JP4662699B2 - Polymer fine particles having metal film and method for producing the same - Google Patents

Description

  The present invention relates to polymer fine particles having a metal film and a method for producing the same.

  Polyamide or polyimide is a material that excels in heat resistance, chemical resistance, mechanical properties, etc. In addition to applications such as aerospace, space, electronic / electric parts, automobiles, clothing, cosmetics, etc., it is an alternative material for metals or ceramics. Is widely used. In particular, polyamide or polyimide microparticles (including ultrafine particles) are effective for applications such as insulating materials, spacers, pastes, films, etc., and various methods for efficiently producing them have been proposed (for example, Patent Document 1, Patent Document 2, etc.).

Recently, research for imparting functionality to polyamide or polyimide microparticles has also been conducted. For example, if a metal film can be formed on these fine particles, a function such as conductivity can be imparted, and the application can be expanded.
JP-A-11-140181 JP 2000-248063 A

  The main object of the present invention is to provide polymer fine particles having a metal film.

  As a result of intensive studies in view of the problems of the prior art, the present inventors have found that the above object can be achieved by forming a metal film on the surface of polymer fine particles by a specific method, and complete the present invention. It came to.

  That is, the present invention relates to polymer fine particles having the following metal film and a method for producing the same.

  1. A polymer fine particle characterized in that a metal film is formed on the surface of polyimide fine particles or polyamide fine particles having an average particle diameter of 30 nm to 10 μm.

  2. Item 2. The polymer fine particle according to Item 1, wherein the metal film contains at least one of copper and nickel.

  3. A method for producing polymer fine particles having a metal film, wherein the surface of polyimide fine particles or polyamide fine particles having an average particle size of 30 nm to 10 μm is subjected to electroless plating to form a metal film on the surfaces of the fine particles. .

  4). Item 4. The manufacturing method according to Item 3, wherein the electroless plating treatment is performed without performing the etching treatment as a pretreatment of the electroless plating treatment.

  5. Item 5. The method according to Item 3 or 4, wherein the electroless plating treatment is performed in a plating bath having a pH of 1 to 10.

  6). Item 6. The method according to any one of Items 3 to 5, wherein the metal film contains at least one of copper and nickel.

  7. Prior to the electroless plating treatment, the polyimide fine particles or polyamide fine particles are treated with an aqueous solution in which stannous chloride is dissolved in an aqueous hydrochloric acid solution, and then the polyimide fine particles or polyamide fine particles are treated with an aqueous solution in which palladium chloride is dissolved in an aqueous hydrochloric acid solution. The manufacturing method in any one of said claim | item 3-6 which has the process to do.

  8). Prior to the electroless plating treatment, the polyimide fine particles or polyamide fine particles are treated with an aqueous solution in which palladium chloride and stannous chloride are dissolved in an aqueous hydrochloric acid solution, and then the polyimide fine particles or polyamide fine particles are treated with an aqueous hydrochloric acid solution. Item 7. The production method according to any one of Items 3 to 6.

  9. In the method in which the polyimide fine particles synthesize polyimide from tetracarboxylic anhydride and diamine compound, (a) a first step of preparing a first solution containing tetracarboxylic anhydride and a second solution containing diamine compound, respectively ( b) mixing the first solution with the second solution and ultrasonically stirring to precipitate the polyamic acid fine particles from the mixed solution; and (c) imidizing the obtained polyamic acid fine particles to obtain the polyimide fine particles. Item 3. The polymer fine particle according to Item 1, which is obtained by a method for producing a polyimide fine particle, which comprises a third step to be obtained.

  10. In the method in which polyamide fine particles synthesize polyamide from acid chloride and diamine compound, (a) a first step of preparing a first solution containing an acid chloride and a second solution containing a diamine compound, respectively; A second step of mixing the first solution and the second solution in the presence of a solvent that is soluble in both the solvent of the one solution and the second solution, and precipitating polyamide fine particles from the mixed solution by ultrasonic stirring; Item 2. The polymer particle according to Item 1, which is obtained by a method for producing a polyamide particle characterized by comprising:

  According to the present invention, polymer fine particles having a metal film on the particle surface can be provided. In particular, when electroless plating is performed under specific conditions, it is possible to form a metal film while effectively maintaining the particle properties of the raw material polyimide fine particles or polyamide fine particles.

  The polymer fine particles of the present invention can exhibit specific properties (for example, conductivity, catalytic activity, antibacterial properties, protein affinity, magnetism, etc.) due to the metal film. Therefore, the polymer fine particles of the present invention can be used as conductive nanoparticles, anisotropic conductive fine particles, anisotropic conductive films, conductive pastes, etc., and can be used in a wide range of fields such as electronic fields, medical fields, and chemical synthesis. There is expected.

1. Polymer fine particles The polymer fine particles of the present invention are characterized in that a metal film is formed on the surface of polyimide fine particles or polyamide fine particles having an average particle diameter of 30 nm to 10 μm.

  The material of the polymer fine particles is polyimide or polyamide. In the present invention, polyimide amide is also included as the polyamide. These may be obtained by a known production method, but are described later in the point that monodispersibility is high and the particle diameter is controlled. What is obtained by the manufacturing method shown in (5) is desirable.

  The average particle diameter of the polymer fine particles is usually 30 nm to 10 μm, preferably 30 nm to 6 μm, more preferably 50 nm to 1000 nm. In particular, when the polymer particles are polyimide, the thickness is preferably 30 nm to 3 μm, more preferably 50 nm to 1000 nm, and most preferably 50 nm to 700 nm. When the polymer particles are polyamide, the thickness is preferably 30 nm to 3 μm, more preferably 100 nm to 2 μm, and most preferably 200 nm to 2 μm.

  The shape of the polymer fine particles is not limited, and may be any of spherical, flat, indefinite shape, and the like.

The fine polymer particles preferably have a coefficient of variation of about 3 to 25% (particularly about 3 to 15%). Furthermore, the specific surface area of the polymer fine particles is not particularly limited, but it may be generally about 30 to 300 m ² / g.

  For the metal film formed on the surface of the polymer fine particles, the type of metal can be appropriately selected according to the use of the final product. For example, gold, silver, copper, nickel, palladium, platinum, chromium, cobalt, iron, zinc, tin, cadmium, and the like can be given. These can use 1 type (s) or 2 or more types. Among these, it is preferable that at least one of copper and nickel is included. In addition, when using 2 or more types, the one part or all may form the alloy or the intermetallic compound.

  The thickness of the metal film can be set as appropriate depending on the use of the final product, but is generally about 5 nm to 5 μm, preferably 10 nm to 1 μm.

