WO2020090607A1 - Dispersion - Google Patents

Dispersion Download PDF

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Publication number
WO2020090607A1
WO2020090607A1 PCT/JP2019/041648 JP2019041648W WO2020090607A1 WO 2020090607 A1 WO2020090607 A1 WO 2020090607A1 JP 2019041648 W JP2019041648 W JP 2019041648W WO 2020090607 A1 WO2020090607 A1 WO 2020090607A1
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Prior art keywords
polymer
group
monomer
dispersion
mass
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PCT/JP2019/041648
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English (en)
Japanese (ja)
Inventor
敦美 山邊
細田　朋也
渉 笠井
達也 寺田
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Ａｇｃ株式会社
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Priority to CN201980072237.1A priority Critical patent/CN113348208B/zh
Priority to JP2020553828A priority patent/JP7435462B2/ja
Publication of WO2020090607A1 publication Critical patent/WO2020090607A1/fr

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    • 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
    • C08F220/22—Esters containing halogen
    • 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques

Definitions

  • the present invention relates to a dispersion liquid in which a powder containing a tetrafluoroethylene-based polymer is dispersed in a polar solvent.
  • Tetrafluoroethylene-based polymers such as polytetrafluoroethylene (PTFE) have excellent physical properties such as chemical resistance, water / oil repellency, heat resistance, and electrical properties, and are used in various forms such as powders, dispersions, and films. And various uses of the physical properties thereof are known.
  • PTFE polytetrafluoroethylene
  • tetrafluoroethylene-based polymers have been attracting attention as a printed circuit board material corresponding to a frequency in a high frequency band, which is excellent in electrical characteristics such as low dielectric constant and low dielectric loss tangent, and heat resistance that can withstand solder reflow. ..
  • Patent Document 1 describes a resin-coated metal foil having a PTFE layer formed from a dispersion liquid in which PTFE powder is dispersed in a solvent, and a method of forming a transmission line on the metal foil to form a printed circuit board.
  • Patent Document 2 describes, as such a dispersion, a dispersion containing PTFE powder.
  • the tetrafluoroethylene-based polymer Since the tetrafluoroethylene-based polymer has essentially low surface tension and low interaction with other materials, its powder dispersion has low dispersibility. In order to improve the dispersibility, a method of blending a fluorine-based dispersant in the dispersion liquid is known, but the effect may not be sufficient in some cases. Furthermore, when a layer (coating film) containing a tetrafluoroethylene-based polymer formed from a dispersion liquid contains a fluorine-based dispersant, the physical properties (wettability, adhesiveness, smoothness, etc.) of the layer (coating film) are improved. It may decrease.
  • the present inventors have found that when the dispersion medium of the dispersion liquid is a polar solvent, such a decrease in dispersibility and layer (coating film) formability tends to be remarkable.
  • a dispersion liquid of a powder containing a tetrafluoroethylene-based polymer which has a dispersibility and a layer (coating film) forming property, using a polar solvent as a dispersion medium.
  • the present invention has the following aspects. ⁇ 1> A dispersion containing a powder containing a tetrafluoroethylene-based polymer, a polar solvent and a dispersant, wherein the powder is dispersed in the polar solvent, wherein the dispersant is a unit based on a monomer having a fluoroalkyl group. And a unit based on a monomer having an oxyalkylene glycol group, the fluorine content, the oxyalkylene group content and the hydroxyl value are 10 to 50% by mass, 5 to 75% by mass and 10 to 100 mgKOH / g in this order. A dispersion that is a polymer.
  • ⁇ 6> The dispersion liquid according to any one of the above items ⁇ 1> to ⁇ 5>, wherein the oxyalkylene group content of the polymer is 20 to 50% by mass.
  • ⁇ 7> The dispersion liquid according to any one of the above items ⁇ 1> to ⁇ 6>, wherein the hydroxyl value of the polymer is 10 to 45 mgKOH / g.
  • ⁇ 8> The dispersion liquid according to any one of the above items ⁇ 1> to ⁇ 7>, wherein the polymer contains 60 to 90 mol% of units based on the monomer having a fluoroalkyl group with respect to all units contained in the polymer. ..
  • the polymer contains 10 to 40 mol% of units based on the monomer having an oxyalkylene glycol group with respect to all units included in the polymer. liquid.
  • the polymer contains a total of 90 to 100 mol% of units based on the fluoromonomer and units based on the monomer having an oxyalkylene glycol group, with respect to all units contained in the polymer.
  • the dispersion liquid according to any one of > ⁇ 11> The dispersion liquid according to any one of the above items ⁇ 1> to ⁇ 10>, wherein the polar solvent is water, a ketone, an ester or an amide.
  • the polar solvent is methyl ethyl ketone, cyclohexanone, ⁇ -butyrolactone, 3-methoxy-N, N-dimethylpropanamide or N-methyl-2-pyrrolidone.
  • ⁇ 13> The dispersion liquid according to any one of the above items ⁇ 1> to ⁇ 12>, wherein the volume-based cumulative 50% diameter of the powder is 0.05 to 6 ⁇ m.
  • ⁇ 14> The dispersion liquid according to any one of the above items ⁇ 1> to ⁇ 13>, wherein the content of the tetrafluoroethylene-based polymer is 5 to 60% by mass.
  • ⁇ 15> The dispersion liquid according to any one of the above items ⁇ 1> to ⁇ 14>, wherein the ratio of the content of the dispersant to the content of the tetrafluoroethylene-based polymer is 0.25 or less.
  • a dispersion liquid of a powder containing a tetrafluoroethylene-based polymer which is excellent in dispersibility and wettability, adhesiveness, thixotropy, smoothness, and other layer (coating film) forming properties.
  • the layer (coating film) formed from the dispersion liquid of the present invention is particularly excellent in wettability and adhesiveness, and the dispersion liquid of the present invention is suitable for production of a resin-coated metal foil useful as a material for a printed circuit board. Can be used for
  • D50 of powder is a particle size distribution of powder measured by a laser diffraction / scattering method, and a cumulative curve is obtained by setting the total volume of particles (hereinafter, also referred to as “powder particles”) constituting the powder as 100%. , And the particle diameter at the point where the cumulative volume becomes 50% on the cumulative curve (volume-based cumulative 50% diameter).
  • Powder D90 is a point where the particle size distribution of powder is measured by a laser diffraction / scattering method, the cumulative volume is calculated with the total volume of the powder particle group as 100%, and the cumulative volume becomes 90% on the cumulative curve. Is the particle size (volume-based cumulative 90% size).
  • D50 and D90 of the powder are the volume-based cumulative 50% diameter and the volume-based cumulative 90% diameter of the powder particles, respectively.
  • the “melt viscosity of the polymer” is based on ASTM D 1238, and a sample of the polymer (2 g) which was heated in advance for 5 minutes at the measurement temperature using a flow tester and a die of 2 ⁇ -8L was loaded with 0.7 MPa. It is the value measured by holding at the measurement temperature at.
