Particle dispersion, method for manufacturing the same, particle containing plating solution, particle containing plating film, and particle containing plating method

Abstract

To provide a particle dispersion excellent in the dispersibility of particles, and a particle containing plating solution.SOLUTION: A particle dispersion includes particles and a nonion based surfactant A represented by the following general formula (1), (where, R1-1 and R1-2 are the same or different and show an oxyalkylene group; R1-3 and R1-4 are the same or different and show a hydrocarbon group having a carbon number of 1 or more and 10 or less; m and n are the same or different and show integers; and m+n=0-30).SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] In recent years, by incorporating various particles into a plating film, various properties have been imparted to the plating film and it has been utilized.

[0003] For example, electroless nickel-phosphorus / polytetrafluoroethylene (Ni-P / PTFE) composite plating is a plating film having both the low friction property and non-stick property of PTFE and the uniform deposition property of electroless plating, and has recently begun to be applied in various fields.

[0004] It is very difficult to uniformly disperse strongly water-repellent PTFE particles in an electroless plating solution. Conventionally, as a method for uniformly dispersing PTFE particles in an electroless plating solution, a method of using a fluorine-based surfactant as a dispersant has been used.

[0005] However, in recent years, due to regulations on the use of fluorine-based materials in Europe, fluorine-based surfactants can no longer be used sequentially, and a method for dispersing PTFE particles without using a fluorine-based surfactant has been demanded.

[0006] An electroless composite plating bath containing PTFE fine particles and not using a fluorine-based surfactant has been proposed (see Patent Document 1). In Patent Document 1, an amphoteric surfactant having a specific structure is used as a surfactant for dispersing 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 that the dispersibility is not sufficient.

[0008] In addition, not only the plating solution using the fluorine-containing particles as described above, but also the plating solution using particles not containing fluorine affects the dispersibility of the particles, as well as the properties of the plating solution and the plating film. Therefore, a particle dispersion liquid excellent in dispersibility is required to produce a particle-containing plating solution excellent in dispersibility.

[0009] Therefore, it is desired to develop a particle dispersion liquid excellent in particle dispersibility and a particle-containing plating solution excellent in particle dispersibility using the particle dispersion liquid.

Prior Art Documents

Patent Documents

[0010]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

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

Means for Solving the Problems

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

[0013] That is, the present invention relates to the following particle dispersion liquid, its production method, particle-containing plating solution, particle-containing plating film, and particle-containing plating method. 1. Particles, and The following general formula (1)

Chemical Formula

Chemical formula

Chemical formula

[0014] The particle dispersion of the present invention has excellent particle dispersibility. In addition, 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. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[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 having 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] (particle) The particles are not particularly limited, and known particles can be used. As such particles, fluorine-containing particles and fluorine-free particles can be used. These particles can be used alone or in combination of two or more kinds.

[0018] As the fluorine-containing particles, there are no particular limitations as long as they are fluorine-containing particles containing fluorine, and known fluorine-containing particles can be used. Examples of such fluorine-containing particles include fluorine-containing particles containing fluororesins such as 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); fluorine-containing particles containing metal fluorides, and the like. Among these, fluorine-containing particles containing polytetrafluoroethylene (PTFE) are preferred in that the dispersibility of the fluorine-containing particles in the particle dispersion is further improved and the surface potential of the particles can be well controlled.

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

[0020] The average particle diameter of the fluorine-containing particles is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably 0.15 μm or more. Also, the average particle diameter of the fluorine-containing particles is preferably 100 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, and particularly preferably 1 μm or less. When the average particle diameter of the fluorine-containing particles is within the above range, the fluorine-containing particles can be more dispersed in the particle dispersion, 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, still more preferably 70 g / L or more, and particularly preferably 80 g / L or more. Also, 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, still 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 the fluorine-containing particles can be used. Examples of such fluorine-free particles include particles of synthetic resin, ceramics, glass, talc, plastic, diamond, graphite, oxide, silicate, carbonate, carbide, sulfide, phosphate ester, boride, silicate, nitride, metal, etc.

[0023] Among the above fluorine-free particles, more specifically, examples of the 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 polyether ketone, etc. Further, examples of the aromatic polyether ketone include polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ether ketone ketone (PEEKK), etc.

