WO2020129649A1 - 高分子及び金属微粒子を含む無電解めっき下地剤 - Google Patents
高分子及び金属微粒子を含む無電解めっき下地剤 Download PDFInfo
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- WO2020129649A1 WO2020129649A1 PCT/JP2019/047444 JP2019047444W WO2020129649A1 WO 2020129649 A1 WO2020129649 A1 WO 2020129649A1 JP 2019047444 W JP2019047444 W JP 2019047444W WO 2020129649 A1 WO2020129649 A1 WO 2020129649A1
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- 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
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
- C23C18/2066—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
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- 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
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- 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
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
- C23C18/206—Use of metal other than noble metals and tin, e.g. activation, sensitisation with metals
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- 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
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/208—Multistep pretreatment with use of metal first
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- 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
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- 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
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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- 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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
Definitions
- the present invention relates to an electroless plating base agent containing a polymer and metal fine particles.
- a film with a uniform thickness can be obtained regardless of the type and shape of the base material simply by immersing the base material in a plating solution.
- Metal plating film can also be applied to non-conductive materials such as plastic, ceramics and glass. Therefore, it is widely used in various fields such as decorative applications such as imparting a sense of quality and aesthetics to resin molded articles such as automobile parts, electromagnetic shielding, wiring technology for printed circuit boards and large-scale integrated circuits, etc. ing.
- decorative applications such as imparting a sense of quality and aesthetics to resin molded articles such as automobile parts, electromagnetic shielding, wiring technology for printed circuit boards and large-scale integrated circuits, etc. ing.
- a pretreatment is performed to enhance the adhesion between the base material and the metal plating film.
- the surface to be processed is roughened and/or made hydrophilic by various etching means, and then an adsorbing substance that promotes adsorption of the plating catalyst onto the surface to be processed is supplied to the surface to be processed.
- a process (sensitization) and an activation process (activation) for adsorbing the plating catalyst on the surface to be processed are performed.
- the sensitizing treatment involves immersing the object to be treated in an acidic solution of stannous chloride, which causes the metal (Sn 2+ ) that can act as a reducing agent to adhere to the surface to be treated.
- the object to be treated is immersed in an acidic solution of palladium chloride as an activation treatment with respect to the sensitized surface to be treated.
- the palladium ion in the solution is reduced by the metal (tin ion: Sn 2+ ) which is a reducing agent, and is attached to the surface to be treated as an active palladium catalyst nucleus.
- an electroless plating solution After such pretreatment, it is immersed in an electroless plating solution to form a metal plating film on the surface to be treated.
- the hyperbranched polymer contained therein is included. Since the heat resistant temperature of the polymer is low, the highly branched polymer may be decomposed by solder reflow or high temperature treatment. There is also a problem that it is difficult to provide adhesion to an LCP (liquid crystal polymer) substrate, which is a substrate having excellent electrical characteristics, which is used in next-generation communication equipment such as 5G.
- LCP liquid crystal polymer
- a plating having high heat resistance which does not contain corrosive atoms such as halogen atoms and sulfur atoms.
- Various properties such as varnishing that can be given to various compositions, high varnish stability with high metal fine particles, adhesion to LCP substrate, and operability such as easy production with few processes.
- an electroless plating base material that sufficiently realizes the above characteristics. Focusing on these problems, the present invention is capable of forming a plating underlayer having high heat resistance and excellent adhesion to an LCP substrate, and further, it is possible to realize cost reduction in the production thereof.
- Pretreatment for electroless plating The purpose is to provide a new base material to be used as a process.
- the present inventors have conducted extensive studies to achieve the above object, as a result, studied a polymer containing a metal-dispersing group, but not containing a corrosive atom, combining the polymer with metal fine particles, and The inventors found that the layer obtained by coating on a material has not only plating properties as an underlayer for electroless metal plating but also high heat resistance and excellent adhesion to an LCP substrate, and completed the present invention. ..
- the present invention provides an electroless plating base agent for forming a metal plating film on a base material by electroless plating, (A) A structural unit derived from the monomer a having a metal dispersible group and one radical polymerizable double bond in the molecule, and a monomer having a crosslinkable group and one radical polymerizable double bond in the molecule a copolymer containing a structural unit derived from b,
- the present invention relates to a base material containing (B) fine metal particles and (C) a solvent.
- a second aspect relates to the undercoating agent according to the first aspect, which includes the complex in which the fine metal particles (B) are attached or coordinated to the metal dispersible group in the copolymer (A).
- the base material according to the first aspect or the second aspect wherein the monomer a is a compound having one of a vinyl group and a (meth)acryloyl group.
- the undercoating agent according to the third aspect wherein the monomer a is a compound represented by the following formula (1) or (2).
- R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- L represents O or N
- R 2 is present only when L represents N
- Representing a hydrogen atom, or R 1 and R 2 together with the atom to which they are attached may form a 4- to 6-membered cyclic amide.
- R 3 represents a hydrogen atom or a methyl group
- R 4 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be branched, an alkoxy group which may be branched having 1 to 10 carbon atoms, or an alkoxy group which may be branched having 1 to 10 carbon atoms
- L represents O or N
- R 5 is present only when L represents N, represents a hydrogen atom, or R 4 and R 5 are an atom to which they are bonded; Together, they may form a 4-6 membered cyclic amide or a 4-6 membered cyclic imide.
- a fifth aspect relates to the undercoating agent according to the fourth aspect, wherein the monomer a is N-vinylpyrrolidone, N-vinylacetamide or N-vinylformamide.
- a sixth aspect relates to the undercoating agent according to the first aspect or the second aspect, wherein the monomer b is a compound having one of a vinyl group and a (meth)acryloyl group.
- the undercoating agent according to the sixth aspect wherein the monomer b is a compound represented by the following formula (3).
- X represents a single bond, a carbonyloxy group, an amide group or a phenylene group
- Y is an alkylene group having 1 to 6 carbon atoms, an oxyalkylene group having 1 to 6 carbon atoms, or branched. It represents a good C 1-6 alkyl ether group, C 1-6 thioalkylene group or C 1-6 thioalkyl ether group
- Z represents a crosslinkable group
- R 6 represents a hydrogen atom or a carbon atom.
- the monomer that gives the (A) copolymer contains the monomer b in an amount of 5 to 500% of the number of moles of the monomer a, the first to seventh aspects.
- the (B) metal fine particles are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum (
- a tenth aspect relates to the undercoating agent according to the ninth aspect, wherein the (B) metal fine particles are palladium fine particles.
- An eleventh aspect relates to the undercoating agent according to any one of the first to tenth aspects, wherein the (B) metal fine particles are fine particles having an average primary particle diameter of 1 to 100 nm.
- a twelfth aspect further relates to the undercoating agent according to any one of the first to eleventh aspects, which further comprises (D) a base resin having a non-radical-polymerizable crosslinkable group.
- the thirteenth aspect further relates to the undercoating agent according to any one of the first to twelfth aspects, which further comprises (E) a crosslinking agent.
- a fourteenth aspect relates to an underlayer for electroless metal plating, which is obtained by using the electroless plating undercoating agent according to any one of the first to thirteenth aspects.
- a fifteenth aspect relates to the metal plating film formed on the underlayer of the electroless metal plating according to the fourteenth aspect.
- a base material, a base layer for electroless metal plating according to the fourteenth aspect which is formed on the base material, and a metal plating film formed on the base layer for electroless metal plating.
- a metal coating substrate As a seventeenth aspect, the present invention relates to a method for producing a metal coating substrate, which includes the following step (1) and step (2).
- Step (1) The electroless plating undercoating agent according to any one of the first to thirteenth viewpoints is applied onto a base material, and an underlayer for electroless metal plating is provided on the base material.
- Step (2) a step of immersing the base material provided with the underlayer in an electroless plating bath to form a metal plating film on the underlayer.
- the base agent of the present invention can easily form a base layer for electroless plating simply by coating it on a base material. Further, according to the present invention, it is possible to form an underlayer for plating, which has excellent plating performance and high heat resistance, and has excellent adhesion to an LCP substrate. Moreover, the undercoating agent of the present invention can be easily varnished with various compositions and can have high dispersion stability of metal fine particles. Furthermore, since the polymer used for the undercoating agent of the present invention can be easily prepared by a small number of processes, it is possible to simplify the manufacturing process of the plating undercoating agent and reduce the manufacturing cost.
- the underlayer of the electroless metal plating formed from the electroless plating undercoating agent of the present invention can be easily formed into a metal plating film by simply immersing it in an electroless plating bath. It is possible to easily obtain a metal-coated substrate including a film. That is, by forming a base layer on a base material using the electroless plating base agent of the present invention, a metal plating film having excellent heat resistance and excellent adhesion to a base material, particularly an LCP substrate, is formed. You can
- the base agent of the present invention is a base agent containing (A) a copolymer having the above-mentioned specific structural unit, (B) metal fine particles, and (C) a solvent, and optionally other components.
- the base agent of the present invention is suitably used as a catalyst for forming a metal plating film on a substrate by electroless plating.
- each component will be described.
- the component (A) includes a structural unit derived from the monomer a having a metal dispersible group and one radical-polymerizable double bond in the molecule, a crosslinkable group and one radical-polymerizable double bond in the molecule. It is a copolymer containing a constitutional unit derived from the monomer b having
- the monomer a is a compound having a metal dispersible group and one radically polymerizable double bond in the molecule.
- the metal-dispersing group improves the dispersibility of the metal fine particles in the composition by interacting with the metal fine particles of the component (B) such as adhesion and/or coordination, and thereby the metal fine particles in the composition. It is a group for stable existence in.
- the radically polymerizable double bond is preferably a compound having one of a vinyl group and a (meth)acryloyl group.
- the monomer a include compounds represented by the following formula (1) or formula (2).
