WO2001063005A1

WO2001063005A1 - Method of pretreatment of plastic for plating and method of plating

Info

Publication number: WO2001063005A1
Application number: PCT/JP2001/001193
Authority: WO
Inventors: Motonobu Goto; Teruo Hori; Yoshihiro Sugawa; Takashi Mizoguchi; Hiroki Kamiyama
Original assignee: Cosmo Research Institute; Cosmo Oil Co., Ltd.
Priority date: 2000-02-22
Filing date: 2001-02-20
Publication date: 2001-08-30
Also published as: JP4660661B2; JP2001316832A

Abstract

A method of the pretreatment for plating, characterized as contacting a plastic with a supercritical fluid to thereby treat the surface of the plastic so that the surface can be plated; a method of the pretreatment for plating, characterized as contacting a plastic with a supercritical fluid containing a plating catalyst, to thereby bind the plating catalyst to the plastic; a method of plating characterized as contacting a plastic with a supercritical fluid and then plating the plastic; a method for producing a plated product, characterized as contacting a plastic product with a supercritical fluid and then plating the product; and a plating apparatus characterized as having a reactor for contacting a plastic with a supercritical fluid.

Description

Description Metal plating pretreatment method and plating method for plastics

The present invention relates to a plating pretreatment method and a plating method for a plastic which can be plated in a simple process without using a chromic sulfuric acid solution or an alkali solution used for etching in a usual plating pretreatment. Background art

The plating process of plastics varies slightly depending on the material and purpose, but generally includes the steps of degreasing, etching, neutralizing, moistening, applying a catalyst, activating the catalyst (pre-treatment), and applying a plating film to the molded product. Become.

Generally, etching methods include (1) etching using a chromic acid solution, (2) etching using an alkali metal hydroxide solution, (3) swelling using an organic solvent, and (4) a combination of (1) to (3). It is performed in combination of ① and ②.

Since the above pretreatment method uses a highly concentrated acid solution, alkali solution, and chromium metal, post-treatment of these reagents is indispensable. This is one of the problems that raises costs. Further, the complexity and number of pretreatment steps occupying the plating step are another problem. Disclosure of the invention

The present invention relates to a plastic pretreatment method that can be processed in a simple process without discharging environmental pollutants because the supercritical fluid and catalyst to be used are easy to recover and can be reused. It is an object of the present invention to provide a method, a method for manufacturing a metal plate, and a metal plate device. As a result of intensive studies to solve the above problems, the present investigators have found that the above problems can be solved by bringing plastics into contact with a supercritical fluid, and based on this finding, complete the present invention. Reached.

That is, the present invention relates to the following (1) to (21).

(1) A plating pretreatment method, which comprises applying a supercritical fluid to a plastic so that the plastic is subjected to a plating surface treatment.

(2) A plating pretreatment method, wherein the plating catalyst is attached to the plastic by bringing a supercritical fluid containing the plating catalyst into contact with the plastic.

(3) A plating pretreatment method, which comprises: bringing a supercritical fluid containing a plating catalyst into contact with a plastic so as to apply a plating surface treatment to the plastic; and further attaching the plating catalyst.

(4) The method of mounting the serial to any of the supercritical fluid contains supercritical C0 ₂ (1) to (3).

(5) The method according to any one of the above (1) to (4), wherein the treatment is performed under a temperature condition of 304 to 673 K.

(6) The method according to any one of (1) to (5) above, wherein the treatment is performed at a pressure of 73 to 600 atm.

(7) The plating pretreatment method according to any one of the above (2) to (6), wherein the plating catalyst is a compound containing palladium, copper or nickel metal.

(8) The above (1) to (1) wherein the plastic is at least one member selected from the group consisting of polyamide, polyimide, polyester, polyether, vinyl polymer, epoxy resin, fluorinated polymer and io-containing polymer. 7) The plating pretreatment method according to any one of the above.

(9) A plating method characterized in that a plastic is brought into contact with a supercritical fluid and then subjected to a plating treatment.

(10) The method according to the above (9), wherein wetting, catalyst application, and catalyst activation are performed before the plating treatment. (11) The method according to the above (9) or (10), wherein the supercritical fluid contains a plating catalyst.

(1 2) A method for producing a stamped product, which comprises subjecting a plastic to a supercritical fluid and then subjecting the plastic to a stamping process.

(13) The method according to the above (12), wherein wetting, catalyst application, and catalyst activation are performed before the plating treatment.

(14) The method according to the above (12) or (13), wherein the supercritical fluid contains a plating catalyst.

(15) The method according to any one of the above (12) to (14), wherein the supercritical fluid contains supercritical CO ₂ .

(16) The method according to any one of (12) to (15) above, wherein the treatment is performed under a temperature condition of 304 to 673 K.

(17) The method according to any one of (12) to (16), wherein the treatment is performed at a pressure of 73 to 600 atm.

(18) The method according to any one of the above (14) to (17), wherein the plating catalyst is a compound containing palladium, copper or nickel metal.