The metal film may be a single layer or a laminate of two or more layers.
2. Production method of polymer fine particles The production method of the present invention is characterized in that a metal film is formed on the surface of the fine particles by performing electroless plating treatment on the surface of polyimide fine particles or polyamide fine particles having an average particle size of 30 nm to 10 μm. And

The polyimide fine particles or polyamide fine particles used as the raw material are the above-mentioned 1. It is preferable to use the same fine polyimide particles or polyamide fine particles as described above. As such polyimide fine particles or polyamide fine particles, known products or commercially available products can be used, or those obtained by a known production method can also be used.
For example, in the case of fine particles having an average particle size of about 1 μm or more, for example, polyamic acid which is a polyimide prepolymer is varnished in an aprotic polar solvent, imidized by heating it, and polyimide is formed as fine particles by precipitation. Can be mentioned.
Specifically, an aprotic polar solvent such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), etc., with aromatic diamine and tetracarboxylic anhydride. After preparing a polyamic acid varnish by polymerization at room temperature, polyimide fine particles are obtained by adding a predetermined amount of toluene to the varnish and refluxing and imidizing at a constant speed. Precipitation of imidized fine particles starts about 30 minutes to 1 hour after the start of refluxing, and the reaction is almost finished in about 4 hours. After completion of the reaction, the precipitated polyimide fine particles may be separated by filtration or centrifugal separation, and purified by washing with the solvent used in the reaction, methanol or acetone. The addition of toluene is to reduce the water generated in the imidation reaction from the reaction system by azeotropic distillation and reduce hydrolysis of the unreacted polyamic acid moiety.

  In particular, if the fine particles have an average particle size of 1 μm or less, polyimide fine particles or polyamide fine particles obtained by the following production methods 1) and 2) can be suitably used.

1) Polyimide fine particles In the method of synthesizing polyimide from tetracarboxylic anhydride and diamine compound, polyimide fine particles are prepared by (a) preparing a first solution containing tetracarboxylic anhydride and a second solution containing diamine compound, respectively. One step, (b) a second step of mixing the first solution and the second solution and precipitating the polyamic acid fine particles from the mixed solution; and (c) imidizing the obtained polyamic acid fine particles to obtain polyimide fine particles. What is obtained by the manufacturing method of the polyimide microparticle characterized by including the 3rd process to obtain can be used suitably. Hereafter, this manufacturing method is demonstrated for every process.

(1) 1st process Polyamide acid microparticles | fine-particles are prepared using an anhydrous tetracarboxylic acid and a diamine compound as a raw material. First, as a first step, a first solution containing tetracarboxylic anhydride and a second solution containing a diamine compound are prepared. That is, it is essential to prepare the tetracarboxylic anhydride and the diamine compound as separate solutions.

(A) First solution The tetracarboxylic anhydride used in the first solution is not particularly limited, and for example, the same ones used in conventional polyimide synthesis can be used. For example, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4 ′ -Biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (2,3-dicarboxyphenoxy) benzene Dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′- Biphenyltetracarboxylic dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, anthracene-2,3,6 , 7-Tetracarboxylic dianhydride Aromatic tetracarboxylic anhydrides such as phenanthrene-1,8,9,10-tetracarboxylic dianhydride; aliphatic tetracarboxylic anhydrides such as butane-1,2,3,4-tetracarboxylic dianhydride Alicyclic tetracarboxylic anhydrides such as cyclobutane-1,2,3,4-tetracarboxylic dianhydride; thiophene-2,3,4,5-tetracarboxylic anhydride, pyridine-2,3 , 5,6-tetracarboxylic acid anhydrides and the like can be used. These can use 1 type (s) or 2 or more types. In the present invention, BTDA, pyromellitic dianhydride and the like are particularly preferable.

  Moreover, in this invention, what substituted a part of tetracarboxylic anhydride with the acid chloride can be used. By substituting with acid chloride, it is possible to obtain effects such as increasing the reaction rate depending on conditions and making the particle size of the particles obtained finer. As the acid chloride, for example, diethyl pyromellitate diacyl chloride and the like can be used.

    The solvent used in the first solution is not particularly limited as long as tetracarboxylic anhydride is substantially dissolved and the produced polyamic acid is not dissolved. Examples include 2-propanone, 3-pentanone, tetrahydropyrene, epichlorohydrin, acetone, methyl ethyl ketone (MEK), tetrahydrofuran (THF), ethyl acetate, acetanilide, methanol, ethanol, isopropanol, toluene, xylene, and the like. A solvent containing at least one of the above can be used. Further, it is a solvent in which polyamic acid dissolves such as an aprotic polar solvent such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP). However, these can also be used if they are mixed with a poor solvent of polyamic acid such as acetone, ethyl acetate, MEK, toluene, xylene and the like so as to precipitate the polyamic acid.

  The concentration of tetracarboxylic anhydride in the first solution may be appropriately set according to the type of tetracarboxylic anhydride to be used, the concentration of the second solution, etc., but is usually about 0.001 to 0.20 mol / liter, Preferably, the content is 0.01 to 0.10 mol / liter.

(B) Second Solution The diamine compound used in the second solution is not particularly limited, and for example, the same diamine compound as used in conventional polyimide synthesis can be used. For example, 4,4′-diaminodiphenylmethane (DDM), 4,4′-diaminodiphenyl ether (DPE), 4,4′-bis (4-aminophenoxy) biphenyl (BAPB), 1,4′-bis (4- Aminophenoxy) benzene (TPE-Q), 1,3′-bis (4-aminophenoxy) benzene (TPE-R), o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,4′-diamino Diphenyl ether, 4,4′-diaminodiphenyl sulfone, 3,4-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-methylene-bis (2-chloroaniline), 3,3′-dimethyl- 4,4′-diaminobiphenyl, 4,4′-diaminodiphenyl sulfide, 2,6′-diaminotoluene, 2 , 4-diaminochlorobenzene, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 3,3′-diaminobenzophenone, 3,4-diaminobenzophenone, 4,4′-diaminobenzophenone, 4,4′-diaminobi Aromatic diamines such as benzyl, R (+)-2,2′-diamino-1,1′-binaphthalene, S (+)-2,2′-diamino-1,1′-binaphthalene; 1,2-diamino Methane, 1,4-diaminobutane, tetramethylenediamine, aliphatic diamine such as 1,10-diaminododecane, 1,4-diaminocyclohexane, 1,2-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 4, In addition to alicyclic diamines such as 4'-diaminodicyclohexylmethane, 3,4-diaminopyridine, 1,4-dia It can be used Roh-2-butanone. These can use 1 type (s) or 2 or more types. In the present invention, DPE, TPE-R and the like are particularly preferable.

  In the present invention, in addition to the diamine compound, other amine compounds (monoamine compounds, polyamine compounds, etc.) can also be used. By these, the characteristic of the polyamic acid or polyimide obtained can be changed.