- R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
- L represents O or N
- R 2 is present only when L represents N
- Representing a hydrogen atom, or R 1 and R 2 together with the atom to which they are attached may form a 4- to 6-membered cyclic amide.
- R 3 represents a hydrogen atom or a methyl group
- R 4 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be branched, an alkoxy group which may be branched having 1 to 10 carbon atoms, or an alkoxy group which may be branched having 1 to 10 carbon atoms
- L represents O or N
- R 5 is present only when L represents N, represents a hydrogen atom, or R 4 and R 5 are an atom to which they are bonded; Together, they may form a 4-6 membered cyclic amide or a 4-6 membered cyclic imide.
- Examples of such a monomer a include N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth).
- Acrylamide N-butyl(meth)acrylamide, N-isobutyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-octyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-methoxybutyl(meth) Acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-isobutoxymethyl(meth)acrylamide, N-isobutoxyethyl(meth)acrylamide, N-vinylphthalimide, N-vinylsuccinimide Etc.
- the monomer a is preferably a monomer represented by the formula (1) from the viewpoint of the ability of the monomer to coordinate with a metal, more preferably a monomer having an N-vinylamide group, and in consideration of availability, N- Vinylpyrrolidone, N-vinylformamide and N-vinylacetamide are more preferable. These monomers a may be used alone or in combination of two or more.
- the monomer b is a monomer having a crosslinkable group and one radically polymerizable double bond in the molecule.
- the crosslinkable group include an N-alkoxymethyl group, an N-hydroxymethyl group, an epoxy group which may have a substituent Q, an alicyclic epoxy group which may have a substituent Q, and a substituent Q.
- an oxetane group which may be used.
- the substituent Q include an alkyl group having 1 to 4 carbon atoms which may be substituted with halogen, a phenyl group and the like.
- the monomer b include compounds represented by the following formula (3).
- X represents a single bond, a carbonyloxy group, an amido group or a phenylene group
- Y is an alkylene group having 1 to 6 carbon atoms, an oxyalkylene group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms.
- 6 alkyl ether groups, to 6 thioalkylene group or C 1 -C of 1 -C represents the thio ether group of 6
- Z represents a crosslinkable group
- R 6 is a 1 -C 4 hydrogen or C Represents an alkyl group.
- the alkylene group having 1 to 6 carbon atoms represented by Y may be linear or branched, and its specific examples are not limited, and include methylene group and ethane-1,1-diyl group.
- the oxyalkylene group having 1 to 6 carbon atoms may be linear or branched, and is a group satisfying —O—R 7 —, and specific examples of R 7 are the same as the above-mentioned 1 to 6 alkylene groups. Is.
- the alkyl ether group having 1 to 6 carbon atoms may be linear or branched and is a group satisfying —R 8 —O—R 8 — and the specific example of R 8 is not limited.
- R 8 is not limited.
- methylene group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, propane-2,2 -Diyl group, butane-1,4-diyl group, pentane-1,5-diyl group and the like can be mentioned.
- the total number of carbon atoms of the two R 8 is up to 6.
- the thioalkylene group having 1 to 6 carbon atoms may be linear or branched and is a group satisfying —S—R 7 —, and R 7 is as described above.
- the alkyl ether group having 1 to 6 carbon atoms may be linear or branched, and —R 8 —O—R 8 — is as described above.
- Such monomers include, but are not limited to, the following.
- Examples of the monomer having one radical-polymerizable double bond and further having an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide and N-methoxymethylmethacrylamide. , N-methylol acrylamide and the like.
- Examples of the monomer having one radical-polymerizable double bond and further having an N-hydroxymethyl group include, but are not limited to, N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide.
- Examples of the monomer having one radical-polymerizable double bond and further having an epoxy group include, but are not limited to, glycidyl acrylate, glycidyl methacrylate, ⁇ -ethyl glycidyl acrylate, ⁇ -n-propyl.
- Examples include epoxyheptyl, ⁇ -ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and 3,4-epoxycyclohexyl methacrylate. ..
- glycidyl methacrylate -6,7-epoxyheptyl methacrylate
- o-vinylbenzyl glycidyl ether o-vinylbenzyl glycidyl ether
- m-vinylbenzyl glycidyl ether p-vinylbenzyl glycidyl ether
- 3,4-epoxycyclohexyl methacrylate etc. It is preferably used. These may be used alone or in combination.
- the monomer having one radical-polymerizable double bond and further having an oxetane group is not limited, and examples thereof include (meth)acrylic acid ester having an oxetane group.
- monomers 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3- Ethyl-oxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyl-oxetane, 3- (Acryloyloxymethyl)-2-phenyl-oxetane, 2-(methacryloyloxymethyl)oxetane
- other monomers may be used in addition to the monomer a and the monomer b.
- Such other monomers include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol methacrylate, 2 -Ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, ⁇ -butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl
- the method for obtaining the specific copolymer used in the present invention is not particularly limited.
- a solvent in which the monomer a, the monomer b, and optionally other monomers and a polymerization initiator are allowed to coexist at 50 to 110° C. It is obtained by carrying out a polymerization reaction at a temperature.
- the solvent to be used is not particularly limited as long as it dissolves the monomer having a specific functional group, the optionally used monomer having no specific functional group, the polymerization initiator and the like. Specific examples are described in ⁇ (C) Solvent> described later.
- the specific copolymer obtained by the above method is usually in the state of a solution dissolved in a solvent.
- the solution of the specific copolymer obtained by the above method is poured into agitating diethyl ether, water or the like to cause precipitation, and the generated precipitate is filtered and washed, and then at normal pressure or reduced pressure at room temperature.
- the powder of the specific copolymer can be obtained by drying or heating and drying. By the above operation, the polymerization initiator and the unreacted monomer that coexist with the specific copolymer can be removed, and as a result, a purified specific copolymer powder can be obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
- the specific copolymer may be used in the form of powder or in the form of a solution in which purified powder is redissolved in a solvent described later.
- the specific copolymer as the component (A) may be a mixture of a plurality of types of specific copolymers.
- the ratio of copolymerizing the monomer a and the monomer b is preferably 0.05 mol to 5 mol of the monomer b, particularly 1 mol of the monomer a, from the viewpoint of reactivity and plating property. It is preferably 0.1 mol to 3 mol.
- the above-mentioned other monomer when used in the production of the copolymer as the component (A), it is used in an amount of 1 to 200% of the total number of moles of the monomer a and the monomer b. Amounts, more preferably amounts of 10 to 100% moles.
- the (B) fine metal particles used in the base agent of the present invention are not particularly limited, and the metal species include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), and silver. Examples thereof include (Ag), tin (Sn), platinum (Pt), gold (Au), and alloys thereof. One kind of these metals may be used, or two or more kinds of alloys may be used. Among them, preferable metal fine particles include palladium fine particles.
- the metal oxide may be an oxide of the above metal.
- the metal fine particles can be obtained by reducing metal ions by, for example, irradiating a solution of a metal salt with a high-pressure mercury lamp, or adding a compound having a reducing action (so-called reducing agent) to the solution.
- a compound having a reducing action for example, by adding a solution of a metal salt to a solution in which the component (A) polymer is dissolved and irradiating the solution with ultraviolet rays, or by adding a solution of the metal salt and a reducing agent to the solution, a metal ion is added.
- reducing it is possible to prepare a base agent containing the component (A) polymer and the metal fine particles while forming a complex of the component (A) 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 depending on the metal species contained in the obtained base agent.
- the reducing agent that can be used include sodium borohydride, potassium borohydride, and other metal borohydrides; lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, beryllium aluminum hydride, hydrogenation
- Aluminum hydride salts such as aluminum magnesium and aluminum calcium hydride; hydrazine compounds; citric acid and its salts; succinic acid and its salts; ascorbic acid and its salts; primary or secondary of methanol, ethanol, isopropanol, polyols, etc.
- Tertiary alcohols such as trimethylamine, triethylamine, diisopropylethylamine, diethylmethylamine, tetramethylethylenediamine [TMEDA], ethylenediaminetetraacetic acid [EDTA]; hydroxylamine; tri-n-propylphosphine, tri-n- Butylphosphine, tricyclohexylphosphine, tribenzylphosphine, triphenylphosphine, triethoxyphosphine, 1,2-bis(diphenylphosphino)ethane [DPPE], 1,3-bis(diphenylphosphino)propane [DPPP], 1 And 1'-bis(diphenylphosphino)ferrocene [DPPF] and 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl [BINAP].
- DPPE 1,2-bis(diphenylphosphino)ethane
- the average primary particle diameter of the metal fine particles is preferably 1 to 100 nm. By setting the average primary particle diameter of the metal fine particles to 100 nm or less, the surface area is less reduced and sufficient catalytic activity can be obtained.
- the average particle diameter of primary particles is more preferably 75 nm or less, particularly preferably 1 to 30 nm.
- the average particle diameter of primary particles can be measured by the following method. [Measurement of average particle size of primary particles] After dispersing the metal fine particles in ethanol, dropping them on a carbon support film and drying them to prepare a sample, the obtained sample is a primary particle by a TEM device (Hitachi: H-8000 accelerating voltage 200 kV) by a microscopic method. The average particle size can be determined.
- the addition amount of the copolymer as the component (A) in the base agent of the present invention is preferably 20 parts by mass or more and 10,000 parts by mass or less based on 100 parts by mass of the (B) metal fine particles.
- the addition amount of the (A) copolymer is preferably 20 parts by mass or more and 10,000 parts by mass or less based on 100 parts by mass of the (B) metal fine particles.
- the metal fine particles can be sufficiently dispersed, and if it is 20 parts by mass or less, The dispersibility of the metal fine particles is insufficient, and precipitates and aggregates are easily generated. More preferably, it is 30 parts by mass or more.
