin composition, formed on a support film, wherein the resin composition is a resin composition according to the first invention of prepreg.
  • the invention still further provides a metal foil with a resin, comprising a B-stage resin layer formed using a resin composition and a metal foil formed on at least one side of the resin layer, wherein the resin composition is a resin composition according to the second invention of prepreg.
  • the invention still further provides a film with a resin, comprising a B-stage resin film formed using a resin composition, formed on a support film, wherein the resin composition is a resin composition according to the second invention of prepreg.
  • the invention still further provides a metal-clad laminate comprising a substrate having a fiber base material embedded in a cured resin and a metal foil formed on at least one side of the substrate, wherein the cured resin is formed by curing a resin composition according to the first invention of prepreg.
  • the invention still further provides a metal-clad laminate comprising a substrate having a fiber base material embedded in a cured resin and a metal foil formed on at least one side of the substrate, wherein the cured resin is formed by curing a resin composition according to the second invention of prepreg.
  • the prepreg, film with a resin, metal foil with a resin and metal-clad laminate according to the invention exhibit excellent bending resistance while also prevent ion migration and have excellent insulating reliability when printed wiring boards are fabricated.
  • the abundance of nitrile groups in the resin composition is expressed as the ratio of the peak height of carbonyl groups and the peak height of nitrile groups in the IR spectrum of the cured resin composition.
  • a P CN /P CO ratio of no greater than 0.001 means that the resin composition contains substantially no nitrile groups, i.e. contains them only at an impurity level. According to the invention, the effect described above is obtained by this construction. If P CN /P CO is greater than 0.001, the migration resistance, in particular, will be reduced.
  • the “cured resin composition” is the resin composition in a cured state up to the C-stage, and for example, it is the cured product of the resin composition that has been cured under conditions of 170° C., 90 minutes, 4.0 MPa.
  • the “peak height near 1730 cm ⁇ 1 due to carbonyl groups (P CO )” and the “peak height near 2240 cm ⁇ 1 due to nitrile groups (P CN )” are the values determined by the IR measurement method described in the examples.
  • the IR measurement is preferably accomplished by the KBr tablet method. Measurement by the ATR method tends to give smaller peaks at the high wavenumber end.
  • the “substrate having a fiber base material embedded in a cured resin” is generally a substrate in which the prepreg has been cured to the C-stage. However, unreacted functional groups may partially remain in the resin (composition), both in the cured product and in the substrate.
  • the acrylic resin is preferably an acrylic resin obtained by polymerizing a monomer mixture containing 5-30 parts by weight of a compound represented by the following formula (1), 0.5-30 parts by weight of a functional group-containing monomer, and 40-94.5 parts by weight of another monomer that is copolymerizable with these components and has no nitrile groups in the structure, combined to a total amount of 100 parts by weight. This will further improve the insulating reliability.
  • R 1 represents hydrogen or a methyl group and R 2 represents a C5-10 cycloalkyl, C6-13 cycloalkylalkyl, C6-10 aryl or C7-13 aralkyl group.
  • R 2 represents a C5-10 cycloalkyl, C6-13 cycloalkylalkyl, C6-10 aryl or C7-13 aralkyl group.
  • Specific examples for the another monomer include monomers selected from among acrylic acid esters, methacrylic acid esters, aromatic vinyl compounds and N-substituted maleimides.
  • the starting monomer for the acrylic resin is limited to one containing no nitrile groups, since this may be the main factor of the presence of nitrile groups in the resin composition.
  • the acrylic resin is an acrylic resin obtained by polymerizing a monomer mixture containing 5-30 parts by weight of a compound represented by the following formula (1), 0.5-30 parts by weight of a functional group-containing monomer, and 40-94.5 parts by weight of another monomer that is copolymerizable with these components and has no nitrile groups in the structure, combined to a total amount of 100 parts by weight.
  • R 1 represents hydrogen or a methyl group and R 2 represents a C5-10 cycloalkyl, C6-13 cycloalkylalkyl, C6-10 aryl or C7-13 aralkyl group.
  • the acrylic resin is preferably an acrylic resin employing a methacrylic acid ester or acrylic acid ester having a C5-10 cycloalkyl group in the ester portion as a compound represented by the following formula (1), i.e.
  • the C5-10 cycloalkyl group preferably contains at least one group selected from the group consisting of cyclohexyl, norbornyl, tricyclodecanyl, isobornyl and adamantyl. This will still further improve the insulating reliability.
  • the weight-average molecular weight (Mw) of the acrylic resin according to the first and second inventions is preferably 50,000-1,500,000. This will allow a higher degree of adhesion and strength to be ensured.
  • the invention further provides a printed wiring board that employs at least a prepreg, a film with a resin, a metal foil with a resin or a metal-clad laminate according to the first or second invention.
  • a printed wiring board exhibits excellent bending resistance while also prevents ion migration and has excellent insulating reliability.
  • the prepreg, film with a resin, metal foil with a resin and metal-clad laminate according to the invention exhibit excellent bending resistance while also prevent ion migration and have excellent insulating reliability when printed wiring boards are fabricated.
