Particle dispersion, production method therefor, particle-containing plating solution, particle-containing plating film, and particle-containing plating method

Abstract

The present invention provides a particle dispersion and a particle-containing plating solution which have excellent particle dispersibility.　The present invention provides a particle dispersion comprising: particles; and a nonionic surfactant A represented by general formula (1) (in the formula, R1-1 and R1-2 are the same as or different from each other and represent oxyalkylene groups, and R1-3 and R1-4 are the same as or different from each other and represent C1-C10 hydrocarbon groups. m and n are the same as or different from each other and represent integers, and m+n=0-30).

Description

Particle dispersion and its manufacturing method, particle-containing plating solution, particle-containing plating film, and particle-containing plating method

[0001] The present invention relates to a particle dispersion and a method for producing the same, a particle-containing plating solution, a particle-containing plating film, and a particle-containing plating method.

[0002] In recent years, plating films have been used to impart various properties to them by incorporating various particles into the plating films.

[0003] For example, electroless nickel-phosphorus / polytetrafluoroethylene (Ni-P / PTFE) composite plating is a plating film that combines the low friction and non-stickiness of PTFE with the uniform deposition properties of electroless plating, and has begun to be applied in various fields in recent years.

[0004] It is extremely difficult to uniformly disperse highly water-repellent PTFE particles in an electroless plating solution. Conventionally, a method of using a fluorochemical surfactant as a dispersant has been used to uniformly disperse PTFE particles in an electroless plating solution.

[0005] However, in recent years, due to restrictions on the use of fluorine-based materials in Europe, the use of fluorine-based surfactants has gradually become prohibited, and there is a demand for a method for dispersing PTFE particles without using fluorine-based surfactants.

[0006] An electroless composite plating bath containing PTFE fine particles and not using a fluorochemical surfactant has been proposed (see Patent Document 1). In Patent Document 1, an amphoteric surfactant with a specific structure is used as the surfactant for dispersing the PTFE particles (claim 1 of Patent Document 1).

[0007] However, the amphoteric surfactant used in Patent Document 1 is not suitable as a dispersant for fluorine particles, and there is a problem in that the dispersibility is insufficient.

[0008] Furthermore, not only in plating solutions using fluorine-containing particles as described above, but also in plating solutions using fluorine-free particles, the dispersibility of particles affects the properties of the plating solution and the plating film. Therefore, a particle dispersion with excellent particle dispersibility is required, which can produce a particle-containing plating solution with excellent dispersibility.

[0009] Therefore, there is a demand for the development of a particle dispersion liquid with excellent particle dispersibility, and a particle-containing plating solution with excellent particle dispersibility that uses the particle dispersion liquid.

[0010] Japanese Patent Application Laid-Open No. 2004-60050

[0011] An object of the present invention is to provide a particle dispersion and a particle-containing plating solution that have excellent particle dispersibility.

[0012] As a result of extensive research, the present inventors have found that the above-mentioned object can be achieved by a particle dispersion containing particles and a nonionic surfactant A exhibiting a specific structure, and a particle-containing plating solution containing the particle dispersion, and have thus completed the present invention.

[0013] That is, the present invention relates to the following particle dispersion and its manufacturing method, particle-containing plating solution, particle-containing plating film, and particle-containing plating method: 1. Particles, and (In the formula, R １－１ and R １－２ are the same or different and represent an oxyalkylene group; R １－３ and R １－４Item 1. A particle dispersion containing a nonionic surfactant A represented by the following formula: where m and n are the same or different and represent a hydrocarbon group having 1 to 10 carbon atoms. m and n are the same or different and represent an integer, and m+n=0 to 30. 2. The particle dispersion according to item 1, wherein the number of carbon atoms in the oxyalkylene group is 1 to 5. 3. The particle dispersion according to item 1 or 2, wherein the content of the nonionic surfactant A is 1 g / L to 100 g / L. 4. The particle dispersion according to any one of items 1 to 3, wherein the particles are fluorine-containing particles and / or fluorine-free particles. 5. 5. The particle dispersion according to Item 4, wherein the fluorine-containing particles contain at least one selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), perfluoroalkoxyalkane (PFA), perfluoroethylene propene copolymer (FEP), ethylene tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene copolymer (ECTFE), and polytetrafluoroethylene oxide (PTFEO). The fluorine-free particles include polyethylene (PE), polyethersulfone (PES), polyetherimide (PEI), polyarylate (PAR), polyamideimide (PAI), polyphenylene ether (PPE), polylactic acid (PLA), polyamide (PA), ester-based thermoplastic elastomer (TPC), polyurethane (PU), aromatic polyether ketone, silicon carbide (SiC), diamond, boron nitride (BN), aluminum oxide (Al2O3), graphite fluoride, tungsten carbide (WC), molybdenum disulfide (MoS2), boron carbide (B ４Item 4 or 5, containing at least one selected from the group consisting of graphene, graphite, and tetrahydrofuran. 7. The particle dispersion according to any one of items 1 to 6, wherein the particle content is 10 g / L or more and 1000 g / L or less. 8. The particle dispersion according to any one of items 1 to 7, further containing an amphoteric surfactant. 9. The particle dispersion according to item 8, wherein the content of the amphoteric surfactant is 1 g / L or more and 100 g / L or less. 10. The particle dispersion according to any one of items 1 to 9, further containing a cationic surfactant. 11. The particle dispersion according to item 10, wherein the content of the cationic surfactant is 1 g / L or more and 100 g / L or less. 12. The particle dispersion according to item 10, further containing a compound represented by the following general formula (4): (In the formula, R ４－１ represents a hydrocarbon group having 5 to 30 carbon atoms. ４－２ and R ４－３ Item 13. The particle dispersion according to any one of items 1 to 11, containing a nonionic surfactant B represented by the following general formula (1): (In the formula, R １－１ and R １－２ are the same or different and represent an oxyalkylene group; R １－３ and R １－４are the same or different and represent a hydrocarbon group having 1 to 10 carbon atoms. m and n are the same or different and represent an integer, and m+n=0 to 30. 15. A particle-containing plating solution comprising the particle dispersion according to any one of items 1 to 14 and a plating solution. 16. The particle-containing plating solution according to item 15, which is an electroless particle-containing nickel-phosphorus plating solution or an electrolytic particle-containing nickel plating solution. 17. The particle-containing plating solution according to item 15 or 16, which has a content of the particle dispersion of 1 ml / L to 100 ml / L. 18. A particle-containing plating film formed using the particle-containing plating solution according to any one of items 15 to 17. 19. A particle-containing plating method comprising the step of immersing an object to be plated in the particle-containing plating solution according to any one of items 15 to 17.