  • “Viscosity” is a value measured with a B-type viscometer at room temperature (25 ° C.) under the condition of a rotation speed of 30 rpm. The measurement is repeated three times, and the average value of the three measured values is used.
  • Ten-point average roughness (Rz JIS )" is a value defined in Annex JA of JIS B 0601: 2013.
  • the “unit” in a polymer may be an atomic group formed directly from a monomer by a polymerization reaction, and the polymer obtained by the polymerization reaction is treated by a predetermined method to convert an atomic group in which a part of the structure is converted.
  • May be "(Meth) acryloyloxy group” is a general term for an acryloyloxy group and a methacryloyloxy group.
  • (Meth) acrylate” is a general term for acrylate and methacrylate.
  • the “unit” in a polymer means an atomic group based on the above-mentioned monomer, which is formed by polymerizing the monomer.
  • the unit may be a unit directly formed by a polymerization reaction, or a unit in which a part of the above unit is converted into another structure by treating the polymer.
  • the unit based on the monomer a is also simply referred to as a “monomer a unit”.
  • a unit based on tetrafluoroethylene (TFE) is also simply referred to as “TFE unit”.
  • the dispersion liquid of the present invention is a dispersion liquid containing a powder containing a tetrafluoroethylene-based polymer (hereinafter, also referred to as “F polymer”), a polar solvent, and a dispersant, and the powder being dispersed in the polar solvent.
  • the dispersant is a polymer containing a unit based on a monomer having a fluoroalkyl group (hereinafter, also referred to as “monomer F”) and a unit based on a monomer having an oxyalkylene glycol group (hereinafter, also referred to as “monomer AO”). (Hereinafter, also referred to as “AO polymer”).
  • the fluorine content, oxyalkylene group content and hydroxyl value of the AO polymer are 10 to 50% by mass, 5 to 75% by mass and 10 to 100 mgKOH / g in this order.
  • the oxyalkylene glycol group is an oxyalkylene glycol residue (group represented by the formula- (OZ) n —OH, or the like, in which Z is an alkylene group and n is a number of 2 or more. It is).
  • the dispersion of the present invention is excellent in dispersibility and is also excellent in layer (coating film) forming properties such as wettability, adhesiveness, thixotropy and smoothness.
  • the AO polymer which is a dispersant, has a fluorine-containing moiety, a hydroxyl group, and a polyoxyalkylene moiety, and the hydroxyl value, the fluorine content, and the oxyalkylene content are each within the above predetermined range. It is thought that it is adjusted.
  • the hydroxyl value and oxyalkylene content of the AO polymer and the fluorine content have a trade-off relationship, and it is not easy to adjust the respective values to balance the affinity for the F polymer and the polar solvent.
  • the fluorine content of the AO polymer is due to the structure of the monomer F (fluorine content) and the amount of the monomer F units in the polymer
  • the hydroxyl value and oxyalkylene group content of the AO polymer are the structure of the monomer AO and Due to the amount of monomeric AO units in the polymer.
  • a monomer F having a high fluorine content and increasing the content thereof makes it possible to prepare an AO polymer having a high fluorine content.
  • an AO polymer has improved affinity with the F polymer, its hydroxyl value and oxyalkylene group content are relatively reduced, so that the affinity with polar solvents is reduced.
  • the dispersibility of the dispersion liquid containing such an AO polymer decreases.
  • the present inventors selected the structure of the monomer F and the structure of the monomer AO, respectively, and set the respective values of the fluorine content, the hydroxyl value and the oxyalkylene group content of the AO polymer to the above values. It was found that the dispersibility of the dispersion liquid is improved by using a dispersant adjusted to a predetermined range. Furthermore, they have completed the present invention by discovering that the layer (coating film) formed from such a dispersion has excellent physical properties.
  • the powder in the present invention preferably contains F polymer as a main component.
  • the content of the F polymer in the powder is preferably 80% by mass or more, and particularly preferably 100% by mass.
  • Other resins that can be contained in the powder include aromatic polyester, polyamideimide, thermoplastic polyimide, polyphenylene ether, polyphenylene oxide and the like.
  • the D50 of the powder is preferably 0.05 to 6 ⁇ m, particularly preferably 0.1 to 3 ⁇ m.
  • the D50 of the powder is preferably 8 ⁇ m or less, and particularly preferably 1.5 to 5 ⁇ m.
  • the loosely packed bulk density and the densely packed bulk density of the powder are preferably 0.08 to 0.5 g / mL and 0.1 to 0.8 g / mL in this order.
  • the F polymer in the present invention is a polymer containing a unit based on TFE (TFE unit).
  • TFE unit The F polymer is a homopolymer composed of TFE units (hereinafter also referred to as "PTFE"), a copolymer containing TFE units and units based on perfluoro (alkyl vinyl ether) (PAVE) (PAVE units) (hereinafter also referred to as "PFA”).
  • a copolymer hereinafter, also referred to as “FEP”) containing a TFE unit and a unit based on hexafluoropropylene (HFP) (HFP unit), or a unit based on a TFE unit and fluoroalkyl ethylene (FAE) (FAE unit).
  • the PTFE also includes a low molecular weight polymer and a polymer containing an extremely small amount of a unit other than the TFE unit.
  • the polymer preferably contains 99.5 mol% or more, and particularly preferably 99.9 mol% or more of TFE units with respect to all units contained in the polymer.
  • the melt viscosity of the polymer at 380 ° C. is preferably 1 ⁇ 10 2 to 1 ⁇ 10 8 Pa ⁇ s, particularly preferably 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa ⁇ s.
  • the low-molecular-weight PTFE may be PTFE obtained by irradiating high-molecular-weight PTFE with radiation (polymers described in International Publication No. 2018/026012, International Publication No. 2018/026017, etc.), and polymerization of TFE.
  • PTFE obtained by using a chain transfer agent polymers described in JP2009-1745A, WO2010 / 114033, JP2015-232082, and the like
  • a core-shell structure may be obtained.
  • PTFE polymer described in JP-A-2005-527652, WO2016 / 170918, JP-A-09-087334, etc.
  • the standard specific gravity of low-molecular-weight PTFE is preferably 2.14 to 2.22, more preferably 2.16 to 2.20.
  • F polymers also include polymers containing units other than TFE units.
  • the polymer preferably contains more than 0.5 mol% of units based on monomers other than TFE units, based on all units of the polymer.
  • the units other than TFE are preferably PAVE units, HFP units, FAE units or units having a functional group described later.
  • the F polymer preferably has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an oxetanyl group, an amino group, a nitrile group and an isocyanate group.
  • the F polymer has the above-mentioned functional group
  • the interaction between the hydroxyl group and the oxyalkylene moiety contained in the AO polymer with the F polymer is likely to be strengthened, and the dispersibility of the dispersion liquid and the layer (coating film) formability are likely to be further improved.
  • the carbonyl group-containing group includes an amide group.
  • the functional group may be contained in a unit constituting the F polymer, may be contained in an end group of the polymer main chain, or may be introduced into the F polymer by plasma treatment or the like.