  • a printed wiring board of the invention exhibits excellent bending resistance while also prevents ion migration and has excellent insulating reliability.
  • FIG. 1 is a perspective view of an embodiment of a prepreg according to the invention.
  • FIG. 2 is a partial cross-sectional view of an embodiment of a metal-clad laminate according to the invention.
  • FIG. 3 is a partial cross-sectional view of an embodiment of a printed wiring board of the invention, obtained by forming a wiring pattern on a metal-clad laminate.
  • FIG. 4 shows the IR spectrum measurement results for Example 9 and Comparative Example 1.
  • FIG. 5 is a photomicrograph of the electrode section of the evaluation substrate of Example 1 after a 120-hr insulating reliability evaluation test.
  • FIG. 6 is a photomicrograph of the electrode section of the evaluation substrate of Comparative Example 1 after a 120-hr insulating reliability evaluation test.
  • FIG. 7 is a photomicrograph of the electrode section of the evaluation substrate of Comparative Example 2 after a 120-hr insulating reliability evaluation test.
  • FIG. 1 is a perspective view of an embodiment of a prepreg of the invention.
  • the prepreg 100 of FIG. 1 is a sheet-like prepreg composed of a fiber base material and a resin composition impregnated in it.
  • the thickness of the prepreg is preferably 20-100 ⁇ m, since a prepreg with a thickness in this range will have satisfactory flexibility.
  • the fiber base material in the prepreg 100 may be arbitrarily bendable, flexible fiber base material, and its thickness is preferably 10-80 ⁇ m.
  • the form of the fiber base material may be appropriately selected among forms commonly used for production of metal-clad laminates or multilayer printed wiring boards, but usually the fiber base material used will be a woven fabric or nonwoven fabric.
  • the fibers composing the fiber base material may be inorganic fiber such as glass, alumina, boron, silica-alumina glass, silica glass, tyranno, silicon carbide, silicon nitride, zirconia or the like, or organic fiber such as aramid, polyetherketone, polyetherimide, polyethersulfone, carbon, cellulose or the like, or a mixed fiber sheet of the above.
  • Glass fiber is preferred among the above.
  • Particularly preferred as the fiber base material is glass cloth, which is a woven fabric made of glass fiber.
  • the glass cloth used for the invention may be subjected to coupling treatment with an aminosilane, epoxysilane or the like if necessary, as surface treatment.
  • the resin composition of the invention preferably contains no nitrile groups, but it may contain a slight amount of nitrile groups as impurities, so long as the ratio of the peak height near 2240 cm ⁇ 1 due to nitrile groups (P CN ) to the peak height near 1730 cm ⁇ 1 due to carbonyl groups (P CO ) in the IR spectrum of the cured resin composition (P CN /P CO ) is no greater than 0.001. This ratio can be determined by transmission IR spectrum measurement of the cured resin composition.
  • the carbonyl group is a characteristic functional group of the acrylic resin present as an essential component in the resin composition, and the carbonyl group (—CO) peak height is used as the standard for specifying the amount of nitrile groups.
  • the resin composition comprises an acrylic resin.
  • acrylic resins there may be used polymers obtained by polymerization of an acrylic acid ester or methacrylic acid ester alone, or copolymers obtained by copolymerization of acrylic acid esters, methacrylic acid esters, functional group-containing monomers or monomer mixtures of these components with monomers that are copolymerizable therewith.
  • the monomers in a monomer mixture preferably contain no nitrile groups, in order to more effectively prevent ion migration, while in order to further improve the insulating reliability they preferably contain no nitrogen atoms, and most preferably comprise only carbon, hydrogen and oxygen atoms.
  • the acrylic resin preferably contains no nitrile groups, and more preferably it is an acrylic resin obtained by polymerizing a monomer mixture containing 5-30 parts by weight of a compound represented by the following formula (1), 0.5-30 parts by weight of a functional group-containing monomer, and 40-94.5 parts by weight of monomer(s) (monomer(s) other than the aforementioned two components) that is copolymerizable with them, combined to a total amount of 100 parts by weight.
  • the amount of the compound represented by formula (1) below is more preferably 10-30 parts by weight, from the viewpoint of hygroscopicity.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a C5-10 cycloalkyl, C6-13 cycloalkylalkyl, C6-10 aryl or C7-13 aralkyl group, and preferably a C5-10 cycloalkyl or C7-13 aralkyl group.
  • C5-10 cycloalkyl groups for R 2 include cyclohexyl, norbornyl, tricyclodecanyl, isobornyl and adamantyl, with tricyclodecanyl being preferred from the viewpoint of low hygroscopicity.
  • C6-13 cycloalkylalkyl groups for R 2 include C1-3 alkyl groups wherein one hydrogen atom has been replaced with one of the aforementioned C5-10 cycloalkyl groups. Specific examples include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, norbornylmethyl, tricyclodecanylmethyl, isobornylmethyl and adamantylmethyl.