- 10,000 parts by mass or more of the copolymer (A) is added to 100 parts by mass of the metal fine particles (B)
- the amount of Pd per unit area after coating becomes insufficient, so that the depositability of plating is increased. It may decrease.
- the electroless plating base agent of the present invention contains the above-mentioned (A) copolymer, (B) metal fine particles, and (C) solvent, and further contains other components as necessary.
- the copolymer as the component (A) and the fine metal particles (B) form a complex, that is, the base agent is the component (A). It is preferable to include a composite formed by a certain copolymer and the (B) fine metal particles.
- composite means a particle-like morphology in which both of them coexist in the state of contacting or in close proximity to the fine metal particles by the action of the metal-dispersing group of the side chain of the copolymer as the component (A).
- the "attached or coordinated structure” refers to a state in which a part or all of the metal-dispersing groups of the copolymer as the component (A) interacts with the metal fine particles, whereby a structure such as a complex is obtained. It is thought to form. Therefore, when palladium fine particles are used as the metal fine particles, it is considered that the Pd atom in the surface layer interacts with the metal dispersible group to form the structure in which the component (A) polymer surrounds the metal fine particles.
- the "composite" in the present invention is not limited to the one in which the metal fine particles and the copolymer as the component (A) are bonded to each other to form one composite as described above.
- the copolymer which is the component (A) may be present independently of each other without forming a binding portion (apparently forming one particle). ..
- the formation of the composite of the copolymer as the component (A) and the fine metal particles (B) is carried out at the same time as the preparation of the base agent containing the copolymer as the component (A) and the fine metal particles.
- the solution of the metal salt is added to the solution in which the copolymer as the component (A) is dissolved, and the solution is irradiated with ultraviolet rays, or the solution of the metal salt and the reducing agent are added to the solution.
- the complex can also be formed by reducing the metal ion, for example, by adding it.
- a metal ion and a copolymer which is the component (A) are dissolved in a solvent and reduced with a primary or secondary alcohol such as methanol, ethanol, 2-propanol or polyol.
- a primary or secondary alcohol such as methanol, ethanol, 2-propanol or polyol.
- the target metal fine particle composite can be obtained.
- the metal salts described above can be used as the metal ion source used here.
- the solvent to be used is not particularly limited as long as it can dissolve the metal ion and the polymer having a metal dispersible group in a required concentration or more, and specifically, methanol, ethanol, n-propanol, 2-propanol and the like.
- Alcohols such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, tetrahydropyran; nitriles such as acetonitrile and butyronitrile; N,N-dimethylformamide (DMF) ), amides such as N-methyl-2-pyrrolidone (NMP); sulfoxides such as dimethyl sulfoxide and the like, and a mixed solution of these solvents, preferably alcohols, halogenated hydrocarbons and cyclic ethers. And more preferably ethanol, 2-propanol, chloroform, tetrahydrofuran and the like.
- the temperature of the reduction reaction (mixing the metal ion and the copolymer which is the component (A)) can be usually in the range of 0°C to the boiling point of the solvent, preferably room temperature (about 25°C) to 100°C. Is the range.
- the target metal fine particle complex can be obtained by dissolving the metal ion and the copolymer as the component (A) in a solvent and reacting them in a hydrogen gas atmosphere.
- the metal ion source used here include the above-mentioned metal salts, hexacarbonylchromium [Cr(CO) 6 ], pentacarbonyliron [Fe(Co) 5 ], octacarbonyldicobalt [Co 2 (CO) 8 ].
- a metal carbonyl complex such as tetracarbonyl nickel [Ni(CO) 4 ] can be used.
- a zero-valent metal complex such as a metal olefin complex, a metal phosphine complex, and a metal nitrogen complex can also be used.
- the solvent to be used is not particularly limited as long as it is a solvent capable of dissolving the metal ion and the copolymer as the component (A) in a required concentration or more, and specifically, alcohols such as ethanol and propanol; methylene chloride.
- Halogenated hydrocarbons such as chloroform; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran; nitriles such as acetonitrile and butyronitrile; and mixed solutions of these solvents, and preferably tetrahydrofuran. ..
- the temperature at which the metal ion and the copolymer which is the component (A) are mixed is usually 0° C. to the boiling point of the solvent.
- the target metal fine particle complex can be obtained by dissolving the metal ion and the copolymer which is the component (A) in a solvent and causing a thermal decomposition reaction.
- the metal ion source used here the above-mentioned 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 is a solvent capable of dissolving the metal ion and the copolymer which is the component (A) in a required concentration or more, and specifically, methanol, ethanol, n-propanol, isopropanol, Alcohols such as ethylene glycol; halogenated hydrocarbons such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; benzene, toluene and the like Examples thereof include aromatic hydrocarbons and the like, and a mixed solution of these solvents, with preference given to toluene.
- the temperature for mixing the metal ion and the copolymer which is the component (A) having a metal dispersible group can be usually in the range of 0° C. to the boiling point of the solvent, preferably in the vicinity of the boiling point of the solvent, for example, in toluene. In the case, it is 110° C. (heating under reflux).
- the composite of the copolymer (A) as the component (A) thus obtained and the fine metal particles can be made into a solid form such as a powder through a purification treatment such as reprecipitation.
- the undercoating agent of the present invention contains the copolymer which is the component (A), the metal fine particles (B) (preferably a complex composed of these), and the solvent (C), and further, if necessary.
- the undercoating agent, which contains other components, may be in the form of a varnish used when forming the [undercoating layer for electroless metal plating] described later.
- the electroless plating base agent of the present invention may contain a base resin as the component (D), if desired.
- a base resin as the component (D)
- those having a non-radical-polymerizable crosslinkable group which is a group that undergoes a crosslinking reaction with the crosslinkable group in the component (A) by heat are preferable.
- the component (B) is described. Those described as are preferred. By adding such a component (D), it may be possible to further improve the adhesiveness of the obtained underlayer.
- the content is 0 parts by mass based on a total of 100 parts by mass of the copolymer of the component (A) and the fine metal particles of the component (B). To 200 parts by mass, more preferably 0 parts by mass to 150 parts by mass. When the content of the component (D) is excessively large, the plating depositability may decrease.
- the electroless plating base agent of the present invention may contain a crosslinking agent which is the component (E), if desired.
- an epoxy compound As the crosslinking agent which is the component (E), an epoxy compound, a methylol compound, a blocked isocyanate compound, a phenoplast compound, a compound having two or more trialkoxysilyl groups, a compound such as an alkoxysilane compound having an amino group, an alkoxy group and / Or organometallic compound having chelate ligand, polymer of N-alkoxymethylacrylamide, polymer of compound having epoxy group, polymer of compound having alkoxysilyl group, polymer of compound having isocyanate group, and Examples thereof include polymers such as melamine formaldehyde resin.
- epoxy compound examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N', N',-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphen
- methylol compound examples include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.
- alkoxymethylated glycoluril examples include, for example, 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4. ,6-Tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl) Examples include urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone.
- glycoluril compound (trade name: Cymel (registered trademark) 1170, powder link (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resin (trade name: UFR (registered trademark) 65) ), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea/formaldehyde resin (high condensation type, trade name: Beckamine (trade name) manufactured by DIC Corporation. Registered trademark) J-300S, same P-955, same N) and the like.
- alkoxymethylated benzoguanamine examples include tetramethoxymethyl benzoguanamine and the like.
- Commercially available products include Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade names: Nicalac (registered trademark) BX-4000, BX-37, and BL- 60, BX-55H) and the like.
- alkoxymethylated melamine examples include hexamethoxymethylmelamine and the like.
- Mitsui Cytec Co., Ltd. methoxymethyl type melamine compound (trade name: Cymel (registered trademark) 300, 301, 303, 350), butoxymethyl type melamine compound (trade name: Mycoat (registered trademark) 506, 508), methoxymethyl type melamine compound manufactured by Sanwa Chemical Co., Ltd.
- it may be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound, in which the hydrogen atom of such an amino group is substituted with a methylol group or an alkoxymethyl group.
- a melamine compound a urea compound, a glycoluril compound and a benzoguanamine compound, in which the hydrogen atom of such an amino group is substituted with a methylol group or an alkoxymethyl group.
- high molecular weight compounds prepared from melamine compounds and benzoguanamine compounds described in US Pat. No. 6,323,310 may be mentioned.
- Examples of commercial products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and examples of commercial products of the benzoguanamine compound include trade name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd., etc. may be mentioned.
- the above-mentioned blocked isocyanate compound has two or more isocyanate groups in one molecule whose isocyanate group is blocked by a suitable protective group, and when exposed to high temperature during thermosetting, the protective group (blocking portion) is heated.
- the isocyanate group generated by dissociation and dissociation causes a crosslinking reaction with the resin.
- Such a polyfunctional blocked isocyanate compound can be obtained, for example, by reacting a polyfunctional isocyanate compound having two or more isocyanate groups in one molecule with an appropriate blocking agent.
- polyfunctional isocyanate compound examples include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,3,6-hexamethylene triisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-cyclohexyl diisocyanate, 2,6 -Bis(isocyanate methyl) tetrahydrodicyclopentadiene, bis(isocyanate methyl) dicyclopentadiene, bis(isocyanate methyl) adamantane, 2,5-diisocyanate methyl norbornene, norbornane diisocyanate, dicycloheptane triis
- the blocking agent examples include methanol, ethanol, isopropanol, n-butanol, heptanol, hexanol, 2-ethoxyhexanol, cyclohexanol, octanol, isononyl alcohol, stearyl alcohol, benzyl alcohol, 2-ethoxyethanol, methyl lactate, Ethyl lactate, amyl lactate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether), tri Alcohols such as ethylene glycol monoethyl ether, N,N-dimethylaminoethanol, N,N-diethylaminoethanol, N,N-dibutylaminoethanol
- Oximes such as acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, diethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3, Pyrazoles such as 5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole and 3-methyl-5-phenylpyrazole, butyl mercaptan, hexyl mercaptan, dodecyl mercaptan, benzene Active methylene compounds such as thiol and other mercaptans, malonic acid diesters, acetoacetic acid esters, malonic acid dinitriles, acetylacetone, methylenedisulfone, dibenzo
- Examples thereof include amides, acid imides such as succinimide, maleic acid imide, and phthalic acid imide, and urea compounds such as urea, thiourea, and ethylene urea. Further, it may be an internal block type by uretdione bond (dimerization of isocyanate group).