  • the F polymer having the above functional group in the terminal group of the polymer main chain include F polymers having a functional group as the terminal group derived from a polymerization initiator, a chain transfer agent and the like.
  • the functional group is preferably a hydroxy group or a carbonyl group-containing group, particularly preferably a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group or an acid anhydride residue (-C (O) OC (O)-). Most preferred are groups or acid anhydride residues.
  • the F polymer is preferably a polymer containing a TFE unit, a PAVE unit, an HFP unit or a FAE unit, and a unit having a functional group.
  • the unit having a functional group is preferably a unit based on a monomer having a functional group.
  • a monomer having a hydroxy group or a carbonyl group-containing group is preferable, a monomer having an acid anhydride residue or a monomer having a carboxy group is more preferable, and a cyclic monomer having an acid anhydride residue is particularly preferable.
  • the cyclic monomer include itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride (also known as hymic acid anhydride; hereinafter also referred to as “NAH”) or maleic anhydride. Is preferred.
  • CF 2 CFOCF 3
  • CF 2 CFOCF 2 CF 2 CF 3
  • CF 2 CFOCF 2 CF 2 CF 3
  • CF 2 CFO (CF 2 ) 8 F
  • PPVE is preferable.
  • the TFE unit, the PAVE unit, the HFP unit or the FAE unit, and the unit having a functional group are contained in this order in an amount of 90 to 99 mol% and 0.5 to 9 with respect to all units contained in the F polymer. It is preferably contained in an amount of 0.97 mol%, 0.01 to 3 mol%.
  • the melting point of the F polymer is preferably 250 to 380 ° C, particularly preferably 280 to 350 ° C. Specific examples of such F polymers include the polymers described in WO2018 / 16644.
  • the polar solvent in the present invention is a polar solvent that is liquid at 25 ° C., and may be protic or aprotic.
  • the polar solvent may be an aqueous solvent or a non-aqueous solvent.
  • the polar solvent may be used alone or in combination of two or more.
  • the polar solvent is preferably water, amide, alcohol, sulfoxide, ester, ketone or glycol ether, more preferably water, ketone, ester or amide, particularly preferably ketone, ester or amide.
  • the polar solvent include water, methanol, ethanol, isopropanol, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, dimethyl sulfoxide, diethyl ether, dioxane, ethyl lactate, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isopropyl ketone, cyclopentanone, cyclohexanone, ethylene glycol monoisopropyl ether, cellosolve (methyl Cellosolve, ethyl cellosolve and the like).
  • the polar solvent is more preferably methyl ethyl ketone, cyclohexanone, ⁇ -butyrolactone, 3-methoxy-N, N-dimethylprop
  • the AO polymer in the present invention is a unit based on a monomer having a fluoroalkyl group (monomer F) (hereinafter, also referred to as “unit F”) and a unit based on a monomer having an oxyalkylene glycol group (monomer AO) (hereinafter, “ Unit AO ").
  • the AO polymer is a polymer other than the F polymer.
  • An etheric oxygen atom may be present between the carbon atom-carbon atom bonds of the polyfluoroalkyl group, and the carbon atom-carbon atom bond may form a double bond.
  • the polyfluoroalkyl group preferably has 4 to 8 carbon atoms.
  • the monomer F is preferably a compound represented by the following formula F.
  • the acrylate-based monomer F having such a relatively short chain length of the fluorine-containing moiety is selected, not only the dispersibility of the dispersion liquid is excellent, but also the physical properties such as wettability and adhesiveness of the F layer are easily improved.
  • Formula F: CH 2 CX F C (O) O-Q F- R F
  • X F is a hydrogen atom, a chlorine atom or a methyl group.
  • Q F is an alkylene group having 1 to 4 carbon atoms, and a methylene group (—CH 2 —) or an ethylene group (—CH 2 CH 2 —) is preferable.
  • R F is a C 1-6 polyfluoroalkyl group or a C 3-6 polyfluoroalkyl group containing an etheric oxygen atom.
  • R F include-(CF 2 ) 4 F,-(CF 2 ) 6 F, -CF 2 OCF 2 CF 2 OCF 2 CF 3 or -CF (CF 3 ) OCF 2 CF 2 CF 3 .
  • the physical properties of the F layer (wettability, adhesiveness, smoothness, etc.) from the viewpoint of further excellent, R F is, - (CF 2) 4 F or - (CF 2) 6 F are preferred, - (CF 2) 6 F is more preferred.
  • Monomer AO means a polymerizable group such as CH 2 ⁇ CHO—, CH 2 ⁇ CHCH 2 O—, CH 2 ⁇ CHC (O) O—, CH 2 ⁇ CCH 3 C (O) O—, and oxyalkylene glycol. Is a general term for compounds having a residue.
  • the monomer AO is preferably oxyalkylene glycol mono (meth) acrylate, more preferably a compound represented by the following formula H.
  • an acrylate-based monomer AO having such a hydroxyl group and a polyoxyalkylene moiety is selected, not only the dispersibility of the dispersion is excellent, but also the physical properties such as wettability and adhesiveness of the F layer (coating) are easily improved. ..
  • X H is a hydrogen atom or a methyl group
  • Z H is an alkylene group having 1 to 4 carbon atoms, and is an ethylene group (—CH 2 CH 2 —), a propylene group (—CH 2 CH (CH 3 ) —) or an n-butylene group (—CH 2 CH 2 CH 2 CH 2 —) is preferred.
  • Z H may be composed of one kind of group or may be composed of two or more kinds of groups. In the latter case, the different alkylene groups may be arranged in a random pattern or a block pattern.
  • m is 3 to 200, preferably 6 to 100, more preferably 9 to 70, and particularly preferably 12 to 40 from the viewpoint that the wettability and smoothness of the F layer are particularly excellent.
  • Fluorine content of AO polymer is 10 to 50% by mass.
  • the lower limit is preferably 20% by mass and the upper limit is preferably 40% by mass.
  • the dispersibility of the dispersion is excellent.
  • the upper limit of the fluorine content is within the above range, the affinity of the dispersant for each component of the dispersant is balanced, and in addition to the dispersibility of the dispersion liquid, the layer (coating film) formability thereof is easily improved.
  • the F layer is characterized by high wettability and excellent adhesiveness.
  • the hydroxyl value of AO polymer is 10 to 100 mgKOH / g.
  • the lower limit is preferably 15 mgKOH / g.
  • the upper limit is preferably 50 mgKOH / g, more preferably 35 mgKOH / g, particularly preferably 30 mgKOH / g.
  • the lower limit of the hydroxyl value is within the above range, the dispersibility of the dispersion is excellent.
  • the upper limit of the hydroxyl value is within the above range, the affinity of the AO polymer for each of the F polymer and the polar solvent is balanced, and in addition to the dispersibility of the dispersion liquid, the layer (coating film) formability thereof is easily improved. .. Specifically, the F layer easily expresses the physical properties of the F polymer itself.
  • the oxyalkylene group content of the AO polymer (hereinafter, also referred to as “AO content”) is 5 to 75 mass%.