[0014] The particle dispersion of the present invention has excellent particle dispersibility. Also, the particle-containing plating solution of the present invention contains the particle dispersion and has excellent particle dispersibility. Furthermore, according to the method for producing the particle dispersion of the present invention, the particle dispersion of the present invention can be easily produced.

[0015] 1. Particle Dispersion The particle dispersion of the present invention is a particle dispersion containing particles and a nonionic surfactant A represented by general formula (1) described below. The particle dispersion of the present invention having the above characteristics contains the nonionic surfactant A represented by general formula (1), so that the particles can be uniformly dispersed in the particle dispersion, and in particular, fluorine-containing particles with strong water repellency can be uniformly dispersed in the particle dispersion. The particle dispersion of the present invention will be described in detail below.

[0016] In addition, in this specification, "room temperature" means 23°C.

[0017] (Particles) The particles are not particularly limited, and known particles can be used. Such particles include fluorine-containing particles and fluorine-free particles. These particles may be used alone or in combination of two or more types.

[0018] As the fluorine-containing particle, there is no particular limitation as long as it is the fluorine-containing particle that contains fluorine, and known fluorine-containing particle can be used.As such fluorine-containing particle, the fluorine-containing particle that contains fluorine resin such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), perfluoroalkoxyalkane (PFA), perfluoroethylene propene copolymer (FEP), ethylene tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene copolymer (ECTFE), polytetrafluoroethylene oxide (PTFEO) etc.; the fluorine-containing particle that contains metal fluoride etc.Among these, the fluorine-containing particle that contains polytetrafluoroethylene (PTFE) is preferred, because the dispersibility of fluorine-containing particle in particle dispersion liquid is further improved, and the surface potential of particle can be well controlled.

[0019] The above fluorine-containing particles may be used alone or in combination of two or more kinds.

[0020] The average particle size of the fluorine-containing particles is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and particularly preferably 0.15 μm or more. The average particle size of the fluorine-containing particles is preferably 100 μm or less, more preferably 10 μm or less, even more preferably 5 μm or less, and particularly preferably 1 μm or less. When the average particle size of the fluorine-containing particles is within the above range, the fluorine-containing particles can be more dispersed in the particle dispersion liquid, and the surface potential of the fluorine-containing particles can be more suitably controlled.

[0021] The content of the fluorine-containing particles in the particle dispersion is preferably 10 g / L or more, more preferably 60 g / L or more, even more preferably 70 g / L or more, and particularly preferably 80 g / L or more. The content of the fluorine-containing particles in the particle dispersion is preferably 1000 g / L or less, more preferably 800 g / L or less, even more preferably 750 g / L or less, and particularly preferably 600 g / L or less.

[0022] As the fluorine-free particles, known particles other than fluorine-containing particles can be used, including particles of synthetic resin, ceramic, glass, talc, plastic, diamond, graphite, oxide, silicide, carbonate, carbide, sulfide, phosphate ester, boride, silicate, nitride, metal, etc.

[0023] Among the fluorine-free particles, more specific examples of synthetic resin particles include particles of polyethylene (PE), polyethersulfone (PES), polyetherimide (PEI), polyarylate (PAR), polyamideimide (PAI), polyphenylene ether (PPE), polylactic acid (PLA), polyamide (PA), ester-based thermoplastic elastomer (TPC), polyurethane (PU), and aromatic polyetherketone. Examples of the aromatic polyetherketone include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetheretherketoneketone (PEEKK).

[0024] Among the above-mentioned fluorine-free particles, particles other than synthetic resins include, more specifically, silicon carbide (SiC), diamond, boron nitride (BN), aluminum oxide (Al2O3), graphite fluoride, tungsten carbide (WC), molybdenum disulfide (MoS2), boron carbide (B ４ C), graphene, graphite, etc.

[0025] The fluorine-free particles may be used alone or in combination of two or more.

[0026] The content of fluorine-free particles in the particle dispersion is preferably 10 g / L or more, more preferably 60 g / L or more, even more preferably 70 g / L or more, and particularly preferably 80 g / L or more. The content of fluorine-free particles in the particle dispersion is preferably 1000 g / L or less, more preferably 800 g / L or less, even more preferably 750 g / L or less, and particularly preferably 600 g / L or less.

[0027] The average particle size of the fluorine-free particles in the particle dispersion is preferably 1 nm or more, more preferably 100 nm or more, even more preferably 1 μm or more, and particularly preferably 5 μm or more. The average particle size of the fluorine-free particles in the particle dispersion is preferably 200 μm or less, more preferably 100 μm or less, even more preferably 50 μm or less, and particularly preferably 30 μm or less. When the average particle size of the fluorine-free particles is within the above range, the particles can be more dispersed in the particle dispersion and the surface potential of the particles can be more suitably controlled.

[0028] The particle content in the particle dispersion is preferably 10 g / L or more, more preferably 60 g / L or more, even more preferably 70 g / L or more, and particularly preferably 80 g / L or more, and is preferably 1500 g / L or less, more preferably 1000 g / L or less, even more preferably 800 g / L or less, and particularly preferably 600 g / L or less.

[0029] (Nonionic Surfactant A) As the nonionic surfactant A (hereinafter also referred to as "component (A)"), a nonionic surfactant represented by the following general formula (1) is used.

[0030]

[0031] In the above general formula (1), R １－１ and R １－２ are the same or different and represent an oxyalkylene group. The number of carbon atoms in the oxyalkylene group is preferably 1 or more, more preferably 2 or more. The number of carbon atoms in the oxyalkylene group is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. When the number of carbon atoms in the oxyalkylene group is within the above range, the dispersibility of the particles is further improved.