(19) The above-mentioned (12) to (12), wherein the plastic is at least one selected from polyamide, polyimide, polyester, polyether, biel-based polymer, epoxy resin, fluorinated polymer and io-containing polymer. The method according to any one of (18).

(20) A plating apparatus having a reaction tank for bringing plastic into contact with a supercritical fluid.

(21) The apparatus according to (20), further comprising a high-pressure pump, a back-pressure valve, and a cooling device. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 schematically shows an example of a reaction tank included in the plating apparatus of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The plastic used in the present invention is not particularly limited, but preferably includes a polyamide, a polyimide, a polyester, a polyether, a butyl polymer, an epoxy resin, a fluorinated polymer, and an io polymer.

These plastics may be used alone or as a mixture of two or more.

The mixture of two or more kinds may be a polymer alloy or a polymer blend obtained by physically or chemically blending the above plastics at a predetermined composition ratio. Further, the plastic may be a modified product, or may be a copolymer obtained by polymerizing two or more kinds of monomers constituting these at a predetermined ratio. As used herein, the term “copolymer” refers to a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer.

Here, plastic is a concept that includes plastic molded products.

Polyamides include, for example, polyamide 11 (PA11), polyamide 12 (PA12), polyamide 46 (PA46), polyamide 6 (PA6), polyamide 66 (PA66), and the like. And preferably PA12, PA6 and PA66.

Examples of the polyimide include polyimide (PI), polyamide amide (PAI), bismaleide, and polyetherimide (PEI), and preferably PI and PEI.

Examples of polyester include polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polycyclohexane dimethylene terephthalate (PCT), polyarylate (PAR), polybutylene naphthalate (PBN), and polyethylene naphthalate (PET). PEN), liquid crystal polymer (LCP), polycarbonate (PC) and the like, and PBT, PET, PAR, PEN, LCP and PC are preferred. Examples of polyethers include polyacetal (POM), polyether nitrile (PENT), polyether 'ether' ketone (PEEK), polyether ketone (PEK), polyketone (PK), polyether 'ketone' ketone (PEKK) And polyolefin ether (PPE), modified PPE, and the like. POM, PENT, PEEK, PEK, and modified PPE are preferred.

Examples of the bull-based polymer include polyethylene (PE), polypropylene (PP), chlorinated polyethylene (CPE), polystyrene (PS), acrylonitrile'butadiene.styrene (ABS) and the like, preferably PE, PP , PS and ABS.

Examples of the epoxy resin include a combination of a main agent such as phenol glycidyl ether such as bisphenol A, bisphenol F and phenol novolac, or an alcohol glycidyl ether such as polypropylene dalicol, and a curing agent. Examples of the fluorinated polymer include polytetrafluoroethylene (PTFE), polytetrafluoroethylene ethylene (ETFE), polychlorotriphenylene ethylene (PCTFE), and polyfluoroalkyl vinyl ether (PFA). Is PTFE, PFA.

Preferred examples of the i-containing polymer include polyphenylene sulfide (PPS), polyethersulfone (PES), and polysulfone (PSF).

Examples of the copolymer include, in addition to the above-mentioned copolymers, acrylates 'styrene' acrylonitrile (AAS), atarilononitrile 'EPDM rubber' styrene (AES), acrylonitrile styrene (AS), styrene Maleimide and the like.

Further, fillers and additives may be blended in the plastics.

In conventional etching using chromic sulfuric acid, alkali, etc., plastics such as polyethylene and polypropylene, which have excellent chemical resistance, need to contain a filler such as silica. The plastic to be prepared does not need to contain a filler, but may contain a filler. The filler is not particularly limited, but is preferably an inorganic filler.

Examples of inorganic fillers include calcium carbonate, magnesium carbonate, barium carbonate, glass, carbon »1, glass III, glass balloon, shirasu balloon, calcium oxide, dumbbell oxide, titanium oxide, iron oxide, magnesium oxide, calcium sulfate, and sulfuric acid. Magnesium, barium sulfate, aluminum sulfate, pyrophosphate, silicon nitride, aluminum nitride, boron nitride, carbon black, graphite, carbon fiber, activated carbon, silica, alumina, alumina mt, Aluminum hydroxide, magnesium hydroxide, magnesium hydroxide, myriki, kaolin, clay, tanolek, kieselguhr, volcanic ash, limestone, bentonite, calcium titanate, potassium titanate, aluminum borate, magnesium borate, silicon carbide, Molybdenum disulfide And the like. These fillers may be used alone or in combination of two or more.

The shape of the filler is not particularly limited, but is preferably spherical, granular, flaky, dendritic, horn-like, spongy, needle-like, fibrous, plate-like, etc. Is also good. The average particle size of the filler is not particularly limited, but is preferably from 0.01 to 100 μm. The content of the filler is not particularly limited, but is preferably 400 parts by mass or less per 100 parts by mass of the plastic.