  • the lower limit is preferably 20% by mass, more preferably 25% by mass.
  • the upper limit is preferably 50% by mass, more preferably 45% by mass.
  • the lower limit of the AO content is within the above range, the dispersibility of the dispersion is excellent.
  • the upper limit of the AO content is in the above range, the affinity of the AO polymer for each of the F polymer and the polar solvent is balanced, and in addition to the dispersibility of the dispersion liquid, the layer (coating film) formability is improved. easy. Specifically, in the F layer, the physical properties of the F polymer itself are directly expressed, and the smoothness thereof is easily improved.
  • suitable ranges of the fluorine content, the oxyalkylene group content and the hydroxyl value of the AO polymer are 20 to 50% by mass, 20 to 50% by mass and 15 to 35 mgKOH / g in this order. Is an embodiment.
  • the sum of the fluorine content and the AO content of the AO polymer is less than 100% by mass, preferably 45 to 85% by mass.
  • the fluorine content, the hydroxyl value and the AO content of the AO polymer may be calculated from the type of monomer used when synthesizing the AO polymer and the amount used, or may be determined by analyzing the AO polymer. ..
  • the amount of the unit F with respect to all the units contained in the AO polymer is preferably 60 to 90 mol%, particularly preferably 70 to 90 mol%.
  • the amount of the unit AO with respect to all units contained in the AO polymer is preferably 10 to 40 mol%, particularly preferably 10 to 30 mol%.
  • the AO polymer may be composed of only the unit F and the unit AO, and may further include an additional unit other than the unit F and the unit AO as long as the effects of the present invention are not impaired.
  • the total amount of the unit F and the unit AO with respect to all the units contained in the AO polymer is preferably 90 to 100 mol%, particularly preferably 99 to 100 mol%.
  • the AO polymer is preferably a polymer substantially consisting of the unit F and the unit AO.
  • the AO polymer is preferably nonionic.
  • the weight average molecular weight of the AO polymer is preferably 2000 to 80,000, particularly preferably 6000 to 20,000.
  • a preferred specific example of the AO polymer includes a unit based on the compound represented by the following formula F1 and a unit based on the compound represented by the following formula H1, and has a fluorine content, an oxyalkylene group content and a hydroxyl value.
  • a polymer having 20 to 40% by mass, 25 to 45% by mass, and 15 to 30 mgKOH / g can be mentioned.
  • Formula F1: CH 2 CX F1 C (O) O—CH 2 CH 2 —R F1
  • Formula H1: CH 2 CX H1 C (O)-(OCH 2 CH 2 ) m1- OH
  • X F1 is a hydrogen atom or a methyl group.
  • R F1 is — (CF 2 ) 4 F or — (CF 2 ) 6 F.
  • X H1 is a hydrogen atom or a methyl group.
  • m1 is 9 to 70, preferably 12 to 40.
  • the amount of the unit based on the compound represented by the formula F1 with respect to all the units contained in the AO polymer is 60 to 90 mol%, preferably 70 to 90 mol%.
  • the amount of the unit based on the compound represented by the formula H1 with respect to all the units contained in the AO polymer is 10 to 40 mol%, preferably 10 to 30 mol%.
  • the total amount of the unit based on the compound represented by the formula F1 and the compound represented by the formula H1 is 90 to 100 mol%, preferably 100 mol% with respect to all the units contained in the AO polymer.
  • the AO polymer may have a hydroxyl group or a carboxyl group at the main chain terminal. In this case, the leveling property of the dispersion liquid of the present invention is easily improved. Such an AO polymer can be obtained, for example, by adjusting the type of polymerization initiator or chain transfer agent used in the production thereof.
  • the proportion of the F polymer in the dispersion of the present invention is preferably 5 to 60% by mass, particularly preferably 30 to 50% by mass. Within this range, it is easy to form an F layer having excellent electrical characteristics and mechanical strength.
  • the proportion of the dispersant in the dispersion of the present invention is preferably 1 to 30% by mass, particularly preferably 3 to 15% by mass. Within this range, the dispersibility is further improved, and the physical properties (wetability, adhesiveness, etc.) of the F layer are more easily improved.
  • the ratio of the content of the AO polymer to the content of the F polymer in the dispersion liquid of the present invention is preferably 0.25 or less, more preferably 0.2 or less, and particularly preferably 0.1 or less. The lower limit of the ratio is preferably 0.01.
  • the AO polymer Since the AO polymer has a high affinity with both the F polymer and the polar solvent, the dispersion stability of the dispersion is excellent even when the above ratio is small (when the content of the AO polymer is small). Further, when the above ratio is within the above range, it is easy to form an F layer having high wettability and excellent adhesiveness and exhibiting the physical properties of the F polymer itself.
  • the proportion of the polar solvent in the dispersion liquid of the present invention is preferably 15 to 65% by mass, and particularly preferably 25 to 50% by mass. Within this range, the coatability of the dispersion is excellent and the layer (coating film) formability is easily improved.
  • the dispersion liquid of the present invention may contain other materials as long as the effects of the present invention are not impaired.
  • Other materials may or may not dissolve in the dispersion.
  • Such other materials may be organic or inorganic.
  • the organic substance may be a non-curable resin or a curable resin.
  • non-curable resins include heat-meltable resins and non-meltable resins.
  • thermofusible resin include thermoplastic polyimide.
  • Examples of the non-meltable resin include a cured product of a curable resin.
  • the shape of the other material may be granular or fibrous.
  • the curable resin examples include a polymer having a reactive group, an oligomer having a reactive group, a low molecular compound, and a low molecular compound having a reactive group.
  • the reactive group include a carbonyl group-containing group, a hydroxy group, an amino group and an epoxy group.
  • the curable resin includes epoxy resin, thermosetting polyimide, polyamic acid, acrylic resin, phenol resin, polyester resin, polyolefin resin, modified polyphenylene ether resin, polyfunctional cyanate ester resin, polyfunctional maleimide-cyanate ester resin, Examples thereof include functional maleimide resin, vinyl ester resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, and melamine-urea cocondensation resin.
  • Epoxy resins include naphthalene type, cresol novolac type, bisphenol A type, bisphenol F type, bisphenol S type, alicyclic type, aliphatic chain type, cresol novolac type, phenol novolac type, alkylphenol novolac type, aralkyl type, biphenol.
  • Examples include any epoxy resin such as a mold.
  • Examples of the bismaleimide resin include the resin composition (BT resin) described in JP-A-7-70315 and the resin described in International Publication No. 2013/008667.
  • Examples of diamines and polycarboxylic acid dianhydrides that form polyamic acid include [0020] of Japanese Patent No. 5766125, [0019] of Japanese Patent No. 5766125, [0055] of Japanese Patent Laid-Open No. 2012-145676, and [0055]. [0057] and the like.