[0032] In the general formula (1), m and n are the same or different and represent an integer. m and n are preferably 0 or greater, more preferably 2 or greater. m and n are preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 5 or less. When m and n are within the above ranges, the dispersibility of the particles is further improved.

[0033] In the above general formula (1), m+n is 0 to 30. If m+n exceeds 30, the dispersibility of the particles will be poor. m+n is preferably 20 or less, and more preferably 10 or less.

[0034] In the above general formula (1), R １－３ and R １－４ R may be the same or different and represent a hydrocarbon group having 1 to 10 carbon atoms. If the number of carbon atoms is less than 1 or 11 or more, the dispersibility of the particles will be poor. １－３ and R １－４ The number of carbon atoms in R may be the same or different and is preferably 2 or more. １－３ and R １－４ The number of carbon atoms in R may be the same or different and is preferably 5 or less, more preferably 4 or less. １－３ and R １－４ is preferably an alkyl group.

[0035] The component (A) is preferably a nonionic surfactant represented by the following general formula (1-2).

[0036]

[0037] In the general formula (1-2), m, n, and m+n are the same as those explained in the general formula (1).

[0038] More specific examples of the component (A) include polyoxyethylene (C0) acetylenic glycol ether, polyoxyethylene (C1.3) acetylenic glycol ether (a mixture of a compound where m+n=2 and a compound where m+n=0 in a mixing ratio of 65%:35%), polyoxyethylene (C4) acetylenic glycol ether, polyoxyethylene (C6) acetylenic glycol ether, polyoxyethylene (C10) acetylenic glycol ether, and polyoxyethylene (C20) acetylenic glycol ether.

[0039] The component (A) may be used alone or in combination of two or more.

[0040] The content of component (A) in the particle dispersion is preferably 1 g / L or more, more preferably 5 g / L or more, even more preferably 10 g / L or more, and particularly preferably 15 g / L or more. The content of component (A) in the particle dispersion is preferably 100 g / L or less, more preferably 80 g / L or less, even more preferably 60 g / L or less, and particularly preferably 50 g / L or less. By setting the lower limit of the content of component (A) within the above range, the dispersibility of the particles is further improved. By setting the upper limit of the content of component (A) within the above range, the dispersibility of the particles in a nickel plating solution such as a nickel-phosphorus plating solution is further improved.

[0041] (B) Amphoteric Surfactant) The particle dispersion of the present invention may further contain (B) an amphoteric surfactant (hereinafter also referred to as "component (B)"). When the particle dispersion contains component (B), particles can be more uniformly dispersed in a particle-containing plating film formed with the particle-containing plating solution containing the particle dispersion of the present invention.

[0042] The amphoteric surfactant (B) is not particularly limited, and any known amphoteric surfactant can be used. As such an amphoteric surfactant, an amphoteric surfactant represented by the following general formula (2) is preferred:

[0043]

[0044] In the above general formula (2), R ２－１ is preferably a hydrocarbon group, more preferably an alkyl group. ２－１ The number of carbon atoms in R is preferably 5 or more, more preferably 8 or more, and even more preferably 10 or more. ２－１ The number of carbon atoms is preferably 30 or less, more preferably 20 or less, and even more preferably 18 or less.

[0045] In the above general formula (2), R ２－２ , and R ２－３ are the same or different and are preferably hydrocarbon groups having 1 to 10 carbon atoms, more preferably alkyl groups having 1 to 10 carbon atoms. ２－２ , and R ２－３ may be the same or different and each has preferably 5 or less, more preferably 3 or less, and even more preferably 1 carbon atom.

[0046] In the above general formula (2), R ２－４ is preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms. ２－４ The number of carbon atoms is preferably 5 or less, more preferably 3 or less, and even more preferably 1.

[0047] More specific examples of the component (B) include coconut oil dimethylaminoacetic acid betaine, lauryl dimethylaminoacetic acid betaine, stearyl dimethylaminoacetic acid betaine, etc. Among these, coconut oil dimethylaminoacetic acid betaine is preferred in that it can disperse particles more uniformly in a particle-containing plating film formed with a particle-containing plating solution containing the particle dispersion of the present invention.

[0048] The component (B) may be used alone or in combination of two or more.

[0049] The content of component (B) in the particle dispersion is preferably 1 g / L or more, more preferably 2 g / L or more, even more preferably 5 g / L or more, and particularly preferably 7 g / L or more. The content of component (B) in the particle dispersion is preferably 100 g / L or less, more preferably 80 g / L or less, even more preferably 70 g / L or less, and particularly preferably 60 g / L or less. When the lower limit of the content of component (B) is within the above range, the particle-containing plating solution containing the particle dispersion of the present invention can more easily form a particle-containing plating film. When the upper limit of the content of component (B) is within the above range, the particles can be more uniformly dispersed in the particle-containing plating film formed by the particle-containing plating solution containing the particle dispersion of the present invention.

[0050] (C) Cationic Surfactant The particle dispersion of the present invention may further contain (C) a cationic surfactant (hereinafter also referred to as "component (C)"). When the particle dispersion contains component (C), the particle-containing plating solution containing the particle dispersion of the present invention can more easily form a particle-containing plating film.

[0051] The cationic surfactant (C) is not particularly limited, and known cationic surfactants can be used. As such cationic surfactants, cationic surfactants represented by the following general formulas (3-1) and (3-2) are preferred.

[0052]

[0053]

[0054] In the above general formula (3-1), R ３－１－１ is preferably a hydrocarbon group, more preferably an alkyl group. ３－１－１ The number of carbon atoms in R is preferably 5 or more, more preferably 8 or more, and even more preferably 10 or more. ３－１－１ The number of carbon atoms is preferably 30 or less, more preferably 20 or less, and even more preferably 18 or less.

[0055] In the above general formula (3-1), R ３－１－２ , R ３－１－３ , and R ３－１－４ R may be the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms. ３－１－２ , R ３－１－３ , and R ３－１－４ may be the same or different and each has preferably 7 or less, more preferably 3 or less, and even more preferably 1 carbon atom.

[0056] In the general formula (3-1), X represents a halogen element, a sulfate group, or the like. Examples of the halogen element include chlorine and bromine, with chlorine being preferred. Furthermore, the sulfate group is preferably an alkyl sulfate group, more preferably a methyl sulfate group. By using the above-mentioned group for X, the particle-containing plating solution containing the particle dispersion of the present invention can more easily form a particle-containing plating film.