- Examples of commercially available products of the polyfunctional blocked isocyanate compound include the following products. Takenate [registered trademark] B-815N, B-830, B-842N, B-846N, B-870, B-870N, B-874, B-874N, B-882, B-882 B-882N, B-5010, B-7005, B-7030, B-7075 (above, Mitsui Chemicals, Inc.).
- Sumidule [registered trademark] BL-3175, same BL-4165, same BL-4265, same BL-1100, same BL-1265, death module [registered trademark] TPLS-2957, same TPLS-2062, same TPLS-2078, TPLS-2117, BL-3475, Desmosam [registered trademark] 2170, 2265 (all manufactured by Sumika Bayer Urethane Co., Ltd.).
- VESTANAT [registered trademark] B1358A, B1358/100, B1370, VESTAGON [registered trademark] B1065, B1400, B1530, BF1320, BF1540 (above, manufactured by Evonik Industries).
- examples of the polyfunctional blocked isocyanate compound include a homopolymer or a copolymer obtained by radical polymerization of a (meth)acrylate having a blocked isocyanate group.
- the copolymer means a polymer obtained by polymerizing two or more kinds of monomers.
- the copolymer may be a copolymer obtained by polymerizing two or more kinds of (meth)acrylates having a blocked isocyanate group, or may be a copolymer obtained by polymerizing a (meth)acrylate having a blocked isocyanate group and another (meth)acrylate. It may be the resulting copolymer.
- Examples of commercially available products of such a (meth)acrylate having a blocked isocyanate group include Karenz [registered trademark] MOI-BM, AOI-BM, MOI-BP, and AOI-BP manufactured by Showa Denko KK Examples thereof include MOI-DEM, MOI-CP, MOI-MP, MOI-OEt, MOI-OBu, and MOI-OiPr.
- These polyfunctional blocked isocyanate compounds may be used alone or in combination of two or more kinds.
- phenoplast compound examples include the following compounds, but the phenoplast compound is not limited to the following compound examples.
- the compound having two or more trialkoxysilyl groups include, for example, 1,4-bis(trimethoxysilyl)benzene, 1,4-bis(triethoxysilyl)benzene, and 4,4′-bis(tri).
- alkoxysilane compound having an amino group examples include, for example, N,N'-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine and N,N'-bis[3-(tri Ethoxysilyl)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, trimethoxy ⁇ 3 -(Methylamino)propylsilane, 3-(N-allylamino)propyltrimethoxysilane, 3-(N-allylamino)propyl
- organometallic compound having an alkoxy group and/or a chelate ligand include, for example, diisopropoxyethylacetoacetate aluminum, diisopropoxyacetylacetonate aluminum, triacetylacetonate aluminum, tetrakisisopropoxytitanium, tetrakis.
- N-alkoxymethylacrylamide polymer examples include N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, and N-butoxymethyl(meth).
- Such a polymer include, for example, poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, N Examples thereof include a copolymer of ethoxymethyl methacrylamide and benzyl methacrylate, a copolymer of N-butoxymethyl acrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.
- the weight average molecular weight of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and further preferably 3,000 to 50,000.
- Examples of the polymer of the compound having an epoxy group include polymers produced by using a compound having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylethyl methacrylate.
- Such a polymer examples include poly(3,4-epoxycyclohexylmethyl methacrylate), poly(glycidyl methacrylate), a copolymer of glycidyl methacrylate and methyl methacrylate, and 3,4-epoxycyclohexyl methyl methacrylate.
- examples thereof include a copolymer with methyl methacrylate and a copolymer with glycidyl methacrylate and styrene.
- the weight average molecular weight of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and further preferably 3,000 to 50,000.
- the polymer of the compound having an alkoxysilyl group mentioned above includes, for example, a polymer produced by using a compound having an alkoxysilyl group such as 3-methacryloxypropyltrimethoxysilane.
- poly(3-methacryloxypropyltrimethoxysilane) examples include, for example, poly(3-methacryloxypropyltrimethoxysilane), a copolymer of 3-methacryloxypropyltrimethoxysilane and styrene, 3-methacryloxypropyltrimethoxysilane and methyl.
- examples thereof include copolymers with methacrylate.
- the weight average molecular weight of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and further preferably 3,000 to 50,000.
- the above-mentioned “poly((meth)acryloxypropyltrimethoxysilane)” means poly(meth)acrylate having an alkoxysilyl group.
- cross-linking agents can be used alone or in combination of two or more kinds.
- the content is 0 parts by mass based on a total of 100 parts by mass of the copolymer of the component (A) and the fine metal particles of the component (B). To 100 parts by mass, more preferably 0 to 50 parts by mass.
- the base agent of the present invention may be appropriately added with an additive such as a surfactant, various surface modifiers and thickeners, as long as the effect of the present invention is not impaired.
- surfactant examples include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and other polyoxyethylene alkyl ethers; polyoxyethylene octylphenyl 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 nonionic surfactants such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan trioleate
- F-top registered trademark
- EF-301, EF-303, EF-352 [above, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.]
- Megafac registered trademark
- F-171, F-173, and R -08 the same R-30 [above, manufactured by DIC Corporation]
- Novec registered trademark
- the surface conditioner examples include silicone 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. No. 330, No. 333, No. 370, No. 375, No. 375, No. 378 [above, manufactured by Big Chemie Japan KK] and the like.
- thickener examples include polyacrylic acids (including crosslinked ones) such as carboxyvinyl polymer (carbomer); polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), polystyrene (PS). ) Etc. vinyl polymers; polyethylene oxides; polyesters; polycarbonates; polyamides; polyurethanes; dextrin, agar, carrageenan, alginic acid, gum arabic, guar gum, tragacanth gum, locust bean gum, starch, pectin, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose. And the like; proteins such as gelatin and casein.
- polyacrylic acids including crosslinked ones
- carboxyvinyl polymer carboxyvinyl polymer
- PVP polyvinylpyrrolidone
- PVA polyvinyl alcohol
- PVAc polyvinyl acetate
- PS poly
- each of the above polymers includes not only homopolymers but also copolymers. These thickeners may be used alone or in combination of two or more.
- the undercoating agent of the present invention can be adjusted in viscosity and rheological properties of the undercoating agent by blending a thickening agent as necessary, and is appropriately applied depending on its application such as the application method or application site of the undercoating agent. Can be adopted/selected.
- 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 mass, and 0.005 parts by mass based on 100 parts by mass of the composite formed from the polymer as the component (A) and the fine metal particles as the component (B). It is more preferably to 10 parts by mass, and even more preferably 0.01 to 5 parts by mass.
- the above-described electroless plating base agent of the present invention can form a base layer for electroless metal plating by applying it on a base material.
- the underlying layer of this electroless metal plating is also an object of the present invention.
- the base material is not particularly limited, but a non-conductive base material or a conductive base material can be preferably used.
- the non-conductive substrate include glass, ceramics, 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 (polyether ether ketone) resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, epoxy resin, polyacetal resin, LCP (liquid crystal polymer) resin and the like; paper and the like.
- 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 brass, phosphor bronze, copper alloys such as white copper and beryllium copper, nickel and nickel alloys, and metals such as silver and silver alloys such as silver. Etc. Further, a base material in which a thin film is formed of these conductive base materials on the above non-conductive base material can also be used. Further, the base material may be a three-dimensional molded body.
- the component (A) polymer and (B) metal fine particles preferably a composite comprising these
- the component (A) polymer and (B) metal fine particles are used.
- (And optionally (D) base polymer, (E) crosslinking agent and other components) are dissolved or dispersed in (C) a solvent to form a varnish, and the varnish is a base for forming a metal plating film.
- bar coating method, flexographic printing, gravure printing, spin coating method, spray coating method, ink jet method, pen lithography, contact printing, ⁇ CP, NIL and nTP are preferable.
- spin coating method since the coating can be performed in a single time, even a highly volatile solution can be used, and coating with high uniformity can be performed.
- spray coating method highly uniform coating can be performed with a very small amount of varnish, which is very industrially advantageous.
- the inkjet 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 industrially very advantageous.
- the polymer as the component (A) and the metal fine particles (B) preferably a composite comprising these
- the component (D), the component (E) and other components are dissolved.
- it is not particularly limited as long as it is dispersed for example, water; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene; methanol, ethanol, n-propanol, isopropanol, n-butanol, Alcohols such as 2-butanol, n-hexanol, n-octanol, 2-octanol, 2-ethylhexanol; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve; propylene glycol monomethyl
- solvents may be used alone or in combination of two or more kinds.
- glycols such as ethylene glycol, propylene glycol and butylene glycol may be added for the purpose of adjusting the viscosity of the varnish.
- concentration of the solvent dissolved or dispersed in the above-mentioned solvent is arbitrary, but the concentration of the non-solvent component in the varnish [all components ((A) component polymer except the solvent contained in the base agent (B) metal fine particles (preferably Is a complex composed of these, and optionally (D) base polymer, (E) cross-linking agent and other components)] is 0.05 to 90% by mass, preferably 0.1 to 80% by mass. is there.