  • thermoplastic polyimide As the heat-meltable resin, thermoplastic polyimide, polyester resin, polyolefin resin, styrene resin, polycarbonate, thermoplastic polyimide, polyarylate, polysulfone, polyallylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, poly Examples thereof include allyl ether ketone, polyamide imide, liquid crystalline polyester, polyphenylene ether, and thermosetting cured products of a curable resin, and thermoplastic polyimide, liquid crystalline polyester, or polyphenylene ether is preferable.
  • Examples of such other materials include thixotropic agents, antifoaming agents, fillers, reactive alkoxysilanes, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, and whitening agents. Examples also include agents, colorants, conductive agents, release agents, surface treatment agents, viscosity modifiers, flame retardants and the like.
  • Suitable specific examples of other materials include fillers having a low relative dielectric constant and a low dielectric loss tangent. If the dispersion of the present invention contains such a filler, the electrical characteristics of the laminate or printed circuit board described later can be more easily improved.
  • the filler or the compound forming the filler silica, clay, talc, calcium carbonate, mica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, cerium oxide, tin oxide, oxidation Antimony, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, non-basic magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, boron nitride , Aluminum nitride, montmorillonite, forsterite, steatite, cordierite, bentonite, activated clay, sepiolite, im
  • Suitable specific examples of other materials include magnesium oxide, forsterite, boron nitride, and aluminum nitride, which are fillers having a particularly low dielectric loss tangent.
  • the dispersion of the present invention contains such a filler, its content is determined so that the linear expansion coefficient of the F layer formed from the dispersion, particularly the annealed F layer is 10 to 100 ppm / ° C. Is preferred.
  • the content can be determined by the kind and shape of the filler, and if the aspect ratio is 2 or more, 1 to 50% by mass is preferable, 10 to 50% by mass is more preferable, and the aspect ratio is If it is 1 to 2 spherical fillers, 1 to 80 mass% is preferable, and 10 to 80 mass% is more preferable.
  • the former filler include fibrous magnesium sulfate (manufactured by Ube Materials Co., Ltd., trade name “MOS HEIGH”, etc.), glass cut fiber (manufactured by Nitto Boseki Co., Ltd., trade names “PF”, “SS”). Etc.).
  • the F layer formed from the dispersion liquid containing these fillers improves absorption of light having a wavelength in the ultraviolet region, particularly absorption of light having a wavelength of 266 nm and 355 nm, and thus UV-rays using such a wavelength are used. YAG laser processability is improved. Therefore, a highly accurate printed circuit board can be easily manufactured from the laminated body described later.
  • the dispersion of the present invention contains a filler from the viewpoint of maintaining or improving the bendability of the F layer, its shape is preferably granular, and more preferably 1 ⁇ m or less. Further, a filler having an aspect ratio of 2 or more and a filler having an aspect ratio of 1 to 2 may be used in combination.
  • the filler may be surface-treated with a silane coupling agent or the like. The water absorption of the filler is preferably 3% or less, more preferably 1% or less.
  • the viscosity of the dispersion liquid of the present invention is preferably 10,000 mPa ⁇ s or less, more preferably 50 to 10,000 mPa ⁇ s, further preferably 75 to 1,000 mPa ⁇ s, particularly preferably 100 to 500 mPa ⁇ s. In this case, not only is the dispersibility of the dispersion liquid excellent, but also its coatability and compatibility with varnishes of different resin materials are excellent.
  • the thixo ratio ( ⁇ 1 / ⁇ 2 ) of the dispersion liquid of the present invention is preferably 1.0 to 2.2, more preferably 1.4 to 2.2, and particularly preferably 1.5 to 2.0.
  • the thixo ratio ( ⁇ 1 / ⁇ 2 ) is obtained by dividing the viscosity ⁇ 1 of the dispersion liquid measured at the rotation speed of 30 rpm by the viscosity ⁇ 2 of the dispersion liquid measured at the rotation speed of 60 rpm. Is calculated.
  • the dispersion liquid of the present invention can form an F layer having excellent adhesiveness. It is preferable to form the F layer on the surface of the substrate from the dispersion liquid of the present invention.
  • the F layer may be a single layer or a laminated body including a plurality of layers. Further, each of the F layers may include the above-mentioned other materials (various organic resins, fillers, etc.).
  • a first F layer is formed on the surface of a substrate by using the dispersion liquid of the present invention containing no other material or containing a small amount of the other material, and further, a material containing a high content of the other material.
  • a second F layer may be formed on the surface of the first F layer using the dispersion of the invention.
  • the base material is preferably a metal foil.
  • the material of the metal foil include copper, copper alloy, stainless steel, nickel, nickel alloy (including 42 alloy), aluminum, aluminum alloy, titanium, titanium alloy and the like.
  • the metal foil include rolled copper foil and electrolytic copper foil. The surface of the metal foil may be subjected to rust prevention treatment (oxide coating such as chromate) and may be subjected to roughening treatment.
  • the ten-point average roughness of the surface of the metal foil is preferably 0.2 to 1.5 ⁇ m. In this case, the adhesiveness with the F layer tends to be good.
  • the metal foil may have any thickness as long as it can exhibit its function in the application of the resin-coated metal foil.
  • the thickness of the metal foil is not less than the ten-point average roughness of the surface thereof, and is preferably 2 to 40 ⁇ m.
  • the entire surface of the metal foil may be treated with a silane coupling agent, or only a part thereof may be treated with a silane coupling agent.
  • a laminated metal foil in which an ultrathin metal foil and a carrier metal foil are laminated can also be used.
  • the thickness of the ultrathin metal foil is preferably 2 to 5 ⁇ m.
  • a peeling layer is preferably formed between the metal foils of the carrier-attached metal foil.
  • the peeling layer is preferably a metal layer containing nickel or chromium, or a multilayer metal layer obtained by stacking such metal layers. With such a peeling layer, the carrier copper foil can be easily peeled from the ultrathin copper foil even after being subjected to the step of 300 ° C. or higher.
  • a specific example of the metal foil with a carrier is "FUTF-5DAF-2" manufactured by Fukuda Metal Foil & Powder Co., Ltd.
  • the dispersion liquid of the present invention is applied (supplied) to the surface of a metal foil, and the metal foil is heated to produce a resin-coated metal foil having an F layer.
  • the resin-coated metal foil according to the present invention has an F layer on at least one surface of the metal foil. That is, the resin-coated metal foil may have the F layer only on one side of the metal foil, or may have the F layer on both sides of the metal foil.
  • the warp rate of the resin-coated metal foil is preferably 25% or less, particularly preferably 7% or less. In this case, the handling property when processing the resin-coated metal foil into a printed board and the transmission characteristics of the resulting printed board are excellent.
  • the dimensional change rate of the resin-coated metal foil is preferably ⁇ 1% or less, and particularly preferably ⁇ 0.2% or less. In this case, it is easy to process the resin-coated metal foil into a printed circuit board and further to form it into multiple layers.
  • the water contact angle of the surface of the F layer is preferably 70 to 100 °, particularly preferably 70 to 90 °. In this case, the adhesiveness between the F layer and another substrate is more excellent.