  The solvent used in the second solution is not particularly limited as long as the diamine compound is substantially dissolved and the produced polyamic acid is not dissolved. Examples include 2-propanone, 3-pentanone, tetrahydropyrene, epichlorohydrin, acetone, methyl ethyl ketone (MEK), tetrahydrofuran (THF), ethyl acetate, acetanilide, methanol, ethanol, isopropanol, and the like, and at least one of these A solvent containing can be used. In addition, for example, those that dissolve a polyamic acid such as an aprotic polar solvent such as DMF, DMAc, and NMP are mixed with a poor polyamic acid solvent such as acetone, ethyl acetate, MEK, toluene, and xylene to form a polyamide. These can also be used if they are adjusted to precipitate the acid.

  The concentration of the diamine compound in the second solution may be appropriately set according to the type of the diamine compound to be used, the concentration of the first solution, etc., but is usually about 0.001 to 0.20 mol / liter, preferably about 0.000. 01-0.10 mol / liter.

(2) Second Step In the second step, the first solution and the second solution are mixed and the polyamic acid fine particles are precipitated from the mixed solution. The mixing ratio of the first solution and the second solution can be appropriately changed depending on the type of tetracarboxylic anhydride / diamine compound, the concentration of each solution, etc., but usually tetracarboxylic anhydride: diamine compound = 1: 0.5- What is necessary is just to mix so that it may become about 1.5 (molar ratio), Preferably it is 1: 0.9-1.1.

  In the second step, it is preferable to deposit the polyamic acid with stirring. As a stirring method, it can implement by a well-known stirring method (stirring apparatus). In the present invention, it is particularly preferable to stir by ultrasonic waves. By stirring with ultrasonic waves, it is possible to reduce the average particle size by about 50% as compared with a normal stirring method. For stirring by ultrasonic waves, a known ultrasonic device (for example, an ultrasonic cleaner) and operating conditions can be employed as they are. What is necessary is just to set the frequency of an ultrasonic wave suitably according to a desired particle size etc., Usually, it may be about 28-100 kHz, Preferably it may be 28-45 kHz.

  The temperature in the second step is not particularly limited, and is usually about 0 to 130 ° C, preferably 20 to 40 ° C. The stirring time may be performed until the precipitation of the polyamic acid is substantially completed, and is usually about 30 seconds to 30 minutes, but may be outside this range.

  The polyamic acid fine particles precipitated in the second step may be recovered by solid-liquid separation according to a known method such as a centrifugal separation method. When the polyamic acid fine particles (powder) obtained in the second step are produced as a sphere, generally the average particle size is 0.03 to 0.7 μm (preferably 0.03 to 0.55 μm), A monodispersed material having a standard deviation of 0.02 to 0.07 (preferably 0.02 to 0.055) and a coefficient of variation of 3 to 15% (preferably 3 to 9%). In the case of an indefinite shape, the size (average) of one piece is usually about 0.5 to 1.0 μm.

(3) Third Step As the third step, polyimide fine particles are obtained by imidizing the polyamic acid fine particles in the second step. The imidization method is not particularly limited as long as polyimide fine particles can be obtained as they are from the polyamic acid fine particles. In the present invention, in particular, (i) a method of imidizing by heating in an organic solvent (thermal ring closure), (ii) organic A method of imidizing by a chemical reaction in a solvent (chemical ring closure) or (iii) a method of heating and ring-closing imidization in a dry manner can be suitably used.

  In the method according to (i), for example, polyamic acid fine particles are dispersed in an organic solvent and heated at a temperature of usually 130 ° C. or higher, preferably about 130 to 250 ° C. The organic solvent is not limited as long as it is a poor solvent for polyamic acid and has a boiling point equal to or higher than the temperature required for the imidization reaction. In particular, in the present invention, the organic solvent preferably contains a solvent capable of forming an azeotrope with water (hereinafter also referred to as “azeotropic solvent”). That is, in the present invention, it is preferable to use an azeotropic solvent as a part or all of the organic solvent. As the azeotropic solvent, for example, xylene, ethylbenzene, octane, cyclohexane, diphenyl ether, nonane, pyridine, dodecane and the like can be used. These can use 1 type (s) or 2 or more types. In the present invention, the azeotropic solvent is preferably contained in the organic solvent in an amount of 10% by volume or more. By using an azeotropic solvent, water produced as a by-product (mainly condensed water) can be azeotropically removed and removed from the reaction system by refluxing, etc., thereby suppressing hydrolysis of unreacted amide bonds, As a result of preventing changes in particle shape, lowering of molecular weight, and the like, polyimide fine particles having excellent monodispersibility can be obtained more reliably.

  The proportion of the polyamic acid fine particles dispersed in the organic solvent may be appropriately set according to the type of the organic solvent, but is usually about 1 to 50 g / liter, preferably 5 to 10 g / liter.

  In the method according to (ii) above, a known chemical ring closure method can be applied. For example, polyamic acid fine particles may be dispersed in an organic solvent composed of pyridine and acetic anhydride and heated at a temperature of usually about 15 to 115 ° C. for about 24 hours while stirring. What is necessary is just to set the mixture ratio of both solvents suitably.

  In the method according to (iii) above, the particles may be heated to about 130 to 300 ° C. while flowing in an atmosphere such as air, vacuum, or inert gas. Also by this method, it is possible to imidize without agglomerating particles.

  The polyimide fine particles generated in the third step may be collected by a known method and washed with an organic solvent such as petroleum ether, methanol, acetone or the like as necessary.

2) Polyamide fine particles In the method of synthesizing polyamide from acid chloride and diamine compound, polyamide fine particles (a) a first step of preparing a first solution containing acid chloride and a second solution containing diamine compound, and (B) a second step of mixing the first solution and the second solution in the presence of a solvent that is soluble in both the solvent of the first solution and the second solution, and precipitating polyamide fine particles from the mixed solution; What is obtained by the manufacturing method of the polyamide fine particle characterized by containing can be used suitably. Hereinafter, this manufacturing method is demonstrated for every process.

(1) First Step Using an acid chloride and a diamine compound as raw materials, polyamide fine particles are prepared. First, as a first step, a first solution containing an acid chloride compound and a second solution containing a diamine compound are prepared. That is, it is essential to prepare the acid chloride and the diamine compound as separate solutions.

(A) First solution The acid chloride used in the first solution is not particularly limited, and for example, the same one used in conventional polyamide synthesis can be used.