[0057] In the above general formula (3-2), R ３－２－１ is preferably a hydrocarbon group, more preferably an alkyl group. ３－２－１ The number of carbon atoms in R is preferably 5 or more, more preferably 8 or more, and even more preferably 10 or more. ３－２－１ The number of carbon atoms is preferably 30 or less, more preferably 20 or less, and even more preferably 18 or less.

[0058] In the above general formula (3-2), R ３－２－２ , and R ３－２－３ R may be the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms. ３－２－２ , and R ３－２－３ The number of carbon atoms in R may be the same or different and is preferably 1 or more and 5 or less, and more preferably 1 or more and 3 or less. ３－２－２ , and R ３－２－３ may have a hydroxyl group at the end.

[0059] In the general formula (3-2), X represents a halogen element, a sulfate group, or the like. Examples of the halogen element include chlorine and bromine, with chlorine being preferred. Furthermore, the sulfate group is preferably an alkyl sulfate group, more preferably a methyl sulfate group. By using the above-mentioned group for X, the particle-containing plating solution containing the particle dispersion of the present invention can more easily form a particle-containing plating film.

[0060] More specific examples of the component (C) include hexadecyltrimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, coconut alkyltrimethylammonium chloride, methylhexadecyltrimethylammonium sulfate, didecyldimethylammonium chloride, dilauryldimethylammonium chloride, distearyldimethylammonium chloride, dioleyldimethylammonium chloride, dihydrogenated tallow alkyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, benzalkonium chloride, methyldidecyldimethylammonium sulfate, 1-methyl-1-hydroxyethyl-2-tallow alkyl-imidazonium chloride, etc. Among these, hexadecyltrimethylammonium chloride is preferred in that a particle-containing plating solution containing the particle dispersion of the present invention more easily forms a particle-containing plating film.

[0061] The component (C) may be used either individually or in combination of two or more.

[0062] The content of component (C) in the particle dispersion is preferably 1 g / L or more, more preferably 2 g / L or more, even more preferably 5 g / L or more, and particularly preferably 10 g / L or more. The content of component (C) in the particle dispersion is preferably 100 g / L or less, more preferably 80 g / L or less, even more preferably 70 g / L or less, and particularly preferably 60 g / L or less. When the lower limit of the content of component (C) is within the above range, the particle-containing plating solution containing the particle dispersion of the present invention can more easily form a particle-containing plating film. When the upper limit of the content of component (C) is within the above range, the dispersibility of the particles is further improved.

[0063] (D) Nonionic Surfactant B) The particle dispersion of the present invention may further contain a nonionic surfactant B (hereinafter also referred to as "component (D)"). When the particle dispersion contains component (D), particles can be more uniformly dispersed in a particle-containing plating film formed with the particle-containing plating solution containing the particle dispersion of the present invention.

[0064] The nonionic surfactant (D) B is not particularly limited as long as it is a surfactant other than the above-mentioned nonionic surfactant A, and any known nonionic surfactant can be used. As such a nonionic surfactant, a nonionic surfactant represented by the following general formula (4) is preferred.

[0065]

[0066] In the above general formula (4), R ４－１ is preferably a hydrocarbon group, more preferably an alkyl group. ４－１ The number of carbon atoms in R is preferably 5 or more, more preferably 8 or more, and even more preferably 10 or more. ４－１ The number of carbon atoms is preferably 30 or less, more preferably 20 or less, and even more preferably 18 or less.

[0067] In the above general formula (4), R ４－２ , and R ４－３are the same or different and represent an oxyalkylene group. The number of carbon atoms in the oxyalkylene group is preferably 1 or more, more preferably 2 or more. The number of carbon atoms in the oxyalkylene group is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. When the number of carbon atoms in the oxyalkylene group is within the above range, particles can be more uniformly dispersed in the particle-containing plating film formed with the particle-containing plating solution containing the particle dispersion of the present invention.

[0068] In the general formula (4), p and q are the same or different and represent an integer. p and q are preferably 0 or greater, more preferably 2 or greater. Furthermore, p and q are preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 5 or less. When p and q are within the above ranges, particles can be more uniformly dispersed in the particle-containing plating film formed with the particle-containing plating solution containing the particle dispersion of the present invention.

[0069] In the general formula (4), p+q is preferably 0 or greater. Furthermore, p+q is preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less. Since p and q are integers, p+q is also an integer.

[0070] More specific examples of the component (D) include polyoxyethylene stearylamine, polyoxyethylene laurylamine, polyoxyethylene oleylamine, polyoxyethylene alkyl (coconut)amine, polyoxyethylene tallow alkylamine, etc. Among these, polyoxyethylene stearylamine is preferred in that it can disperse particles more uniformly in the particle-containing plating film formed with the particle-containing plating solution containing the particle dispersion of the present invention.

[0071] The component (D) may be used alone or in combination of two or more.

[0072] The content of component (D) in the particle dispersion is preferably 0.1 g / L or more, more preferably 5 g / L or more, and even more preferably 10 g / L or more. The content of component (D) in the particle dispersion is preferably 100 g / L or less, more preferably 70 g / L or less, even more preferably 50 g / L or less, and particularly preferably 40 g / L or less. When the lower limit of the content of component (D) is within the above range, the particle-containing plating solution containing the particle dispersion of the present invention can more easily form a particle-containing plating film. When the upper limit of the content of component (D) is within the above range, the particles can be more uniformly dispersed in the particle-containing plating film formed by the particle-containing plating solution containing the particle dispersion of the present invention.

[0073] (Other Components) The particle dispersion of the present invention may contain an acid or a salt thereof that is used as a component of a plating solution other than the above components (A) to (D). Suitable examples of such acids or salts thereof include complexing agents such as malic acid and succinic acid, or salts thereof (e.g., sodium salt, potassium salt, ammonium salt, etc.); hypophosphorous acid or salts thereof (e.g., sodium salt, potassium salt, ammonium salt, etc.); sulfuric acid, phosphorous acid, or salts thereof (e.g., sodium salt, potassium salt, ammonium salt, etc.).