- the method of drying the solvent is not particularly limited, and for example, a hot plate or an oven may be used to evaporate in a suitable atmosphere, that is, in the atmosphere, an inert gas such as nitrogen, or in a vacuum. This makes it possible to obtain a base layer having a uniform film-forming surface.
- the baking temperature is not particularly limited as long as the solvent can be evaporated, but it is preferably 40 to 250°C.
- electroless plating treatment metal plating film, metal coating substrate
- a metal plating film is formed on the underlayer.
- the metal-plated film thus obtained, and the metal-coated substrate provided on the substrate in the order of the electroless metal-plated underlayer and the metal-plated film are also covered by the present invention.
- the electroless plating treatment is not particularly limited, and any generally known electroless plating treatment can be performed.
- a general method is to immerse a base layer of electroless metal plating formed on a substrate in a liquid (bath).
- the electroless plating solution mainly contains a metal ion (metal salt), a complexing agent and a reducing agent, and a pH adjusting agent, a pH buffering agent, a reaction accelerator (a second complexing agent) depending on other uses.
- a metal ion metal salt
- a complexing agent and a reducing agent a complexing agent and a reducing agent
- a pH adjusting agent a pH buffering agent
- a reaction accelerator a second complexing agent
- Stabilizers, and surfactants application of gloss to plating film, application of improving wettability of surface to be treated, etc.
- the metal used for 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. To be done. Further, the complexing agent and the reducing agent may be appropriately selected according to the metal ion.
- electroless plating solution a commercially available plating solution may be used.
- an electroless nickel plating chemical (Melplate (registered trademark) NI series) manufactured by Meltex Co., an electroless copper plating chemical (Melplate ( (Registered trademark) CU series); electroless nickel plating solution (ICP Nicoron (registered trademark) series, Top Piena 650) manufactured by Okuno Chemical Industries 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 (Palette II) manufactured by Kojima Chemical Co., Ltd., electroless gold plating solution (DIP G series, NC gold series); Sasaki Chemical
- the electroless copper plating solution (Print Gant (registered trademark) PV, the same PVE) manufactured by Atotech Japan Co., Ltd. can be preferably used.
- the rate of formation of the metal film is controlled by adjusting the temperature, pH, immersion time, metal ion concentration, presence/absence of stirring, agitation rate, presence/absence of air/oxygen supply, supply rate, etc. in the electroless plating step. And the film thickness can be controlled.
- the number average molecular weight and the weight average molecular weight are measured as follows. [Measurement of number average molecular weight and weight average molecular weight] The number average molecular weight and the weight average molecular weight of the copolymer obtained according to the following synthesis examples were measured using a GPC device (Shodex column KD800 and TOSOH column TSK-GEL) manufactured by Tosoh Corporation as an elution solvent N,N-dimethylformamide.
- Mn number average molecular weight
- Mw weight average molecular weight
- MMA methyl methacrylate
- HEA 2-hydroxyethyl acrylate
- NVA N-vinyl acetamide
- GMA glycidyl methacrylate cyclomer
- M100 3,4-epoxycyclohexylmethyl methacrylate (manufactured by Daicel)
- AMBN 2,2'-azobis-2-methylbutyronitrile
- PGME Propylene glycol monomethyl ether
- IPE Diisopropyl ether
- DAA Diacetone alcohol
- BL-10 Polyvinyl acetal resin (Sekisui Chemical Co., Ltd.)
- ⁇ Synthesis example 1> A copolymer solution obtained by dissolving 2.00 g of styrene, 1.63 g of NVA, 2.73 g of GMA, and 0.32 g of AMBN in 15.59 g of PGME and reacting at 80° C. for 20 hours (solid content concentration 30 (% by mass) was added to 500 mL of diethyl ether while stirring to precipitate a polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50° C. to obtain a copolymer powder (P1). The Mn of the obtained copolymer was 6,057 and the Mw was 8,884.
- ⁇ Synthesis example 2> A copolymer solution (solid content) obtained by dissolving 2.00 g of styrene, 1.63 g of NVA, 3.76 g of cyclomer M100, and 0.37 g of AMBN in 18.14 g of PGME and reacting at 80° C. for 20 hours. (Concentration: 30% by mass) was added to 500 mL of diethyl ether while stirring to precipitate a polymer. The precipitated polymer was filtered under reduced pressure and vacuum dried at 50° C. to obtain a copolymer powder (P2). The obtained copolymer had Mn of 5,336 and Mw of 8,669.
- Preparation of plating solution ⁇ Preparation Example 1> A 300 mL beaker was charged with 20 mL of top nicolon SA-98-MLF (manufactured by Okuno Seiyaku) and 11 mL of top nicolon SA-98-1LF (manufactured by Okuno Seiyaku), and pure water was further added to make the total amount of the solution 200 mL. This solution was stirred to obtain an electroless nickel plating solution.