  Examples of the acid chloride include aliphatics such as oxalic acid dichloride, malonic acid dichloride, succinic acid dichloride, fumaric acid dichloride, glutaric acid dichloride, adipic acid dichloride, muconic acid dichloride, sebacic acid dichloride, nonanoic acid dichloride, undecanoic acid dichloride, and the like. 1,2-cyclopropanedicarboxylic acid dichloride, 1,3-cyclobutanedicarboxylic acid dichloride, 1,3-cyclopentanedicarboxylic acid dichloride, 1,3-cyclohexanedicarboxylic acid dichloride, 1,4-cyclohexanedicarboxylic acid dichloride Alicyclic dicarboxylic acid dichloride such as phthalic acid dichloride, isophthalic acid dichloride, terephthalic acid dichloride, 1,4-naphthalene dicarboxylic acid Acid dichloride, 1,5- (9-oxofluorene) dicarboxylic acid dichloride, 1,4-anthracene dicarboxylic acid dichloride, 1,4-anthraquinone dicarboxylic acid dichloride, 2,5-biphenyldicarboxylic acid dichloride, 1,5-biphenylenedicarboxylic acid Acid dichloride, 4,4′-biphenyldicarbonyl chloride, 4,4′-methylene dibenzoic acid dichloride, 4,4′-isopropylidene dibenzoic acid dichloride, 4,4′-bibenzyldicarboxylic acid dichloride, 4,4 '-Stilbene dicarboxylic acid dichloride, 4,4'-transidicarboxylic acid dichloride, 4,4'-carbonyldibenzoic acid dichloride, 4,4'-oxydibenzoic acid dichloride, 4,4'-sulfonyldibenzoic acid dichloride, 4,4'-dithio dibenzo Dichloride, p- phenylene diacetic acid dichloride, and aromatic dicarboxylic acid dichloride such as 3,3'-p-phenylene acid dichloride. These acid chlorides can be used alone or in combination of two or more.

  The acid chloride can be appropriately selected according to the desired characteristics of the resulting polyamide fine particles. For example, when an aromatic dicarboxylic acid dichloride (especially at least one of terephthalic acid dichloride, 4,4′-biphenyldicarbonyl chloride and isophthalic acid dichloride) is used as the acid chloride, the heat resistance and monodispersity of the resulting polyamide fine particles can be improved. Can be improved. For example, when isophthalic acid chloride is used as the acid chloride, polyamide fine particles exhibiting a glass transition temperature can be obtained. The polyamide fine particles have a smooth surface property with relatively few irregularities on the particle surface.

  The polyamide of the present invention includes polyamideimide. Accordingly, acid chlorides used in conventional polyamideimide synthesis, such as trimellitic acid chloride, pyromellitic acid chloride, oxydiphthalic acid chloride, biphenyl-3,4,3 ′, 4′-tetracarboxylic acid chloride. , Benzophenone-3,4,3 ′, 4′-tetracarboxylic acid chloride, diethyl pyromellitate diacyl chloride, diphenylsulfone-3,4,3 ′, 4′-tetracarboxylic acid chloride, 4,4 ′-(2 , 2-hexafluoroisopropylidene) phthalic acid chloride, m (p) -phenyl-3,4,3 ′, 4′-tetracarboxylic acid chloride, cyclobutane-1,2,3,4-tetracarboxylic acid chloride, 1 -Carboxymethyl-2,3-5 cyclopentanetricarboxylic acid chloride Acid chlorides and the like may be used. These acid chlorides may be any of dichloride, trichloride, and tetrachloride. In addition, when producing polyamideimide, in addition to acid chloride, as carboxylic acid anhydride, trimellitic dianhydride, pyromellitic dianhydride, oxydiphthalic dianhydride, biphenyl-3,4, 3 ′, 4′-tetracarboxylic dianhydride, benzophenone-3,4,3 ′, 4′-tetracarboxylic dianhydride, diethyl pyromellitic diacyl dianhydride, diphenylsulfone-3,4,3 ', 4'-tetracarboxylic dianhydride, 4,4'-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, m (p) -phenyl-3,4,3 ', 4'- It is possible to use tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1-carboxymethyl-2,3-5 cyclopentanetricarboxylic dianhydride Kill.

  The solvent used in the first solution is not particularly limited as long as the acid chloride is substantially dissolved and the produced polyamide is not dissolved. Examples thereof include solvents soluble in a solvent having water or a hydroxyl group, such as acetone, dioxane, acetylacetone, methyl ethyl ketone, and methyl acetate, and a solvent containing at least one of these can be used. Among these, in the first solution, a solvent containing at least one of acetone and dioxane is preferable. Depending on the type of acid chloride used, it may not be immediately dissolved in a solvent such as acetone. In such a case, it may be dissolved in water or a solvent having a hydroxyl group in advance and then dissolved in acetone or the like. .

  The concentration of acid chloride in the first solution may be appropriately set according to the type of acid chloride used, the concentration of the second solution, etc., but is usually about 0.005 to 1 mol / liter, preferably 0.01 to About 0.5 mol / liter. It is preferable that the acid chloride concentration in the first solution be within such a range because aggregation and coalescence between particles can be suppressed and a monodispersed one can be easily obtained.

(B) Second solution The diamine compound used in the second solution is not particularly limited, and for example, the same diamine compound as used in conventional polyamide synthesis can be used. For example, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 1,4 ′ -Bis (4-aminophenoxy) benzene, 1,3'-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, o-phenylenediamine, m-phenylenediamine, p-phenylene Diamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-methylene-bis (2-chloroaniline) 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminodiphenylsulfur 2,6′-diaminotoluene, 2,4-diaminochlorobenzene, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 3,3′-diaminobenzophenone, 3,4-diaminobenzophenone, 4,4 '-Diaminobenzophenone, 4,4'-diaminobibenzyl, R (+)-2,2'-diamino-1,1'-binaphthalene, S (+)-2,2'-diamino-1,1'- 1, n-bis (4- (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy) alkane, etc. Aminophenoxy) alkane (n is 3 to 10), 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-aminophenyl) fluorene Aromatic diamines such as 4,4′-diaminobenzanilide; 1,2-diaminomethane, 1,4-diaminobutane, tetramethylenediamine, 1,5-diaminopentane, 1,6-diaminohexane, 1,8- Aliphatic diamines such as diaminooctane, 1,10-diaminododecane, 1,11-diaminoundecane; 1,4-diaminocyclohexane, 1,2-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 4,4′- In addition to alicyclic diamines such as diaminodicyclohexylmethane, 3,4-diaminopyridine, 1,4-diamino-2-butanone, and the like can be used. These can use 1 type (s) or 2 or more types. In particular, when at least one of 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone and 3,3′-diaminodiphenyl sulfone is used, heat resistance and monodispersity are improved. This is preferable.

  In the present invention, in addition to the diamine compound, other amine compounds (monoamine compounds, polyamine compounds, etc.) can also be used. By these, the characteristic of the polyamide obtained can be changed.

