WO2017154919A1 - Agent de sous-couche de dépôt autocatalytique comprenant des microparticules métalliques et un polymère hyper-ramifié - Google Patents

Agent de sous-couche de dépôt autocatalytique comprenant des microparticules métalliques et un polymère hyper-ramifié Download PDF

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WO2017154919A1
WO2017154919A1 PCT/JP2017/009042 JP2017009042W WO2017154919A1 WO 2017154919 A1 WO2017154919 A1 WO 2017154919A1 JP 2017009042 W JP2017009042 W JP 2017009042W WO 2017154919 A1 WO2017154919 A1 WO 2017154919A1
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group
metal
compound
hyperbranched polymer
electroless plating
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PCT/JP2017/009042
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English (en)
Japanese (ja)
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小島　圭介
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日産化学工業株式会社
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Priority to JP2018504520A priority Critical patent/JP6882721B2/ja
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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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/26—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material

Definitions

  • the present invention relates to a photosensitive base material containing a hyperbranched polymer, metal fine particles, a polymerizable compound and a photopolymerization initiator.
  • Patent Document 1 a method of performing electroless plating after patterning an electroless plating catalyst by photolithography is disclosed.
  • a material in which a metal complex, metal ion, or metal colloid that serves as a catalyst for electroless plating is mixed with a photosensitive resin is used, and UV exposure and development through a photomask can be used to form an arbitrary lattice shape or the like.
  • a method for obtaining a conductive pattern by forming a base of a pattern and applying electroless plating thereto is disclosed.
  • the electroless plating can be directly immersed in the electroless plating solution without going through an activation process after coating.
  • An example in which plating is formed is disclosed (Patent Document 2).
  • Patent Document 1 protective colloids such as PVP and surfactants such as dodecylbenzenesulfonic acid are used as metal colloid stabilizers. Stability of varnish due to decomposition of protective colloids and aggregation of metal colloids is used. In the process, it is often difficult to clean the catalyst during development. In addition, when the electroless plating is performed, it is a problem that the plating is deposited in addition to the target portion. Furthermore, since a water-soluble resist or metal stabilizer is used, there is a problem in maintaining pattern shapes such as pattern bleeding and line thickening. In this patent document, only the transmittance and resistance value of the obtained transparent conductive film are discussed, and the line width (shape) of the obtained pattern is not described in detail.
  • the visibility of images is required for transparent electrodes used in liquid crystal display elements and the like.
  • the formed metal film has a metallic luster and reflects external light, so that the metal wiring is not conspicuous and a clear display device with high image visibility is manufactured. There is a problem that it is difficult to do. Therefore, in the technique of forming a transparent electrode by electroless plating, suppression of metallic luster due to blackening on the back surface (transparent substrate surface) of the formed metal plating film is required.
  • the present invention pays attention to such problems, considers the environment, can be easily processed with a small number of steps, and can be easily formed with a fine wiring having a width of several ⁇ m by photolithography.
  • the object is to provide a new electroless plating base material to be used.
  • the inventors of the present invention have a hyperbranched polymer and metal fine particles having an ammonium group at the molecular end, and a specific polymerizable compound, a photopolymerization initiator, and an amino group.
  • a layer obtained by combining a compound and a polyfunctional thiol to obtain a photosensitive base agent and coating it on a substrate can be patterned by photolithography, and a patterned electroless metal plating base layer is formed. It has been found that the obtained base layer has excellent plating properties and is useful for improving the adhesion between the metal plating film and the substrate to be plated.
  • the back surface of the plating film forming portion is found to be black. It was.
  • the compounding of amino group-containing compounds and thiol compounds can improve the dispersibility and reactivity of metal fine particles, and enables highly sensitive patterning. I let you.
  • the present invention is a base agent for forming a metal plating film on a substrate by electroless plating treatment, (A) a hyperbranched polymer having an ammonium group at the molecular end and a weight average molecular weight of 1,000 to 5,000,000, (B) metal fine particles, (C) One or more terminals in the molecule have a side chain having a polymerizable unsaturated bond, 15 to 50 moles of oxyalkylene group per 100 moles of all repeating units, and a weight average molecular weight of 10,000.
  • the present invention relates to a photosensitive base material comprising (e) a compound having an amino group, and (f) a polyfunctional thiol.
  • the present invention relates to the photosensitive base agent according to the first aspect, in which the polymer compound (c) is a compound having three or more (meth) acryloyl groups in the molecule.
  • the present invention relates to the photosensitive base agent according to any one of the first aspect and the second aspect, in which the oxyalkylene group of the polymer compound (c) is a poly (oxyalkylene) group.
  • the present invention relates to the photosensitive base material according to any one of the first to fourth aspects, in which the weight average molecular weight of the polymer compound (c) is 20,000 to 50,000.
  • the present invention relates to the photosensitive base material according to any one of the first aspect to the fourth aspect, in which (f) the polyfunctional thiol is a tetrafunctional thiol.
  • the present invention relates to the photosensitive base agent according to any one of the first aspect to the fifth aspect, in which the compound (e) having an amino group is an alkoxysilane compound having an amino group.
  • the present invention relates to the photosensitive base material according to any one of the first aspect to the sixth aspect, in which the (a) hyperbranched polymer is a hyperbranched polymer represented by the formula [1].
  • each R 1 independently represents a hydrogen atom or a methyl group
  • R 2 to R 4 each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
  • the alkyl group and the arylalkyl group may be substituted with an alkoxy group, a hydroxy group, an ammonium group, a carboxy group, or a cyano group), or two of R 2 to R 4 may be bonded together.
  • a number of unit structures represents an integer of 5 to 100,000
  • a 1 represents a structure represented by the formula [2].)
  • a 2 represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond
  • Y 1 to Y 4 are each independently hydrogen.
  • And represents an atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, a carboxy group, or a cyano group.
  • the present invention relates to the photosensitive base material according to the seventh aspect, in which the (a) hyperbranched polymer is a hyperbranched polymer represented by the formula [3].
  • the metal fine particles (b) are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum
  • the present invention relates to the photosensitive base material according to the ninth aspect, wherein the (b) metal fine particles are palladium fine particles.
  • the present invention relates to the photosensitive base material according to any one of the first to tenth aspects, wherein the metal fine particles (b) are fine particles having an average particle diameter of 1 to 100 nm.
  • the present invention relates to the photosensitive base material according to any one of the first aspect to the eleventh aspect, in which a pattern can be formed by photolithography.
  • the present invention relates to an electroless plating base layer, which is a patterned layer formed by photolithography, comprising the photosensitive base agent according to any one of the first aspect to the twelfth aspect.
  • the metal plating film which consists of an electroless-plating layer formed on the electroless-plating base layer as described in a 13th viewpoint.
  • the base material, the electroless plating base layer according to the thirteenth aspect formed on the base material, and the metal plating film according to the fourteenth aspect formed on the electroless plating base layer And a metal-coated substrate.
  • Step A a step of applying the photosensitive base agent according to any one of the first aspect to the twelfth aspect on a base material and providing a base layer;
  • Step B a step of forming an underlayer having a desired pattern by photolithography,
  • Step C Step of forming a metal plating film by immersing a substrate having a patterned underlayer in an electroless plating bath.
  • the photosensitive undercoating agent of the present invention can be applied onto a base material, and an electroless metal plating undercoating layer can be easily formed by performing photolithography through a mask.