  • Examples of C6-10 aryl groups for R 2 include phenyl and naphthyl.
  • C7-13 aralkyl groups for R 2 include C1-3 alkyl groups wherein one hydrogen atom has been replaced with one of the aforementioned C6-10 aryl groups.
  • Specific examples include benzyl, phenethyl and naphthylmethyl, with benzyl being particularly preferred from the viewpoint of low hygroscopicity.
  • the acrylic resin is more preferably one employing a methacrylic acid ester or acrylic acid ester having a C5-10 cycloalkyl group in the ester portion (hereunder also referred to as “alicyclic monomer”) as a compound represented by the following formula (1), i.e. an acrylic resin obtained by polymerizing a monomer mixture containing 5-30 parts by weight of a methacrylic acid ester or acrylic acid ester having a C5-10 cycloalkyl group in the ester portion, 0.5-30 parts by weight of a functional group-containing monomer, and 40-94.5 parts by weight of a monomer (other than the aforementioned components) that is copolymerizable with these components combined to a total amount of 100 parts by weight.
  • the alicyclic monomer content is more preferably 10-30 parts by weight from the viewpoint of hygroscopicity.
  • the alicyclic monomer content is less than 5 parts by weight the hygroscopicity will tend to be increased, and if it is greater than 30 parts by weight the mechanical strength will tend to be reduced. If the functional group-containing monomer content is less than 0.5 part by weight the adhesion will tend to be reduced and the strength lowered, while if it is greater than 30 parts by weight, crosslinking reaction will tend to occur during copolymerization and the storage stability will tend to be impaired.
  • a C5-10 cycloalkyl group as the alicyclic monomer is preferably a methacrylic acid ester or acrylic acid ester containing at least one group selected from the group consisting of cyclohexyl, norbornyl, tricyclodecanyl, isobornyl and adamantyl groups.
  • alicyclic monomers include cyclopentyl acrylate, cyclohexyl acrylate, methylcyclohexyl acrylate, norbornyl acrylate, norbornylmethyl acrylate, phenylnorbornyl acrylate, isobornyl acrylate, bornyl acrylate, menthyl acrylate, fenchyl acrylate, adamantyl acrylate, tricyclo[5.2.1.0 2,6 ]deca-8-yl acrylate, tricyclo[5.2.1.0 2,6 ]deca-4-methyl acrylate, cyclodecyl acrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, norbornyl methacrylate, norbornylmethyl methacrylate, phenylnorbornyl methacrylate, isobornyl acryl
  • cyclohexyl acrylate isobornyl acrylate, norbornylmethyl acrylate, tricyclo[5.2.1.0 2,6 ]deca-8-yl acrylate, tricyclo[5.2.1.0 2,6 ]deca-4-methyl acrylate, adamantyl acrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, methylcyclohexyl methacrylate, tricyclohexyl methacrylate, norbornyl methacrylate, norbornylmethyl methacrylate, isobornyl methacrylate, bornyl methacrylate, menthyl methacrylate, adamantyl methacrylate, tricyclo[5.2.1.0 2,6 ]deca-8-yl methacrylate, tricyclo[5.2.1.0 2,6 ]deca-4-methyl methacrylate and cyclodecyl me
  • cyclohexyl acrylate isobornyl acrylate, norbornyl acrylate, tricyclohexyl[5.2.1.0 2,6 ]deca-8-yl acrylate, tricyclohexyl[5.2.1.0 2,6 ]deca-4-methyl acrylate and adamantyl acrylate.
  • the alicyclic monomer in this case is preferably one with no nitrile groups in the structure.
  • a functional group-containing monomer is a group having a functional group and at least one polymerizable carbon-carbon double bond in the molecule, and preferably having as the functional group at least one functional group selected from the group consisting of carboxyl, hydroxyl, acid anhydride, amino, amide and epoxy groups.
  • functional group-containing monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid and itaconic acid, hydroxyl group-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, N-methylolmethacrylamide and (o-, m-, p-)hydroxystyrene, acid anhydride group-containing monomers such as maleic anhydride, amino group-containing monomers such as diethylaminoethyl acrylate and diethylaminoethyl methacrylate, epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethylacrylate, glycidyl ⁇ -n-propylacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacryl
  • Epoxy group-containing monomers are preferred among the above from the viewpoint of storage stability, while acrylic acid esters or methacrylic acid esters with glycidyl groups are preferred, and glycidyl acrylate and glycidyl methacrylate are especially preferred, from the viewpoint of increased heat resistance by reaction with crosslinking components other than the acrylic resin.
  • the monomer that is copolymerizable with the aforementioned components is not particularly restricted so long as it does not basically impair the low hygroscopicity, heat resistance and stability of the polymer, but it preferably has no nitrile groups in the structure.
  • monomers that are copolymerizable with the aforementioned components include acrylic acid esters including alkyl acrylate esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, dodecyl acrylate and octadecyl acrylate, and alkoxyalkyl acrylates such as butoxyethyl acrylate, methacrylic acid esters including alkyl methacrylate esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacryl
  • alkyl acrylate esters or alkyl methacrylate esters are preferred, and methyl acrylate, ethyl acrylate and n-butyl acrylate are more preferred.