Additives are not particularly limited, but basic properties of plastics, such as mechanical properties, electrical properties, heat resistance, moldability, flowability, flame retardancy, UV resistance, chemical resistance, resin phase Various additives may be blended for the purpose of improving the solubility, the appearance of the molded article, or coloring or imparting gloss. Examples of the additive include a plasticizer, a heat stabilizer, an oxidation stabilizer, a cross-linking agent, a flame retardant, an ultraviolet absorber, a compatibilizer, a colorant, and a gloss imparting agent. These additives may be used alone or in combination of two or more.

The shape of the plastic can be any shape, for example, various shapes such as a particle shape, a plate shape, a rod shape, and a three-dimensional shape.

In the present invention, the supercritical fluid into contact with the plastic is not particularly limited, as the type of fluid, preferably _{air, A r, B r 2,} CO, C 0 2, C 1 2, F 2, _{H 2, HB r, HC 1} , HF, H 2 0, H 2 S,, He, Kr, N 2, NH 3, Ne, O 2, S0 2, S0 3, Xe, methane, Etan, propane, heptane , pentane, hexane, heptane, octane, ethylene, propylene, 1, 3-butadiene, _{_{acetylene, CC 1 4, CHC 1 3}} , CH 2 C 1 2, methanol, ethanol, 1 Purono Nord, 2-propanol, 1- Butanol, allylic alcohol, methyl ether, methyl ethyl ether, ethyl ethyl ether, ethyl alcohol, honole munor aldehyde, acetone, ethyl ethyl methyl ketone, benzene, toluene, xylene, ethyl benzene, thiophene, pyridine, etc. Is received. More preferably, _{_{air, CO, C0 2, H 2}} 0, N 2, NH 3, 0 2, methane, E Tan, hexane propane, butane, pentane, ethylene, propylene, acetylene, CHC 1 _3, CH ₂ C 1 _2, methanol, Etanonore, 1-propanol one Honoré, 2 Puroha ⁰ Nonore, Echirueteru, acetone, E chill methyl ketone, benzene, Tonoreen, such as pin lysine. More preferably, like C0 _{_2,} H ₂ 0. These may be used alone or as a mixture of two or more.

Since supercritical fluids have different supercritical conditions for each fluid, the temperature and pressure ranges of these supercritical fluids are different. For example, C0 ₂ is 304K, 73 atm or more becomes a supercritical fluid, called respectively the critical temperature and critical pressure. H ₂₀ has a critical temperature of 647 K and a critical pressure of 218 atm.

The supercritical fluid may be brought into contact with the plastic at a critical temperature or higher and a critical pressure or higher. Preferred conditions differ depending on the plastic to be treated and the supercritical fluid used. It should be more than 1000 a tm. The concrete example, the case of C0 _2, the preferred temperature 304～800K, pressure is seventy-three to one 000 atm. More preferably, the temperature is 304-673 K: and the pressure is 73-60 O atm.

When two or more fluids are mixed, they are brought into contact with the plastic at a temperature higher than the critical temperature of the fluid having the lower critical temperature and higher than the critical pressure of the fluid having the lower critical pressure. I'll do it. That is, supercritical with lower critical temperature and critical pressure The other type should be dissolved or dispersed in the fluid. Specifically, when mixing the C 0 ₂ and H ₂ O is 3 0 4 K or more, and 7 3 atm or more.

The time for bringing the supercritical fluid into contact with the plastic varies depending on the plastic to be treated, the fluid to be used, the temperature conditions and the pressure conditions, but is generally within 24 hours, preferably within 10 hours. It is.

The method of bringing the supercritical fluid into contact with the plastic is not particularly limited, and examples include a method of immersing the plastic in the supercritical fluid. Specifically, there are methods of leaving plastic in a supercritical fluid in a sealed state or stirring in a sealed state, methods of leaving plastic in a flow of supercritical fluid, or methods of leaving and further stirring. Is received.

The time for returning from the supercritical state to the steady state is not particularly limited and may be appropriately selected, but is preferably 2 hours or less, and more preferably 1 hour or less.

According to the plating pretreatment of the present invention, the plastic is subjected to a surface treatment capable of being plated. The surface of the plastic is usually rough, and as a specific example, for example, fine irregularities are formed. These fine irregularities vary depending on the plastic, supercritical fluid, and processing conditions to be treated. However, they are usually caused by (1) desorption of low molecular weight components (oligomer components) in plastic, and (2) penetration of supercritical fluid into plastic. Swelling, ③ In addition, even if it is a high molecular weight component, it changes to an oligomer state by separation and is formed by desorption. In (3), decomposition can be promoted by including oxidizing components (eg, air, oxygen, hydrogen peroxide, ozone, etc.) in the supercritical fluid. Further, the plastic surface is oxidized by the oxidizing component, and a polar group is provided.

In the present invention, the supercritical fluid may contain a plating catalyst.

Here, the plating catalyst is a substance that catalyzes the plating reaction on the plastic surface. In general, since a redox reaction occurs, a catalyst suitable for the redox reaction with the red metal is used. Examples of the plating catalyst include various metals. For example, iron, cobalt, nickel, chromium, tin, lead, rhodium, palladium, platinum, ruthenium, copper, silver, gold, zinc, and cadmium are preferable. These may be used alone or in combination of two or more.