  • the photosensitive base agent of the present invention is a base layer that is excellent in adhesion to a base material without forming a primer layer that has been formed on the base material in order to improve the adhesiveness to a metal plating film. Can be formed.
  • the photosensitive base material of the present invention can form a plating base layer patterned on the order of ⁇ m, and can be suitably used for various wiring techniques.
  • the photosensitive base material of the present invention can improve the dispersion stability of the metal fine particles in the base material by blending a compound having an amino group capable of coordinating with metal fine particles such as palladium to form an ammine complex.
  • the polyfunctional thiol added at the same time plays a role not only as a crosslinking agent but also as a chain transfer agent, so that an underlayer of a patterned electroless metal plating having high sensitivity and excellent developability at the time of photolithography. Can be formed.
  • the electroless metal plating base layer formed from the photosensitive base material of the present invention can be easily formed by simply immersing it in an electroless plating bath.
  • the substrate, the base layer, and the metal plating film A metal-coated substrate provided with can be easily obtained. And the said metal plating film is excellent in adhesiveness with a lower base layer. That is, by forming the underlayer on the base material using the photosensitive base material of the present invention, it is possible to form a metal plating film having excellent adhesion to the base material. Furthermore, when the metal plating film is formed on the photosensitive base material of the present invention, the back surface thereof is black. Therefore, when these are formed on a transparent base material such as a glass substrate, the image visibility is high. Use as an electrode can be expected.
  • FIG. 1 is a diagram showing a 1 H NMR spectrum of a hyperbranched polymer (HPS-Cl) having a chlorine atom at the molecular end produced in Production Example 1.
  • FIG. 2 is a diagram showing a 13 C NMR spectrum of a hyperbranched polymer (HPS-N (Me) 2 OctCl) having a dimethyloctylammonium group at the molecular end, which was produced in Production Example 2.
  • the (a) hyperbranched polymer used in the photosensitive base material of the present invention is a polymer having an ammonium group at the molecular end and a weight average molecular weight of 1,000 to 5,000,000.
  • Examples include hyperbranched polymers represented by the following formula [1].
  • R 1 represents a hydrogen atom or a methyl group independently.
  • R 2 to R 4 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or — ( CH 2 CH 2 O) m R 5 (wherein R 5 represents a hydrogen atom or a methyl group, and m represents an arbitrary integer of 2 to 100).
  • the alkyl group and arylalkyl group may be substituted with an alkoxy group, a hydroxy group, an ammonium group, a carboxy group, or a cyano group.
  • R 2 to R 4 are taken together to represent a linear, branched or cyclic alkylene group, or R 2 to R 4 and the nitrogen atom to which they are bonded together To form a ring.
  • X ⁇ represents an anion
  • n represents the number of repeating unit structures, and represents an integer of 5 to 100,000.
  • Examples of the linear alkyl group having 1 to 20 carbon atoms in R 2 to R 4 include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n -Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n -Heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, etc., and a group having 8 or more carbon atoms is preferred in that the base agent is difficult to elute into the electroless plating solution.
  • Octyl groups are preferred.
  • Examples of the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and the like.
  • Examples of the cyclic alkyl group include a cyclopentyl ring and a group having a cyclohexyl ring structure.
  • Examples of the arylalkyl group having 7 to 20 carbon atoms in R 2 to R 4 include a benzyl group and a phenethyl group.
  • examples of the linear alkylene group in which two of R 2 to R 4 are combined include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group.
  • examples of the branched alkylene group include a methylethylene group, a butane-1,3-diyl group, and a 2-methylpropane-1,3-diyl group.
  • the cyclic alkylene group include alicyclic aliphatic groups having a monocyclic, polycyclic or bridged cyclic structure having 3 to 30 carbon atoms.
  • alkylene groups may contain a nitrogen atom, a sulfur atom or an oxygen atom in the group.
  • the ring formed by combining R 2 to R 4 and the nitrogen atom bonded thereto may contain a nitrogen atom, a sulfur atom or an oxygen atom in the ring.
  • pyridine ring, pyrimidine ring, pyrazine ring, quinoline ring, bipyridyl ring and the like can be mentioned.
  • R 2 to R 4 examples include [methyl group, methyl group, methyl group], [methyl group, methyl group, ethyl group], [methyl group, methyl group, n-butyl group], [methyl group] Group, methyl group, n-hexyl group], [methyl group, methyl group, n-octyl group], [methyl group, methyl group, n-decyl group], [methyl group, methyl group, n-dodecyl group], [Methyl group, methyl group, n-tetradecyl group], [methyl group, methyl group, n-hexadecyl group], [methyl group, methyl group, n-octadecyl group], [ethyl group, ethyl group, ethyl group], [N-butyl group, n-butyl group, n-butyl group], [n-hexyl group, n-hexyl group, n-buty
  • a 1 represents a structure represented by the following formula [2].
  • a 2 represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond.
  • Y 1 to Y 4 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, a carboxy group, or a cyano group.
  • alkylene group of A 2 examples include a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, a methylethylene group, a butane-1,3-diyl group, 2 -Branched alkylene groups such as methylpropane-1,3-diyl group.
  • cyclic alkylene group include alicyclic aliphatic groups having a monocyclic, polycyclic and bridged cyclic structure having 3 to 30 carbon atoms.
  • Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo, or pentacyclo structure having 4 or more carbon atoms.
  • structural examples (a) to (s) of the alicyclic portion of the alicyclic aliphatic group are shown below.
  • examples of the alkyl group having 1 to 20 carbon atoms of Y 1 to Y 4 in the above formula [2] include a methyl group, an ethyl group, an isopropyl group, an n-pentyl group, and a cyclohexyl group.
  • examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, isopropoxy group, n-pentyloxy group, cyclohexyloxy group and the like.
  • Y 1 to Y 4 are preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • the hyperbranched polymer used in the present invention includes a hyperbranched polymer represented by the following formula [3].
  • R 1, R 2 to R 4 and n are as defined above.
  • the hyperbranched polymer having an ammonium group at the molecular end used in the present invention can be obtained, for example, by reacting an amine compound with a hyperbranched polymer having a halogen atom at the molecular end.
  • a hyperbranched polymer having a halogen atom at the molecular end can be produced from a hyperbranched polymer having a dithiocarbamate group at the molecular end in accordance with the description in WO 2008/029688.
  • As the hyperbranched polymer having a dithiocarbamate group at the molecular end a commercially available product can be used, and Hypertech (registered trademark) HPS-200 manufactured by Nissan Chemical Industries, Ltd. can be preferably used.
  • the amine compounds that can be used in this reaction are, as primary amines, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n -Hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine , N-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecylamine, n-eicosylamine and other aliphatic amines;
  • Secondary amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-n-pentylamine, ethylmethylamine, methyl- n-propylamine, methyl-n-butylamine, methyl-n-pentylamine, ethylisopropylamine, ethyl-n-butylamine, ethyl-n-pentylamine, methyl-n-octylamine, methyl-n-decylamine, methyl- n-dodecylamine, methyl-n-tetradecylamine, methyl-n-hexadecylamine, methyl-n-octadecylamine, ethylisopropylamine, ethyl-n-octylamine, di
  • Tertiary amines include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-octylamine, tri-n-dodecyl.