[0024] Among the above fluorine-free particles, more specifically, examples of the particles other than synthetic resin include particles of silicon carbide (SiC), diamond, boron nitride (BN), aluminum oxide (Al2O3), graphite fluoride, tungsten carbide (WC), molybdenum disulfide (MoS2), boron carbide (B4C), graphene, graphite, etc.

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

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

[0027] The average particle diameter of the fluorine-free particles in the particle dispersion is preferably 1 nm or more, more preferably 100 nm or more, still more preferably 1 μm or more, and particularly preferably 5 μm or more. Also, the average particle diameter of the fluorine-free particles in the particle dispersion is preferably 200 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, and particularly preferably 30 μm or less. When the average particle diameter 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 content of the particles in the particle dispersion is preferably 10 g / L or more, more preferably 60 g / L or more, still more preferably 70 g / L or more, and particularly preferably 80 g / L or more. Also, the content of the particles in the particle dispersion is preferably 1500 g / L or less, more preferably 1000 g / L or less, still 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 the “component (A)”), a nonionic surfactant represented by the following general formula (1) is used.

[0030] [Chemical formula]

[0031] In the above general formula (1), R 1-1 and R 1-2 each independently represents an oxyalkylene group. The number of carbon atoms of the oxyalkylene group is preferably 1 or more, more preferably 2 or more. Also, the number of carbon atoms of the oxyalkylene group is preferably 5 or less, more preferably 4 or less, and still more preferably 3 or less. When the number of carbon atoms of the oxyalkylene group is within the above range, the dispersibility of the particles is further improved.

[0032] In the above general formula (1), m and n represent the same or different integers. m and n are preferably 0 or more, more preferably 2 or more. Also, m and n are preferably 30 or less, more preferably 20 or less, still 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 from 0 to 30. When m + n exceeds 30, the dispersibility of the particles is poor. m + n is preferably 20 or less, more preferably 10 or less.

[0034] In the above general formula (1), R 1-3 and R 1-4 represent the same or different hydrocarbon groups having 1 to 10 carbon atoms. When the number of carbon atoms is less than 1 or 11 or more, the dispersibility of the particles is poor. The number of carbon atoms of R 1-3 and R 1-4 is preferably 2 or more, the same or different. Also, the number of carbon atoms of R 1-3 and R 1-4 is preferably 5 or less, more preferably 4 or less, the same or different. Also, R 1-3 and R 1-4 are preferably alkyl groups.

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

[0036]

Chemical formula

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

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

[0039] The above component (A) can 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, still more preferably 10 g / L or more, and particularly preferably 15 g / L or more. Also, the content of component (A) in the particle dispersion is preferably 100 g / L or less, more preferably 80 g / L or less, still more preferably 60 g / L or less, and particularly preferably 50 g / L or less. When the lower limit of the content of component (A) is within the above range, the dispersibility of the particles is further improved. Also, when the upper limit of the content of component (A) is 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), 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.

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

[0043]

Chem.

[0044] In the above general formula (2), R 2-1 is preferably a hydrocarbon group, more preferably an alkyl group. Also, the number of carbon atoms of R 2-1 is preferably 5 or more, more preferably 8 or more, and still more preferably 10 or more. Also, the number of carbon atoms of R 2-1 is preferably 30 or less, more preferably 20 or less, and still 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. Also, the number of carbon atoms of R 2-2 , and R 2-3 is the same or different and is preferably 5 or less, more preferably 3 or less, and still more preferably 1.

[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. Also, the number of carbon atoms of R 2-4 is preferably 5 or less, more preferably 3 or less, and still more preferably 1.

[0047] More specifically, examples of the component (B) include coconut oil dimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, and the like. Among these, coconut oil dimethylaminoacetic acid betaine is preferable in that particles can be more uniformly dispersed in the particle-containing plating film formed with the particle-containing plating solution containing the particle dispersion liquid of the present invention.

[0048] The component (B) can 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, still more preferably 5 g / L or more, and particularly preferably 7 g / L or more. Also, the content of component (B) in the particle dispersion is preferably 100 g / L or less, more preferably 80 g / L or less, still 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 is more likely to form a particle-containing plating film. Also, 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 a (C) cationic surfactant (hereinafter also referred to as "(C) component"). When the particle dispersion contains the (C) component, the particle-containing plating solution containing the particle dispersion of the present invention is more likely to form a particle-containing plating film.