The plating catalyst may be a simple metal, but a compound containing a metal is preferred, and a compound containing a soluble metal is particularly preferred. Examples of the compound containing a metal include the following.

Mx X y (where M is a metal, X is 0, S, SO ₄ or PO ₄ ); MX z (where M is a metal, X is F, C 1, Br, _{I, CN, N0 3, C} 10 4 or NRR 'R''R'' , (R, R', R '' or R '', it is hydrogen, a hydrocarbon group or a CF _3, R, R ', R''andR'', may be the same or different, and may be a polyvalent ligand such as phthalocyanine.));

M (OR) _n or M (OCOR) _n (wherein, M is a metal, R represents hydrogen, a hydrocarbon group or a CF _3.);

M (OS〇 ₃ R) _n or M (RCOCH ₂ COR) „(where M is a metal and R is hydrogen, a hydrocarbon group or CF ₃ ).

Further, when the metal of the plating catalyst is divalent or more, there are a plurality of X, R, R ′, R ′ ″ or R ′ ″ in the metal-containing compound, and these are the same even if they are the same. , May be different.

Note that x, y, z, and n are integers and are determined by the valence of the metal. For example, for an a-valent metal, z = a. Where a is an integer from 1 to 6.

Also, for example, (X, y) = (1, b / 2) for a b-valent metal. Where b is an even number from 1 to 6.

Also, for example, for a b-valent metal, (X, y) = (2, b). Where b is an odd number from 1 to 6. In the above formula, the number of carbon atoms of the hydrocarbon group represented by R, R ', R "or is not particularly limited as long as it is 1 or more, and is preferably 1 to 50. Is, for example, a saturated aliphatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an alicyclic monoaliphatic hydrocarbon group, an aromatic hydrocarbon group, an aromatic monoaliphatic hydrocarbon group, etc. Is raised.

Examples of saturated aliphatic hydrocarbon groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentinole, neopentinole, ieri-pentinole, 2-methinolebutinole, n-hexinole, isohexyl, 3-methylpentyl, ethylpentyl, n-heptyl, 2-methylhexyl, n-octinole, isooctyl, ier-octinole, 2-ethylhexyl, 3-methylheptyl, _n — Nonyl, isonoel, 1-methinoleoctynole, ethylheptyl, n-decyl, 1-methinorenonyl, n-indesinole, 1,1-dimethinorennonole, n-dodecyl, n-tetradecyl, n-heptadecyl, n-octadecyl , And polymers of ethylene, propylene, butylene or copolymers thereof And hydrocarbon groups such as a more composed group.

Suitable specific examples of unsaturated aliphatic hydrocarbon groups include, for example, vinyl, aryl, isopropeninole, 2-butul, 2-methinorealinole, 1,1-dimethylaryl, 3-methinole 1-2-buteninole, 3-methinole Examples thereof include 3-buteninole, 4-penteninole, hexeninole, 2-phenylvinyl, octenyl, nonenyl, decenyl groups, and a group made of a polymer of acetylene, butadiene, or isopropylene, or a copolymer thereof. Suitable specific examples of the alicyclic hydrocarbon group include, for example, cyclopropyl, cyclobutyl, cyclopentynole, cyclohexinole, cycloheptinol, cyclooctynole, 3-methynolecyclohexynole, 4-methynolecyclohexynole, 4-ethynolecyclo Hexinole, 2-Methynole Cyclooctinole, Cyclopropeninole, Cyclobuteninole, Cyclopenteninole, Cyclohexeninole, Cyclohepteninole, Cyclootateninole, 4-Methinolecyclohexeninole, 4-Ethylcyclohexenyl, Cycopene, etc. . Suitable specific examples of the alicyclic monoaliphatic hydrocarbon group include, for example, cyclopropylethyl, cyclobutynoletinol, cyclopentynoletinol, cyclohexynolemethinol, cyclohexynoletyl, cycloheptylmethyl, cycloalkyl Octyllechinole, 3-methinolecyclohexynolepropinole, 4-methylenolecinol hexinoletinole, 4-ethylen / resin mouth hexinoletinole, 2-methinolecyclootatinoleetinole, cyclopropeninolebutinole, cyclobutenole , Cyclopenteninoletinol, cyclohexeninolemethinole, cyclohexeninolemethinole, cyclohexeninoletinol, 4-methinolecyclohexeninolepropynole, 4-ethynolecyclohexenylpentyl group, etc. Can be

Suitable specific examples of the aromatic hydrocarbon group include, for example, aryl groups such as phenyl and naphthyl; 4-methylphenyl, 3,4-dimethynolephenyl, 3,4,5-trimethynolephenyl, 2-Echinolefeninore, n-Buchinorefeninore, ίe / · And aryl groups such as 2-methoxy-14-tert-butylpheninole, dodecylphenyl, and the like.