  • Amine dimethylethylamine, dimethyl-n-butylamine, dimethyl-n-hexylamine, dimethyl-n-octylamine, dimethyl-n-decylamine, diethyl-n-decylamine, dimethyl-n-dodecylamine, dimethyl-n-tetradecyl Aliphatic amines such as amine, dimethyl-n-hexadecylamine, dimethyl-n-octadecylamine, dimethyl-n-eicosylamine; pyridine, pyrazine, pyrimidine, quinoline, 1-methylimidazole, 4,4′-bipyridyl, 4-methyl-4,4 - Nitrogen-containing heterocyclic compounds such as bipyridyl and the like.
  • the amount of the amine compound that can be used in these reactions is 0.1 to 20 molar equivalents, preferably 0.5 to 10 molar equivalents, based on 1 mol of the halogen atom of the hyperbranched polymer having a halogen atom at the molecular end. Preferably, it is 1 to 5 molar equivalents.
  • the reaction between the hyperbranched polymer having a halogen atom at the molecular end and the amine compound can be carried out in water or an organic solvent in the presence or absence of a base.
  • the solvent to be used is preferably a solvent capable of dissolving a hyperbranched polymer having a halogen atom at the molecular end and an amine compound.
  • a hyperbranched polymer having a halogen atom at the molecular end and an amine compound can be dissolved, but a solvent that does not dissolve the hyperbranched polymer having an ammonium group at the molecular end is more preferable because it can be easily isolated.
  • Solvents that can be used in this reaction are not particularly limited as long as they do not significantly inhibit the progress of this reaction.
  • the amides can be used. These solvents may be used alone or in combination of two or more.
  • the amount used is 0.2 to 1,000 times, preferably 1 to 500 times, more preferably 5 to 100 times, most preferably the mass of the hyperbranched polymer having a halogen atom at the molecular end. It is preferable to use a solvent having a mass of 5 to 50 times.
  • Suitable bases generally include alkali metal hydroxides and alkaline earth metal hydroxides (eg sodium hydroxide, potassium hydroxide, calcium hydroxide), alkali metal oxides and alkaline earth metal oxides (eg lithium oxide). Calcium oxide), alkali metal hydrides and alkaline earth metal hydrides (eg sodium hydride, potassium hydride, calcium hydride), alkali metal amides (eg sodium amide), alkali metal carbonates and alkaline earth metal carbonates Inorganic compounds such as salts (eg lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate), alkali metal bicarbonates (eg sodium bicarbonate), and alkali metal alkyls, alkylmagnesium halides, alkali metal alkoxides, alkaline earth metals Alkoki De, organometallic compounds such as dimethoxy magnesium was used.
  • alkali metal hydroxides and alkaline earth metal hydroxides eg sodium hydroxide, potassium hydroxide,
  • potassium carbonate and sodium carbonate are particularly preferred.
  • the amount used is 0.2 to 10 molar equivalents, preferably 0.5 to 10 molar equivalents, most preferably 1 to 5 molar equivalents per mole of halogen atoms of the hyperbranched polymer having a halogen atom at the molecular end. It is preferable to use the base.
  • reaction conditions are appropriately selected from a reaction time of 0.01 to 100 hours and a reaction temperature of 0 to 300 ° C.
  • the reaction time is 0.1 to 72 hours, and the reaction temperature is 20 to 150 ° C.
  • a hyperbranched polymer represented by the formula [1] can be obtained regardless of the presence / absence of a base.
  • a hyperbranched polymer having a halogen atom at the molecular end is reacted with a primary amine or secondary amine compound in the absence of a base, the terminal secondary amine and tertiary tertiary of the corresponding hyperbranched polymer are respectively reacted.
  • a hyperbranched polymer having ammonium groups terminated with protonated primary amines is obtained.
  • the terminal secondary amine of the corresponding hyperbranched polymer can be obtained by mixing with an aqueous solution of an acid such as hydrogen chloride, hydrogen bromide, or hydrogen iodide in an organic solvent. And a hyperbranched polymer having an ammonium group terminated with a tertiary amine protonated.
  • the hyperbranched polymer has a weight average molecular weight Mw measured in terms of polystyrene by gel permeation chromatography of 1,000 to 5,000,000, more preferably 2,000 to 200,000, most preferably 3,000 to 100,000. Further, the dispersity Mw (weight average molecular weight) / Mn (number average molecular weight) is 1.0 to 7.0, preferably 1.1 to 6.0, and more preferably 1.2 to 5. 0.
  • the metal fine particles used in the photosensitive base material of the present invention are not particularly limited, and the metal species are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd). Silver (Ag), tin (Sn), platinum (Pt), gold (Au), and alloys thereof may be used, and one kind of these metals may be used or two or more kinds may be used in combination. Among these, preferable metal fine particles include palladium fine particles.
  • the metal oxide may be used as the metal fine particles.
  • the metal fine particles can be obtained by reducing metal ions by, for example, a method of irradiating an aqueous solution of a metal salt with a high-pressure mercury lamp or a method of adding a compound having a reducing action (so-called reducing agent) to the aqueous solution.
  • a compound having a reducing action for example, by adding an aqueous solution of a metal salt to the solution in which the hyperbranched polymer is dissolved and irradiating it with ultraviolet light, or adding an aqueous solution of a metal salt and a reducing agent to the hyperbranched polymer solution, etc.
  • the base agent containing the hyperbranched polymer and the metal fine particles can be prepared while forming a complex of the hyperbranched polymer and the metal fine particles.
  • the reducing agent is not particularly limited, and various reducing agents can be used, and it is preferable to select the reducing agent according to the metal species to be contained in the obtained base material.
  • the reducing agent that can be used include metal borohydrides such as sodium borohydride and potassium borohydride; lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, aluminum beryllium hydride, hydrogenation
  • Aluminum hydride salts such as aluminum magnesium and calcium aluminum hydride; hydrazine compounds; citric acid and salts thereof; succinic acid and salts thereof; ascorbic acid and salts thereof; primary or secondary such as methanol, ethanol, isopropanol and polyol Tertiary alcohols; tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, diethylmethylamine, tetramethylethylenediamine (TMEDA), ethylenediaminetetraacetic acid (EDTA); Rox
  • the average particle size of the metal fine particles is preferably 1 to 100 nm. By setting the average particle size of the metal fine particles to 100 nm or less, a sufficient catalytic activity can be obtained with little reduction in surface area.
  • the average particle size is more preferably 75 nm or less, and particularly preferably 1 to 30 nm.
  • the amount of (a) hyperbranched polymer added to the photosensitive base material of the present invention is preferably 50 to 2,000 parts by mass with respect to 100 parts by mass of (b) metal fine particles.
  • the metal fine particles can be sufficiently dispersed, and by setting it to 2,000 parts by mass or less, problems such as physical properties due to an increase in organic content can be suppressed. it can. More preferably, it is 100 to 1,000 parts by mass.
  • the component (c) used in the photosensitive base material of the present invention has a side chain in which one or more terminals are polymerizable unsaturated bonds in the molecule, and the oxyalkylene group is 15 per 100 moles of all repeating units.
  • a polymer compound having a (meth) acryloyl group in two or more side chains in the molecule is preferable.
  • the oxyalkylene group includes a polymer compound having a (meth) acryloyl group and having an oxyalkylene group in three or more side chains in the molecule.
  • an oxyalkylene group having 2 to 4 carbon atoms is preferable, and among them, an oxyethylene group [—OCH 2 CH 2 —] or an oxypropylene group [—OCH 2 C (CH 3 ) H—] is preferable.
  • the oxyalkylene group may be a poly (oxyalkylene) group in which a plurality of oxyalkylene groups are connected. In that case, the oxyalkylene group may have a single oxyalkylene group or a combination of two or more. Also good.