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

[0052] [Chemical formula]

[0053] [Chemical formula]

[0054] In the above general formula (3-1), R 3-1-1 is preferably a hydrocarbon group, more preferably an alkyl group. Also, the number of carbon atoms of R 3-1-1 is preferably 5 or more, more preferably 8 or more, still more preferably 10 or more. Also, R 3-1-1The 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 and R 3-1-3 and R 3-1-4 independently represent a hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms of R 3-1-2 , R 3-1-3 , and R 3-1-4 is preferably 7 or less, more preferably 3 or less, and even more preferably 1, either the same or different.

[0056] In the above general formula (3-1), X represents a halogen element, a sulfate group, etc. Examples of the halogen element include chlorine, bromine, etc., and chlorine is preferred. As the sulfate group, a sulfuric acid alkyl group is preferred, and a sulfuric acid methyl group is more preferred. By setting X as the above-mentioned group, the particle-containing plating solution containing the particle dispersion liquid of the present invention is more likely to form a particle-containing plating film.

[0057] In the above general formula (3-2), R 3-2-1 is preferably a hydrocarbon group, and more preferably an alkyl group. The number of carbon atoms of R 3-2-1 is preferably 5 or more, more preferably 8 or more, and even more preferably 10 or more. The number of carbon atoms of R 3-2-1 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 independently represent a hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms of R 3-2-2 and R 3-2-3 is preferably 1 to 5, more preferably 1 to 3, either the same or different. R 3-2-2 and R 3-2-3 may have a hydroxyl group at the terminal.

[0059] In the general formula (3-2) above, X represents a halogen element, a sulfate group, etc. Examples of the halogen element include chlorine, bromine, etc., and chlorine is preferred. Further, as the sulfate group, an alkyl sulfate group is preferred, and a methyl sulfate group is more preferred. By setting X as the above-described group, the particle-containing plating solution containing the particle dispersion liquid of the present invention becomes more likely to form a particle-containing plating film.

[0060] More specifically, examples of the component (C) include hexadecyltrimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, coconut alkyltrimethylammonium chloride, methylhexadecyltrimethylammonium sulfate, didecyldimethylammonium chloride, dilauryl dimethylammonium chloride, distearyldimethylammonium chloride, dioleyldimethylammonium chloride, dichlorinated tallow alkyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, benzalkonium chloride, methyldidecyldimethylammonium sulfate, 1-methyl-1-hydroxyethyl-2-tallow alkyl-imidazolinium chloride, and the like. Among these, hexadecyltrimethylammonium chloride is preferred in that the particle-containing plating solution containing the particle dispersion liquid of the present invention becomes more likely to form a particle-containing plating film.

[0061] The component (C) can be used alone or in combination of two or more.

[0062] The content of the component (C) in the particle dispersion liquid is preferably 1 g / L or more, more preferably 2 g / L or more, still more preferably 5 g / L or more, and particularly preferably 10 g / L or more. Further, the content of the component (C) in the particle dispersion liquid is preferably 100 g / L or less, more preferably 80 g / L or less, still more preferably 70 g / L or less, and particularly preferably 60 g / L or less. When the lower limit of the content of the component (C) is within the above range, the particle-containing plating solution containing the particle dispersion liquid of the present invention becomes more likely to form a particle-containing plating film. Further, when the upper limit of the content of the 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)”). By containing component (D) in the particle dispersion, the particles can be more uniformly dispersed in the particle-containing plating film formed from the particle-containing plating solution containing the particle dispersion of the present invention.

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

[0065] [Chemical formula]

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

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

[0068] In the above general formula (4), p and q represent integers which may be the same or different. p and q are preferably 0 or more, more preferably 2 or more. Also, p and q are preferably 30 or less, more preferably 20 or less, still more preferably 10 or less, and particularly preferably 5 or less. When p and q are within the above ranges, the particles can be more uniformly dispersed in the particle-containing plating film formed from the particle-containing plating solution containing the particle dispersion liquid of the present invention.

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

[0070] More specifically, examples of the component (D) include polyoxyethylene stearylamine, polyoxyethylene laurylamine, polyoxyethylene oleylamine, polyoxyethylene alkyl (coconut) amine, polyoxyethylene tallow alkylamine, and the like. Among these, polyoxyethylene stearylamine is preferable in that the particles can be more uniformly dispersed in the particle-containing plating film formed from the particle-containing plating solution containing the particle dispersion liquid of the present invention.