Specific examples of the aromatic monoaliphatic hydrocarbon group include, for example, benzyl, 1-phenylethyl, 2-phenylenoethyl, 2-phenylenopropyl, 3-phenylinopropyl, 4-phenylenobutynole, and 5-phenylene. Examples thereof include quinolepentinole, 6-phenylenohexenole, 1- (4-methylinophenyl) ethynole, 2- (4-methylphenyl) ethyl, 2-methinolebenzyl, 1,1-dimethyl-12-phenylethyl and the like.

The number of carbon atoms of the acyl group is not particularly limited as long as it is 1 or more, but is preferably 1 to 40. Suitable examples of the acyl group include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, oxalyl, succinyl, pivaloyl, stearoyl, benzoyl, phenylpropionyl, toluoyl, naphthoyl, phthalonynole, indanyl, and indanyl benzoyl. , P-methynolebenzoinole, cyclohexynolecanolevonyl group and the like. In the above formula, Pd, Cu, Ni and the like are preferable as the metal that is M. The content of the plating catalyst is not particularly limited, and varies depending on the reaction conditions, the type and shape of the plastic, and the type of the catalyst to be used. The amount is preferably from 0.01 to 100 parts by mass, more preferably from 0.001 to 50 parts by mass, and particularly preferably from 0.01 to 30 parts by mass.

There is no particular limitation on the introduction of the plating catalyst into the supercritical fluid, and examples thereof include a method in which the catalyst is put into a container to be brought into contact with the plastic and a method in which the catalyst is put into the container in contact with the plastic in a state of being dissolved.

By bringing the supercritical fluid containing the plating catalyst into contact with the plastic, the plastic is subjected to a plating surface treatment and the plating catalyst adheres, but the plastic surface is usually rough. Specifically, for example, fine irregularities are formed.

After the supercritical fluid containing the plating catalyst is brought into contact with the plastic, the plating catalyst can be separated and recovered, or it can be directly contacted with the next plastic without being separated. As a method of recovering the catalyst, after the supercritical fluid is dissolved in the supercritical state, the catalyst and the supercritical fluid component remain in the vessel (column), but the supercritical fluid component is removed by distillation. And the like. Further, for example if the supercritical fluid component such as C◦ _{_2,} CO ₂ at room temperature and atmospheric pressure can be separated easily catalyst for a gas.

If a supercritical fluid is flowing, it can be recovered by an extractor. The catalyst can be recovered by an extractor using the difference in solubility of the catalyst in the supercritical fluid due to pressure change or temperature change.

The plating method of the present invention can be carried out by a normal plating treatment after the supercritical fluid is brought into contact with the plastic, but the plating treatment is preferably an electroless plating treatment. In the electroless plating process, before the electroless plating process, after the surface roughening process, each process of usually wetting, applying a catalyst, and activating the catalyst is applied. The wetting is a step of improving the wettability of the plastic surface in order to adhere the plating catalyst, and can be usually carried out by treating the plastic with an aqueous solution containing a surfactant.

The catalyst application is a process of attaching the catalyst to the plastic surface. For example, in the case of a palladium catalyst, the plastic is usually impregnated with an aqueous hydrochloric acid solution of tin chloride and palladium chloride. d (0)).

The catalyst activation is a step of activating the plating catalyst attached to the surface of the plastic, and can be usually performed by contacting with an acid such as sulfuric acid.

The steps of wetting, providing a catalyst, and activating a catalyst can be performed under ordinary conditions.

The plating process is preferably a forceless electroless plating process that can be performed by a normal plating process. In addition, an electric plating process can be performed after the electroless plating process.

Examples of the metal of the metal include various metals. For example, iron, cobalt, nickel, chromium, tin, lead, rhodium, palladium, platinum, ruthenium, copper, silver, gold, zinc, cadmium and the like are preferable. These may be used alone or in combination of two or more. The plating layer may be a single layer or a multilayer of the same or different metals.

The plating film is provided for decoration, protection, and various other functions. The plating metal species and plating film thickness are different depending on the purpose, and the thickness is not particularly limited. When a three-layer plating of, for example, copper, nickel, and gold is applied to a plastic for the purpose of conductivity, the thickness of the plating layer is not particularly limited, but copper is preferably 5 to 40 // in, and nickel is 0. 1 to 5 / χm is preferable, and gold is preferably 0.1 to 0.5 Aim.

In the plating method of the present invention, when a supercritical fluid containing a plating catalyst is brought into contact with plastic, plating can be performed without performing wetting, applying a catalyst, and activating the catalyst. The plating in the method for producing a plating according to the present invention refers to a plastic plating, and examples of plastic include those described above.

The plating apparatus of the present invention has a reaction tank for bringing plastic into contact with a supercritical fluid, and can carry out the plating pretreatment method or plating method of the present invention. The reaction tank for bringing the plastic into contact with the supercritical fluid is not particularly limited as long as it is a pressure-resistant container, and examples thereof include a pressure-resistant ram (hereinafter, also referred to as a reaction column) and an autoclave. The reaction tank is preferably arranged in a thermostat. The constant temperature bath is not particularly limited as long as the reaction bath can be heated, and examples thereof include a constant temperature oven and a mantle heater. Preferable specific examples of the plating device include a plating device provided with a high-pressure pump, a back pressure valve, and a cooling device in addition to the reaction tank. The high-pressure pump is not particularly limited as long as it can be pressurized, and examples thereof include a pump and a compressor.