  • the thickness of the F layer is preferably 1 to 200 ⁇ m, more preferably 1 to 50 ⁇ m, further preferably 1 to 15 ⁇ m, and particularly preferably 1 to 9 ⁇ m. In this range, it is easy to balance the electrical characteristics when the resin-coated metal foil is processed into a printed board and the warp suppression of the resin-coated metal foil.
  • the composition and thickness of the two F layers are preferably the same from the viewpoint of suppressing warpage of the resin-coated metal foil.
  • the relative dielectric constant of the F layer is preferably 2.0 to 3.5, more preferably 2.0 to 3.0.
  • the resin-coated metal foil can be preferably used for a printed circuit board or the like that requires a low dielectric constant.
  • the coating method may be any method capable of forming a stable wet film made of a dispersion liquid on the surface of the metal foil after coating, a spray method, a roll coating method, a spin coating method, a gravure coating method, a micro gravure coating method, Examples thereof include a gravure offset method, a knife coating method, a kiss coating method, a bar coating method, a die coating method, a fountain Mayer bar method, and a slot die coating method.
  • the temperature in the low temperature region is preferably 80 ° C. or higher and lower than 180 ° C., particularly preferably 120 ° C. to 170 ° C.
  • Holding at the temperature in the low temperature region may be carried out in one step, or may be carried out in two or more steps at different temperatures.
  • Examples of the method of maintaining the temperature in the low temperature region include a method using an oven, a method using a ventilation drying furnace, and a method of irradiating heat rays such as infrared rays.
  • the atmosphere for maintaining the temperature in the low temperature region may be either under normal pressure or under reduced pressure.
  • the atmosphere may be any of an oxidizing gas atmosphere, a reducing gas atmosphere, and an inert gas atmosphere.
  • the inert gas include helium gas, neon gas, argon gas and nitrogen gas, and nitrogen gas is preferable.
  • the reducing gas include hydrogen gas.
  • the oxidizing gas may be oxygen gas.
  • the atmosphere for holding the temperature in the low temperature region is preferably an atmosphere containing oxygen gas from the viewpoint of promoting the oxidative decomposition of the dispersant and further improving the adhesiveness of the F layer.
  • the oxygen gas concentration (volume basis) in the atmosphere containing oxygen gas is preferably 1 ⁇ 10 2 to 3 ⁇ 10 5 ppm, particularly preferably 0.5 ⁇ 10 3 to 1 ⁇ 10 4 ppm. Within this range, it is easy to balance the oxidative decomposition of the dispersant and the suppression of oxidation of the metal foil.
  • the time for maintaining the temperature in the low temperature region is preferably 0.1 to 10 minutes, particularly preferably 0.5 to 5 minutes.
  • the F polymer is further fired on the surface of the metal foil in a temperature region (hereinafter, also referred to as a “firing region”) that exceeds the holding temperature in the low temperature region. It is preferable to form the F layer.
  • the temperature of the firing region means the temperature of the atmosphere during firing. It is considered that the formation of the F layer in the present invention proceeds because the powder particles are densely packed and the F polymer is fused. If the dispersion liquid contains a thermofusible resin, an F layer made of a mixture of an F polymer and a soluble resin is formed, and if the dispersion liquid contains a thermosetting resin, the F polymer and the thermosetting resin are cured. An F layer composed of a material is formed.
  • the firing method examples include a method using an oven, a method using a ventilation drying furnace, and a method of irradiating heat rays such as infrared rays.
  • a heating method a method of irradiating with far infrared rays is preferable because it can be fired in a short time and the far infrared ray furnace is relatively compact.
  • the heating method may be a combination of infrared heating and hot air heating.
  • the effective wavelength band of far infrared rays is preferably 2 to 20 ⁇ m, more preferably 3 to 7 ⁇ m from the viewpoint of promoting uniform fusion of the F polymer.
  • the atmosphere during firing may be either under normal pressure or under reduced pressure.
  • the atmosphere in the firing may be any of an oxidizing gas atmosphere, a reducing gas atmosphere, and an inert gas atmosphere.
  • the reducing property is A gas atmosphere or an inert gas atmosphere is preferred.
  • the inert gas include helium gas, neon gas, argon gas and nitrogen gas, and nitrogen gas is preferable.
  • the reducing gas include hydrogen gas.
  • the oxidizing gas may be oxygen gas.
  • the atmosphere for firing is preferably a gas atmosphere composed of an inert gas and having a low oxygen gas concentration, and more preferably a gas atmosphere composed of nitrogen gas and having an oxygen gas concentration (volume basis) of less than 500 ppm.
  • the oxygen gas concentration (volume basis) is particularly preferably 300 ppm or less.
  • the oxygen gas concentration (volume basis) is usually 1 ppm or more. In this range, further oxidative decomposition of the dispersant is suppressed, and the hydrophilicity of the F layer is easily improved.
  • the temperature of the firing region is preferably 250 ° C. to 400 ° C. or lower, and particularly preferably 300 to 380 ° C.
  • the time for maintaining the temperature in the firing region is preferably 30 seconds to 5 minutes, and particularly preferably 1 to 2 minutes.
  • the resin-coated metal foil of the present invention may be surface-treated on the surface of the F layer in order to control the linear expansion of the F layer and further improve the adhesiveness of the F layer.
  • the surface treatment method for forming the surface of the F layer include annealing treatment, corona discharge treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, UV ozone treatment, excimer treatment, chemical etching, silane coupling treatment, and fine surface roughening treatment. Can be mentioned.
  • the temperature in the annealing treatment is preferably 120 to 180 ° C.
  • the pressure in the annealing treatment is preferably 0.005 to 0.015 MPa.
  • the annealing time is preferably 30 to 120 minutes.
  • Examples of the plasma irradiation device in the plasma treatment include a high frequency induction system, a capacitive coupling type electrode system, a corona discharge electrode-plasma jet system, a parallel plate type, a remote plasma type, an atmospheric pressure plasma type and an ICP type high density plasma type. ..
  • Examples of the gas used in the plasma treatment include oxygen gas, nitrogen gas, rare gas (argon or the like), hydrogen gas, ammonia gas and the like, and rare gas or nitrogen gas is preferable.
  • Specific examples of the gas used for the plasma treatment include argon gas, a mixed gas of hydrogen gas and nitrogen gas, and a mixed gas of hydrogen gas, nitrogen gas, and argon gas.
  • the surface of the F layer of the resin-coated metal foil obtained in the present invention has excellent adhesiveness, it can be easily and firmly laminated on another substrate.
  • substrates include a heat resistant resin film, a prepreg that is a precursor of a fiber reinforced resin plate, a laminate having a heat resistant resin film layer, and a laminate having a prepreg layer.
  • the prepreg is a sheet-like substrate in which a base material (tow, woven fabric, etc.) of reinforcing fibers (glass fiber, carbon fiber, etc.) is impregnated with a thermosetting resin or a thermoplastic resin.
  • the heat resistant resin film is a film containing at least one kind of heat resistant resin, and may be a single layer film or a multilayer film.