- the LCP (Pericule (registered trademark) LCP manufactured by Chiyoda Integre Co., Ltd.) base material was subjected to a surface treatment for 30 seconds using a UV ozone cleaning device (UV-208 manufactured by Technovision Co., Ltd.).
- a bar coating was applied on the surface-treated LCP with an electroless plating undercoat in a film thickness of 6 ⁇ m, and then heated at 80° C. for 5 minutes to form a coating film.
- This coating film was further cured by heating at 200° C. for 10 minutes.
- the obtained cured film was immersed in the electroless nickel plating solution prepared in Preparation Example 1 for 2 minutes. Then, the obtained plating base material was washed with water, and then the state of the metal plating film was visually evaluated. The evaluation results are shown later in Table 2.
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Abstract
Description
通常、無電解めっきにより基材(被めっき体)上に金属めっき膜を形成する場合、基材と金属めっき膜の密着性を高めるための前処理が行われる。具体的には、まず種々のエッチング手段によって被処理面を粗面化及び/又は親水化し、次いで、被処理面上へのめっき触媒の吸着を促す吸着物質を被処理面上に供給する感受性化処理(sensitization)と、被処理面上にめっき触媒を吸着させる活性化処理(activation)とを行う。典型的には、感受性化処理は塩化第一スズの酸性溶液中に被処理物を浸漬し、これにより、還元剤として作用し得る金属(Sn2+)が被処理面に付着する。そして、感受性化された被処理面に対して、活性化処理として塩化パラジウムの酸性溶液中に被処理物を浸漬させる。これにより、溶液中のパラジウムイオンは還元剤である金属(スズイオン:Sn2+)によって還元され、活性なパラジウム触媒核として被処理面に付着する。こうした前処理後、無電解めっき液に浸漬して、金属めっき膜を被処理面上に形成する。
このように、これまで提案された無電解めっき下地剤にあっては、めっき下地剤としてのめっき性能に加え、ハロゲン原子や硫黄原子等の腐食性原子を含まず、高耐熱性を有するめっきを与えることができ、様々な組成に容易にワニス化可能で、高い金属微粒子分散安定性を有するといった種々の性能、LCP基板への密着性、さらには少ないプロセスで簡便に製造できるといった操作性、これらの特性を十分に実現した無電解めっき下地剤の提案はこれまでにない。
本発明はこうした課題に着目し、高い耐熱性を有し、LCP基板への密着性に優れるめっき下地層を形成でき、さらにはその製造においても低コスト化を実現できる、無電解めっきの前処理工程として用いられる新たな下地剤の提供を目的とする。
(A)分子内に金属分散性基及び1個のラジカル重合性二重結合を有するモノマーaに由来する構成単位と、分子内に架橋性基及び1個のラジカル重合性二重結合を有するモノマーbに由来する構成単位を含む共重合体、
(B)金属微粒子、及び
(C)溶剤
を含む下地剤に関する。
第2観点として、前記(A)共重合体中の金属分散性基に、前記(B)金属微粒子が付着又は配位した複合体を含む、第1観点に記載の下地剤に関する。
第3観点として、前記モノマーaが、ビニル基及び(メタ)アクリロイル基の何れか一方を有する化合物である、第1観点又は第2観点に記載の下地剤に関する。
第4観点として、前記モノマーaが、下式(1)又は(2)で表される化合物である第3観点に記載の下地剤に関する。
式(2)中、R3は水素原子またはメチル基を表し、
R4は水素原子又は炭素原子数1乃至10の分岐しても良いアルキル基、炭素原子数1乃至10の分岐しても良いアルコキシル基又は、炭素原子数1乃至10の分岐しても良いアルコキシルアルキル基を表し、Lは、O又はNを表し、R5は、LがNを表す場合にのみ存在し、水素原子を表すか、又は、R4及びR5は、それらが結合する原子と一緒になって、4乃至6員の環状アミド、又は、4乃至6員の環状イミドを形成してもよい。)
第5観点として、前記モノマーaがN-ビニルピロリドン、N-ビニルアセトアミド又はN-ビニルホルムアミドである第4観点に記載の下地剤に関する。
第6観点として、前記モノマーbが、ビニル基及び(メタ)アクリロイル基の何れか一方を有する化合物である、第1観点又は第2観点に記載の下地剤に関する。
第7観点として、前記モノマーbが、下式(3)で表される化合物である第6観点に記載の下地剤に関する。
第8観点として、前記(A)共重合体を与えるモノマーは、前記モノマーaのモル数に対して5~500%のモル数となる量の前記モノマーbを含む、第1観点乃至第7観点のうちいずれか一つに記載の下地剤に関する。
第9観点として、前記(B)金属微粒子が、鉄(Fe)、コバルト(Co)、ニッケル(Ni)、銅(Cu)、パラジウム(Pd)、銀(Ag)、スズ(Sn)、白金(Pt)及び金(Au)からなる群より選択される少なくとも一種の金属の微粒子である、第1観点乃至第8観点のうちいずれか一つに記載の下地剤に関する。
第10観点として、前記(B)金属微粒子が、パラジウム微粒子である、第9観点に記載の下地剤に関する。
第11観点として、前記(B)金属微粒子が、1~100nmの一次粒子平均粒径を有する微粒子である、第1観点乃至第10観点のうちいずれか一つに記載の下地剤に関する。
第12観点として、さらに、(D)非ラジカル重合性架橋性基を有するベース樹脂を含有する第1観点乃至第11観点の何れか一つに記載の下地剤に関する。
第13観点として、さらに、(E)架橋剤を含有する第1観点乃至第12観点の何れか一つに記載の下地剤に関する。
第14観点として、第1観点乃至第13観点のうち何れか一つに記載の無電解めっき下地剤を用いて得られる、無電解金属めっきの下地層に関する。
第15観点として、第14観点に記載の無電解金属めっきの下地層の上に形成された金属めっき膜に関する。
第16観点として、基材と、該基材上に形成された第14観点に記載の無電解金属めっきの下地層と、該無電解金属めっきの下地層の上に形成された金属めっき膜とを具備する、金属被膜基材に関する。
第17観点として、下記(1)工程及び(2)工程を含む、金属被膜基材の製造方法に関する。
(1)工程:第1観点乃至第13観点のうち何れか一つに記載の無電解めっき下地剤を基材上に塗布し、無電解金属めっきの下地層を該基材の上に具備する工程、
(2)工程:該下地層を具備した基材を無電解めっき浴に浸漬し、金属めっき膜を該下地層の上に形成する工程。
さらに本発明の下地剤に使用するポリマーは、少ないプロセスで簡便に調製可能であることから、めっき下地剤の製造工程の簡略化と製造コストの低減も図ることができる。
また本発明の無電解めっき下地剤から形成された無電解金属めっきの下地層は、無電解めっき浴に浸漬するだけで、容易に金属めっき膜を形成でき、基材と下地層、そして金属めっき膜とを備える金属被膜基材を容易に得ることができる。
すなわち、本発明の無電解めっき下地剤を用いて基材上に下地層を形成することにより、基材、特に、LCP基板との密着性に優れ、耐熱性を有する金属めっき膜を形成することができる。
本発明の下地剤は、(A)上述の特定の構成単位を有する共重合体、(B)金属微粒子、及び(C)溶剤を含み、必要に応じてその他成分を含む下地剤である。
本発明の下地剤は基材上に無電解めっき処理により金属めっき膜を形成するための触媒として好適に使用される。以下、各成分について説明する。
<(A)共重合体>
本発明において、モノマーaは、分子内に金属分散性基及び1個のラジカル重合性二重結合を有する化合物である。
金属分散性基は、(B)成分の金属微粒子と付着及び/又は配位等の相互作用をすることによって、金属微粒子の組成物中における分散性を向上させ、それにより金属微粒子を組成物中に安定に存在させるための基である。このような金属分散性基としては、カルボニルと、それに共有結合で結合した窒素原子を有する部位、すなわち、-C(=O)-N-部位を有する置換基が好ましく、より具体的には、アミド結合を有する基及びイミド結合を有する基からなる群から選ばれる基が好ましい。
ラジカル重合性二重結合としては、好ましくはビニル基及び(メタ)アクリロイル基の何れか一方を有する化合物であることが好ましい。なお、モノマーaがラジカル重合性二重結合として(メタ)アクリロイル基を有する化合物である場合、該(メタ)アクリロイル基に含まれるカルボニル基[-C(=O)-]が、金属分散性基としてのアミド基におけるカルボニル基と重複する構造となっていてもよい。
式(2)中、R3は水素原子またはメチル基を表し、
R4は水素原子又は炭素原子数1乃至10の分岐しても良いアルキル基、炭素原子数1乃至10の分岐しても良いアルコキシル基又は、炭素原子数1乃至10の分岐しても良いアルコキシルアルキル基を表し、Lは、O又はNを表し、R5は、LがNを表す場合にのみ存在し、水素原子を表すか、又は、R4及びR5は、それらが結合する原子と一緒になって、4乃至6員の環状アミド、又は、4乃至6員の環状イミドを形成してもよい。)
これらモノマーaは一種を単独で使用してもよく、また二種以上を併用してもよい
モノマーbは、分子内に架橋性基及び1個のラジカル重合性二重結合を有するモノマーである。
架橋性基としては、N-アルコキシメチル基、N-ヒドロキシメチル基、置換基Qを有しても良いエポキシ基、置換基Qを有しても良い脂環式エポキシ基、置換基Qを有しても良いオキセタン基等が挙げられる。置換基Qとしてはハロゲンで置換されても良い炭素数1ないし4のアルキル基、フェニル基等が挙げられる。
これらの中でも、基板との密着性の観点からXはカルボニルオキシ基又はメチレン基であることが好ましく、Zはエポキシ基であることが好ましい。
前記方法により得られる特定共重合体は、通常、溶剤に溶解した溶液の状態である。
本発明の下地剤に用いられる(B)金属微粒子としては特に限定されず、金属種としては鉄(Fe)、コバルト(Co)、ニッケル(Ni)、銅(Cu)、パラジウム(Pd)、銀(Ag)、スズ(Sn)、白金(Pt)及び金(Au)並びにこれらの合金が挙げられ、これらの金属の1種類でもよいし2種以上の合金でも構わない。中でも好ましい金属微粒子としてはパラジウム微粒子が挙げられる。なお、金属微粒子として、前記金属の酸化物を用いてもよい。
