CN107201074B - Laser activator and preparation method thereof, slurry containing laser activator and preparation method thereof, and preparation method of flexible circuit board - Google Patents
Laser activator and preparation method thereof, slurry containing laser activator and preparation method thereof, and preparation method of flexible circuit board Download PDFInfo
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- CN107201074B CN107201074B CN201710282380.6A CN201710282380A CN107201074B CN 107201074 B CN107201074 B CN 107201074B CN 201710282380 A CN201710282380 A CN 201710282380A CN 107201074 B CN107201074 B CN 107201074B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
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- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
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- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K7/22—Expanded, porous or hollow particles
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/027—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed by irradiation, e.g. by photons, alpha or beta particles
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- C—CHEMISTRY; METALLURGY
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- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
- H05K2203/107—Using laser light
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a laser activator, which comprises an active main body and epoxy resin coated on the surface of the active main body, wherein the active main body comprises porous mica particles and metal compounds filled in the pores of the porous mica particles and/or loaded on the surfaces of the porous mica particles, the metal compounds comprise at least one of metal oxides and metal sulfides, and metal elements in the metal compounds comprise at least one of copper, bismuth, tin, zinc, silver, antimony, manganese, iron, nickel and magnesium. The porous mica particles in the laser activator are stable in property and contain a porous structure, and can be well used as a carrier of a metal compound. And subsequently, under the action of laser, the porous structure in the mica particles can more firmly adsorb metal simple substances and promote the aggregation of metal ions in the chemical plating solution. The epoxy resin coated on the surface can improve the compatibility of the laser activator and the main resin and improve the adhesive force of the coating on the base material. The invention also provides a flexible circuit board and a preparation method thereof.
Description
Technical Field
The invention relates to the technical field of circuit board material preparation, in particular to a laser activator and a preparation method thereof, slurry containing the laser activator and a preparation method thereof, and a preparation method of a flexible circuit board.
Background
A Flexible Printed Circuit (FPC) is also called a Flexible Printed Circuit (FPC) or a Flexible Printed Circuit (FPC), and has the characteristics of high wiring density, light weight, and thin thickness, so that the Flexible Printed Circuit is widely used in various products such as a mobile phone, a notebook computer, a Personal Digital Assistant (PDA), a digital camera, a liquid crystal display (LCM), and the like.
The traditional FPC manufacturing process adopts a printing corrosion method, and the method specifically comprises the following steps: and printing photoresist on the cut flexible copper clad laminate, then exposing and developing to form a circuit pattern, and etching the copper foil on the non-circuit pattern part in etching solution to form the FPC. The method has the advantages of complex process, long flow and high cost. Therefore, it is necessary to provide a method for manufacturing a flexible circuit board with simple process and low cost.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a flexible circuit board, which has the advantages of simple process and low cost.
In a first aspect, the present invention provides a laser activator, including an active body and an epoxy resin coated on a surface of the active body, where the active body includes a porous mica particle and a metal compound filled in pores of the porous mica particle and/or loaded on a surface of the porous mica particle, the metal compound includes at least one of a metal oxide and a metal sulfide, and a metal element in the metal compound includes at least one of copper, bismuth, tin, zinc, silver, antimony, manganese, iron, nickel, and magnesium.
Wherein the mass ratio of the metal compound to the porous mica particles is 0.1-1: 1.
Wherein the mass ratio of the active main body to the epoxy resin is 1: 0.3-0.7.
Wherein the average particle diameter of the porous mica particles is 0.5 to 50 μm, and the porous pore diameter of the porous mica particles is 0.1 to 10 μm.
The average particle diameter in the present specification means an average particle diameter of equivalent volume diameters of particles.
According to the laser activator provided by the first aspect of the invention, the metal compound in the laser activator is filled in the pores of the mica particles and/or loaded on the surfaces of the porous mica particles, and the porous mica particles in the laser activator are relatively stable in property and have a porous structure, so that the laser activator can be well used as a carrier of the metal compound. And subsequently, under the action of laser, the porous structure in the mica particles can more firmly adsorb metal simple substances and promote the aggregation of metal ions in the chemical plating solution. The epoxy resin is coated on the surface of the active main body, so that the subsequent binding force between the inorganic metal compound and the main body resin can be improved, and a coating with stronger binding force is formed on the base material.