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

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

[0073] (Other components) The particle dispersion of the present invention may contain an acid or a salt thereof used as a component of the plating solution, other than the components (A) to (D) above. Examples of such an acid or a salt thereof include complexing agent components such as malic acid and succinic acid, or salts thereof (for example, sodium salt, potassium salt, ammonium salt, etc.); hypophosphorous acid, or a salt thereof (for example, sodium salt, potassium salt, ammonium salt, etc.); sulfuric acid, phosphorous acid, or salts thereof (for example, sodium salt, potassium salt, ammonium salt, etc.). These can be preferably used.

[0074] The above acid or a salt thereof can be used alone or in combination of two or more.

[0075] The content of the above acid or a salt thereof in the particle dispersion is preferably 1 g / L or more, more preferably 10 g / L or more, still more preferably 30 g / L or more, and particularly preferably 50 g / L or more. When the lower limit of the content is within the above range, the dispersibility of the particle dispersion of the present invention is further improved. Also, the content of the above acid or a salt thereof in the particle dispersion is preferably 500 g / L or less, more preferably 250 g / L or less, still 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 respective components are contained in a solvent.

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

[0078] Note that the particle dispersion of the present invention may be configured to contain particles in a solvent and also contain some of the above-described components. That is, each of the above components (A), (B), (C), and (D) may be separately added to the particle-containing plating solution described later in both cases where the particle dispersion contains them and where it does not contain them, so that the particle dispersion of the present invention may be configured to 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 components (A), (B), (C), and (D).

[0079] (Properties of the particle dispersion) The particle dispersion of the present invention is preferably neutral or alkaline. The particle dispersion 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. Also, the pH is preferably 12 or less, more preferably 10 or less. When the pH of the particle dispersion is within the above range, the dispersibility of the particles is further improved, and the surface potential of the particles can be better controlled.

[0080] 2. Method for producing particle dispersion The method for producing the particle dispersion of the present invention is not particularly limited. For example, the following general formula (1) [Chemical formula] (In the formula, R 1-1 and R 1-2 are the same or different and represent an oxyalkylene group, and 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 integers, and m + n = 0 to 30.) It can be produced by a production method having a step of dispersing particles in a solvent containing a nonionic surfactant A represented by the formula. Hereinafter, the above production method will be exemplarily described.

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

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

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

[0084] The temperature of the solvent containing the nonionic surfactant A in the above step is not particularly limited. Generally, it is 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, 25°C or higher and 30°C or lower is preferable.

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

[0086] A particle dispersion 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 electroplating. 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] In addition, each of the components (A), (B), (C), and (D) described in the particle dispersion liquid of the present invention may be separately added to the particle-containing plating solution so that the particle-containing plating solution of the present invention contains them, whether the particle dispersion liquid contains them or not.

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

[0091] The content of the particle dispersion liquid in the particle-containing plating solution is preferably 1 ml / L or more, more preferably 5 ml / L or more, and still more preferably 10 ml / L or more. Also, the content of the particle dispersion liquid in the particle-containing plating solution is preferably 100 ml / L or less, more preferably 90 ml / L or less, and still more preferably 80 ml / L or less. When the lower limit of the content of the particle dispersion liquid is within the above range, the particles can be more uniformly dispersed in the particle-containing plating film. Also, when the upper limit of the content of the particle dispersion liquid is within the above range, it becomes easier to form the particle-containing plating film.

[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. Also, 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 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; electrolytic silver plating solutions, etc. 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; electroless silver plating solutions and the like. 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 exemplarily described.

[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 known nickel compounds used in electroless Ni-P plating baths can be used. The water-soluble nickel compound is preferably, for example, water-soluble nickel inorganic salts such as nickel sulfate, nickel chloride, nickel hypophosphite, nickel carbonate, etc.; water-soluble nickel organic salts such as nickel acetate, nickel malate, etc., and hydrates thereof.

[0098] The water-soluble nickel compound 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 as appropriate. The concentration of the water-soluble nickel compound can preferably be, for example, 0.01 g / L or more, more preferably 0.5 g / L or more, and still more preferably 1 g / L or more in terms of nickel metal. Also, the concentration of the water-soluble nickel compound can preferably be, for example, 100 g / L or less, more preferably 50 g / L or less, and still more preferably 10 g / L or less in terms of nickel metal. If the concentration of the water-soluble nickel compound is less than 0.01 g / L in terms of nickel metal, the deposition rate may be slow, and if it exceeds 100 g / L, the bath stability may decrease. Therefore, it is preferable to be within the above-described range.