  • bonds may be block bonds or random bonds.
  • the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound.
  • (meth) acrylic acid refers to acrylic acid and methacrylic acid.
  • a polymer compound containing at least one (meth) acryloyl group such as urethane acrylic, epoxy acrylic, various (meth) acrylates, etc., particularly containing at least three (meth) acryloyl groups.
  • a polyfunctional polymer compound Among these polymerizable polymer compounds, compounds having three or more (meth) acryloyl groups and an oxyalkylene group in the side chain are preferable.
  • the weight average molecular weight of the polymer compound (c) is preferably 10,000 to 100,000, more preferably 20,000 to 50,000. If the molecular weight is less than 10,000, the effect of the present invention is not achieved. On the other hand, if the molecular weight exceeds 100,000, it may not dissolve in the composition.
  • the polymer compound (c) is preferably a polyethylene oxide modified polymer having a polymerizable unsaturated double bond in two or more side chains.
  • the modification rate is preferably 15% to 50%, more preferably 20% to 40%. When the modification rate is less than 15%, the solubility in the developer is lowered, so that the developability may be lowered. If the modification rate is over 50%, the pattern may flow during development.
  • the compound as the component (c) include EO-modified acrylic polymers such as 8KX-078H manufactured by Taisei Fine Chemical Co., Ltd.
  • the addition amount of the polymerizable compound (c) in the photosensitive base material of the present invention is 100 parts by mass of a composite formed from the hyperbranched polymer and metal fine particles described later (or the total mass of the hyperbranched polymer and metal fine particles).
  • the amount is preferably 10 to 10,000 parts by mass. More preferred is 100 to 2,000 parts by mass.
  • (C) When the addition amount of the polymerizable compound is less than 10 parts by mass, it becomes difficult to form a pattern of a plating base layer by photolithography described later, and when the amount exceeds 10,000 parts by mass, the base There is a possibility that the metal plating film is not formed on the base layer formed by the agent.
  • photopolymerization initiator (d) used in the photosensitive base material of the present invention known ones can be used.
  • photocleavable photoradical polymerization initiators are preferred.
  • examples of the photocleavable photoradical polymerization initiator include those described in the latest UV curing technology (p. 159, publisher: Kazuhiro Takahisa, publisher: Technical Information Association, published in 1991). .
  • radical photopolymerization initiators examples include IRGACURE (registered trademark) 184, 369, 500, 651, 784, 819, 907, 1000, 1300, 1700, and 1800. 1850, 2959, CGI 1700, CGI 1750, CGI 1850, CGI 1850, CG 24-61, TPO, Darocur (registered trademark) 1116, 1173, OXE 01 [above, manufactured by BASF Japan Ltd.], ESACURE KIP150 , KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 [above, manufactured by Lamberti Co., Ltd.], etc., but are not limited thereto. These polymerization initiators can be used in combination of two or more.
  • the amount of the (d) polymerization initiator added to the photosensitive base material of the present invention is, for example, 0.1 to 100% by mass, preferably 1 to 50% by mass, based on the polymerizable compound (c).
  • the content is preferably 10 to 30% by mass.
  • ⁇ (E) Compound having an amino group As the compound having an amino group (e) used in the photosensitive base material of the present invention, known compounds can be used, for example, aliphatic amines such as alkylamines and hydroxyalkylamines, Examples include amines having a cyclic substituent, aromatic amines (arylamines), and alkoxysilane compounds having an amino group. Among these compounds having an amino group, alkoxysilane compounds having an amino group are preferred. In addition, from the viewpoint of improving the storage stability of the plating base agent, the amino group of the amine compound is preferably protected by a ketone (protected by an alkylidene group).
  • the amino group is protected by an alkylidene group. Both the amine compound and the amine compound thus formed are included in the component (e).
  • the solvent for the base agent to be described later is not an alcohol solvent that will remove the protection by the alkylidene group, but ketones, ethers, It is preferable to use an ester solvent.
  • a compound containing an amino group to a photosensitive base material, dispersion stability in a base material of a composite composed of metal fine particles, specifically, a hyperbranched polymer having metal fine particles and an ammonium group described later. The effect of improving the property is obtained, and contributes to the formation of a fine plating pattern.
  • alkylamines examples include ethylamine (CH 3 CH 2 NH 2 ), propylamine (CH 3 (CH 2 ) 2 NH 2 ), butylamine (CH 3 (CH 2 ) 3 NH 2 ), pentylamine (CH 3 ( CH 2) 4 NH 2), hexylamine (CH 3 (CH 2) 5 NH 2), heptyl amine (CH 3 (CH 2) 6 NH 2), octylamine (CH 3 (CH 2) 7 NH 2), Nonylamine (CH 3 (CH 2 ) 8 NH 2 ), decylamine (CH 3 (CH 2 ) 9 NH 2 ), undecylamine (CH 3 (CH 2 ) 10 NH 2 ), dodecylamine (CH 3 (CH 2 )) 11 NH 2), tridecyl amine (CH 3 (CH 2) 12 NH 2), tetradecyl amine (CH 3 (CH 2) 13 NH ), Pentadecyl amine (CH 3
  • hydroxyalkylamines examples include methanolamine (OHCH 2 NH 2 ), ethanolamine (OH (CH 2 ) 2 NH 2 ), propanolamine (OH (CH 2 ) 3 NH 2 ), butanolamine.
  • aliphatic amines include methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, propoxypropylamine, propoxy Examples thereof include alkoxyalkylamines such as butylamine, butoxymethylamine, butoxyethylamine, butoxypropylamine, and butoxybutylamine.
  • R 11 is a monovalent cyclic group having 3 to 10 carbon atoms, preferably 3 to 12 carbon atoms, and may be any of alicyclic groups, aromatic groups, and combinations thereof. Good. These cyclic groups may be substituted with any substituent, for example, an alkyl group having 1 to 10 carbon atoms.
  • R 12 represents a single bond or an alkylene group having 1 to 17 carbon atoms, preferably 1 to 3 carbon atoms.
  • preferred specific examples of the amine compound represented by the formula R 11 —R 12 —NH 2 include compounds represented by the following formulas (A-1) to (A-10).
  • aromatic amines include aniline, N-methylaniline, o-, m-, or p-anisidine, o-, m-, or p-toluidine, o-, m-, or Examples thereof include p-chloroaniline, o-, m-, or p-bromoaniline, o-, m-, or p-iodoaniline.
  • alkoxysilane compound having an amino group examples include N, N′-bis [3- (trimethoxysilyl) propyl] -1,2-ethanediamine, N, N′-bis [3- (triethoxysilyl) Propyl] -1,2-ethanediamine, N- [3- (trimethoxysilyl) propyl] -1,2-ethanediamine, N- [3- (triethoxysilyl) propyl] -1,2-ethanediamine, Bis- [3- (trimethoxysilyl) propyl] amine, bis- [3- (triethoxysilyl) propyl] amine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxy Silane, 3-aminopropylmethyldiethoxysilane, trimethoxy [3- (methylamino)] propylsilane,
  • alkylamines, hydroxyalkylamines, other aliphatic amines, amines having a cyclic substituent, aromatic amines (arylamines), and amine compounds having an alkoxysilyl group which are specific examples above.
  • Examples include amino compounds in which an amino group is protected by an alkylidene group with ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • the content of the compound having an (e) amino group in the photosensitive base material of the present invention is a composite formed from the hyperbranched polymer and metal fine particles described later (or the total mass of the hyperbranched polymer and metal fine particles) 100.