In a second aspect, the present invention provides a method for preparing a laser activator, comprising:
taking a porous mica sheet as a substrate, depositing a metal compound in holes and/or on the surface of the porous mica sheet by a physical vapor deposition method, and then crushing the porous mica sheet deposited with the metal compound to prepare an active main body; the active body comprises porous mica particles and metal compounds filled in the pores of the porous mica particles and/or loaded on the surfaces of the porous mica particles, wherein the metal compounds comprise at least one of metal oxides and metal sulfides, and the metal elements in the metal compounds comprise at least one of copper, bismuth, tin, zinc, silver, antimony, manganese, iron, nickel and magnesium;
and ball-milling the active main body and epoxy resin to coat the epoxy resin on the surface of the active main body, and drying to obtain the laser activator, wherein the laser activator comprises the active main body and the epoxy resin coated on the surface of the active main body, and the active main body comprises porous mica particles and metal compounds filled in holes of the porous mica particles and/or loaded on the surfaces of the porous mica particles.
The physical vapor deposition method comprises the following specific operations:
(1) sintering metal oxide, metal sulfide or carbonate powder containing metal elements at 900-1800 ℃ for 1-3 h, and then pressing to form a target material; the metal element is at least one of copper, bismuth, tin, zinc, silver, antimony, manganese, iron, nickel and magnesium;
(2) taking a porous mica sheet as a substrate, loading the porous mica sheet and the target material into a cavity for magnetron sputtering, and pumping the vacuum degree of the cavity to 1.0 multiplied by 10-3Pa～1.0×10-5Pa, adjusting the distance between the substrate and the target to be 45-95 mm, introducing inert gas, wherein the flow of the inert gas is 10-35 sccm, the pressure of the inert gas is 0.2-4 Pa, and depositing a metal compound in the holes and/or on the surface of the porous mica sheet through magnetron sputtering.
The preparation method of the laser-containing activator provided by the second aspect of the invention is simple and easy to operate, and the process is easy to control.
In a third aspect, the present invention provides a slurry containing a laser activator, comprising, by weight: 100 parts of main resin, 5-20 parts of curing agent, 30-120 parts of organic solvent and 2.5-75 parts of laser activator as described in the first aspect.
The paste containing the laser activator provided by the third aspect of the invention can be used for preparing a flexible circuit board.
In a fourth aspect, the present invention provides a method for preparing a slurry containing a laser activator, comprising:
mixing 100 parts by weight of main body resin, 5-20 parts by weight of curing agent, 30-120 parts by weight of organic solvent and 2.5-75 parts by weight of the laser activator in the first aspect, stirring for 20-50 minutes, and ball-milling for 1-4 hours to obtain slurry containing the laser activator.
The preparation method of the slurry containing the laser activator provided by the fourth aspect of the invention is simple and easy to operate.
In a fifth aspect, the present invention provides a method for manufacturing a flexible circuit board, including:
(1) coating or printing the slurry containing the laser activator in the third aspect 7 on the surface of a substrate, and curing at 80-150 ℃ for 0.5-3 h to obtain a coating;
(2) carrying out selective laser ablation activation on the coating to form a circuit pattern layer;
(3) and carrying out chemical plating treatment on the circuit pattern layer, and forming a metal plating layer at the position ablated by the laser in the circuit pattern layer so as to obtain the flexible circuit board.
Wherein the laser wavelength range of the laser ablation activation is 193-1064 nm, and the laser scanning speed is 50-8000 mm/s.
Compared with the traditional chemical etching process, the preparation method of the flexible circuit board provided by the fifth aspect of the invention can omit processes of printing photoresist, exposure, development, etching and the like for manufacturing circuit patterns, has short and simple process flow, reduces the production cost and equipment investment cost, and can realize automatic continuous production of whole rolls of materials.
In conclusion, the beneficial effects of the invention include the following aspects:
1. according to the laser activator provided by the invention, the metal compound in the laser activator is filled in the holes of the mica particles and/or loaded on the surfaces of the porous mica particles, the adhesive force of the metal compound is strong, and subsequently, under the action of laser, the porous structure in the mica particles can more firmly adsorb a metal simple substance and promote the aggregation of metal ions in a chemical plating solution. The epoxy resin is coated on the surface of the active main body, so that the subsequent binding force between the inorganic metal compound and the main body resin can be improved, and a coating with stronger binding force is formed on the base material;
2. the preparation method containing the laser activator is simple and easy to operate, and the process is easy to control;
3. compared with the traditional chemical etching process, the preparation method of the flexible circuit board provided by the invention can omit processes of printing photoresist, exposure, development, etching and the like for manufacturing circuit patterns, has short and simple process flow, reduces the production cost and equipment investment cost, and can realize automatic continuous production of whole rolls of materials.
Drawings
Fig. 1 is a schematic diagram of a manufacturing process of a flexible circuit board according to an embodiment of the present invention.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
In a first aspect, the present invention provides a laser activator, including an active body and an epoxy resin coated on a surface of the active body, where the active body includes a porous mica particle and a metal compound filled in pores of the porous mica particle and/or loaded on a surface of the porous mica particle, the metal compound includes at least one of a metal oxide and a metal sulfide, and a metal element in the metal compound includes at least one of copper, bismuth, tin, zinc, silver, antimony, manganese, iron, nickel, and magnesium.