前記還元剤としては、特に限定されるものではなく、種々の還元剤を用いることができ、得られる下地剤に含有させる金属種等により還元剤を選択することが好ましい。用いることができる還元剤としては、例えば、水素化ホウ素ナトリウム、水素化ホウ素カリウム等の水素化ホウ素金属塩;水素化アルミニウムリチウム、水素化アルミニウムカリウム、水素化アルミニウムセシウム、水素化アルミニウムベリリウム、水素化アルミニウムマグネシウム、水素化アルミニウムカルシウム等の水素化アルミニウム塩;ヒドラジン化合物;クエン酸及びその塩;コハク酸及びその塩;アスコルビン酸及びその塩;メタノール、エタノール、イソプロパノール、ポリオール等の第一級又は第二級アルコール類;トリメチルアミン、トリエチルアミン、ジイソプロピルエチルアミン、ジエチルメチルアミン、テトラメチルエチレンジアミン[TMEDA]、エチレンジアミン四酢酸[EDTA]等の第三級アミン類;ヒドロキシルアミン;トリ-n-プロピルホスフィン、トリ-n-ブチルホスフィン、トリシクロヘキシルホスフィン、トリベンジルホスフィン、トリフェニルホスフィン、トリエトキシホスフィン、1,2-ビス(ジフェニルホスフィノ)エタン[DPPE]、1,3-ビス(ジフェニルホスフィノ)プロパン[DPPP]、1,1’-ビス(ジフェニルホスフィノ)フェロセン[DPPF]、2,2’-ビス(ジフェニルホスフィノ)-1,1’-ビナフチル[BINAP]等のホスフィン類などが挙げられる。
一次粒子平均粒径は次の方法により測定することができる。
[一次粒子平均粒径の測定]
金属微粒子をエタノールに分散後、カーボン支持膜上に滴下し、乾燥させてサンプルを作製後、得られたサンプルをTEM装置(日立製作所製:H-8000加速電圧200kV)にて顕微鏡法で一次粒子平均粒径を求めることができる。
本発明の無電解めっき下地剤は、前記(A)共重合体、(B)金属微粒子、及び(C)溶剤を含むものであり、さらに、必要に応じてその他成分を含むものである。本発明の無電解めっき下地剤において、前記(A)成分である共重合体と前記(B)金属微粒子が複合体を形成していることが好ましく、すなわち前記下地剤が前記(A)成分である共重合体と前記(B)金属微粒子により形成された複合体を含むことが好ましい。
ここで“付着又は配位した構造”とは、(A)成分である共重合体の金属分散性基の一部又は全部が金属微粒子と相互作用した状態をいい、これによって錯体のような構造を形成していると考えられる。そのため、金属微粒子としてパラジウム微粒子を採用した場合、表層のPd原子が金属分散性基と相互作用することにより、(A)成分ポリマーが金属微粒子を取り囲む構造を形成していると考えられる。
ここで用いられる金属イオン源としては、上述の金属塩が使用できる。
使用する溶媒としては、金属イオンと金属分散性基を有するポリマーを必要濃度以上に溶解できる溶媒であれば特に限定はされないが、具体的には、メタノール、エタノール、n-プロパノール、2-プロパノール等のアルコール類;塩化メチレン、クロロホルム等のハロゲン化炭化水素類;テトラヒドロフラン(THF)、2-メチルテトラヒドロフラン、テトラヒドロピラン等の環状エーテル類;アセトニトリル、ブチロニトリル等のニトリル類;N,N-ジメチルホルムアミド(DMF)、N-メチル-2-ピロリドン(NMP)等のアミド類;ジメチルスルホキシド等のスルホキシド類など及びこれらの溶媒の混合液が挙げられ、好ましくは、アルコール類、ハロゲン化炭化水素類、環状エーテル類が挙げられ、より好ましくは、エタノール、2-プロパノール、クロロホルム、テトラヒドロフランなどが挙げられる。
還元反応(金属イオンと(A)成分である共重合体を混合する)の温度は、通常0℃乃至溶媒の沸点の範囲を使用することができ、好ましくは室温(およそ25℃)乃至100℃の範囲である。
ここで用いられる金属イオン源としては、上述の金属塩や、ヘキサカルボニルクロム[Cr(CO)6]、ペンタカルボニル鉄[Fe(Co)5]、オクタカルボニルジコバルト[Co2(CO)8]、テトラカルボニルニッケル[Ni(CO)4]等の金属カルボニル錯体が使用できる。また金属オレフィン錯体や金属ホスフィン錯体、金属窒素錯体等の0価の金属錯体も使用できる。
使用する溶媒としては、金属イオンと(A)成分である共重合体を必要濃度以上に溶解できる溶媒であれば特に限定はされないが、具体的には、エタノール、プロパノール等のアルコール類;塩化メチレン、クロロホルム等のハロゲン化炭化水素類;テトラヒドロフラン、2-メチルテトラヒドロフラン、テトラヒドロピラン等の環状エーテル類;アセトニトリル、ブチロニトリル等のニトリル類など及びこれらの溶媒の混合液が挙げられ、好ましくはテトラヒドロフランが挙げられる。
金属イオンと(A)成分である共重合体を混合する温度は、通常0℃乃至溶媒の沸点の範囲を使用することができる。
ここで用いられる金属イオン源としては、上述の金属塩や金属カルボニル錯体やその他の0価の金属錯体、酸化銀等の金属酸化物が使用できる。
使用する溶媒としては、金属イオンと(A)成分である共重合体を必要濃度以上に溶解できる溶媒であれば特に限定はされないが、具体的には、メタノール、エタノール、n-プロパノール、イソプロパノール、エチレングリコール等のアルコール類;塩化メチレン、クロロホルム等のハロゲン化炭化水素類;テトラヒドロフラン(THF)、2-メチルテトラヒドロフラン、テトラヒドロピラン等の環状エーテル類;アセトニトリル、ブチロニトリル等のニトリル類;ベンゼン、トルエン等の芳香族炭化水素類など及びこれらの溶媒の混合液が挙げられ、好ましくはトルエンが挙げられる。
金属イオンと金属分散性基を有する(A)成分である共重合体を混合する温度は、通常0℃乃至溶媒の沸点の範囲を使用することができ、好ましくは溶媒の沸点近傍、例えばトルエンの場合は110℃(加熱還流)である。
タケネート〔登録商標〕B-815N、同B-830、同B-842N、同B-846N、同B-870、同B-870N、同B-874、同B-874N、同B-882、同B-882N、同B-5010、同B-7005、同B-7030、同B-7075(以上、三井化学(株)製)。
本発明の下地剤は、本発明の効果を損なわない限りにおいて、さらに界面活性剤、各種表面調整剤、増粘剤等の添加剤などを適宜添加してもよい。
本発明の下地剤は、必要に応じて増粘剤を配合することにより、下地剤の粘度やレオロジー特性を調整することができ、下地剤の適用方法や適用箇所など、その用途に応じて適宜採用・選択し得る。
上述の本発明の無電解めっき下地剤は、基材上に塗布することにより、無電解金属めっきの下地層を形成することができる。この無電解金属めっきの下地層も本発明の対象である。
非導電性基材としては、例えばガラス、セラミック等;ポリエチレン樹脂、ポリプロピレン樹脂、塩化ビニル樹脂、ナイロン(ポリアミド樹脂)、ポリイミド樹脂、ポリカーボネート樹脂、アクリル樹脂、PEN(ポリエチレンナフタラート)樹脂、PET(ポリエチレンテレフタラート)樹脂、PEEK(ポリエーテルエーテルケトン)樹脂、ABS(アクリロニトリル-ブタジエン-スチレン共重合体)樹脂、エポキシ樹脂、ポリアセタール樹脂、LCP(液晶ポリマー)樹脂等;紙などが挙げられる。これらはシートあるいはフィルム等の形態にて好適に使用され、この場合の厚さについては特に限定されない。
また導電性基材としては、例えばITO(スズドープ酸化インジウム)や、ATO(アンチモンドープ酸化スズ)、FTO(フッ素ドープ酸化スズ)、AZO(アルミニウムドープ酸化亜鉛)、GZO(ガリウムドープ酸化亜鉛)、また各種ステンレス鋼、アルミニウム並びにジュラルミン等のアルミニウム合金、鉄並びに鉄合金、銅並びに真鍮、燐青銅、白銅及びベリリウム銅等の銅合金、ニッケル並びにニッケル合金、そして、銀並びに洋銀等の銀合金などの金属等が挙げられる。
さらに上記非導電性基材上にこれらの導電性基材で薄膜が形成された基材も使用可能である。
また、上記基材は、三次元成形体であってもよい。
これらの塗布方法の中でもバーコート法、フレキソ印刷、グラビア印刷、スピンコート法、スプレーコート法、インクジェット法、ペンリソグラフィー、コンタクトプリンティング、μCP、NIL及びnTPが好ましい。スピンコート法を用いる場合には、単時間で塗布することができるために、揮発性の高い溶液であっても利用でき、また、均一性の高い塗布を行うことができるという利点がある。スプレーコート法を用いる場合には、極少量のワニスで均一性の高い塗布を行うことができ、工業的に非常に有利となる。インクジェット法、ペンリソグラフィー、コンタクトプリンティング、μCP、NIL、nTPを用いる場合には、例えば配線などの微細パターンを効率的に形成(描画)することができ、工業的に非常に有利となる。
またここで用いられる溶媒としては、上記(A)成分であるポリマーと(B)金属微粒子(好ましくはこれらよりなる複合体)、及び所望により(D)成分、(E)成分及びその他成分を溶解又は分散するものであれば特に限定されないが、たとえば、水;ベンゼン、トルエン、キシレン、エチルベンゼン、クロロベンゼン、ジクロロベンゼン等の芳香族炭化水素類;メタノール、エタノール、n-プロパノール、イソプロパノール、n-ブタノール、2-ブタノール、n-ヘキサノール、n-オクタノール、2-オクタノール、2-エチルヘキサノール等のアルコール類;メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、フェニルセロソルブ等のセロソルブ類;プロピレングリコールモノメチルエーテル(PGME)、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、トリエチレングリコールモノメチルエーテル、トリプロピレングリコールモノメチルエーテル、エチレングリコールジメチルエーテル、プロピレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールブチルメチルエーテル、ジエチレングリコールイソプロピルメチルエーテル、ジプロピレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、トリプロピレングリコールジメチルエーテル等のグリコールエーテル類;エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート(PGMEA)等のグリコールエステル類;テトラヒドロフラン(THF)、メチルテトラヒドロフラン、1,4-ジオキサン、ジエチルエーテル等のエーテル類;酢酸エチル、酢酸ブチル等のエステル類;アセトン、メチルエチルケトン(MEK)、メチルイソブチルケトン(MIBK)、シクロペンタノン、シクロヘキサノン等のケトン類;n-ヘプタン、n-ヘキサン、シクロヘキサン等の脂肪族炭化水素類;1,2-ジクロロエタン、クロロホルム等のハロゲン化脂肪族炭化水素類;N-メチル-2-ピロリドン(NMP)、N,N-ジメチルホルムアミド(DMF)、N,N-ジメチルアセトアミド等のアミド類;ジメチルスルホキシドなどが使用できる。これら溶媒は単独で使用してもよく、2種類以上の溶媒を混合してもよい。さらに、ワニスの粘度を調整する目的で、エチレングリコール、プロピレングリコール、ブチレングリコール等のグリコール類を添加してもよい。