  • heat-resistant resin examples include polyimide, polyarylate, polysulfone, polyallylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyallyl ether ketone, polyamideimide, and liquid crystalline polyester.
  • Examples of the method of laminating another base material on the surface of the F layer of the resin-coated metal foil in the present invention include a method of hot pressing the resin-coated metal foil and another substrate.
  • the pressing temperature is preferably not higher than the melting point of the F polymer, more preferably 120 to 300 ° C.
  • the pressing temperature is preferably 310 to 400 ° C.
  • the hot pressing is particularly preferably performed at a vacuum degree of 20 kPa or less from the viewpoints of suppressing bubble inclusion and suppressing deterioration due to oxidation. Further, during hot pressing, it is preferable to raise the temperature after reaching the above vacuum degree.
  • the F layer is softened, that is, pressure-bonded in a state where it has a certain degree of fluidity and adhesiveness, which causes bubbles.
  • the pressure in the hot press is preferably 0.2 to 10 MPa from the viewpoint of firmly adhering the F layer and the substrate while suppressing damage to the substrate.
  • the resin-coated metal foil and the laminate thereof according to the present invention can be used as a flexible copper-clad laminate or a rigid copper-clad laminate for manufacturing a printed circuit board.
  • an interlayer insulating film may be formed on the pattern circuit, and a conductor circuit may be further formed on the interlayer insulating film.
  • the interlayer insulating film may be formed by the dispersion liquid of the present invention.
  • a solder resist may be laminated on the pattern circuit.
  • the solder resist may be formed by the dispersion liquid of the present invention.
  • a coverlay film may be laminated on the pattern circuit.
  • dispersion of the present invention has been described above, but the present invention is not limited to the configuration of the above-described embodiment.
  • the dispersion of the present invention may have any other configuration added to the configuration of the above-described embodiment or may be replaced with any configuration exhibiting the same function.
  • ⁇ Water contact angle of layer F> When pure water (about 2 ⁇ L) is placed on the surface of the F layer of the metal foil with resin at 25 ° C., the contact angle meter (CA-X manufactured by Kyowa Interface Science Co., Ltd. Type) and evaluated according to the following criteria. ⁇ : The water contact angle is 80 ° or less. X: The water contact angle is more than 80 °. ⁇ Flatness of F layer> The unevenness of the surface of the F layer was observed with an optical interference microscope, and the unevenness of the central portion and the end portions (5 places) was evaluated according to the following criteria. ⁇ : The uneven width (average value) of the end portion with respect to the central portion is 10% or less.
  • X The unevenness width (average value) of the end portion with respect to the central portion is more than 10%.
  • ⁇ Peel strength of laminate The position of 50 mm from one end in the length direction of the laminate cut out in a rectangular shape (length 100 mm, width 10 mm) was fixed, the pulling speed was 50 mm / min, and 90 ° from one end in the length direction to the laminate, The maximum load applied when the metal foil and the F layer were separated was defined as the peel strength (N / cm).
  • F polymer A copolymer containing 97.9 mol%, 0.1 mol% and 2.0 mol% of TFE units, NAH units and PPVE units in this order.
  • Powder 1 Powder made of Polymer 1 having D50 of 1.7 ⁇ m and D90 of 3.8 ⁇ m.
  • Dispersant 1 Polymer containing 81 mol% and 19 mol% of monomer F 1 unit and monomer AO 2 unit in this order (fluorine content: 35% by mass, hydroxyl value: 19 mgKOH / g, AO content: 34% by mass) ).
  • Dispersant 2 Polymer containing 68 mol% and 32 mol% of a monomer F 1 unit and a monomer AO 3 unit in this order (fluorine content: 13% by mass, hydroxyl value: 14 mgKOH / g, AO content: 74% by mass) ).
  • Dispersant 3 Polymer containing 56 mol% and 44 mol% of a monomer F 1 unit and a monomer AO 2 unit in this order (fluorine content: 19% by mass, hydroxyl value: 33 mgKOH / g, AO content: 60% by mass) ).
  • Dispersant 4 Polymer containing 42 mol% and 58 mol% of a monomer F 1 unit and a monomer AO 2 unit in this order (fluorine content: 12% by mass, hydroxyl value: 39 mgKOH / g, AO content: 70% by mass) ).
  • Dispersant 5 Copolymer of monomer F 2 unit and monomer AO 1 unit (fluorine content: 35% by mass, hydroxyl value: 47 mgKOH / g, AO content: 38% by mass).
  • the AO content in each dispersant is the amount of (OCH 2 CH 2 ) units contained in the used monomer AO.
  • Monomer AO 1 CH 2 ⁇ C (CH 3 ) C (O) (OCH 2 CH 2 ) 9 OH.
  • Monomer AO 2: CH 2 C ( CH 3) C (O) (OCH 2 CH 2) 23 OH.
  • Monomer AO 3: CH 2 C ( CH 3) C (O) (OCH 2 CH 2) 66 OH.
  • the number of (OCH 2 CH 2 ) units in the monomer AO is an average value.
  • Copper foil 1 Copper foil having a roughening treatment layer (thickness 12 ⁇ m, surface ten-point average roughness 0.6 ⁇ m).
  • Filler 1 Silica particles (NIPSIL (registered trademark) VN3 manufactured by Tosoh Corporation)
  • Filler 2 Magnesium oxide (manufactured by Tateho Chemical Co., Dispermag TN-1)
  • Filler 3 Glass cut fiber (PF manufactured by Nitto Boseki Co., Ltd.)
  • Example 1 Production Example of Dispersion Liquid 40 parts by mass of N-methyl-2-pyrrolidone and 12 parts by mass of Dispersant 1 were further mixed, and further 48 parts by mass of Powder 1 were mixed to prepare an F polymer content. A dispersion having a dispersant content ratio of 0.25 was obtained. Dispersants 2, 3 and 4 were used instead of Dispersant 1 to obtain dispersions, respectively. Powder 1 was uniformly dispersed in all the dispersions.
  • Example 2 Production Example and Evaluation Example of Dispersion Liquid 64 parts by mass of N-methyl-2-pyrrolidone and 3 parts by mass of Dispersant 1 were mixed, and further 33 parts by mass of Powder 1 were mixed to obtain an F polymer.
  • Dispersion 1 having a ratio of the content of the dispersant to the content of 0.1 was prepared.
  • Dispersions 2, 3, 4, and 5 were produced in the same manner except that Dispersants 2, 3, 4, and 5 were used instead of Dispersant 1, and the dispersion stability of the dispersions was evaluated. The results are summarized in Table 1.
  • Example 3 Production Example and Evaluation Example of Metal Foil with Resin
  • the dispersion liquid 1 was applied to the surface of the copper foil 1 using a die coater, passed through a ventilation drying oven (atmosphere temperature: 120 ° C) and held for 1 minute, It was further passed through a far infrared furnace (temperature: 340 ° C.) and held for 3 minutes to obtain a resin-coated copper foil 1 having an F layer (thickness 5 ⁇ m) of polymer 1 on the surface of the copper foil 1. Further, a resin-coated copper foil 5 was manufactured in the same manner except that the dispersion liquid 5 was used instead of the dispersion liquid 1. The water contact angle and flatness of the F layer in each resin-coated copper foil were evaluated. The results are summarized in Table 2.