  • the mixing ratio of the acrylic resin is preferably 10-90 wt % and more preferably 15-70 wt %, with respect to the total solid portion of the resin composition (i.e. the total amount of components other than the solvent). If it is less than 10 wt % the bendability will tend to be reduced, and if it is greater than 90 wt % the flame retardance will tend to be reduced.
  • the polymerization method used for production of the acrylic resin may be a known method such as bulk polymerization, suspension polymerization, solution polymerization, precipitation polymerization or emulsion polymerization. Suspension polymerization is most preferred from the standpoint of cost.
  • Suspension polymerization is conducted with addition of a suspending agent in an aqueous medium.
  • the suspending agent may be a water-soluble polymer such as polyvinyl alcohol, methylcellulose or polyacrylamide, or a hardly-soluble inorganic material such as calcium phosphate or magnesium pyrophosphate, among which nonionic water-soluble polymers such as polyvinyl alcohol are preferred.
  • a water-soluble polymer such as polyvinyl alcohol, methylcellulose or polyacrylamide
  • a hardly-soluble inorganic material such as calcium phosphate or magnesium pyrophosphate
  • nonionic water-soluble polymers such as polyvinyl alcohol are preferred.
  • the water-soluble polymer is preferably used at 0.01-1 parts by weight with respect to 100 parts by weight as the total monomer mixture.
  • a radical polymerization initiator may be used for the polymerization.
  • the radical polymerization initiator used may be any one that can normally be used for radical polymerization, including an organic peroxide such as benzoyl peroxide, lauroyl peroxide, di-t-butylperoxy hexahydroterephthalate, t-butylperoxy-2-ethyl hexanoate, 1,1-t-butylperoxy-3,3,5-trimethylcyclohexane or t-butylperoxyisopropyl carbonate, an azo compound such as azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile or azodibenzoyl, a water-soluble catalyst such as potassium persulfate or ammonium persulfate, or a redox catalyst obtained by combining a peroxide or a persul
  • a mercaptan-based compound, thioglycol, carbon tetrachloride, ⁇ -methylstyrene dimer or the like may be added as a molecular weight modifier, if necessary during the polymerization.
  • the polymerization temperature may be appropriately set between 0-200° C., and preferably 40-120° C.
  • the molecular weight of the acrylic resin is not particularly restricted, but the weight-average molecular weight (standard polystyrene conversion according to gel permeation chromatography) is preferably in the range of 10,000-2,000,000 and most preferably in the range of 100,000-1,500,000. If the weight-average molecular weight is less than 10,000 the adhesion and strength will tend to be reduced, and if it is greater than 2,000,000 the solubility in solvents will tend to be lowered and the workability will tend to be impaired.
  • the resin composition preferably further comprises a thermosetting resin and a curing agent.
  • the resin composition preferably contains no components with nitrile groups in the composition.
  • thermosetting resin is preferably a resin with a glycidyl group, and also preferably comprises a high molecular weight resin component for the purpose of improving flexibility and heat resistance.
  • thermosetting resins to be used include epoxy resin-based, polyimide resin-based, polyamideimide resin-based, triazine resin-based, phenol resin-based, melamine resin-based, polyester resin-based and cyanate ester resin-based substances, as well as modified forms of these resins. These resins may be used in combinations of two or more, and if necessary they may be used as solutions in various solvents.
  • Such solvents may be alcohol-based, ether-based, ketone-based, amide-based, aromatic hydrocarbon-based, ester-based or nitrile-based solvents, and mixed solvents comprising several different types may also be used.
  • a system of the same solvent is preferred since the same solvent will allow more satisfactory adhesion within the resin.
  • Epoxy resins include polyglycidyl ethers obtained by reaction between epichlorohydrin and polyvalent phenols such as bisphenol A, biphenylnovolac-type epoxy resin, naphthalene-type epoxy resin, novolac-type phenol resin and orthocresol-novolac-type phenol resin, or polyhydric alcohols such as 1,4-butanediol, polyglycidyl esters obtained by reaction between epichlorohydrin and polybasic acids such as phthalic acid or hexahydrophthalic acid, N-glycidyl derivatives of compounds with amine, amide or heterocyclic nitrogen base, and alicyclic epoxy resins.
  • polyvalent phenols such as bisphenol A, biphenylnovolac-type epoxy resin, naphthalene-type epoxy resin, novolac-type phenol resin and orthocresol-novolac-type phenol resin
  • polyhydric alcohols such as 1,4-butanediol
  • the curing agent used may be any of those known in the prior art, and when an epoxy resin is used as the resin, for example, it may be a dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, phthalic anhydride or pyromellitic anhydride, or a polyfunctional phenol such as phenol-novolac or cresol-novolac, a naphthalene-type phenol resin or triazine ring-containing cresol-novolac.