[0074] The above acids or salts thereof may be used alone or in combination of two or more.

[0075] The content of the acid or salt thereof in the particle dispersion is preferably 1 g / L or more, more preferably 10 g / L or more, even more preferably 30 g / L or more, and particularly preferably 50 g / L or more. The lower limit of the content within the above range further improves the dispersibility of the particle dispersion of the present invention. Furthermore, the content of the acid or salt thereof in the particle dispersion is preferably 500 g / L or less, more preferably 250 g / L or less, even more preferably 200 g / L or less, and particularly preferably 150 g / L or less.

[0076] (Solvent) The particle dispersion of the present invention preferably has a configuration in which the above-mentioned components are contained in a solvent.

[0077] The solvent is not particularly limited as long as it can contain the above-mentioned components, and examples thereof include water, isopropyl alcohol, etc. Among these, water is preferred from the viewpoint of high safety.

[0078] The particle dispersion of the present invention may contain particles in a solvent and some of the above-mentioned components. That is, the particle dispersion of the present invention may contain the above-mentioned components (A), (B), (C), and (D) by separately adding them to the particle-containing plating solution described below, both in the case where the particle dispersion contains them and in the case where the particle dispersion does not contain them. From the above viewpoint, the particle dispersion of the present invention may be a particle dispersion containing particles and at least one selected from the group consisting of the above-mentioned components (A), (B), (C), and (D).

[0079] (Characteristics of Particle Dispersion Liquid) The particle dispersion liquid of the present invention is preferably neutral or alkaline. The particle dispersion liquid of the present invention preferably has a pH of 5 or more, more preferably 5.5 or more, and even more preferably 6 or more. The pH is preferably 12 or less, and more preferably 10 or less. When the pH of the particle dispersion liquid is in the above range, the dispersibility of the particles is further improved, and the surface potential of the particles can be more effectively controlled.

[0080] 2. Method for Producing Particle Dispersion Liquid The method for producing the particle dispersion liquid of the present invention is not particularly limited, and examples thereof include a method for producing a particle dispersion liquid of the present invention by using a compound represented by the following general formula (1): (In the formula, R １－１ and R １－２ are the same or different and represent an oxyalkylene group; R １－３ and R １－４ are the same or different and represent a hydrocarbon group having 1 to 10 carbon atoms. m and n are the same or different and represent an integer, and m+n=0 to 30.) The nonionic surfactant A can be produced by a production method including a step of dispersing particles in a solvent containing the nonionic surfactant A represented by the formula:

[0081] The nonionic surfactant A represented by the above general formula (1) is the same as the nonionic surfactant A explained in the particle dispersion liquid of the present invention.

[0082] In the above step, particles are dispersed in a solvent containing the nonionic surfactant A. The particles are the same as those described above in the particle dispersion of the present invention.

[0083] In the above step, the method for dispersing the particles in the solvent containing the nonionic surfactant A is not particularly limited, and the particles can be dispersed by a conventionally known method, for example, a method in which the particles are added to the solvent containing the nonionic surfactant A while stirring it with a stirrer such as a homogenizer.

[0084] In the above step, the temperature of the solvent containing the nonionic surfactant A is not particularly limited. It is generally in the range of 20° C. or higher and 40° C. or lower, and from the viewpoint of further improving the dispersibility of the particles, it is preferably 25° C. or higher and 30° C. or lower.

[0085] In the production method of the present invention, particles are dispersed in a solvent containing the nonionic surfactant A represented by the above general formula (1). That is, the nonionic surfactant A is first added to the solvent, and then the particles are added. If the particles are dispersed in the solvent first, the particles aggregate, resulting in poor particle dispersibility.

[0086] The particle dispersion liquid can be produced by the production method described above.

[0087] 3. Particle-Containing Plating Solution The particle-containing plating solution of the present invention is a particle-containing plating solution containing a particle dispersion and a plating solution.

[0088] The particle-containing plating solution of the present invention may be used for either electroless plating or electrolytic plating. That is, the particle-containing plating solution of the present invention can be used as an electroless particle-containing plating solution or an electrolytic particle-containing plating solution.

[0089] The component (A), the component (B), the component (C), and the component (D) described above in connection with the particle dispersion of the present invention may be separately added to the particle-containing plating solution, both in the case where the particle dispersion contains the component (A), the component (B), the component (C), and the component (D), and the particle dispersion may contain the component (D).

[0090] The particle dispersion is the particle dispersion of the present invention described above, and the blending, production method, etc. are the same as those of the particle dispersion of the present invention described above.

[0091] The content of the particle dispersion in the particle-containing plating solution is preferably 1 ml / L or more, more preferably 5 ml / L or more, and even more preferably 10 ml / L or more. The content of the particle dispersion in the particle-containing plating solution is preferably 100 ml / L or less, more preferably 90 ml / L or less, and even more preferably 80 ml / L or less. By setting the lower limit of the particle dispersion content within the above range, the particles can be more uniformly dispersed in the particle-containing plating film. By setting the upper limit of the particle dispersion content within the above range, the particle-containing plating film can be more easily formed.

[0092] The plating solution contained in the particle-containing plating solution of the present invention is not particularly limited, and a known plating solution can be used. Examples of such plating solutions include electroless plating solutions and electrolytic plating solutions. When an electroless plating solution is used as the plating solution contained in the particle-containing plating solution of the present invention, the particle-containing plating solution of the present invention becomes an electroless particle-containing plating solution. Furthermore, when an electrolytic plating solution is used as the plating solution contained in the particle-containing plating solution of the present invention, the particle-containing plating solution of the present invention becomes an electrolytic particle-containing plating solution.

[0093] The electrolytic plating solution is not particularly limited, and examples thereof include electrolytic nickel plating solutions such as electrolytic nickel-phosphorus plating solutions and electrolytic nickel-boron plating solutions; electrolytic copper plating solutions; electrolytic gold plating solutions; and electrolytic silver plating solutions. Among these, electrolytic nickel plating solutions are preferably used. That is, the particle-containing plating solution of the present invention is preferably an electrolytic particle-containing nickel plating solution.