  • the amount is preferably 1 part by mass to 100 parts by mass, more preferably 5 parts by mass to 50 parts by mass, and particularly 10 parts by mass to 15 parts by mass with respect to parts by mass.
  • E When the content of the compound having an amino group is less than the above numerical range, a complex formed from the hyperbranched polymer and metal fine particles described later, and further (f) a polyfunctional thiol dispersibility described later -If the effect of stabilizing the solubility is not obtained, and if it is added exceeding the above range (for example, 10 times the amount of the above composite), the appearance of the plating film may be deteriorated.
  • the polyfunctional thiol that is the component (f) used in the photosensitive base agent of the present invention is not particularly limited as long as it is a compound having two or more mercapto groups.
  • the hydrocarbons having the above mercapto groups and other polyfunctional compounds include mercaptocarboxylic acid esters of polyhydric alcohols such as poly (mercaptoacetate) s of polyhydric alcohols, poly (3-mercaptopro of polyhydric alcohols). Pionate), polyhydric alcohol poly (2-mercaptopropionate), polyhydric alcohol poly (3-mercaptobutyrate), polyhydric alcohol poly (3-mercaptoisobutyrate), etc. Can be mentioned.
  • the polyfunctional thiol plays a role not only as a crosslinking agent but also as a chain transfer agent, and contributes to realization of high sensitivity and excellent developability during photolithography.
  • hydrocarbons having two or more mercapto groups as the substituent include hexane-1,6-dithiol, decane-1,10-dithiol, 1,4-benzenedithiol, 1,4-bis ( And mercaptomethyl) benzene.
  • bifunctional compounds include ethylene glycol bis (mercaptoacetate), propylene glycol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), propylene glycol bis (3-mercaptopropionate), Ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), ethylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate) Rate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptobutyrate), ethylene
  • Trifunctional compounds include glycerin tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), glycerin tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane.
  • Tris (2-mercaptopropionate), trimethylolpropane tris (3-mercaptoisobutyrate) and the like can be mentioned.
  • pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), pentaerythritol tetrakis (3-mercaptoisobutyrate) , Etc.
  • the hexafunctional compounds include dipentaerythritol hexakis (mercaptoacetate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (2-mercaptopropionate), dipentaerythritol hexakis. (3-mercaptoisobutyrate), octanediol bis (3-mercaptobutyrate) and the like.
  • polyfunctional thiols it is preferable to use a tetrafunctional thiol compound from the viewpoint of improving the developability of the photosensitive base agent.
  • (f) polyfunctional thiols can be used alone or in admixture of two or more.
  • the blending amount of the (f) polyfunctional thiol in the photosensitive base material of the present invention is the total mass of a composite formed from the hyperbranched polymer and metal fine particles described later (or the total mass of the hyperbranched polymer and metal fine particles).
  • the content is preferably 0.01% by mass to 200% by mass, and more preferably 0.05% by mass to 50% by mass. If the blending ratio is less than the above range, the desired effect cannot be obtained. On the other hand, if it exceeds the above range, the stability, odor, sensitivity, resolution, developability, adhesion, plating of the photosensitive base agent There is a possibility that the precipitation of the material will deteriorate.
  • the photosensitive base agent of the present invention comprises (a) a hyperbranched polymer having an ammonium group at the molecular end, (b) metal fine particles, (c) a polymerizable compound, (d) a photopolymerization initiator, (e) an amino group. And (f) a polyfunctional thiol, and optionally further other components.
  • the hyperbranched polymer and the metal fine particles form a complex.
  • the composite is a particle that is in contact with or close to the metal fine particles due to the action of the ammonium group at the end of the hyperbranched polymer to form a particulate form.
  • the “composite” in the present invention not only the metal fine particles and the hyperbranched polymer are combined to form one composite as described above, but also the metal fine particles and the hyperbranched polymer have bonding portions. Those that are present independently without being formed may also be included.
  • Formation of a complex of a hyperbranched polymer having an ammonium group and metal fine particles is performed simultaneously with the preparation of a base material containing the hyperbranched polymer and metal fine particles, and the method includes a metal stabilized to some extent by a lower ammonium ligand.
  • a complex can also be formed by reducing.
  • fine metal particles stabilized to some extent by a lower ammonium ligand as a raw material can be produced by the method described in Journal of Organometallic Chemistry 1996, 520, 143-162 and the like.
  • the target metal fine particle composite can be obtained by dissolving the hyperbranched polymer having an ammonium group in the obtained reaction mixture solution of metal fine particles and stirring at room temperature (approximately 25 ° C.) or with heating.
  • the solvent to be used is not particularly limited as long as it is a solvent capable of dissolving the metal fine particles and the hyperbranched polymer having an ammonium group at a required concentration or more. Specifically, alcohols such as ethanol, n-propanol, and isopropanol are used.
  • Halogenated hydrocarbons such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; and mixtures of these solvents.
  • tetrahydrofuran is used.
  • the temperature at which the reaction mixture of the metal fine particles and the hyperbranched polymer having an ammonium group are mixed usually ranges from 0 ° C. to the boiling point of the solvent, preferably from room temperature (approximately 25 ° C.) to 60 ° C. It is a range.
  • the metal fine particles can be stabilized to some extent in advance by using a phosphine dispersant (phosphine ligand) in addition to the amine dispersant (lower ammonium ligand).
  • the direct reduction method involves dissolving a hyperbranched polymer having a metal ion and an ammonium group in a solvent and reducing it with a primary or secondary alcohol such as methanol, ethanol, isopropanol, polyol, etc.
  • a primary or secondary alcohol such as methanol, ethanol, isopropanol, polyol, etc.
  • a fine particle composite can be obtained.
  • the metal ion source used here the above-mentioned metal salts can be used.
  • the solvent to be used is not particularly limited as long as it is a solvent capable of dissolving the hyperbranched polymer having a metal ion and an ammonium group at a required concentration or more, and specifically, alcohols such as methanol, ethanol, propanol, isopropanol; Halogenated hydrocarbons such as methylene chloride and chloroform; Cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran; Nitriles such as acetonitrile and butyronitrile; N, N-dimethylformamide (DMF), N- Amides such as methyl-2-pyrrolidone (NMP); Sulfoxides such as dimethyl sulfoxide and the like, and mixtures of these solvents are preferable.
  • alcohols such as methanol, ethanol, propanol, isopropanol
  • Halogenated hydrocarbons such as methylene chloride and chloroform
  • Mashiku are ethanol, isopropanol, chloroform, tetrahydrofuran, and the like.
  • the temperature of the reduction reaction can usually be in the range of 0 ° C. to the boiling point of the solvent, and is preferably in the range of room temperature (approximately 25 ° C.) to 60 ° C.
  • a target metal fine particle composite can be obtained by dissolving a hyperbranched polymer having a metal ion and an ammonium group in a solvent and reacting them in a hydrogen gas atmosphere.
  • a metal ion source used here the above-mentioned metal salt, hexacarbonyl chromium [Cr (CO) 6 ], pentacarbonyl iron [Fe (CO) 5 ], octacarbonyl dicobalt [Co 2 (CO) 8 ].
  • a metal carbonyl complex such as tetracarbonyl nickel [Ni (CO) 4 ] can be used.
  • zero-valent metal complexes such as metal olefin complexes, metal phosphine complexes, and metal nitrogen complexes can also be used.