  • the curing agent content will differ depending on the type of curing agent, but in the case of an amine it is preferably an amount such that the amine active hydrogen equivalents and the epoxy equivalents of the epoxy resin are approximately equal, and in terms of amount it is generally preferred to be about 0.001-10 parts by weight with respect to 100 parts by weight of the epoxy resin.
  • the amount is preferably 0.6-1.2 equivalents of its phenolic hydroxyl or carboxyl groups per equivalent of the epoxy resin.
  • An accelerator will often be used to promote reaction between the resin and curing agent.
  • an imidazole-based compound, organic phosphorus-based compound, tertiary amine, quaternary ammonium salt, blocked isocyanate or the like may be used, even in combinations of two or more.
  • the mixing ratio of the thermosetting resin is preferably 5-90 wt % and more preferably 10-60 wt %, with respect to the total solid portion of the resin composition.
  • the mixing ratio of the curing agent is preferably 1-95 wt % and more preferably 1-30 wt %, with respect to the total solid portion of the resin composition.
  • the resin composition may also contain a flame retardant, flow adjuster, coupling agent, antioxidant or the like.
  • the prepreg 100 is obtained, for example, by using the aforementioned resin composition for dipping or coating of the fiber base material, allowing impregnation to occur, and drying it.
  • drying is preferably performed at least at a temperature allowing volatilization of the solvent, with volatilization of at least 80 wt % of the solvent used in the varnish.
  • the drying temperature is preferably 80° C.-180° C.
  • the varnish impregnation content is preferably such for a varnish solid portion of 30-80 wt % with respect to the total of the varnish solid portion and base material.
  • Such solvents may be alcohol-based, ether-based, ketone-based, amide-based, aromatic hydrocarbon-based, ester-based or nitrile-based solvents, and mixed solvents comprising several types may also be used.
  • FIG. 2 is a partial cross-sectional view of an embodiment of a metal-clad laminate according to the invention.
  • the metal-clad laminate 200 shown in FIG. 2 comprises a substrate 30 composed of a single prepreg 100 , and two metal foils 10 formed in a bonded manner on either side of the substrate 30 .
  • the metal-clad laminate 200 is obtained, for example, by stacking the metal foils onto either side of the prepreg 100 , and heating and pressing them.
  • the heating and pressing conditions are not particularly restricted, but will usually be a molding temperature of 80° C.-250° C. and a molding pressure of 0.5 MPa-8.0 MPa, and preferably a molding temperature of 130° C.-230° C. and a molding pressure of 1.5 MPa-5.0 MPa.
  • the thickness of the metal-clad laminate 200 is preferably no greater than 200 ⁇ m and more preferably 20-180 ⁇ m. If the thickness is greater than 200 ⁇ m, the flexibility may be reduced and cracking may tend to occur more easily during bending. Also, metal-clad laminates with thicknesses of less than 20 ⁇ m are extremely difficult to produce.
  • Examples of commonly used metal foils include copper foil, aluminum foil and nickel foil, but copper foil is preferred for the metal-clad laminate of this embodiment.
  • the thickness is preferably 0.01 ⁇ m-35 ⁇ m, and the bending performance is improved by using a copper foil with a thickness of 20 ⁇ m or smaller.
  • Examples of copper foils with such thicknesses include electrolytic copper foils and rolled copper foils.
  • the method of stacking, heating and pressing the prepreg and metal foil may be a press lamination method or heated roll continuous lamination method, with no particular restrictions.
  • hot press lamination in a vacuum is preferred from the viewpoint of efficiently forming a metal-clad laminate.
  • a heated roll continuous lamination method in which continuous lamination of a prepreg and metal foil is carried out through the spacing between heated rolls and laterally conveyed to a continuous thermosetting furnace for curing followed by take-up, is a preferred method as a countermeasure against wrinkles, folds and the like caused by cure shrinkage of the viscoelastic resin composition during curing.
  • the curing and take-up may be followed by post-heat treatment for a prescribed period of time for more stable quality.
  • Embodiments of the metal-clad laminate are not limited to the mode described above.
  • multiple prepregs 100 may be used to form the substrate as a multilayer fiber-reinforced resin layer, or the metal foil may be formed on only one side of the substrate.
  • FIG. 3 is a partial cross-sectional view of an embodiment of a printed wiring board of the invention, obtained by forming a wiring pattern on the aforementioned metal-clad laminate 200 .
  • the printed wiring board 300 shown in FIG. 3 is composed mainly of the substrate 30 and a wiring pattern 11 formed of a patterned metal foil provided on both sides of the substrate 30 . Also, a plurality of through-holes 70 are formed running through the substrate 30 in a direction roughly perpendicular to its main side, and metal-plated layers 60 of a prescribed thickness are formed on the hole walls of the through-holes 70 .
  • the printed wiring board 300 is obtained by forming a wiring pattern on the metal foil 10 .
  • the wiring pattern formation may be accomplished by a process known in the prior art, such as a subtractive process.
  • the printed wiring board 300 can be suitably used as a bendable printed wiring board or rigid-flexible wiring board.