また上記溶媒に溶解又は分散させる濃度は任意であるが、ワニス中の非溶媒成分の濃度[下地剤に含まれる溶媒を除く全成分((A)成分であるポリマーと(B)金属微粒子(好ましくはこれらよりなる複合体)、所望により(D)ベースポリマー、(E)架橋剤及びその他成分等)の濃度]は0.05~90質量%であり、好ましくは0.1~80質量%である。
上記のようにして得られた基材上に形成された無電解金属めっきの下地層を無電解めっきすることにより、該下地層の上に金属めっき膜が形成される。こうして得られる金属めっき膜、並びに、基材上に無電解金属めっきの下地層、金属めっき膜の順にて具備する金属被膜基材も本発明の対象である。
無電解めっき処理(工程)は特に限定されず、一般的に知られている何れの無電解めっき処理にて行うことができ、例えば、従来一般に知られている無電解めっき液を用い、該めっき液(浴)に基材上に形成された無電解金属めっきの下地層を浸漬する方法が一般的である。
ここで無電解めっきにより形成される金属めっき膜に用いられる金属としては、鉄、コバルト、ニッケル、銅、パラジウム、銀、スズ、白金、金及びそれらの合金が挙げられ、目的に応じて適宜選択される。
また上記錯化剤、還元剤についても金属イオンに応じて適宜選択すればよい。
[数平均分子量及び重量平均分子量の測定]
以下の合成例に従い得られた共重合体の数平均分子量及び重量平均分子量を、東ソー(株)製GPC装置(ShodexカラムKD800およびTOSOHカラムTSK-GEL)を用い、溶出溶媒N,N-ジメチルホルムアミド(添加剤として、臭化リチウム-水和物(LiBr・H2O)を10mmol/L(リットル)混合)を流量1mL/分でカラム中に(カラム温度40℃)流して溶離させるという条件で測定した。なお、下記の数平均分子量(以下、Mnと称す。)及び重量平均分子量(以下、Mwと称す。)は、ポリスチレン換算値にて表される。
MMA:メチルメタクリレート
HEA:2-ヒドロキシエチルアクリレート
NVA:N-ビニルアセトアミド
GMA:グリシジルメタクリレート
サイクロマーM100:3,4-エポキシシクロヘキシルメチルメタアクリレート(ダイセル製)
AMBN:2,2’-アゾビス-2-メチルブチロニトリル
PGME:プロピレングリコールモノメチルエーテル
IPE:ジイソプロピルエーテル
DAA:ジアセトンアルコール
BL-10:ポリビニルアセタール樹脂(積水化学工業社製)
スチレン 2.00g、NVA 1.63g、GMA 2.73g、AMBN 0.32gをPGME 15.59gに溶解し、80℃にて20時間反応させることにより得られた共重合体溶液(固形分濃度30質量%)をジエチルエーテル500mLに撹拌しながら投入し、ポリマーを析出させた。析出したポリマーを減圧ろ過し、50℃で真空乾燥して、共重合体粉末を得た(P1)。得られた共重合体のMnは6,057、Mwは8,884であった。
スチレン 2.00g、NVA 1.63g、サイクロマーM100 3.76g、AMBN 0.37gをPGME 18.14gに溶解し、80℃にて20時間反応させることにより得られた共重合体溶液(固形分濃度30質量%)をジエチルエーテル500mLに撹拌しながら投入し、ポリマーを析出させた。析出したポリマーを減圧ろ過し、50℃で真空乾燥して、共重合体粉末を得た(P2)。得られた共重合体のMnは5,336、Mwは8,669であった。
スチレン 2.00g、NVA 1.63g、HEA 2.23g、AMBN 0.29gをPGME 14.37gに溶解し、80℃にて20時間反応させることにより得られた重合体溶液(固形分濃度30質量%)をジエチルエーテル500mlに再沈精製した。析出したポリマーを減圧ろ過し、50℃で真空乾燥して、重合体粉末を得た(P3)。得られた重合体のMnは6,806、Mwは11,797であった。
MMA 2.00g、HEMA 1.11g、AMBN 0.16gをPGME 7.63gに溶解し、80℃にて20時間反応させることにより得られた共重合体溶液(固形分濃度30質量%)をジエチルエーテル500mLに撹拌しながら投入し、ポリマーを析出させた。析出したポリマーを減圧ろ過し、50℃で真空乾燥して、共重合体粉末を得た(P4)。得られた共重合体のMnは13,186、Mwは24,452であった。
冷却器を設置した100mLの反応フラスコに、酢酸パラジウム[和光純薬(株)製] 0.90g及びクロロホルム 9.10gを仕込み、均一になるまで撹拌した。この溶液へ、合成例1で重合したP1 l.0gをクロロホルム 16.40g、エタノール 6.40gに溶解させた溶液を、滴下ロートを使用して加えた。この混合物を、窒素雰囲気下60℃で8時間撹拌した。
液温30℃まで冷却後、この溶液をIPE/ヘキサン溶液(質量比10:1) 341gに撹拌しながら投入し、ポリマー/Pd粒子複合体を析出させた。析出したポリマー/Pd粒子複合体を減圧ろ過し、50℃で真空乾燥して、Pd粒子の複合体(M1) 0.9gを黒色粉末として得た。
冷却器を設置した100mLの反応フラスコに、酢酸パラジウム[和光純薬(株)製] 0.90g及びクロロホルム 9.10gを仕込み、均一になるまで撹拌した。この溶液へ、合成例2で重合したP2 l.0gをクロロホルム 16.40g、エタノール 6.40gに溶解させた溶液を、滴下ロートを使用して加えた。この混合物を、窒素雰囲気下60℃で8時間撹拌した。
液温30℃まで冷却後、この溶液をIPE/ヘキサン溶液(質量比10:1) 341gに撹拌しながら投入し、ポリマー/Pd粒子複合体を析出させた。析出したポリマー/Pd粒子複合体を減圧ろ過し、50℃で真空乾燥して、Pd粒子の複合体(M2) 0.9gを黒色粉末として得た。
冷却器を設置した100mLの反応フラスコに、酢酸パラジウム[和光純薬(株)製] 0.90g及びクロロホルム 9.10gを仕込み、均一になるまで撹拌した。この溶液へ、合成例3で重合したP3 l.0gをクロロホルム 16.40g、エタノール 6.40gに溶解させた溶液を、滴下ロートを使用して加えた。この混合物を、窒素雰囲気下60℃で8時間撹拌した。
液温30℃まで冷却後、この溶液をIPE/ヘキサン溶液(質量比10:1) 341gに撹拌しながら投入し、ポリマー/Pd粒子複合体を析出させた。析出したポリマー/Pd粒子複合体を減圧ろ過し、50℃で真空乾燥して、Pd粒子の複合体(M3) 0.9gを黒色粉末として得た。
<調製例1>
300mLビーカーにトップニコロンSA-98-MLF(奥野製薬製) 20mL、トップニコロンSA-98-1LF(奥野製薬製) 11mLを仕込み、さらに純水を加えて溶液の総量を200mLとした。この溶液を撹拌し、無電解ニッケルめっき液とした。
得られたPd粒子の複合体を表1の通りに仕込み、1時間撹拌後、静置して溶液の状態を目視で評価した。評価結果は、後に表2にまとめて示す。
○:均一な溶液が得られた。
×:沈殿物が見られ、均一な溶液が得られていない。
LCP(千代田インテグレ株式会社製ペリキュール(登録商標)LCP)基材に対しUVオゾン洗浄装置(株式会社テクノビジョン製UV-208)を用いて30秒間表面処理を行った。表面処理したLCP上に無電解めっき下地剤を膜厚6μmでバーコート塗布した後、80℃で5分間加熱することにより塗膜を形成した。この塗膜をさらに200℃で10分間加熱することにより硬化させた。得られた硬化膜を調製例1で調製した無電解ニッケルめっき液に2分間浸漬した。その後、得られためっき基材を水洗した後、金属めっき膜の状態を目視で評価した。評価結果は、後に表2にまとめて示す。
○:塗膜全面に均一にめっきが析出している。
-:均一な溶液が得られないため未実施
上記で得られためっき基材上の金属めっき膜部分に、縦横1mm間隔で10×10マスとなるようカッターナイフで切込みをつけた。この切り込みの上にニチバン(株)製 セロテープ(登録商標)を貼り、強く擦りつけてしっかり密着させた後、密着させた粘着テープを一気に剥がし、金属めっき膜の状態を以下の基準に従って目視で評価した。評価結果は、後に表2にまとめて示す。
○:100マス全て剥がれずに残っている。
×:1マスでも剥がれている。
-:均一な溶液が得られないため未実施。
Claims (17)
- 基材上に無電解めっき処理により金属めっき膜を形成するための無電解めっき下地剤であって、
(A)分子内に金属分散性基及び1個のラジカル重合性二重結合を有するモノマーaに由来する構成単位と、分子内に架橋性基及び1個のラジカル重合性二重結合を有するモノマーbに由来する構成単位を含む共重合体、
(B)金属微粒子、及び
(C)溶剤
を含む下地剤。 - 前記(A)共重合体中の金属分散性基に、前記(B)金属微粒子が付着又は配位した複合体を含む、請求項1に記載の下地剤。
- 前記モノマーaが、ビニル基及び(メタ)アクリロイル基の何れか一方を有する化合物である、請求項1又は請求項2に記載の下地剤。
- 前記モノマーaが、下式(1)又は(2)で表される化合物である請求項3に記載の下地剤。
式(2)中、R3は水素原子またはメチル基を表し、
R4は水素原子又は炭素原子数1乃至10の分岐しても良いアルキル基、炭素原子数1乃至10の分岐しても良いアルコキシル基又は、炭素原子数1乃至10の分岐しても良いアルコキシルアルキル基を表し、Lは、O又はNを表し、R5は、LがNを表す場合にのみ存在し、水素原子を表すか、又は、R4及びR5は、それらが結合する原子と一緒になって、4乃至6員の環状アミド、又は、4乃至6員の環状イミドを形成してもよい。) - 前記モノマーaがN-ビニルピロリドン、N-ビニルアセトアミド又はN-ビニルホルムアミドである請求項4に記載の下地剤。
- 前記モノマーbが、ビニル基及び(メタ)アクリロイル基の何れか一方を有する化合物である、請求項1又は請求項2に記載の下地剤。
- 前記(A)共重合体を与えるモノマーは、前記モノマーaのモル数に対して5~500%のモル数となる量の前記モノマーbを含む、請求項1乃至請求項7のうちいずれか一項に記載の下地剤。
- 前記(B)金属微粒子が、鉄(Fe)、コバルト(Co)、ニッケル(Ni)、銅(Cu)、パラジウム(Pd)、銀(Ag)、スズ(Sn)、白金(Pt)及び金(Au)からなる群より選択される少なくとも一種の金属の微粒子である、請求項1乃至請求項8のうちいずれか一項に記載の下地剤。
- 前記(B)金属微粒子が、パラジウム微粒子である、請求項9に記載の下地剤。
- 前記(B)金属微粒子が、1~100nmの一次粒子平均粒径を有する微粒子である、請求項1乃至請求項10のうちいずれか一項に記載の下地剤。
- さらに、(D)非ラジカル重合性架橋性基を有するベース樹脂を含有する請求項1乃至請求項11の何れか一項に記載の下地剤。
- さらに、(E)架橋剤を含有する請求項1乃至請求項12の何れか一項に記載の下地剤。
- 請求項1乃至請求項13のうち何れか一項に記載の無電解めっき下地剤を用いて得られる、無電解金属めっきの下地層。
- 請求項14に記載の無電解金属めっきの下地層の上に形成された金属めっき膜。
- 基材と、該基材上に形成された請求項14に記載の無電解金属めっきの下地層と、該無電解金属めっきの下地層の上に形成された金属めっき膜とを具備する、金属被膜基材。
- 下記(1)工程及び(2)工程を含む、金属被膜基材の製造方法。
(1)工程:請求項1乃至請求項13のうち何れか一項に記載の無電解めっき下地剤を基材上に塗布し、無電解金属めっきの下地層を該基材の上に具備する工程、
(2)工程:該下地層を具備した基材を無電解めっき浴に浸漬し、金属めっき膜を該下地層の上に形成する工程。
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