[0094] The electroless plating solution is not particularly limited, and examples thereof include electroless nickel plating solutions such as electroless nickel-phosphorus plating solutions and electroless nickel-boron plating solutions; electroless copper plating solutions; electroless gold plating solutions; and electroless silver plating solutions. Among these, electroless nickel plating solutions such as electroless nickel-phosphorus plating solutions and electroless nickel-boron plating solutions are preferably used, and electroless nickel-phosphorus plating solutions are more preferably used. That is, the particle-containing plating solution of the present invention is preferably an electroless particle-containing nickel plating solution, and more preferably an electroless particle-containing nickel-phosphorus plating solution.

[0095] Hereinafter, each component contained in the electroless nickel-phosphorus (Ni-P) plating solution will be described as an example.

[0096] (Water-soluble nickel compound) The electroless Ni-P plating solution preferably contains a water-soluble nickel compound.

[0097] The water-soluble nickel compound is not particularly limited, and any known nickel compound used in electroless Ni-P plating baths can be used. Preferred examples of the water-soluble nickel compound include water-soluble nickel inorganic salts such as nickel sulfate, nickel chloride, nickel hypophosphite, and nickel carbonate; water-soluble nickel organic salts such as nickel acetate and nickel malate; and hydrates thereof.

[0098] The water-soluble nickel compounds may be used alone or in combination of two or more.

[0099] The concentration of the water-soluble nickel compound in the electroless Ni-P plating solution is not particularly limited and can be adjusted appropriately. The concentration of the water-soluble nickel compound, in terms of nickel metal, is preferably, for example, 0.01 g / L or more, more preferably 0.5 g / L or more, and even more preferably 1 g / L or more. The concentration of the water-soluble nickel compound, in terms of nickel metal, is preferably, for example, 100 g / L or less, more preferably 50 g / L or less, and even more preferably 10 g / L or less. If the concentration of the water-soluble nickel compound, in terms of nickel metal, is less than 0.01 g / L, the deposition rate may be slow, and if it exceeds 100 g / L, the bath stability may be reduced. Therefore, it is preferable to keep the concentration within the above range.

[0100] (Reducing Agent) The reducing agent is preferably at least one selected from the group consisting of hypophosphorous acid and hypophosphites (for example, sodium salts, potassium salts, ammonium salts, etc.).

[0101] The reducing agent may be used alone or in combination of two or more kinds.

[0102] The concentration of the reducing agent (hypophosphorous acid, hypophosphites, and hydrates thereof, etc.) in the electroless Ni-P plating solution is preferably 15 g / L or more, more preferably 20 g / L or more. The concentration is preferably 80 g / L or less, more preferably 60 g / L or less. If the reducing agent concentration is less than 15 g / L or more than 80 g / L, the adhesion of the electroless Ni-P plating may decrease, so the above range is preferred.

[0103] (Complexing Agent) The electroless Ni-P plating solution preferably contains, as a complexing agent, glycine, gluconate, etc. The gluconate is preferably, for example, a sodium salt, a potassium salt, an ammonium salt, etc.

[0104] Preferred examples of the other complexing agent include monocarboxylic acids such as formic acid and acetic acid, or salts thereof (e.g., sodium salts, potassium salts, ammonium salts, etc.); dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, and fumaric acid, or salts thereof (e.g., sodium salts, potassium salts, ammonium salts, etc.); hydroxycarboxylic acids such as malic acid, lactic acid, glycolic acid, and citric acid, or salts thereof (e.g., sodium salts, potassium salts, ammonium salts, etc.); ethylenediaminediacetic acid, ethylenediaminetetraacetic acid, or salts thereof (e.g., sodium salts, potassium salts, ammonium salts, etc.); and amino acids such as alanine and arginine.

[0105] The complexing agent may be used alone or in combination of two or more.

[0106] The concentration of the complexing agent in the electroless Ni-P plating solution is not particularly limited and can be adjusted as appropriate. The electroless Ni-P plating bath preferably contains 1 g / L or more of the complexing agent, more preferably 2 g / L or more, and even more preferably 5 g / L or more. The electroless Ni-P plating bath preferably contains 100 g / L or less of the complexing agent, more preferably 50 g / L or less, and even more preferably 30 g / L or less. If the concentration of the complexing agent is less than 1 g / L, the bath stability may decrease, and if it exceeds 100 g / L, the deposition rate may decrease. Therefore, the above-mentioned range is preferable.

[0107] (Stabilizer, pH adjuster, surfactant, etc.) In addition to the above-mentioned components, the electroless Ni-P plating solution may contain known additives used in electroless Ni-P plating solutions, such as stabilizers, pH adjusters, surfactants, etc., as needed.

[0108] Examples of stabilizers include lead compounds (e.g., lead nitrate, lead acetate, etc.), cadmium compounds (e.g., cadmium nitrate, cadmium acetate, etc.), thallium compounds (e.g., thallium sulfate, thallium nitrate, etc.), antimony compounds (e.g., antimony chloride, potassium antimonyl tartrate, etc.), tellurium compounds (e.g., telluric acid, tellurium chloride, etc.), chromium compounds (e.g., chromium oxide, chromium sulfate, etc.), iron compounds (e.g., iron sulfate, iron chloride, etc.), manganese compounds (e.g., manganese sulfate, manganese nitrate, etc.), bismuth compounds (e.g., bismuth nitrate, bismuth acetate, etc.), tin compounds (e.g., tin sulfate, tin chloride, etc.), selenium compounds (e.g., selenic acid, selenious acid, etc.), and cyanides (e.g., methyl cyanide, isopropyl cyanide, etc.).

[0109] The stabilizers may be used alone or in combination of two or more.

[0110] The concentration of the stabilizer in the electroless Ni-P plating solution is not particularly limited and can be, for example, about 0.1 mg / L or more and 500 mg / L or less. To improve the stability of the electroless Ni-P plating solution, the stabilizer concentration is preferably about 0.1 mg / L or more. If the stabilizer concentration exceeds 500 mg / L, areas where a plating film is not formed (undeposited areas) may occur, so the above-mentioned range is preferred.

[0111] The pH adjuster is preferably an acid such as hydrochloric acid, sulfuric acid, or phosphoric acid; or an alkali such as sodium hydroxide, potassium hydroxide, or aqueous ammonia.