  • a multilayer wiring board can be obtained by laminating the resin film side of the metal foil with a resin described hereunder in a manner facing the wiring-formed side of the aforementioned printed wiring board, or by stacking the film with a resin described hereunder and the metal foil and laminating them on the wiring-formed side of the aforementioned printed wiring board.
  • the metal foil with a resin of this embodiment comprises a B-stage resin film made of the resin composition described above, and a metal foil formed on at least one side of the resin film.
  • Examples of commonly used metal foils include copper foil, aluminum foil and nickel foil, but copper foil is preferred for the metal foil with a resin of this embodiment.
  • the thickness is preferably 0.01 ⁇ m-35 ⁇ m, and the bending performance is improved by using a copper foil with a thickness of 20 ⁇ m or smaller.
  • the thickness of the resin film is preferably 5-90 ⁇ m. A resin film thickness of 5-90 ⁇ m will allow satisfactory flexibility to be ensured.
  • the film with a resin of this embodiment has a B-stage resin film made of the resin composition described above, provided on a support film.
  • a multilayer wiring board can be obtained by transferring the resin film of the film with a resin onto the wiring-formed side of a printed wiring board, releasing the support film, and stacking the metal foil or printed wiring board, and heating and pressing, and the resin film of the film with a resin exhibits similar properties to those of the resin film of a metal foil with a resin.
  • Polyethylene terephthalate or the like is preferably used as the support film.
  • thermosetting resin varnish A resin composition composed of the components listed in Table 1 was then dissolved in methyl ethyl ketone and methyl isobutyl ketone, and the resin solid content was adjusted to 30 wt % to prepare a thermosetting resin varnish.
  • Thermosetting resin varnishes were prepared in the same manner as Example 1, except for using monomer mixtures A having the compositional ratios listed in Tables 2-8.
  • thermosetting resin varnish was prepared in the same manner as Example 1, except that acrylic resin B prepared by the method described below was used instead of acrylic resin A.
  • acrylic resin B prepared by the method described below was used instead of acrylic resin A.
  • F-513AS tricyclo[5.2.1.0 2,6 ]deca-8-yl acrylate
  • EA ethyl acrylate
  • BA n-butyl acrylate
  • GMA glycidyl methacrylate
  • methyl isobutyl ketone 400 g of methyl isobutyl ketone and 0.1 g of azobisisobutyronitrile
  • thermosetting resin varnish was prepared in the same manner as Example 1, except that acrylic resin C synthesized by the method described below was used instead of acrylic resin A.
  • acrylic resin C synthesized by the method described below was used instead of acrylic resin A.
  • F-513AS tricyclo[5.2.1.0 2,6 ]deca-8-yl acrylate
  • EA ethyl acrylate
  • BA n-butyl acrylate
  • GMA glycidyl methacrylate
  • GMA glycidyl methacrylate
  • methyl isobutyl ketone 0.1 g of azobisisobutyronitrile
  • Thermosetting resin varnishes were prepared in the same manner as Example 1, except for using the monomer mixtures A having the compositional ratios listed in Tables 4 and 5, and mixing the components in the compositional ratios of the resin compositions listed in Tables 4 and 5.
  • thermosetting resin varnish A resin composition composed of the components listed in Table 9, using an acrylic resin with the same composition as used in Example 34, was dissolved in methyl ethyl ketone and methyl isobutyl ketone, and the resin solid content was adjusted to 30 wt % to prepare a thermosetting resin varnish.
  • thermosetting resin varnish A resin composition composed of the components listed in Table 10, using an acrylic resin with the same composition as used in Example 34, was dissolved in methyl ethyl ketone and methyl isobutyl ketone, and the resin solid content was adjusted to 30 wt % to prepare a thermosetting resin varnish.
  • thermosetting resin varnish An acrylic resin was synthesized by the same method as in Example 1 using a monomer mixture A having the compositional ratio listed in Table 8, a resin composition composed of the components listed in Table 11 was dissolved in methyl ethyl ketone and methyl isobutyl ketone, and the resin solid content was adjusted to 30 wt % to prepare a thermosetting resin varnish.
  • thermosetting resin varnish was prepared in the same manner as Example 37, except for using an acrylic resin having the same composition as that used in Comparative Example 2.
  • thermosetting resin varnish was prepared in the same manner as Example 37, except that the acrylic resin was synthesized by mixing the components in the mixing ratios listed in Table 8.
  • thermosetting resin varnishes obtained in Examples 1-37 and Comparative Examples 1-5 were evaluated by the methods described below. The results are shown in Tables 2 to 8.
  • the weight-average molecular weight was measured by gel permeation chromatography (eluent: tetrahydrofuran, column: Gelpack GL-A 100M by Hitachi Chemical Co., Ltd., standard polystyrene conversion).