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

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

[0102] The concentration of the reducing agent (hypophosphorous acid, hypophosphite, and its hydrates, etc.) in the electroless Ni-P plating solution is preferably 15 g / L or more, more preferably 20 g / L or more. Also, the above concentration is preferably 80 g / L or less, more preferably 60 g / L or less. If the concentration of the reducing agent is less than 15 g / L or exceeds 80 g / L, the adhesion of the electroless Ni-P plating may decrease. Therefore, it is preferable to be within the above range.

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

[0104] As other complexing agents, preferably, monocarboxylic acids such as formic acid and acetic acid or salts thereof (for example, sodium salt, potassium salt, ammonium salt, etc.); dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid or salts thereof (for example, sodium salt, potassium salt, ammonium salt, etc.); hydroxycarboxylic acids such as malic acid, lactic acid, glycolic acid, citric acid or salts thereof (for example, sodium salt, potassium salt, ammonium salt, etc.); ethylenediaminediacetic acid, ethylenediaminetetraacetic acid or salts thereof (for example, sodium salt, potassium salt, ammonium salt, etc.); amino acids such as alanine and arginine are preferred.

[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, more preferably 2 g / L or more, and still more preferably 5 g / L or more of the complexing agent. Further, the electroless Ni-P plating bath preferably contains 100 g / L or less, more preferably 50 g / L or less, and still more preferably 30 g / L or less of the complexing agent. Since the bath stability may decrease when the concentration of the complexing agent is less than 1 g / L and the deposition rate may decrease when it exceeds 100 g / L, it is preferably within the above-mentioned range.

[0107] (Stabilizer, pH adjuster, surfactant, etc.) In addition to the above components, the electroless Ni-P plating solution may contain, if necessary, known additives used in electroless Ni-P plating solutions. Examples of the additives include stabilizers, pH adjusters, surfactants, etc.

[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, selenous acid, etc.), cyanides (e.g., methyl cyanide, isopropyl cyanide, etc.), and the like.

[0109] The stabilizer 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. For the purpose of improving the stability of the electroless Ni-P plating solution, it is preferable that the concentration of the stabilizer be about 0.1 mg / L or more. If the concentration of the stabilizer exceeds 500 mg / L, there may be a case where non-deposited portions (non-precipitated portions) where the plating film is not formed occur, so it is preferable to be within the above range.

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

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

[0113] As the surfactant, various surfactants such as nonionic, anionic, cationic, and amphoteric surfactants can be used. For example, alkali salts of aromatic or aliphatic sulfonic acids, alkali metal salts of aromatic or aliphatic sulfonic acids, etc. can be mentioned. The surfactant can be used alone or in combination of two or more. When using two or more surfactants in combination, the mixing ratio is not particularly limited and can be determined as appropriate.

[0114] The concentration of the surfactant in the electroless Ni-P plating solution is not particularly limited, and can be, for example, about 0.01 mg / L or more and 1000 mg / L or less. For the purpose of further improving the effect of preventing pits in the electroless Ni-P plating bath, it is preferable that the concentration of the surfactant is about 0.01 mg / L or more. Further, when the concentration of the surfactant is 1000 mg / L or less, the decrease in precipitation 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. For example, it can be produced by mixing and stirring the above-mentioned particle dispersion liquid and the above-mentioned plating solution.

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

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

[0118] After mixing the particle dispersion liquid and the plating solution, it is preferable to stir 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 by the above particle-containing plating solution. 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 including a step of immersing an object to be plated in the above 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 various substances for which it is necessary to form a particle-containing plating film that requires characteristics of the particles, such as low friction and non-stickiness of the particles, can be mentioned.

Examples

[0123] Examples and comparative examples are shown below to explain the present invention in more detail. However, the present invention is not limited to the examples.

[0124] Note that the raw materials used in the examples and comparative examples are as follows.

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

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

Chemical formula

[0127]

Table 1

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

[0129] (C) Cationic surfactants C-1: Hexadecyltrimethylammonium chloride C-2: Stearyl trimethyl ammonium chloride C-3: Didecyldimethylammonium chloride C-4: 1-Methyl-1-hydroxyethyl-2-tallow alkyl-imidazonium chloride

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

[0131] Examples and Comparative Examples Production of fluorine-containing particle dispersion The above-mentioned raw materials were added in order to water as a solvent in the amounts shown in Tables 2 to 6 and 8, respectively, and stirred. Next, PTFE was added in the amount shown in Tables 2 to 6 and 8, and stirred with a homogenizer at 25°C for 60 minutes to produce a fluorine-containing particle dispersion.