  The solvent used in the second solution is not particularly limited as long as the diamine compound is substantially dissolved and the produced polyamide is not dissolved. Examples thereof include solvents that are soluble in a solvent having water or a hydroxyl group, such as acetone, methyl ethyl ketone (MEK), dioxane, acetylacetone, and methyl acetate, and a solvent containing at least one of these can be used. Among these, in the second solution, a solvent containing at least one of acetone and dioxane is preferable. Depending on the type of diamine compound used, it may not be dissolved immediately in a solvent such as acetone. In such a case, it may be dissolved in water or a solvent having a hydroxyl group in advance and then dissolved in acetone or the like. .

  The solvent of the first solution and the solvent of the second solution may be the same or different as long as they are compatible with each other.

  The concentration of the diamine compound in the second solution may be appropriately set according to the type of the diamine compound to be used, the concentration of the first solution, etc., but is usually about 0.005 to 1 mol / liter, preferably 0.01 to 0.5 mol / liter. It is preferable that the concentration of the diamine compound in the second solution be within this range because aggregation and coalescence between particles can be suppressed and a monodispersed one can be easily obtained.

(2) Second step In the second step, the first solution and the second solution are mixed, and the presence of a solvent that is soluble in any of the solvents of the two solutions (hereinafter sometimes referred to as “soluble solvent”). Reaction is performed below to precipitate polyamide fine particles from the mixed solution. The mixing ratio of the first solution and the second solution can be appropriately changed according to the type of acid chloride or diamine compound, the concentration of each solution, etc., but usually acid chloride: diamine compound = 1: about 0.5 to 1.5. (Molar ratio), preferably in a ratio of 1: 0.9 to 1.1.

  The soluble solvent is not particularly limited as long as it is soluble in both the first solution and the second solution, but a solvent having water and a hydroxyl group is preferable. Specifically, water; alcohols having about 1 to 10 carbon atoms, for example, monohydric alcohols having about 1 to 10 carbon atoms such as methanol, ethanol, and propanol, ethylene glycol, 1,2-propanediol, 1,3 -C2-C5 dihydric alcohols such as propanediol and 1,5-pentanediol, C3-C6 trivalent alcohols such as 1,2,3-propanetriol and the like. Among these, as the soluble solvent, it is preferable to use water from the viewpoint of monodispersibility and particle size. In addition, when using the solvent which has water and a hydroxyl group as a soluble solvent, the solvent of a 1st solution and a 2nd solution is naturally a solvent soluble in these. For example, when water is used, it is preferable to use acetone and dioxane having high compatibility with water as the solvent for the first solution and the second solution.

  The soluble solvent may be added to the first solution and / or the second solution immediately before mixing the first solution and the second solution, but is preferably added to the second solution.

  The addition amount of the soluble solvent may be appropriately set according to the type of acid chloride and diamine compound to be used, the concentration of the first solution and the second solution, the desired (average) particle size of the obtained polyamide fine particles, etc. Is about 1 to 200 ml, preferably about 3 to 150 ml, with respect to 100 ml of the first solution or the second solution.

  By adding a soluble solvent, it is possible to obtain spherical fine particles with high monodispersibility.

  In the second step, it is particularly preferable to deposit the polyamide while stirring. Stirring can be carried out by a known stirring method (stirring device). In the present invention, it is particularly preferable to stir by ultrasonic waves. By stirring with ultrasonic waves, it is possible to reduce the average particle size by about 50% as compared with a normal stirring method. Moreover, particles with a more uniform particle size can be obtained by ultrasonic stirring. For stirring by ultrasonic waves, a known ultrasonic device (for example, an ultrasonic cleaner) and operating conditions can be employed as they are. The frequency of the ultrasonic wave may be appropriately set according to a desired (average) particle size and the like, and is usually about 28 to 1000 kHz, preferably about 28 to 100 kHz, and more preferably about 28 to 45 kHz.

  The temperature in the second step is not particularly limited, and is usually about 0 to 100 ° C., preferably about 0 to 40 ° C. When the mixed solution is cooled and the reaction rate is reduced, fine particles having a more spherical shape than the particle diameter are obtained. Therefore, the temperature of the second step is about room temperature (25 ° C.) or less, particularly about 0 to 15 ° C. Further preferred. The stirring may be performed until the precipitation of the polyamide is substantially completed, and the stirring time is usually about 30 seconds to 30 minutes, but may be out of this range.

  The polyamide fine particles precipitated in the second step may be recovered by solid-liquid separation according to a known method such as a centrifugal separation method.

  When trying to obtain polyamideimide as polyamide, use the ones used in the synthesis of polyamideimide such as trimellitic acid chloride as acid chloride and trimellitic anhydride as carboxylic anhydride, and fine particles obtained in the second step What is necessary is just to imidize by condensing the carboxyl group and amide group which exist. The method for imidization is not particularly limited. In the present invention, in particular, (i) it is dispersed in an organic solvent and heated (usually 130 ° C. or higher, preferably heated at a temperature of about 130 to 250 ° C.) for imidization. It is desirable to adopt a method (thermal ring closure) to perform (i) a method of imidization by a chemical reaction in an organic solvent (chemical ring closure).

Electroless Plating Treatment In the method of the present invention, a metal film is formed on the surface of the fine particles by subjecting the polyimide fine particles or polyamide fine particles to an electroless plating treatment.

  The method of electroless plating treatment is not limited as long as a desired metal film can be formed on the surface of these fine particles. For example, after pretreatment (degreasing, etching, catalyzing, etc.) is performed on polyimide fine particles or polyamide fine particles. A method of treating with a predetermined electroless plating bath can be employed. Each of these treatments can be performed according to a known electroless plating method.

  Degreasing methods include, for example, volatile paraffinic solvents (pentane, hexane, petroleum ether, ligroin, etc.), ketone solvents (acetone, MEK, etc.), ether solvents (diethyl ether, dimethyl ether, etc.), alcohols (methanol) Ethanol, isopropyl alcohol, etc.), halogen solvents (chloroform, carbon tetrachloride, etc.), surfactant-dispersed aqueous solutions, and the like.

  The etching treatment is not particularly limited, and for example, treatment with ozone, treatment with ultraviolet irradiation, heat oxidation treatment, treatment with a weak alkaline solution, treatment with a surfactant, and the like can be applied.

  The catalyst treatment is not particularly limited, and a method used in a known electroless plating treatment can be adopted. For example, the following method a) or b) can be preferably used.