[0112] The pH of the electroless Ni-P plating solution is preferably 3 or higher, more preferably 4 or higher. The pH of the electroless Ni-P plating solution is preferably 12 or lower, more preferably 9 or lower. The pH of the plating bath can be adjusted using the pH adjuster described above. If the pH is lower than 3, non-precipitation may occur, and if it exceeds 12, bath stability may decrease, so it is preferable to keep the pH within the above range.

[0113] As the surfactant, various surfactants such as nonionic, anionic, cationic, and amphoteric surfactants can be used. Examples include aromatic or aliphatic alkali sulfonate salts, and aromatic or aliphatic alkali metal sulfonate salts. The surfactant can be used alone or in combination of two or more. When two or more surfactants are used in combination, the mixing ratio is not particularly limited and can be determined appropriately.

[0114] The surfactant concentration in the electroless Ni-P plating solution is not particularly limited and can be, for example, about 0.01 mg / L to 1000 mg / L. To further improve the pit prevention effect of the electroless Ni-P plating bath, it is preferable to set the surfactant concentration to about 0.01 mg / L or more. Furthermore, when the surfactant concentration is 1000 mg / L or less, the deterioration of deposition due to foaming is further suppressed.

[0115] 4. Method for Producing Particle-Containing Plating Solution The method for producing the particle-containing plating solution is not particularly limited, and the particle-containing plating solution can be produced, for example, by mixing and stirring the particle dispersion and the plating solution.

[0116] The mixing ratio of the particle dispersion and the plating solution may be such that the content of the particle dispersion in the particle-containing plating solution is the amount described above for the particle-containing plating solution.

[0117] The liquid temperatures of the particle dispersion and the plating solution during mixing are not particularly limited, and they may be mixed at about room temperature.

[0118] After mixing the particle dispersion and the plating solution, it is preferable to stir them by a known stirring method such as stirring with a stirrer.

[0119] The particle-containing plating solution is produced by the production method described above.

[0120] 5. Particle-Containing Plating Film The particle-containing plating film of the present invention is a particle-containing plating film formed using the particle-containing plating solution described above. As the particle-containing plating solution, the particle-containing plating solution of the present invention described above can be used.

[0121] 6. Particle-Containing Plating Method The particle-containing plating method of the present invention is a plating method comprising the step of immersing an object to be plated in the particle-containing plating solution. As the particle-containing plating solution, the particle-containing plating solution of the present invention described above can be used.

[0122] The object to be plated is not particularly limited, and examples thereof include various substances on which it is necessary to form a particle-containing plating film that requires the properties of the particles, such as low friction and non-adhesiveness.

[0123] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0124] The raw materials used in the examples and comparative examples are as follows:

[0125] Fluorine-containing particles: Polytetrafluoroethylene (PTFE) particles: average particle size 0.2 μm Fluorine-free particles: Polyethylene (PE) particles: average particle size 10 μm

[0126] (A) Nonionic Surfactant A Nonionic surfactant A represented by the following general formula (1) and shown in Table 1 was used.

[0127]

[0128] (B) Amphoteric surfactants B-1: Coconut oil dimethylaminoacetic acid betaine B-2: Lauryl dimethylaminoacetic acid betaine B-3: Stearyl dimethylaminoacetic acid betaine

[0129] (C) Cationic surfactants C-1: hexadecyltrimethylammonium chloride C-2: stearyltrimethylammonium chloride C-3: didecyldimethylammonium chloride C-4: 1-methyl-1-hydroxyethyl-2-tallow alkyl-imidazonium chloride

[0130] (D) Amphoteric surfactants D-1: Polyoxyethylene stearylamine D-2: Polyoxyethylene laurylamine D-3: Polyoxyethylene oleylamine

[0131] (Examples and Comparative Examples) Production of Fluorine-Containing Particle Dispersions The above-mentioned raw materials were added sequentially to water as a solvent and stirred in the amounts shown in Tables 2 to 6 and 8. Next, PTFE was added in the amount shown in Tables 2 to 6 and 8, and the mixture was stirred at 25°C for 60 minutes using a homogenizer to produce fluorine-containing particle dispersions.

[0132] Preparation of particle dispersion of fluorine-free particles The above-mentioned raw materials were added sequentially to water as a solvent in the amounts shown in Table 7 and stirred. Next, 100 g / L of PE was added, and the mixture was stirred at 25° C. for 60 minutes using a homogenizer to prepare a particle dispersion of fluorine-free particles.

[0133] Preparation of electroless nickel-phosphorus plating solution The following ingredients were added to water in order and stirred to prepare an electroless nickel-phosphorus plating solution: Nickel sulfate 6H2O: 25 g / L, Malic acid: 15 g / L, Succinic acid: 5 g / L, Sodium hypophosphite: 25 g / L, Stabilizer: appropriate amount, Ammonia water (pH adjuster): pH adjusted to 4.75

[0134] Preparation of electrolytic nickel plating solution The following raw materials were added to water in this order and stirred to prepare an electrolytic nickel plating solution: Nickel sulfate.6H2O: 280 g / L Nickel chloride.6H2O: 45 g / L Boric acid: 40 g / L

[0135] Preparation of Particle-Containing Plating Solution An electroless nickel-phosphorus plating solution or an electrolytic nickel plating solution was mixed with a particle dispersion and stirred to prepare a particle-containing plating solution. The content of the particle dispersion in the particle-containing plating solution was 25 ml / L. In some examples, the above-mentioned components (A), (B), (C), and (D) were added to the particle-containing plating solution.

[0136] Formation of Electroless Particle-Containing Plating Film An electroless particle-containing plating film was formed using a particle-containing plating solution under the following conditions: Bath temperature: 90°C pH: 4.75 Plating time: 60 minutes Thickness of plating film (target): 10 to 12 μm Object to be plated (test piece): Fe plate, 2.5 × 5 cm (0.25 dm ２ ) ・Bath load: 0.50dm ２ / L

[0137] Formation of Electrolytic Particle-Containing Plating Film An electrolytic particle-containing plating film was formed using a particle-containing plating solution under the following conditions: Bath temperature: 50°C pH: 4.20 Plating time: 50 minutes Thickness of plating film (target): 20 μm Object to be plated (test piece): Brass plate, 2.5 × 5 cm (0.25 dm ２ ) ・Current density: 2A / dm ２

[0138] (Evaluation Method) The following evaluations were carried out for the Examples and Comparative Examples.