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

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

[0134] Preparation of electrolytic nickel plating solution An electrolytic nickel plating solution was prepared by sequentially adding the following raw materials to water and stirring.· Nickel sulfate·6H2O: 280 g / L · Nickel chloride·6H2O: 45 g / L · Boric acid: 40 g / L

[0135] Manufacturing of particle-containing plating solution A electroless nickel-phosphorus plating solution, or an electrolytic nickel plating solution and a particle dispersion liquid were mixed and stirred to produce a particle-containing plating solution. The content of the particle dispersion liquid in the particle-containing plating solution was 25 ml / L. Also, in some examples, the above components (A), (B), (C), and (D) were added to the particle-containing plating solution.

[0136] Formation of electroless particle-containing plating film Using the particle-containing plating solution, an electroless particle-containing plating film was formed under the following conditions. · Bath temperature: 90 °C · pH: 4.75 · Plating time: 60 minutes · Target film thickness of the plating film: 10 - 12 μm · Object to be plated (test piece): Fe plate, 2.5 × 5 cm (0.25 dm 2 ) · Bath load: 0.50 dm 2 / L

[0137] Formation of electrolytic particle-containing plating film Using the particle-containing plating solution, an electrolytic particle-containing plating film was formed under the following conditions. · Bath temperature: 50 °C · pH: 4.20 · Plating time: 50 minutes · Target film thickness of the plating film: 20 μm · Object to be plated (test piece): Brass plate, 2.5 × 5 cm (0.25 dm 2 ) · Current density: 2 A / dm 2

[0138] (Evaluation method) For the examples and comparative examples, the following evaluations were carried out.

[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. If the evaluation is Δ or higher, it is evaluated that there is no problem in actual use. 〇: The dispersion state is good. △: Slightly aggregated and not dispersed. ×: Aggregated and the degree of non-dispersion is severe.

[0140] Deposition rate The weight difference of the test piece before and after plating was measured and calculated according to the following formula. In the following formula, the density was calculated as 7.0 g / cm 3 and calculated. Deposition rate (μm / h) = Weight difference (mg) × 0.057

[0141] Dispersion of particles in particle-containing plating film The surface of the particle-containing plating film was observed by the reflected electron composition image of a new type of scanning electron microscope (general-purpose FE-SEM: JSM-IT700HR manufactured by JEOL Ltd.) to confirm the aggregation of PTFE or PE, and evaluated according to the following evaluation criteria. If the evaluation is Δ or higher, it is evaluated that there is no problem in actual use. 〇: The dispersion state is good. △: Slightly aggregated and not dispersed. ×: Aggregated and the degree of non-dispersion is severe.

[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. If the evaluation is Δ or higher, it is evaluated that there is no problem in actual use. 〇: Good △: Appearance unevenness exists ×: Appearance unevenness is very severe

[0143] Co-deposition rate of fluorine-containing particles A SUS plate was subjected to strike Ni plating, and after Ni-P / PTFE plating, the film was dissolved in 30% nitric acid and the resulting solution was filtered. The eutectic ratio of fluorine particles was calculated from the weights of the filtered PTFE particles and the plating film using the following formula.

[0144]

Equation

[0145] The calculated PTFE eutectic ratio was evaluated according to the following evaluation criteria. Note that if the evaluation is Δ or higher, it is evaluated that there is no problem in actual use. 〇: Eutectic ratio exceeds 20 vol.% △: Eutectic ratio is 5 - 20 vol.% ×: Eutectic ratio is less than 5 vol.%

[0146] Co-deposition rate of fluorine-free particles The cross-section of the particle-containing plating film was observed by the reflected electron composition image of a new type of scanning electron microscope (general-purpose FE-SEM: JSM-IT700HR manufactured by JEOL Ltd.), and the PE content was confirmed and calculated from the weights of the PE particles and the plating film.