  • the solvent to be used is not particularly limited as long as it can dissolve a hyperbranched polymer having a metal ion and an ammonium group at a required concentration or higher.
  • alcohols such as ethanol and propanol
  • methylene chloride, chloroform Halogenated hydrocarbons such as tetrahydrofuran
  • cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran and tetrahydropyran
  • nitriles such as acetonitrile and butyronitrile
  • a mixture of these solvents preferably tetrahydrofuran.
  • a range of usually 0 ° C. to the boiling point of the solvent can be used.
  • a target metal fine particle composite can be obtained by dissolving a hyperbranched polymer having a metal ion and an ammonium group in a solvent and causing a thermal decomposition reaction.
  • a metal ion source used here the above metal salts, metal carbonyl complexes, other zero-valent metal complexes, and metal oxides such as silver oxide can be used.
  • the solvent to be used is not particularly limited as long as it can dissolve the hyperbranched polymer having a metal ion and an ammonium group at a required concentration or more.
  • methanol, ethanol, n-propanol, isopropanol, ethylene glycol Alcohols such as: Halogenated hydrocarbons such as methylene chloride and chloroform; Cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran; Nitriles such as acetonitrile and butyronitrile; Aromatics such as benzene and toluene Examples thereof include hydrocarbons and a mixture of these solvents, and preferably toluene.
  • the temperature at which the metal ion and the hyperbranched polymer having an ammonium group are mixed is usually 0 ° C. to the boiling point of the solvent, preferably around the boiling point of the solvent, for example, 110 ° C. (heating reflux) in the case of toluene. It is.
  • the thus obtained complex of the hyperbranched polymer having ammonium groups and the metal fine particles can be made into a solid form such as a powder through a purification treatment such as reprecipitation.
  • the photosensitive base agent of the present invention comprises (a) a hyperbranched polymer having an ammonium group, (b) metal fine particles (preferably a composite comprising them), (c) a polymerizable compound, and (d) photopolymerization. It contains an initiator, (e) a compound having an amino group, and (f) a polyfunctional thiol, and optionally other components.
  • the photosensitive base agent is an electroless plating base layer described later. The form of the varnish used at the time of formation may be sufficient.
  • the photosensitive base agent of the present invention further includes additives such as surfactants, various surface conditioners, sensitizers, polymerization inhibitors, polymerization initiators and the like. You may add suitably.
  • surfactant examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxy Polyoxyethylene alkylaryl ethers such as ethylene nonylphenyl ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, Sorbitan fatty acid esters such as sorbitan trioleate; polyoxyethylene sorbitan monolaurate, polyoxyethylene Polyoxyethylene nonionic surfactants such as sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate; EFTOP (registered trademark) EF-301, EF-303, EF-
  • the surface conditioner examples include silicone-based leveling agents such as Shin-Etsu Silicone (registered trademark) KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.); BYK (registered trademark) -302, 307, 322, and 323. , 330, 333, 370, 375, 378 [above, manufactured by Big Chemie Japan Co., Ltd.] and the like.
  • silicone-based leveling agents such as Shin-Etsu Silicone (registered trademark) KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.); BYK (registered trademark) -302, 307, 322, and 323. , 330, 333, 370, 375, 378 [above, manufactured by Big Chemie Japan Co., Ltd.] and the like.
  • additives may be used alone or in combination of two or more.
  • the amount of the additive used is preferably 0.001 to 50 parts by weight, more preferably 0.005 to 10 parts by weight, based on 100 parts by weight of the composite formed from the hyperbranched polymer and metal fine particles. 01-5 parts by mass is even more preferable.
  • Electroless plating underlayer The above-described photosensitive base material of the present invention can be applied to a base material to form a thin film, and a photolithography process is performed to form a patterned electroless plating base layer.
  • the underlayer is also an object of the present invention.
  • a nonelectroconductive base material or a conductive base material can be used preferably.
  • the non-conductive substrate include glass, ceramic, etc .; polyethylene resin, polypropylene resin, vinyl chloride resin, nylon (polyamide resin), polyimide resin, polycarbonate resin, acrylic resin, PEN (polyethylene naphthalate) resin, PET (polyethylene) Terephthalate) resin, PEEK (polyetheretherketone) resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, epoxy resin, polyacetal resin, etc .; paper and the like. These are suitably used in the form of a sheet or a film, and the thickness in this case is not particularly limited.
  • the conductive substrate examples include ITO (tin doped indium oxide), ATO (antimony doped tin oxide), FTO (fluorine doped tin oxide), AZO (aluminum doped zinc oxide), GZO (gallium doped zinc oxide), and Various stainless steels, aluminum and aluminum alloys such as duralumin, iron and iron alloys, copper and copper alloys such as brass, phosphor bronze, white copper and beryllium copper, metals such as nickel and nickel alloys, and silver alloys such as silver and western silver Etc. Furthermore, the base material in which the thin film was formed with these electroconductive base materials on the said nonelectroconductive base material can also be used. Further, the base material may be a three-dimensional molded body.
  • a specific method of forming an electroless plating base layer from the above-described hyperbranched polymer having an ammonium group and metal fine particles, a polymerizable compound, a photopolymerization initiator, a compound having an amino group, and a photosensitive base agent containing a polyfunctional thiol First, the hyperbranched polymer having an ammonium group and metal fine particles (preferably a composite comprising these), a polymerizable compound, a photopolymerization initiator, a compound having an amino group, and a polyfunctional thiol are used in an appropriate solvent.
  • Dissolve or disperse to form a varnish and apply the varnish onto a substrate on which a metal plating film is to be formed; a blade coating method; a dip coating method; a roll coating method; a bar coating method; a die coating method; ; Inkjet method; fountain pen nanolithography (FPN), dip pen Pen lithography such as nolithography (DPN); letterpress printing, flexographic printing, resin letterpress printing, contact printing, microcontact printing ( ⁇ CP), nanoimprinting lithography (NIL), and letterpress printing methods such as nanotransfer printing (nTP); Intaglio printing methods such as gravure printing and engraving; lithographic printing methods; stencil printing methods such as screen printing and stencil printing; coating by offset printing methods, etc., and then evaporating and drying the solvent to form a thin layer .
  • FPN fountain pen nanolithography
  • DPN dip pen Pen Pen lithography
  • DPN nolithography
  • ⁇ CP microcontact printing
  • NIL nanoimprinting lithography
  • nTP
  • spin coating spin coating, spray coating, ink jet, pen lithography, contact printing, ⁇ CP, NIL, and nTP are preferable.
  • spin coating method since it can be applied in a single time, even a highly volatile solution can be used, and there is an advantage that highly uniform application can be performed.
  • spray coating method highly uniform coating can be performed with a very small amount of varnish, which is industrially very advantageous.
  • ink jet method, pen lithography, contact printing, ⁇ CP, NIL, or nTP is used, a fine pattern such as a wiring can be efficiently formed (drawn), which is very advantageous industrially.
  • the solvent used here is one that dissolves or disperses the complex (hyperbranched polymer and metal fine particles having an ammonium group), a polymerizable compound, a photopolymerization initiator, a compound having an amino group, and a polyfunctional thiol.
  • water for example, water; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene; methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, n -Alcohols such as hexanol, n-octanol, 2-octanol, 2-ethylhexanol; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve; propylene glycol monomethyl ether (PGME) Propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, triprop
  • solvents may be used alone, or two or more kinds of solvents may be mixed.