This reactor will be described with reference to FIG. In Fig. 1, supercritical fluid is supercritical CO

_It will be explained as ₂ .

The reaction column has only to a structure that can contain a plastic therein, when introducing the co ₂ etc. co ₂ gas cylinder to the reaction force ram plastic is placed, before introducing co ₂ It is preferable to cool co ₂ with a cooling device, maintain the supercritical state with a high-pressure pump, and introduce the supercritical co ₂ into the reaction column. CO ₂ introduced into the reaction column can come into contact with plastic in a supercritical state. The reaction column is disposed in a constant temperature bath, and kept co ₂ the reaction temperature. A back pressure valve is provided behind the reaction column, and serves to keep co ₂ in the reaction ram at the reaction pressure. The catalyst passing through the back pressure valve is preferably collected in an extractor.

Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by these examples.

The plastics used in the examples are shown below.

PBT: Polybutylene terephthalate, made of polyplastics "Juranex 3300" PE I: Polyether imide, manufactured by GE Plastics Co., Ltd. “Ultem 10 100—100 OJ

PTFE: Polytetrafluoroethylene, "Teflon plate" manufactured by Tokyo Material Co., Ltd. ABS: Acrylonitrile 'butadiene' styrene copolymer, "GR-2000" manufactured by Denki Kagaku Kogyo Co., Ltd.

PA6: Polyamide 6, manufactured by Hems Japan “A—28J

Teflon: Seifin Corporation "TFW3000F"

Silica: "Fuse-Rex Z A30" manufactured by Tatsumori Co., Ltd., average particle size about 5 / zm

PE I filler composition: PE I // Teflon no silica = 50/1 0/40 (mixing mass ratio)

The above PEI filler composition is a twin-screw extruder (Berstrof) with a feed rate of 20-60 kgZ hours using a PE1 Teflon silica mixture (50Z10 / 40 (mixing mass ratio)) using a quantitative feeder. “ZE40A”), melted and kneaded by heating, cooled with water, and then cut with a pelletizer to produce the strand.

The average pore diameter (Ra) and the maximum diameter (Rmax) of the plastics of the examples were measured using a pore measuring instrument (Surfcom 575A, manufactured by Tokyo Seimitsu Co., Ltd.). Example 1

Surface treatment of PEI filler sheet.

反応 Assemble a reactor (Fig. 1) consisting of a 2 OmmX 5 Omm reaction column, constant temperature bath, high-pressure pump, extractor, back pressure valve, and cooling device. PE is used as a plastic for test pieces in the reaction column. put injection molded piece of Buira one formulation I (1 X 10 X 5 Omm ), pressurized with a high pressure pump to the supercritical C0 ₂ state of 423 K, 300 atm. C0 ₂ to 4 m

After reacting for 1 hour while flowing at 1 min, the pressure was released and the test piece was taken out. As a result of observing the surface of the test piece with an electron microscope, surface roughness was confirmed. In addition, surface treatment As a result, the Ra of the test piece changed from 0.40 μπι to 0.76 μm, and the Rma a changed from 4.76 / xm to 7.42 μπι. Example 2

処理表面 Surface treatment of I-filler-mixed board

In Example 1, 473Κ, with supercritical C0 ₂ state of 300 atm, except that 1 hour of reaction while flowing through the C0 ₂ at lml / min, and the front surface processing of the test piece in the same manner as in Example 1 . As a result of observing the surface of the test piece with an electron microscope, surface roughness was confirmed. In addition, the surface treatment changed the Ra of the specimen from 0.40 / zm to 1.58 μm, and the Rmax from 4.76; / m to 14. Ol / zm. Weird. Example 3

Surface treatment of PTFE plate

In the reaction apparatus of Example 1, an injection-molded product of PTF E (3 X 20 X 4 Omm) was put into a reaction column as a test piece plastic, and pressurized with a high-pressure pump to obtain 423 K, 200 atm supercritical CO _2. State. (0 ₂ 1011 / min at depressurized mixture was reacted for 1 hour while flowing through, was removed specimens. Results The surface of the test piece was observed with an electron microscope, surface roughness was observed. The surface By the treatment, Ra of the test piece changed from 0.41 / zπl to 0.62 m, and Rmax of the test piece changed from 3.96 m to 5.63 μπι.