Method a) Synthesizing activator method Polyimide fine particles or polyamide in an aqueous solution obtained by dissolving 0.1 to 10.0% by weight of stannous chloride in an aqueous hydrochloric acid solution obtained by diluting 12N concentrated hydrochloric acid 5 to 100 times with water. Fine particles are processed (synthesizing process). Subsequently, it is treated with an aqueous solution in which 0.0025 to 2.5% by weight of palladium chloride is dissolved in a hydrochloric acid aqueous solution obtained by diluting 12N concentrated hydrochloric acid 40 times to 4000 times with water (activator treatment).

Method b) Catalyst Accelerator Method 0.001 to 1% by weight of palladium chloride and 0.25 to 25% by weight of stannous chloride are dissolved in an aqueous hydrochloric acid solution obtained by diluting 2N concentrated hydrochloric acid 2 to 6 times with water. The polyimide fine particles or polyamide fine particles are treated with an aqueous solution (preferably a liquid temperature of 40 to 60 ° C.) (catalyst treatment). Then, it is treated with hydrochloric acid having a concentration of 1 to 20% by weight (accelerator treatment).

  In the present invention, in particular, it is desirable that the polyimide fine particles or the polyamide fine particles are subjected to a catalytic treatment without etching, and then treated in an electroless plating bath. By such a method, it is possible to form a metal film while more effectively maintaining the components, shapes, etc. of the polyimide fine particles or polyamide fine particles.

  After the pretreatment, the polyimide fine particles or the polyamide fine particles are treated in an electroless plating bath to form a metal film.

  The electroless plating bath can be appropriately set according to the properties of the desired metal film according to a known electroless plating process. For example, an electroless plating bath containing main components (metal salt, reducing agent) and further containing auxiliary components (pH adjuster, buffer, complexing agent, accelerator, stabilizer, modifier) as necessary. Can be used.

  As a metal salt, it can select suitably according to the kind etc. of a desired metal film. For example, when a metal film made of nickel is formed, a nickel salt such as nickel sulfate or nickel nitrate may be used.

  As the reducing agent, for example, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, glyoxylic acid, sodium borohydride, tartaric acid, glucose, glycerin, hydrogen peroxide and the like can be used. In the present invention, an electroless plating bath containing at least one of sodium hypophosphite and dimethylamine borane as a reducing agent is particularly preferable.

  As a pH adjuster, various inorganic acids and organic acids can be used in addition to basic compounds such as caustic soda and ammonium hydroxide. The pH adjusting agent can mainly control the plating rate, reduction efficiency, and the like.

  The buffer is not limited as long as pH fluctuation can be suppressed. For example, in addition to oxycarboxylate compounds (organic acids) such as sodium citrate and sodium acetate, inorganic salts such as borate and carbonate Examples of the acid salt include alkali salts having a small dissociation constant.

  Any complexing agent may be used as long as it can bring the plating bath into a complex ion state. For example, sodium citrate, sodium acetate, ethylene glycol, alkali salts of organic acids (acetic acid, glycols, citric acid, tartaric acid, etc.), thioglycols, ammonia, hydrazine, triethanolamine, ethylenediamine, glycine, o-aminophenol And pyridines.

  The promoter is used for improving the deposition efficiency of the metal by accelerating the plating rate and suppressing the generation of hydrogen gas. For example, sulfide, fluoride, etc. can be used.

  The stabilizer serves to suppress the oxidation-reduction reaction from occurring on the surface other than the surface of the object to be plated. That is, automatic decomposition of the plating bath can be prevented by adding a stabilizer. Further, it is possible to prevent precipitates and the like generated simultaneously with the aging of the plating bath from reacting with the reducing agent and generating hydrogen gas violently. Examples of such stabilizers include lead chloride, sulfide, and nitrate.

  The modifier is used to improve the state of the plating film such as gloss. In general, polyethylene glycol or the like can be used. However, the addition amount may generally be a trace amount.

  As a more specific plating bath, when performing copper plating, for example, at least one of sodium hypophosphite and dimethylamine borane, water, copper sulfate, nickel sulfate, sodium citrate, boric acid and polyethylene A bath composition containing glycol is preferred. When nickel plating is performed, for example, a bath composition containing at least one of sodium hypophosphite and dimethylamine borane, water, nickel sulfate, sodium citrate, lactic acid, and polyethylene glycol is preferable. Alternatively, when nickel plating is performed, for example, a bath composition containing water, nickel sulfate, glycine, malic acid and polyethylene glycol in addition to at least one of sodium hypophosphite and dimethylamine borane is preferable. The ratio, concentration, etc. of these components can be appropriately determined according to the desired properties of the metal coating. For example, when increasing the thickness of the metal film, the concentration of each component in the electroless plating bath may be increased.

  The operating conditions for the electroless plating process can also be set as appropriate according to a known electroless plating process. The amount of the electroless plating treatment can be appropriately determined according to the properties of the polyimide fine particles or polyamide fine particles used, the composition of the electroless plating bath, and the like. The temperature of the electroless plating bath is not limited, but is generally 40 to 100 ° C., preferably 50 to 90 ° C. The pH of the electroless plating bath is desirably about 1 to 10, particularly about 3 to 10, more preferably about 6 to 10. By setting the pH within the above range, it is possible to perform plating while maintaining the particle properties of the raw material polyimide fine particles or polyamide fine particles more reliably. The treatment time in the electroless plating bath is appropriately changed according to the composition of the plating bath, the liquid temperature, pH, the treatment amount, and the like.

  After the electroless plating process is completed, the obtained polymer fine particles may be collected by a known solid-liquid separation method, and may be washed by water or the like as necessary.

  Examples are given below to clarify the features of the present invention. However, the present invention is not limited to the scope of these examples.

The analysis / evaluation method in each Example was performed by the following method.
(1) Particle morphology: observed with a scanning electron microscope (SEM).
(2) Elemental analysis (metal coating)
The metal component on the surface of the polymer fine particles was examined by energy dispersive X-ray spectroscopy (EDX).
(3) Alteration of polymer fine particles It was examined by infrared absorption spectroscopy (FT-IR) that the polymer fine particles (polyimide or polyamide) after the metal film formation treatment were not altered.
(4) Thermal decomposition temperature It measured with the thermogravimetry apparatus (TGA, in the air).
(5) Ratio of metal film It measured with the thermogravimetry apparatus (TGA, in the air) from the residue weight after polymer particle thermal decomposition.

Reference example 1
Preparation of polyimide fine particles First, prepare a 500 ml solution in which 0.02 mol of pyromellitic dianhydride was dissolved in acetone as the first solution, and a 500 ml solution in which 0.02 mol of p-phenylenediamine was dissolved in acetone as the second solution. did. Next, both solutions were mixed at 25 ° C., stirred for 10 minutes with an ultrasonic wave with a frequency of 38 kHz, and reacted to precipitate polyamic acid fine particles. The recovered polyamic acid fine particles were dispersed in 2 L of xylene and then imidized by refluxing at 135 ° C. for about 4 hours to obtain polyimide fine particles having an average particle size of 366 nm and a coefficient of variation of 7.1%.