  • Example 4 Evaluation example of resin-coated metal foil
  • the surface of the F layer of the resin-coated copper foil 1 was subjected to vacuum plasma treatment.
  • the processing conditions were output: 4.5 kW, introduced gas: argon gas, introduced gas flow rate: 50 cm 3 / minute, pressure: 50 mTorr (6.7 Pa), processing time: 2 minutes.
  • FR-4 as a prepreg (GEA-67N 0.2t (HAN) manufactured by Hitachi Chemical Co., Ltd.), reinforcing fiber: glass fiber, matrix resin: epoxy resin, thickness on the surface of the F layer of the resin-treated copper foil 1 after the treatment. : 0.2 mm), and vacuum hot pressed to obtain a laminate 1.
  • the processing conditions were temperature: 185 ° C., pressurizing pressure: 3.0 MPa, pressurizing time: 60 minutes.
  • the peel strength of the obtained laminate 1 was 8 N / cm.
  • Example 5 Production evaluation example of metal foil with resin 45 parts by mass of NMP, 2.5 parts by mass of a solution containing dispersant 1 (5 parts by mass), and 50 parts by mass of powder 1 were placed in a pot. Then, zirconia balls were put into the pot. Then, the pot was rolled at 150 rpm for 1 hour to prepare powder dispersion liquid 4A. Further, 10 parts by mass of the filler 1 was put into the pot, and the pot was further rolled for 1 hour to prepare a powder dispersion liquid 4B. The powder dispersion 4B was applied to the copper foil 1 by roll-to-roll by the kiss reverse method to form a liquid film.
  • the coating was performed with the copper foil 1 being laminated with an acrylic adhesive film as a support film on the copper foil 1. Then, this liquid coating was passed through a drying oven at 120 ° C. for 5 minutes, heated and dried to obtain a dried coating. The dry coating was then heated under a nitrogen oven at 380 ° C for 3 minutes. As a result, a resin-coated copper foil 4 in which an F layer having a thickness of 3 ⁇ m was formed on the surface of the copper foil 1 was obtained.
  • the resin-coated copper foil 4 had high absorptivity at wavelengths of 266 nm and 355 nm and excellent UV laser processability, and warpage due to the difference in linear expansion coefficient between the copper foil and the F layer was also reduced.
  • a laminated body 4 was formed using the resin-coated copper foil 4 in the same manner as in Example 4, and a transmission line was further formed on the copper foil of the laminated body 4 to obtain a printed board 4.
  • the printed circuit board 4 had a low relative permittivity and a low dielectric loss tangent, and was excellent in high-frequency signal transmission characteristics.
  • Example 6 Production evaluation example of metal foil with resin 100 parts by mass of the powder dispersion 4A and 20 parts by mass of the filler 2 were put into a pot, and the pot was further rolled for 1 hour to prepare a powder dispersion 5B. ..
  • the liquid dispersion 5B was applied to the copper foil 1 by a die coating method to form a liquid film. Then, this liquid coating was passed through a drying oven at 120 ° C. for 5 minutes, heated and dried to obtain a dried coating. Then, the dried film was heated in a far infrared furnace under a nitrogen atmosphere at 380 ° C. for 10 minutes.
  • a resin-coated copper foil 5 having a 100 ⁇ m thick F layer formed on the surface of the copper foil 1 was obtained.
  • the resin-coated copper foil 5 had excellent dielectric properties and reduced warpage.
  • a laminate 5 was formed using the resin-coated copper foil 5 in the same manner as in Example 4, and a transmission line was further formed on the copper foil of the laminate 5 to obtain a printed board 5.
  • the printed circuit board 5 had a low relative permittivity and a low dielectric loss tangent, and was excellent in high-frequency signal transmission characteristics.
  • Example 7 Production evaluation example of metal foil with resin 100 parts by mass of the powder dispersion liquid 4A and 10 parts by mass of the filler 3 were put into a pot, and the pot was further rolled for 1 hour to prepare a powder dispersion liquid 6B. ..
  • the liquid dispersion 6B was applied to the copper foil 1 by a die coating method to form a liquid film. Then, this liquid coating was passed through a drying oven at 120 ° C. for 5 minutes, heated and dried to obtain a dried coating. After that, the dried film was heated with far infrared rays in a nitrogen atmosphere at 380 ° C. for 10 minutes.
  • a resin-coated copper foil 6 having a 100 ⁇ m thick F layer formed on the surface of the copper foil 1 was obtained.
  • the resin-coated copper foil 6 had a reduced warp, was hard to be cracked even when bent, and maintained its flexibility.
  • a laminated body 6 was formed using the resin-coated copper foil 6 in the same manner as in Example 4, and a transmission line was further formed on the copper foil of the laminated body 6 to obtain a printed board 6.
  • the printed circuit board 6 had a low relative permittivity and a low dielectric loss tangent, and was excellent in high-frequency signal transmission characteristics.
  • the dispersion of the present invention is excellent in dispersibility and layer (coating film) formability, and can be easily processed into a film, a fiber reinforced film, a prepreg, a metal laminate (metal foil with resin), and a processed article obtained.

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Abstract

Le problème décrit par la présente invention est de fournir une dispersion qui comprend un solvant polaire et, dispersée dans cette dernière, une poudre comprenant un polymère à base de tétrafluoroéthylène, la dispersion présentant d'excellentes propriétés de dispersibilité et de formation de couches (films de revêtement). La solution selon l'invention porte sur une dispersion qui comprend une poudre comprenant un polymère à base de tétrafluoroéthylène, un solvant polaire et un dispersant, la poudre étant dispersée dans le solvant polaire, le dispersant étant un polymère qui comprend un motif à base d'un monomère ayant un groupe fluoroalkyle et un motif à base d'un monomère ayant un groupe oxyalkylène glycol et qui a une teneur en fluor, une teneur en groupe oxyalkylène et une valeur d'hydroxyle allant respectivement de 10 à 50 % en masse, de 5 à 75 % en masse et de 10 à 100 mg de KOH/g.
PCT/JP2019/041648 2018-10-30 2019-10-24 Dispersion WO2020090607A1 (fr)

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CN201980072237.1A CN113348208B (zh) 2018-10-30 2019-10-24 分散液
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WO2021241547A1 (fr) * 2020-05-28 2021-12-02 Ａｇｃ株式会社 Procédé de production d'une dispersion
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JP2020180245A (ja) * 2019-04-26 2020-11-05 Ａｇｃ株式会社 パウダー分散液、積層体の製造方法、積層体及びプリント基板の製造方法
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JP2023058453A (ja) * 2021-10-13 2023-04-25 ダイキン工業株式会社 組成物、回路基板、及び、組成物の製造方法

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CN113348208A (zh) 2021-09-03
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