  • glycols such as ethylene glycol, propylene glycol and butylene glycol may be added.
  • concentration in which the solvent is dissolved or dispersed is arbitrary, but the solid content concentration in the varnish is 0.005 to 90% by mass, preferably 0.01 to 80% by mass.
  • solid content is a component except the solvent in a varnish.
  • the method for drying the solvent is not particularly limited.
  • the solvent may be evaporated using a hot plate or an oven in an appropriate atmosphere, that is, in an inert gas such as air or nitrogen, or in a vacuum. Thereby, it is possible to obtain an underlayer having a uniform film formation surface.
  • the firing temperature is not particularly limited as long as the solvent can be evaporated, but it is preferably performed at 40 to 250 ° C.
  • the thin film obtained as described above is then exposed at an exposure amount of about 10 to 3,000 mJ / cm 2 through a mask having a predetermined pattern, and then developed using a developer, thereby exposing the exposed portion. By washing out, a patterned electroless plating base layer is obtained.
  • ultraviolet rays such as a mercury lamp, far ultraviolet rays, electron beams, or X-rays are used.
  • a light source used for ultraviolet irradiation sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a UV-LED, or the like can be used.
  • the developing method is not particularly limited, and can be performed by a known method such as a liquid piling method, a paddle method, a dipping method, a spray method, a rocking dipping method, or the like.
  • the development temperature is preferably 20 to 50 ° C., and the development time is, for example, 10 seconds to 10 minutes.
  • an organic solvent such as methanol, ethanol, n-propanol and isopropanol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether (PGME), 3-methoxy-3-methyl-1-butanol and the like.
  • Glycol ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran (THF) and 1,4-dioxane; ether esters such as propylene glycol monomethyl ether acetate (PGMEA); esters such as ethyl acetate and butyl acetate Ketones such as acetone and cyclohexanone; amides such as N-methyl-2-pyrrolidone (NMP) and N, N-dimethylacetamide (DMAc); Etc. sulfoxides such as Kishido like.
  • ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran (THF) and 1,4-dioxane
  • ether esters such as propylene glycol monomethyl ether acetate (PGMEA); esters such as ethyl acetate and
  • alkaline aqueous solutions include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline; ethanolamine. And aqueous amine solutions such as propylamine, ethylenediamine, and morpholine.
  • alkali metal hydroxides such as potassium hydroxide and sodium hydroxide
  • quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline
  • ethanolamine ethanolamine
  • aqueous amine solutions such as propylamine, ethylenediamine, and morpholine.
  • glycols such as ethylene glycol, propylene glycol and polyethylene glycol may be added to these developers.
  • a surfactant or the like may be added in order to improve the removability of the unexposed area.
  • OK73 thinner [Tokyo Ohka Kogyo Co., Ltd.] etc. are mentioned.
  • washing with water or a general organic solvent is preferably performed for about 20 to 90 seconds, for example. Then, the water
  • electroless plating treatment By electrolessly plating the electroless plating base layer formed on the substrate obtained as described above, a metal plating film is formed on the electroless plating base layer.
  • the metal plating film thus obtained, and the metal-coated base material provided in the order of the electroless plating base layer and the metal plating film on the base material are also objects of the present invention.
  • the electroless plating treatment (process) is not particularly limited, and can be performed by any generally known electroless plating treatment.
  • the plating is performed using a conventionally known electroless plating solution.
  • a method of immersing the electroless plating base layer formed on the substrate in a liquid (bath) is common.
  • the electroless plating solution mainly contains a metal ion (metal salt), a complexing agent, and a reducing agent, and a pH adjuster, a pH buffering agent, a reaction accelerator (second complexing agent) according to other uses.
  • a metal ion metal salt
  • a complexing agent complexing agent
  • a reducing agent a pH adjuster
  • a pH buffering agent pH buffering agent
  • a reaction accelerator second complexing agent
  • Stabilizers surfactants (use for imparting gloss to the plating film, use for improving wettability of the surface to be treated, etc.) and the like are appropriately included.
  • the metal used in the metal plating film formed by electroless plating include iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold, and alloys thereof, and are appropriately selected according to the purpose. Is done.
  • the complexing agent and the reducing agent may be appropriately selected according to the metal ion.
  • the electroless plating solution may be a commercially available plating solution.
  • an electroless nickel plating chemical (Melplate (registered trademark) NI series) manufactured by Meltex Co., Ltd., an electroless copper plating chemical (Melplate ( (Registered trademark) CU series); electroless nickel plating solution (ICP Nicolon (registered trademark) series, Top Piena 650) manufactured by Okuno Pharmaceutical Co., Ltd., electroless copper plating solution (OPC-700 electroless copper MK, ATS Ad Copper IW, CT, OPC Copper (registered trademark) AF series, HFS, NCA), electroless tin plating solution (Substar SN-5), electroless gold plating solution (Flash Gold 330, Self Gold OTK) -IT), electroless silver plating solution (muden silver); electroless palladium plating solution (pallet II) manufactured by Kojima Chemical Co., Ltd.
  • Electroless gold plating solution (Dip G series, NC gold series); Electroless silver plating solution (Esdia AG-40) manufactured by Sasaki Chemicals Co., Ltd .; Electroless nickel plating solution (Kanizen (made by Kanisen Co., Ltd.)) (Registered trademark) series, Schuma (registered trademark) series, Schuma (registered trademark) Crab Black (registered trademark) series), electroless palladium plating solution (S-KPD); electroless copper plating solution (Cueposit) manufactured by Dow Chemical (Registered trademark) Coppermix series, Circoposit (registered trademark) series, electroless palladium plating solution (Paramars (registered trademark) series), electroless nickel plating solution (Duraposit (registered trademark) series), electroless gold plating Solution (Aurolectroles (registered trademark) series), electroless tin plating solution ( Inposito (registered trademark) series, electroless copper plating solution manufactured by Uemura
  • Electroless copper plating solution (Print Gantt (registered trademark) PVE) or the like can be suitably used.
  • the electroless plating process adjusts the temperature, pH, immersion time, metal ion concentration, presence / absence of stirring, stirring speed, presence / absence of supply of air / oxygen, supply speed, etc. And the film thickness can be controlled.
  • the metal film base material of the present invention in which a metal plating film is formed on the base layer obtained by using the photosensitive base material of the present invention is a plating film when a transparent base material is used as the base material.
  • the surface seen when observing the transparent substrate from the surface opposite to the side on which the film is formed can be black. Therefore, by applying a metal plating film on the ground layer patterned by photolithography, a metal coating substrate having a black back surface of the patterned plating film forming portion can be obtained. It can be used as a highly transparent electrode.
  • HPS Hyperbranched polystyrene
  • HPS-200 manufactured by Nissan Chemical Industries, Ltd.
  • 8KX-078 Acrylic modified polymer [Akrit (registered trademark) 8KX-078 manufactured by Taisei Fine Chemical Co., Ltd.]
  • 8KX-078HC acrylic-modified ethylene oxide polymer (molecular weight 35,000)
  • 8KX-078H Acrylic modified polymer [Acrit (registered trademark) 8KX-078H manufactured by Taisei Fine Chemical Co., Ltd.]
  • 8KX-128A Acrylic modified polymer [Acrit (registered trademark) 8KX-128A manufactured by Taisei Fine Chemical Co., Ltd.]