Reference example 2
Preparation of polyimide fine particles 500 ml solution of 0.03 mol of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride dissolved in acetone as the first solution, 4,4′-diaminodiphenyl ether as the second solution Except for using a 500 ml solution in which 02 mol was dissolved in acetone, polyimide fine particles having an average particle size of 269 nm and a coefficient of variation of 6.0% were obtained in the same manner as in Reference Example 1.

Reference example 3
Preparation of polyamide fine particles First, as a first solution, a 500 ml solution in which 0.005 mol of isophthalic acid chloride was dissolved in dioxane, and as a second solution, a 500 ml solution in which 0.005 mol of 4,4′-diaminodiphenyl ether was dissolved in dioxane, respectively. As prepared, both solutions were cooled to about 12 ° C. Thereafter, 250 ml of ion exchange water was added to the first solution and stirred. Next, both solutions were mixed in an ice bath, stirred for 20 minutes with an ultrasonic wave having a frequency of 28 kHz, and reacted to obtain polyamide fine particles having an average particle size of 340 nm and a coefficient of variation of 8.2%.

Example 1
(1) Catalytic treatment 10 g of the polyimide fine particles of Reference Example 1 were added to an aqueous solution in which 10 g of stannous chloride was dissolved in hydrochloric acid (40 ml of concentrated hydrochloric acid diluted with 1000 ml of water), and dispersed with a homogenizer at room temperature for about 2 minutes. Thereafter, solid-liquid separation was performed by centrifugation, and the fine particles were washed with water. Next, 10 g of the fine particles are put into an aqueous solution in which 0.25 g of palladium chloride is dissolved in hydrochloric acid (2.5 ml of concentrated hydrochloric acid diluted with 1000 ml of water), dispersed with a homogenizer at room temperature for about 2 minutes, and then solidified by centrifugation. Liquid separation was performed, and the fine particles were washed with water.
(2) Electroless plating Copper sulfate, nickel sulfate, sodium citrate, sodium hypophosphite and polyethylene glycol in the blending amounts shown in Table 1 were dissolved in water. To this, 3 g of the catalyst-treated polyimide fine particles (1) were added and completely dispersed with a homogenizer, and then the liquid temperature was heated to 60 ° C. and boric acid was added. After the boric acid was completely dissolved, the pH was adjusted to the range of 8 to 8.5 by adding an aqueous sodium hydroxide solution while stirring with a stirrer while maintaining 60 ° C. By continuing stirring as it was, the reduction reaction started in about 5 to 10 minutes, and plating started. The reduction reaction was completed in about 7 to 8 minutes. The end of plating was taken as a guide when hydrogen gas was no longer generated by the plating reaction. After the plating was completed, decantation was repeated several times to collect the plated polyimide fine particles.

得られたポリマー微粒子をＳＥＭで観察した結果、形態は球状であり、メッキ処理によって形態が変化することなく、当初の形態が実質的に維持されていることを確認した。このポリマー微粒子は、熱分解温度３５７℃、Ｃｕの含有量２２．５重量％であった。また、上記ポリイミド微粒子の表面をＥＤＸで観察した結果、微粒子表面にＣｕの存在が認められた。さらに、上記ポリイミド微粒子をＦＴ−ＩＲにて分析したところ、無電解メッキ処理後の微粒子がポリイミドのスペクトルを示した。

As a result of observing the obtained polymer fine particles with SEM, the form was spherical, and it was confirmed that the original form was substantially maintained without being changed by plating. The fine polymer particles had a thermal decomposition temperature of 357 ° C. and a Cu content of 22.5% by weight. Moreover, as a result of observing the surface of the said polyimide fine particle by EDX, presence of Cu was recognized by the fine particle surface. Furthermore, when the said polyimide fine particle was analyzed by FT-IR, the fine particle after the electroless-plating process showed the spectrum of the polyimide.

Example 2
(1) Catalytic treatment The polyimide fine particles of Reference Example 1 were used and treated in the same manner as in Example 1 (1) Catalytic Treatment (2) Electroless Plating The composition of the electroless plating bath was as follows: The polyimide fine particles were subjected to electroless plating treatment by the same method as (2) electroless plating in Example 1 except that those shown in Table 2 were applied.

得られたポリマー微粒子をＳＥＭで観察した結果、形態は球状であり、メッキ処理によって形態が変化することなく、当初の形態が実質的に維持されていることを確認した。このポリマー微粒子の熱分解温度は３４２℃であり、Ｃｕ含有量は３８．２重量％であった。また、上記ポリマー微粒子の表面性状をＥＤＸで観察した結果、微粒子表面にＣｕの存在が認められた。さらに、上記ポリマー微粒子をＦＴ−ＩＲにて分析したところ、無電解メッキ処理後の微粒子がポリイミドのスペクトルを示した。

As a result of observing the obtained polymer fine particles with SEM, the form was spherical, and it was confirmed that the original form was substantially maintained without being changed by plating. The thermal decomposition temperature of the fine polymer particles was 342 ° C., and the Cu content was 38.2% by weight. Moreover, as a result of observing the surface properties of the polymer fine particles with EDX, the presence of Cu was observed on the surface of the fine particles. Further, when the polymer fine particles were analyzed by FT-IR, the fine particles after the electroless plating treatment showed a spectrum of polyimide.

Example 3
The electroless plating process was performed in the same manner as in Example 1 except that the polyimide fine particles of Reference Example 2 were used as the polyimide fine particles.

  As a result of observing the obtained polymer fine particles with SEM, the form was spherical, and it was confirmed that the original form was substantially maintained without being changed by plating. The thermal decomposition temperature of the polymer fine particles was 380 ° C., and the Cu content was 90% by weight. Moreover, as a result of observing the surface properties of the polymer fine particles with EDX, the presence of Cu was observed on the surface of the fine particles. Further, when the polymer fine particles were analyzed by FT-IR, the fine particles after the electroless plating treatment showed a spectrum of polyimide.

Example 4
(1) Catalytic treatment Into an aqueous solution in which 0.5 g of palladium chloride and 25 g of stannous chloride were dissolved in hydrochloric acid (300 ml of concentrated hydrochloric acid diluted with 600 ml of water), 10 g of the polyamide fine particles of Reference Example 3 were introduced at room temperature. After dispersing with a homogenizer for 2 minutes, solid-liquid separation was performed by centrifugation, and the fine particles were washed with water. Next, 10 g of the fine particles were put into hydrochloric acid (concentration: 10% by weight), dispersed with a homogenizer at room temperature for about 2 minutes, solid-liquid separated by centrifugation, and the fine particles were washed with water.
(2) Electroless plating The polyamide fine particles treated in the above (1) were treated in the same manner as the method shown in (2) Electroless plating in Example 1.