Surface treatment of AB S plate

In the reaction apparatus of Example 1, an injection molded article of ABS (2 X 13 X 40 mm) was put into a reaction column as a test piece plastic, and pressurized with a high-pressure pump. CO ₂ state. C0 ₂ and allowed to react for 1 hour while flowing through in 4rn l / πl in the Thereafter, the pressure was released for one hour, and the test piece was taken out. As a result of observing the surface of the test piece with an electron microscope, surface roughness was confirmed. In addition, the surface treatment changed the Ra of the test specimen from 0.04 / m to 0.09 / im, and the Rmax increased from 0.60 // m to 1.30 m. changed. Example 5

Applying surface catalyst to PBT plate

In the same apparatus as in Example 1, an injection-molded product of PBT (1 XI 0 X 5 Omm) as a test piece plastic in a reaction column, and 7 mass of PBT. /. Palladium placed § Seto titanate (catalyst plated), pressurized with a high pressure pump to the 4 7 3 K, 3 0 0 atm supercritical C0 ₂ state of. Depressurized after the C0 ₂ was allowed to react for 1 hour while flowing through at 4m 1 / τη in, were removed specimen.

The test piece was discolored from white to gray at the top, confirming that the catalyst was applied to the surface.

The plating catalyst was collected by an extractor. Example 6

Applying surface catalyst to PBT plate

In the same apparatus as in Example 1, an injection-molded product of PBT (1 XI 0 X 5 Omm) as a test piece plastic and 7% by mass of palladium propionate (catalyst for plating) were placed in a reaction column in the same manner as in Example 1. The mixture was pressurized with a high-pressure pump, and brought into a supercritical CO ₂ state of 423 K at 300 atm. C0 ₂ to 4 ml / min at depressurized Chi was allowed to react for 1 hour while flowing through, was removed specimen.

The appearance of the test piece changed from white to black in appearance, confirming that the catalyst was applied to the surface. Example 7

Applying surface catalyst to PA 6 plate

In the same apparatus as in Example 1, an injection molded product of PA6 (2 XI 3 X 4 Omm) was used as a test piece plastic in a reaction column, and 7% by mass of palladium acetate to PA 6 (catalyst for plating) And pressurized with a high-pressure pump to obtain a supercritical CO ₂ state of 408K and 250 atm. C0 ₂ the Chi depressurizing was allowed to react for 20 minutes while flowing through at lml / min, it was taken out of the test piece.

The appearance of the test piece changed from white to black in appearance, confirming that the catalyst was applied to the surface. Example 8

Applying surface catalyst to PTF E plate

In the same apparatus as in Example 1, an extruded product of PT FE (3 X 20 X 40 mm) as a plastic for a test piece and palladium acetate (a catalyst for plating) of 30% by mass based on PTFE were put into a reaction column. The mixture was pressurized with a high-pressure pump to obtain a supercritical CO ₂ state of 423 K at 200 atm. C0 ₂ and depressurizing mixture was reacted for 1 hour while flowing through at lml / min, it was taken out of the test piece.

The appearance of the test piece changed from white to black in appearance, confirming that the catalyst was applied to the surface. Example 9

Application of plating film to the test piece obtained in Example 1

After washing the test piece prepared in Example 1 with pure water, a hole was made in the test piece with a drill, and a string was passed through. A 50 L aqueous solution for surface treatment (“Contilizer I SP” manufactured by Okuno Pharmaceutical) was placed in a 1-L beaker, and the test piece was immersed in a suspended state, stirred at 313 K for 5 minutes, and wetted. The test piece was taken out and subjected to ultrasonic cleaning in pure water for 5 minutes. In addition, 1 L W

First, add 50 mL of L aqueous solution for adding a palladium catalyst ("Catalyst M" manufactured by Okuno Pharmaceutical) and 50 mL / L of HC 1 (36%), and immerse it in a suspended state in the same manner, and stir at room temperature for 10 minutes And Pd was added. The test piece was taken out and subjected to ultrasonic cleaning in pure water for 10 minutes. Next, 5 OmL ZL of concentrated sulfuric acid was placed in a 1 L beaker, immersed in a suspended state in the same manner, and stirred for 3 13 K for 2 minutes to activate the catalyst. The test piece was taken out and washed with pure water. Next, in a 5 L beaker, add 10 OmL / ^ L of an aqueous solution for electroless copper plating (“OPC 700A” 10 OmLZL manufactured by Okuno Pharmaceutical Co., Ltd.) and “OPC 700B” manufactured by Okuno Pharmaceutical Co., Ltd. The mixture was stirred at room temperature for 60 minutes and treated with copper plating. The test piece was taken out and washed with pure water. In addition, a 5 L beaker was added to an aqueous solution for electroless copper plating (“OPC Kappa T 1” manufactured by Okuno Pharmaceutical Industries, Ltd. 6 OmL / L + T3 ”lO OmL / L) was added, and immersed similarly in a suspended state, followed by stirring at 333 K for 120 minutes and air, and then copper plating. The test piece was taken out and subjected to ultrasonic cleaning in pure water for 5 minutes. Finally, methanol was placed in a 50 OmL beaker, immersed in the same suspended state, and ultrasonically washed at room temperature for 10 minutes.