  • a copper foil with a thickness of 18 ⁇ m (HLA18 by Nippon Denkai Co., Ltd.) was coated with each of the thermosetting resin varnishes prepared in Examples 1-37 and Comparative Examples 1-5 to a dried resin thickness of 60 ⁇ m using a horizontal coating machine, and then heated and dried in a drying furnace at 80-140° C. with a residence time of 5-15 minutes, to obtain a copper foil with a resin.
  • a polyethylene terephthalate (PET) film with a thickness of 70 ⁇ m (PUREX A70-25 by Teijin-DuPont Films) was coated with each of the varnishes prepared in Examples 1-37 and Comparative Examples 1-5 to a dried resin thickness of 60 ⁇ m using a horizontal coating machine, and then heated and dried in a drying furnace at 80-140° C. with a residence time of 5-15 minutes, to obtain a film with a resin.
  • a prepreg was obtained by coating a prepared varnish onto a glass cloth WEX-1027 (product of Asahi Shwebel, thickness: 19 ⁇ m) to a dried prepreg thickness of 55 ⁇ m-65 ⁇ m using a vertical coating machine, and then heat-drying it at 120-150° C. for 20 minutes.
  • WEX-1027 product of Asahi Shwebel, thickness: 19 ⁇ m
  • An electrode-attached comb pattern circuit (circuit thickness: 9 ⁇ m) with a line width of 50 ⁇ m and an interline spacing of 50 ⁇ m was formed by etching on one side of a 0.3 mm-thick double-sided copper-clad laminate (MCL-E-679F by Hitachi Chemical Co., Ltd.), while the entire opposite surface was etched.
  • the resin side of the copper foil with a resin, or the prepreg and copper foil, or the film with a resin and the copper foil, were attached to the electrode-attached comb pattern circuit-formed side of the substrate, laminated and pressed under pressing conditions of 170° C., 90 minutes, 4.0 MPa, after which the outer layer copper foil was etched and the laminate was used as the evaluation substrate.
  • the electrode-attached comb pattern circuit-formed side was coated with an acrylic resin to a post-drying thickness of at least 60 ⁇ m using an applicator, to fabricate an evaluation substrate. Specifically, the drying was conducted under conditions of 80° C./10 min and then 135° C./10 min.
  • the resin of the evaluation substrate was chipped off and the transmission IR spectrum was measured by the KBr tablet method and displayed with absorbance on the ordinate.
  • the IR measurement was conducted using a FT-IR6300 by JASCO Corp. (light source: high luminance ceramic light source, detector: DLATGS). The measurement resolution was 4. (Peak Height Near 2240 cm ⁇ 1 Due to Nitrile Groups (P CN ))
  • the peak point was defined as the point of the highest absorbance peak between the two points at 2270 cm ⁇ 1 and 2220 cm ⁇ 1 .
  • FIG. 4 shows the IR spectrum measurement results for Example 9 and Comparative Example 1.
  • the absorbance is plotted on the ordinate, and the wavenumber on the abscissa.
  • no peak due to nitrile groups was observed in the IR spectrum of Example 9.
  • the peak height was recorded as 0 when no peak could be confirmed.
  • the resin was removed from the electrode of the electrode-attached comb pattern circuit for connection between the electrode and an ion migration tester, and the resistance value was continuously measured in a thermostatic bath adjusted to a temperature of 85° C. and a humidity of 85%.
  • the application/measuring voltage was 50 V.
  • the ion migration tester used was a MIG-87C (trade name of IMV Corp.). The sample was placed in a thermostatic bath, and the voltage was applied 3 hrs after reaching a temperature of 85° C. and a humidity of 85%. The state of ion migration was observed with a microscope, 120 hrs and 1000 hrs after the 85° C./85% test.
  • FIG. 5 is a photomicrograph of the electrode section after a 120-hr insulating reliability evaluation test of the evaluation substrate of Example 1
  • FIG. 6 is a photomicrograph of the electrode section after a 120-hr insulating reliability evaluation test of the evaluation substrate of Comparative Example 1
  • FIG. 7 is a photomicrograph of the electrode section after a 120-hr insulating reliability evaluation test of the evaluation substrate of Comparative Example 2.
  • dendrites formed between the electrodes in Comparative Example 1 and dendrites began to form at the spaces between the electrodes in Comparative Example 2, while no formation of dendrites between the electrodes was observed in Example 1.
  • the roughened surface of an 18 ⁇ m-thick copper foil (HLA18, product of Nippon Denkai Co., Ltd.) was placed onto the resin side of a copper foil with a resin, a double-sided copper-clad laminate was produced under pressing conditions of 170° C., 90 minutes, 4.0 MPa, and the outer copper foils were subjected to double-sided etching for use as a test piece.
  • HLA18 product of Nippon Denkai Co., Ltd.
  • the elastic modulus was measured using a DVE (Model: Rheogel-E-4000, product of UBM).
  • the measuring conditions were: tensile mode, 5 ⁇ m amplitude, 10 Hz frequency, 20 mm chuck distance.