  As a result of observing the obtained polymer fine particles with SEM, the form was spherical, and it was confirmed that the original form was substantially maintained without being changed by plating. The thermal decomposition temperature of the fine polymer particles was 372 ° C., and the Cu content was 31.6% by weight. Moreover, as a result of observing the surface properties of the polymer fine particles with EDX, the presence of Cu was observed on the surface of the fine particles. Further, when the polymer fine particles were analyzed by FT-IR, the fine particles after the electroless plating treatment showed a spectrum of polyamide.

Example 5
(1) Catalytic treatment The polyimide fine particles of Reference Example 1 were used and treated in the same manner as in Example 1 (1) Catalytic treatment (2) Electroless plating Nickel sulfate in the blending amounts shown in Table 3 Sodium citrate, lactic acid and polyethylene glycol were dissolved in water. To this, 3 g of the catalyst-treated polyimide fine particles (1) were added and completely dispersed with a homogenizer, and then the liquid temperature was heated to 50 ° C., and dimethylamine borane was added. While maintaining the liquid temperature at 50 ° C., an aqueous ammonia solution was added while stirring with a stirrer to adjust the pH to 7.0. By continuing stirring as it was, the reduction reaction started in about 5 minutes and plating started. The reduction reaction was completed in about 10 minutes. The end of plating was taken as a guide when hydrogen gas was no longer generated by the plating reaction. After the plating was completed, decantation was repeated several times to collect the plated polyimide fine particles.

得られたポリマー微粒子をＳＥＭで観察した結果、形態は球状であり、メッキ処理によって形態が変化することなく、当初の形態が実質的に維持されていることを確認した。このポリマー微粒子の熱分解温度は３６８℃、Ｃｕ含有量は２４．８重量％であった。また、上記ポリイミド微粒子の表面性状をＥＤＸで観察した結果、微粒子表面にＮｉの存在が認められた。さらに、上記ポリマー微粒子をＦＴ−ＩＲにて分析したところ、無電解メッキ処理後の微粒子がポリマーのスペクトルを示した。

As a result of observing the obtained polymer fine particles with SEM, the form was spherical, and it was confirmed that the original form was substantially maintained without being changed by plating. The polymer fine particles had a thermal decomposition temperature of 368 ° C. and a Cu content of 24.8% by weight. Further, as a result of observing the surface properties of the polyimide fine particles with EDX, the presence of Ni was observed on the surface of the fine particles. Furthermore, when the polymer fine particles were analyzed by FT-IR, the fine particles after the electroless plating treatment showed a polymer spectrum.

Example 6
(1) Catalytic treatment The polyamide fine particles of Reference Example 3 were used and treated in the same manner as in Example 4 (1) Catalytic treatment (2) Electroless plating Nickel sulfate in the blending amounts shown in Table 4 Glycine, malic acid and polyethylene glycol were dissolved in water. To this, 5 g of the catalyst-treated polyamide fine particles (1) were added and completely dispersed with a homogenizer, and then the liquid temperature was heated to 70 ° C., and dimethylamine borane was added. The liquid temperature was maintained at 70 ° C., and the pH was adjusted to 7.0 by adding an aqueous ammonia solution while stirring with a stirrer. By continuing stirring as it was, the reduction reaction started in about 5 minutes and plating started. The reduction reaction was completed in about 7 minutes. The end of plating was taken as a guide when hydrogen gas was no longer generated by the plating reaction. After the plating was completed, decantation was repeated several times to collect the plated polyamide fine particles.

得られたポリマー微粒子をＳＥＭで観察した結果、形態は球状であり、メッキ処理によって形態が変化することなく、当初の形態が実質的に維持されていることを確認した。このポリマー微粒子の熱分解温度は３８１℃であった。また、このポリマー微粒子のＮｉの含有量は３４．５重量％であった。上記ポリマー微粒子の表面性状をＥＤＸで観察した結果、微粒子表面にＮｉの存在が認められた。さらに、上記ポリマー微粒子をＦＴ−ＩＲにて分析したところ、無電解メッキ処理後の微粒子がポリアミドのスペクトルを示した。

As a result of observing the obtained polymer fine particles with SEM, the form was spherical, and it was confirmed that the original form was substantially maintained without being changed by plating. The thermal decomposition temperature of the polymer fine particles was 381 ° C. Further, the Ni content of the polymer fine particles was 34.5% by weight. As a result of observing the surface properties of the polymer fine particles with EDX, the presence of Ni was observed on the fine particle surfaces. Further, when the polymer fine particles were analyzed by FT-IR, the fine particles after the electroless plating treatment showed a spectrum of polyamide.

Claims (6)

A method for producing polymer fine particles having a metal film, comprising the following steps (1) and (2):
(1) Manufacturing process of polyamide fine particles having an average particle diameter of 100 nm to 2 μm including the following steps (a) and (b):
(A) A first solution containing a dicarboxylic acid dichloride selected from the group consisting of an aliphatic dicarboxylic acid dichloride, an alicyclic dicarboxylic acid dichloride and an aromatic dicarboxylic acid dichloride, and a second solution containing a diamine compound are prepared. (B) in the presence of a solvent that is at least one of water and a hydroxyl group-containing solvent that is soluble in both the first solution and the second solution;
A second step of mixing the first solution and the second solution and precipitating polyamide fine particles from the mixed solution; and
(2) A step of forming a metal film on the surface of the fine particles by subjecting the surface of the fine particles of polyamide having an average particle size of 100 nm to 2 μm obtained by the production process to electroless plating. The manufacturing method of Claim 1 which performs an electroless-plating process, without performing an etching process as a pre-process of an electroless-plating process. The manufacturing method of Claim 1 or 2 which performs an electroless-plating process in the plating bath of pH 1-10. The manufacturing method in any one of Claims 1-3 in which a metal film contains at least 1 sort (s) of copper and nickel. Prior to the electroless plating treatment, the method includes a step of treating polyamide fine particles with an aqueous solution in which stannous chloride is dissolved in an aqueous hydrochloric acid solution, and then treating the polyamide fine particles with an aqueous solution in which palladium chloride is dissolved in an aqueous hydrochloric acid solution. The manufacturing method in any one of 1-4. Prior to the electroless plating treatment, the method comprises treating the polyamide fine particles with an aqueous solution in which palladium chloride and stannous chloride are dissolved in an aqueous hydrochloric acid solution, and then treating the polyamide fine particles with an aqueous hydrochloric acid solution. The manufacturing method of crab.