[0147]

Equation

[0148] The calculated PE eutectic ratio was evaluated according to the following evaluation criteria. Note that if the evaluation is Δ or higher, it is evaluated that there is no problem in actual use. 〇: Eutectic ratio exceeds 20 vol.% △: Eutectic ratio is 5 - 20 vol.% ×: Eutectic ratio is less than 5 vol.%

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

[0150] [Table 2]

[0151] [Table 3]

[0152] [Table 4]

[0153] [Table 5]

[0154] [Table 6]

[0155] [Table 7]

[0156] [Table 8]

Claims

1. particle, The following general formula (1) 【Chemical 1】 (In the formula, R １－１ and R １－２ are the same or different and each represents an oxyalkylene group, and R １－３ and R １－４ 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 20.) A nonionic surfactant A represented by the formula: At least one amphoteric surfactant selected from the group consisting of coconut dimethylaminoacetate betaine, lauryl dimethylaminoacetate betaine, and stearyl dimethylaminoacetate betaine, and Contains a solvent, Particle dispersion for particle-containing plating solutions.

2. 2. The particle dispersion for a particle-containing plating solution according to claim 1, wherein the oxyalkylene group has 1 or more and 5 or less carbon atoms.

3. 2. The particle dispersion for particle-containing plating solution according to claim 1, wherein the content of the nonionic surfactant A in the particle dispersion for particle-containing plating solution is 1 g / L or more and 100 g / L or less.

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

5. 5. The particle dispersion for a particle-containing plating solution according to claim 4, wherein the fluorine-containing particles include 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 include at least one selected from the group consisting 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), aromatic polyether ketone, silicon carbide (SiC), diamond, boron nitride (BN), aluminum oxide (Al 2 O 3 ), graphite fluoride, tungsten carbide (WC), molybdenum disulfide (MoS 2 ), boron carbide (B ４ C), graphene, and graphite, and the particle dispersion for a particle-containing plating solution according to claim 4.

7. 2. The particle dispersion for particle-containing plating solution according to claim 1, wherein the content of the particles in the particle dispersion for particle-containing plating solution is 10 g / L or more and 1000 g / L or less.

8. 2. The particle dispersion for particle-containing plating solution according to claim 1, wherein the content of the amphoteric surfactant in the particle dispersion for particle-containing plating solution is 1 g / L or more and 100 g / L or less.

9. The particle dispersion for a particle-containing plating solution according to claim 1 , further comprising a cationic surfactant.

10. 10. The particle dispersion for particle-containing plating solution according to claim 9, wherein the content of the cationic surfactant in the particle dispersion for particle-containing plating solution is 1 g / L or more and 100 g / L or less.

11. Furthermore, the following general formula (4) 【Chemical 2】 (In the formula, R ４－１ represents a hydrocarbon group having 5 to 30 carbon atoms. R ４－２ and R ４－３ are the same or different and represent an oxyalkylene group. p and q are the same or different and represent an integer of 0 or more and 30 or less.) The particle dispersion for a particle-containing plating solution according to claim 1 , further comprising a nonionic surfactant B represented by the formula:

12. The content of the nonionic surfactant B in the particle dispersion liquid for the particle-containing plating solution is 0.1 g / L or more and 100 g / L or less. The particle dispersion liquid for the particle-containing plating solution according to claim 11.

13. A method for producing a particle dispersion liquid for a particle-containing plating solution, The following general formula (1) 【Chemical 3】 (wherein, R １－１ and R １－２ are the same or different and each represents an oxyalkylene group, and R １－３ and R １－４ 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 20.) A nonionic surfactant A represented by, and At least one amphoteric surfactant selected from the group consisting of coconut oil dimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, and stearyldimethylaminoacetic acid betaine A step of dispersing particles in a solvent containing A manufacturing method characterized by this.

14. The particle dispersion liquid for the particle-containing plating solution according to claim 1, and a particle-containing plating solution containing the plating solution.

15. The particle-containing plating solution according to claim 14 is an electroless particle-containing nickel-phosphorus plating solution or an electrolytic particle-containing nickel plating solution.

16. The content of the particle dispersion liquid for the particle-containing plating solution in the particle-containing plating solution is 1 ml / L or more and 100 ml / L or less. The particle-containing plating solution according to claim 14.

17. A particle-containing plating film formed by the particle-containing plating solution according to claim 14.

18. A particle-containing plating method including a step of immersing an object to be plated in the particle-containing plating solution according to claim 14.

19. An object to be plated on which the particle-containing plating film according to claim 17 is formed.