  • the resin side of a copper foil with a resin (thickness: 60 ⁇ m, inner copper foil thickness: 18 ⁇ m), or a film with a resin and a copper foil, were attached onto both sides of a prepreg, and a 0.1 mm-thick double-sided copper-clad laminate (product of Hitachi Chemical Co., Ltd., TC-C-300, copper foil thickness: 18 ⁇ m) was fabricated under pressing conditions of 170° C., 90 minutes, 4.0 MPa.
  • the outer copper foil of the double-sided copper-clad laminate was subjected to double-sided etching and a 10 mm width ⁇ 100 mm length test piece was cut out.
  • test piece was clamped with 0.25 mm-diameter pins and set on the stage, and the test piece was locally bent by 10 passes with a roller at a force of 500 gf on the section of the test piece clamped by the pins, assigning an evaluation of “A” for samples that bent without fracture, and “B” for samples that fractured.
  • Prepregs were fabricated by coating each of the thermosetting resin varnishes prepared in Examples 1-37 and Comparative Examples 1-5 onto a WEX-1027 glass cloth (product of Asahi Shwebel, thickness: 19 ⁇ m) to a dried prepreg thickness of 55 ⁇ m-65 ⁇ m using a vertical coating machine, and then heat-drying it at 120-150° C. for 20 minutes.
  • WEX-1027 glass cloth product of Asahi Shwebel, thickness: 19 ⁇ m
  • Example Example Item Units 25 26 Compositional ratio tertBA (tert-Butyl acrylate) wt % 40.0 20.0 — of monomer mixture tertBMA (tert-Butyl methacrylate) — — 20.0 A BA (n-Butyl acrylate) 17.0 45.0 45.0 BMA (n-Butyl methacrylate) — — — EA (Ethyl acrylate) 28.0 — — EMA (Ethyl methacrylate) — — — MMA (Methyl methacrylate) — — — GMA (Glycidyl methacrylate) 5.0 5.0 5.0 5.0 AN (Acrylonitrile) — — — — FA-513AS (Tricyclo[5.2.1.O2,6]deca-8-yl acrylate) 10.0 30.0 30.0 FA-513MS (Tricyclo[5.2.1.O2,6]deca-8-yl — — —
  • Example 37 As clearly seen in Tables 2-8, the evaluation substrates of Examples 1-37 had low occurrence of ion migration and excellent insulating reliability, compared to the evaluation substrates of Comparative Examples 1-5. Examples 13 and 14, which contained only trace nitrile groups, were satisfactory, with no detection of P CN (P CN /P CO ⁇ 0.001) and no ion migration. In Example 37, with P CN /P CO ⁇ 0.0007 (equal to or less than 0.001), no ion migration occurred even after 1000 hrs and the insulating reliability resistance value was also high, indicating stability and excellence, but in Comparative Example 4, with P CN /P CO ⁇ 0.001, a reduced insulation resistance value was observed from 120 hrs to 1000 hrs.
  • the acrylic resins synthesized in Examples 1-37 and Comparative Examples 1-5 were evaluated for insulating reliability by the methods described above. The results are shown in Tables 2 to 8. As clearly seen from Tables 2 to 8, the acrylic resins of Examples 1-37 exhibited no ion migration, while the acrylic resins of Comparative Examples 1-5 exhibited ion migration. These results indicate that the occurrence of ion migration is determined by the amount of nitrile groups in the acrylic resin.

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US13/145,840 2009-01-28 2010-01-28 Pregreg, film with resin, metal foil with resin, metal-clad laminate, and printed wiring board Abandoned US20110272185A1 (en)

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CN104280967A (zh) * 2014-10-31 2015-01-14 京东方科技集团股份有限公司 阵列基板及其制造方法、显示面板和显示装置
WO2016147817A1 (ja) * 2015-03-19 2016-09-22 三菱瓦斯化学株式会社 ドリル孔あけ用エントリーシート、及びそれを用いたドリル孔あけ加工方法
US9894761B2 (en) * 2015-06-12 2018-02-13 Panasonic Intellectual Property Management Co., Ltd. Prepreg, metal-clad laminated plate and printed wiring board
JP6972651B2 (ja) * 2016-05-13 2021-11-24 昭和電工マテリアルズ株式会社 樹脂組成物、プリプレグ、樹脂付き金属箔、積層板及びプリント配線板
EP3456779B1 (en) 2016-05-13 2023-03-01 Showa Denko Materials Co., Ltd. Prepreg, metal foil with resin, laminate and printed wiring board
KR102326454B1 (ko) 2017-03-07 2021-11-17 삼성디스플레이 주식회사 전자 장치

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CN102300909A (zh) 2011-12-28
KR20110110257A (ko) 2011-10-06
US20180098425A1 (en) 2018-04-05
JP2011021174A (ja) 2011-02-03
US10251265B2 (en) 2019-04-02
JP2014221923A (ja) 2014-11-27
KR101297040B1 (ko) 2013-08-14
JP5921800B2 (ja) 2016-05-24
JP5935845B2 (ja) 2016-06-15
WO2010087402A1 (ja) 2010-08-05
CN102300909B (zh) 2014-06-18

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