[0139] Dispersibility of Particle Dispersion The dispersibility of the particle dispersion immediately after production was visually observed and evaluated according to the following evaluation criteria. Evaluations of △ or higher are considered to be satisfactory for practical use. ◯: Good dispersion state △: Slight aggregation and non-dispersion ×: Aggregation and severe non-dispersion

[0140] The deposition rate was calculated by measuring the difference in weight of the test piece before and after plating using the following formula. ３ The calculation was made as follows: Deposition rate (μm / h) = weight difference (mg) × 0.057

[0141] Dispersibility of particles in particle-containing plating film The surface of the particle-containing plating film was observed using a backscattered electron composition image of a new scanning electron microscope (general-purpose FE-SEM: JEOL JSM-IT700HR), and the aggregation of PTFE or PE was confirmed and evaluated according to the following evaluation criteria. An evaluation of △ or higher is considered to be satisfactory for practical use. ◯: Good dispersion △: Slight aggregation and non-dispersion ×: Aggregation and severe non-dispersion

[0142] Appearance of particle-containing plating film The gloss and pits of the particle-containing plating film were visually observed and evaluated according to the following evaluation criteria. A rating of △ or higher is considered to be satisfactory for practical use. ◯: Good △: Uneven appearance ×: Very uneven appearance

[0143] Co-deposition rate of fluorine-containing particles Strike Ni plating was applied to a stainless steel plate, and after Ni-P / PTFE plating, the film was dissolved in 30% nitric acid and the solution was filtered. The co-deposition rate of fluorine particles was calculated from the weights of the filtered PTFE particles and plated film using the following formula.

[0144]

[0145] The calculated PTFE co-deposition ratio was evaluated according to the following evaluation criteria. A rating of △ or higher indicates that there is no problem in practical use. ◯: Co-deposition ratio over 20 vol.% △: Co-deposition ratio 5 to 20 vol.% ×: Co-deposition ratio less than 5 vol.%

[0146] The cross section of the particle-containing plating film was observed using a backscattered electron composition image of a new scanning electron microscope (general-purpose FE-SEM: JEOL JSM-IT700HR), and the PE content was confirmed and calculated from the weight of the PE particles and plating film.

[0147]

[0148] The calculated PE co-deposition ratio was evaluated according to the following evaluation criteria. A rating of △ or higher indicates that there is no problem in practical use. ◯: Co-deposition ratio over 20 vol.% △: Co-deposition ratio 5 to 20 vol.% ×: Co-deposition ratio less than 5 vol.%

[0149] The results are shown in Tables 2 to 8. The unit of the blending amount in the tables is g / L.

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

Claims

1. Particles, and the following general formula (1): (In the formula, R １－１ and R １－２ are the same or different and each represents an oxyalkylene group; R １－３ and R １－４ and m and n are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms. m and n are the same or different and each represents an integer, and m+n=0 to 30.

2. The particle dispersion according to claim 1, wherein the oxyalkylene group has 1 or more and 5 or less carbon atoms.

3. The particle dispersion according to claim 1, wherein the content of the nonionic surfactant A is from 1 g / L to 100 g / L.

4. The particle dispersion according to claim 1, wherein the particles are fluorine-containing particles and / or fluorine-free particles.

5. The particle dispersion liquid according to claim 4, wherein the fluorine-containing particles contain at least one selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), perfluoroalkoxyalkane (PFA), perfluoroethylenepropene copolymer (FEP), ethylenetetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylenechlorotrifluoroethylene copolymer (ECTFE), and polytetrafluoroethylene oxide (PTFEO).

6. The fluorine-free particles are polyethylene (PE), polyethersulfone (PES), polyetherimide (PEI), polyarylate (PAR), polyamideimide (PAI), polyphenylene ether (PPE), polylactic acid (PLA), polyamide (PA), ester-based thermoplastic elastomer (TPC), polyurethane (PU), aromatic polyether ketone, silicon carbide (SiC), diamond, boron nitride (BN), aluminum oxide (Al2O3), graphite fluoride, tungsten carbide (WC), molybdenum disulfide (MoS2), boron carbide (B ４ C), graphene, and at least one selected from the group consisting of graphite.

7. The particle dispersion according to claim 1, wherein the particle content is from 10 g / L to 1000 g / L.

8. The particle dispersion according to claim 1, further comprising an amphoteric surfactant.

9. The particle dispersion according to claim 8, wherein the content of the amphoteric surfactant is 1 g / L or more and 100 g / L or less.

10. The particle dispersion according to claim 1, further comprising a cationic surfactant.

11. The particle dispersion according to claim 10, wherein the content of the cationic surfactant is from 1 g / L to 100 g / L.

12. Furthermore, the following general formula (4) (In the formula, R ４－１ R represents a hydrocarbon group having 5 to 30 carbon atoms. ４－２ and R ４－３ The particle dispersion liquid according to claim 1 , comprising a nonionic surfactant B represented by the following formula:

13. The particle dispersion according to claim 12, wherein the content of the nonionic surfactant B is 0.1 g / L or more and 100 g / L or less.

14. A method for producing a particle dispersion liquid, comprising: (In the formula, R １－１ and R １－２ are the same or different and each represents an oxyalkylene group; R １－３ and R １－４ and m and n are the same or different and represent a hydrocarbon group having 1 to 10 carbon atoms. m and n are the same or different and represent an integer, and m+n=0 to 30.

15. A particle-containing plating solution comprising the particle dispersion according to claim 1 and a plating solution.

16. The particle-containing plating solution according to claim 15, wherein the particle-containing plating solution is an electroless particle-containing nickel-phosphorus plating solution or an electrolytic particle-containing nickel plating solution.

17. The particle-containing plating solution according to claim 15, wherein the content of the particle dispersion is 1 ml / L or more and 100 ml / L or less.

18. A particle-containing plating film formed using the particle-containing plating solution according to claim 15.

19. A particle-containing plating method comprising the step of immersing an object to be plated in the particle-containing plating solution according to claim 15.

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