  • OXE-01 1,2-octanedione 1- [4- (phenylthio) -2- (O-benz
  • IPA isopropanol
  • IPE diisopropyl ether
  • n-PrOH n-propanol
  • MIBK methyl isobutyl ketone
  • KBM-903 3-aminopropyltrimethoxysilane [Shin-Etsu Silicone (registered trademark) KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.]
  • Karenz MT PE1 Pentaerythritol tetrakis (3-mercaptobutyrate) [Karenz MT (registered trademark) PE1 manufactured by Showa Denko KK]
  • the white powder obtained by filtering this precipitate was dissolved in 100 g of chloroform and added to 500 g of IPA to reprecipitate the polymer.
  • the precipitate was filtered under reduced pressure and vacuum dried to obtain 8.5 g of hyperbranched polymer (HPS-Cl) having a chlorine atom at the molecular end as a white powder (yield 99%).
  • the 1 H NMR spectrum of the obtained HPS-Cl is shown in FIG. Since the peak (4.0 ppm, 3.7 ppm) derived from the dithiocarbamate group disappeared, it was confirmed that the obtained HPS-Cl had almost all the dithiocarbamate groups at the HPS molecule terminals substituted with chlorine atoms. It became clear.
  • the weight average molecular weight Mw measured by polystyrene conversion by GPC of the obtained HPS-Cl was 14,000, and the dispersity Mw / Mn was 2.9.
  • HPS-N (Me) 2 OctCl obtained from the peak of the benzene ring and the peak of the methyl group at the end of the octyl group shows that the chlorine atom at the end of the HPS-Cl molecule is almost quantitatively substituted with an ammonium group. Became clear.
  • the weight average molecular weight Mw of HPS-N (Me) 2 OctCl calculated from Mw (14,000) of HPS-Cl and ammonium group introduction rate (100%) was 28,000.
  • Example 1 [Preparation of photosensitive base material] 8 parts by mass of HBP-Pd-1 produced in Production Example 3 as a Pd catalyst, 1 part by mass of KBM-903 as a compound having an amino group, 86 parts by mass of 8KX-078H described in Table 1 as a polymerizable polymer compound, many 0.45 parts by weight of Karenz MT PE1 as a functional thiol (also referred to as RSH), 4.54 parts by weight of OXE-01 as a polymerization initiator, and 8: 1 of n-PrOH and MIBK as a solvent are mixed as non-solvent components (mixture) All components except for the solvent therein) A photosensitive base agent for electroless plating having a concentration of 5% by mass was prepared.
  • the HBP-Pd-1 used above was mixed with a compound having an amino group in advance by the following procedure to form an ammine complex, and this was mixed with the other components of the photosensitive base material.
  • ⁇ Ammine complex formation> 500 mg of HBP-Pd-1 produced in Production Example 3 was dissolved in n-PrOH: MIBK 8: 1 (Solution 1), the total amount of the solution was adjusted to 5 g, and the mixture was stirred with a mix rotor for 30 minutes.
  • the obtained underlayer is a mask aligner provided with a photomask on which patterns of 3 ⁇ m, 5 ⁇ m, 7 ⁇ m, and 9 ⁇ m are drawn.
  • i-line with an illuminance of 11.6 mW / cm 2 is exposed to 600 mJ / cm Irradiated to be 2 and exposed.
  • the exposed substrate was developed using a developing device equipped with a shower nozzle. Development was performed by cleaning the substrate with water while rotating the substrate at 300 rpm for 60 seconds, increasing the number of rotations to 1,500 rpm, and shaking off the water to form a base layer having an electroless plating base layer patterned on the substrate. I got the material.
  • Example 1 The same operation as in Example 1 was conducted except that the polymerizable polymer compound was changed to those described in Table 1.
  • Each plating base material obtained from Example 1 and Comparative Examples 1 to 3 was evaluated based on the following criteria.
  • the plating substrate As the plating substrate, the surface of PET film (Toyobo Co., Ltd., A4100) (surface of easy adhesion treatment) and the surface of PET film (Teijin DuPont Films Co., Ltd., HB3) were used.
  • the electroless plating base material of 1 and Comparative Examples 1 to 3 metal plating films were formed on the respective plating substrates by the same method as described above.
  • a cellophane tape (registered trademark) with a width of 18 mm [CT-18S made by Nichiban Co., Ltd.] was applied to the obtained metal plating film part, and rubbed firmly with fingers of the hand to make it tightly adhere, and then brought into close contact with the tape (registered) Trademark) was peeled off at once, and the state of the metal plating film was visually evaluated according to the following criteria. The results are also shown in Table 2.
  • a plating film is formed on a patterned electroless plating base layer obtained by forming a base layer using the photosensitive base material, exposing the resultant through a mask, and developing the base layer.
  • a base agent containing a polymerizable polymer compound having no hydrophilic portion when used, development was not performed and plating was not deposited.
  • a base agent containing a polymerizable polymer compound having 10% of a hydrophilic portion it was partially developed, but almost the entire surface was plated (Comparative Example 2).
  • the metal plating film obtained by using the photosensitive base material of the present invention is excellent in adhesion to the base material, and the back surface of the metal plating film exhibits a sufficient black color.

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Abstract

[Problème] Fournir un nouvel agent de sous-couche de dépôt autocatalytique qui soit respectueux de l'environnement, puisse être traité facilement en un petit nombre d'étapes, puisse former facilement un câblage fin de quelques micromètres de largeur par photolithographie, impression, etc. et soit utilisé dans une étape de prétraitement d'un dépôt autocatalytique.[Solution] L'invention concerne un agent de sous-couche photosensible qui est un agent de sous-couche destiné à former un film de placage métallique sur un matériau de base à l'aide d'un dépôt autocatalytique, et qui comprend : (a) un polymère hyper-ramifié possédant un groupe ammonium au niveau de ses extrémités moléculaires et possédant une masse moléculaire moyenne en poids de 1.000 à 5.000.000 ; (b) des microparticules métalliques ; (c) un composé polymère comprenant une chaîne latérale comprenant au moins une terminaison qui est une liaison insaturée polymérisable, par molécule, possédant 15 à 50 moles de groupes oxyalkylène pour 100 moles de toutes les unités de répétition, et possédant une masse moléculaire moyenne en poids de 10.000 à 100.000 ; (d) un initiateur de photopolymérisation ; (e) un composé possédant un groupe amino; et (f) un thiol polyfonctionnel.
PCT/JP2017/009042 2016-03-09 2017-03-07 Agent de sous-couche de dépôt autocatalytique comprenant des microparticules métalliques et un polymère hyper-ramifié WO2017154919A1 (fr)

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JP2006121112A (ja) * 2001-05-16 2006-05-11 Matsushita Electric Ind Co Ltd 固体撮像装置およびその駆動方法
JP2010530441A (ja) * 2007-05-15 2010-09-09 エルジー・ケム・リミテッド 電磁波遮蔽層の製造時に無電解メッキに対する触媒前駆体樹脂組成物、これを用いた金属パターンの形成方法及びこれにより製造された金属パターン
JP2015166084A (ja) * 2008-08-22 2015-09-24 日産化学工業株式会社 アンモニウム基を有する分岐高分子化合物からなる金属微粒子分散剤
WO2012141216A1 (fr) * 2011-04-12 2012-10-18 国立大学法人九州大学 Primaire pour dépôt autocatalytique comprenant un polymère hyperramifié, des microparticules métalliques et un acide organique
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WO2016158949A1 (fr) * 2015-03-31 2016-10-06 日産化学工業株式会社 Agent de sous-couche de placage autocatalytique photosensible

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