^ Above, a uniform plating film (thickness of plating layer: 10 m) was formed on the test piece without phthalation. Example 10

Plating film application to the test piece obtained in Example 2

A hole was made in the test piece prepared in Example 2 with a drill, and the string was passed through. 5 OmL / L of concentrated sulfuric acid was placed in a 1-L beaker, the test piece was immersed in a suspended state, and stirred for 3 minutes at 313K to activate the catalyst.

The test piece was taken out and washed with pure water. Next, in a 5 L beaker, add an aqueous solution of electroless copper plating (OPC 700A) (10 OmLZL + Okuno Pharmaceutical (OPC 700B) 10 OmL / L) and immerse it in the same suspended state. , Room temperature, empty for 60 minutes The mixture was air-stirred and treated with copper plating. The test piece was taken out and washed with pure water. In addition, 5 liters of water solution for electroless copper plating (Okuno Pharmaceutical Co., Ltd. (Oji Copper Co. 1) 60m L / L-(Okuno Pharmaceutical Co., Ltd. (OPC Kappa-1 T2) 1 2mL / L + ( Okuno Pharmaceutical

(OPC kappa-T3) 10 OmL / L) was added and immersed similarly in a suspended state, followed by stirring at 333 K for 120 minutes and air, followed by copper plating treatment. The test piece was removed and ultrasonically cleaned in pure water for 5 minutes. Finally, methanol was placed in a 50 OmL beaker, immersed in the same suspended state, and ultrasonically washed at room temperature for 10 minutes.

On the appearance, the test piece formed a uniform plating film without blisters (the thickness of the plating layer: 10 zm). Example 1 1

Plating film application to the test piece obtained in Example 7

In Example 10, the activation was changed to 0.77N—HC1 aqueous solution at 303 K for 5 minutes, and the first electroless copper plating reagent was “OPC 500A” manufactured by Okuno Pharmaceutical Co., Ltd. 10 OmL / L + “OPC 500 B” manufactured by Okuno Pharmaceutical Co., Ltd. 1 O OmL / L, and the plating conditions were changed to 303 K for 30 minutes. Processed.

On the appearance, the test piece had a glossy paint film without blisters (the thickness of the paint layer: 10 / im). Industrial applicability

According to the present invention, there is no need to use a chromic acid solution or an alkaline solution, and the plating pretreatment step can be simplified, so that the cost can be reduced and the catalyst can be recovered. It is possible to make a squeeze on plastic without having to do it, and to obtain a stake.

Claims

The scope of the claims

1. A plating pretreatment method characterized by applying a supercritical fluid to the plastic to perform a plating surface treatment on the plastic.

2. A plating pretreatment method, wherein the plating catalyst is attached to the plastic by contacting the plastic with a supercritical fluid containing the plating catalyst.

3. A plating pretreatment method, which comprises applying a surface treatment capable of plating to a plastic by bringing a supercritical fluid containing a plating catalyst into contact with the plastic, and further attaching the plating catalyst.

4. The method according to any one of claims 1 to 3 according to the supercritical fluid contains supercritical CO _2.

The method according to any one of claims 1 to 4, wherein the treatment is performed under a temperature condition of 5.304 to 6773K.

The method according to any one of claims 1 to 5, wherein the treatment is carried out at a pressure of 6.7 to 600 atm.

7. The plating pretreatment method according to any one of claims 2 to 6, wherein the plating catalyst is a compound containing palladium, copper or nickel metal.

8. The method according to any one of claims 1 to 7, wherein the plastic is at least one selected from polyamides, polyimides, polyesters, polyethers, vinyl polymers, epoxy resins, fluoropolymers, and iopolymers. The plating pretreatment method according to any one of the above.

9. A plating method characterized by contacting a plastic with a supercritical fluid, followed by plating.

10. The method according to claim 9, wherein wetting, catalyst application, and catalyst activation are performed before the plating treatment.

1 1. The method according to claim 9 or 10, wherein the supercritical fluid contains a plating catalyst.

1 2. A method for producing metal products, which comprises contacting a plastic with a supercritical fluid and then performing metal plating.

1 3. The method according to claim 12, wherein wetting, catalyst application, and catalyst activation are performed before plating.

14. The method according to claim 12 or 13, wherein the supercritical fluid contains a plating catalyst.

1 5. The method according to any one of claims 1 2 to 14 according to the supercritical fluid contains supercritical C0 _2.

16. The method according to any one of claims 12 to 15, wherein the treatment is carried out under a temperature condition of 304 to 673 K.

17. The method according to any one of claims 12 to 16, wherein the treatment is performed at a pressure of 73 to 600 atm.

18. The method according to any one of claims 14 to 17, wherein the plating catalyst is a compound containing palladium, copper or nickel metal.

1 9. Claims 12 to 1 wherein the plastic is at least one selected from the group consisting of polyamide, polyimide, polyester, polyether, vinyl polymer, epoxy resin, fluorinated polymer, and iopolymer. The method according to any one of 8 above.

20. A plating apparatus having a reaction tank for bringing plastic into contact with a supercritical fluid.

2 1. The device according to claim 20, comprising a high pressure pump, a back pressure valve and a cooling device.