The porous mica particles have a layered structure and stable properties, and meanwhile, the mica particles contain a porous structure, so that the metal compound can enter the porous structure of the mica particles, and the metal compound can be better used as a carrier of the metal compound. In addition, when a subsequent laser activator acts on the mica particles under the action of laser, the porous structure of the mica particles can more firmly adsorb a metal simple substance which is formed by reducing a metal compound and is used as a catalyst, and meanwhile, metal ions in the chemical plating solution can be gathered, so that the metal plating layer is formed.
In an embodiment of the present invention, the average particle diameter of the porous mica particles is 0.5 to 50 μm, and the pore diameter of the porous mica particles is 0.1 to 10 μm.
In an embodiment of the present invention, the metal compound specifically includes at least one of copper oxide, bismuth oxide, tin oxide, zinc oxide, silver oxide, antimony oxide, manganese oxide, iron oxide, nickel oxide, magnesium oxide, copper sulfide, bismuth sulfide, tin sulfide, zinc sulfide, silver sulfide, antimony sulfide, manganese sulfide, iron sulfide, nickel sulfide, and magnesium sulfide.
In an embodiment of the present invention, the mass ratio of the metal compound to the porous mica particles is 0.1 to 1: 1.
In an embodiment of the present invention, a mass ratio of the active host to the epoxy resin is 1:0.3 to 0.7.
In an embodiment of the present invention, the mass ratio of the epoxy resin to the metal compound is 0.5 to 3: 1.
In an embodiment of the present invention, the average particle diameter of the porous mica particles is 0.5 to 50 μm, and the porous pore diameter of the porous mica particles is 0.1 to 10 μm.
In an embodiment of the present invention, the average particle size of the laser activator is 0.5 to 70 μm.
Because the metal compound is an inorganic substance, when the subsequent laser activator is prepared into slurry, the compatibility of the inorganic substance with organic substances such as main body resin, curing agent and the like is poor, the surface of the porous mica particle is coated with the epoxy resin, and the epoxy resin coated on the surface can react with the main body resin and the curing agent to form a chemical bond, so that the compatibility of the active main body and the main body resin is improved, and the adhesive force of the coating containing the laser activator on a base material is improved.
According to the laser activator provided by the first aspect of the invention, the laser activator can be well attached to the surface of a base material, after laser ablation, a metal compound in the laser activator is reduced into a metal simple substance, the metal simple substance is filled in holes of mica particles and/or loaded on the surface of the porous mica particles, the adhesion of the metal simple substance is strong, and meanwhile, the porous mica particles can adsorb metal ions in metal electroplating liquid, so that a formed metal coating is facilitated. The epoxy resin is an organic matter, and the epoxy resin is coated on the surface of the active main body, so that the subsequent binding force between the inorganic metal compound and the main body resin can be improved, and a coating with strong binding force is formed on the base material.
In a second aspect, the present invention provides a method for preparing a laser activator, comprising:
taking a porous mica sheet as a substrate, depositing a metal compound in holes and/or on the surface of the porous mica sheet by a Physical Vapor Deposition (PVD) method, and then crushing the porous mica sheet deposited with the metal compound to prepare an active main body; the active body comprises porous mica particles and metal compounds filled in the pores of the porous mica particles and/or loaded on the surfaces of the porous mica particles, wherein the metal compounds comprise at least one of metal oxides and metal sulfides, and the metal elements in the metal compounds comprise at least one of copper, bismuth, tin, zinc, silver, antimony, manganese, iron, nickel and magnesium;
and ball-milling the active main body and epoxy resin to coat the epoxy resin on the surface of the active main body, and drying to obtain the laser activator, wherein the laser activator comprises the active main body and the epoxy resin coated on the surface of the active main body, and the active main body comprises porous mica particles and metal compounds filled in holes of the porous mica particles and/or loaded on the surfaces of the porous mica particles.
In an embodiment of the invention, the physical vapor deposition comprises magnetron sputtering or vacuum plating. Optionally, the specific operations of the Physical Vapor Deposition (PVD) method include:
(1) sintering metal oxide, metal sulfide or carbonate powder containing metal elements at 900-1800 ℃ for 1-3 h, and pressing into a target material; the metal element comprises at least one of copper, bismuth, tin, zinc, silver, antimony, manganese, iron, nickel and magnesium;
(2) taking a porous mica sheet as a substrate, loading the porous mica sheet and the target material into a cavity for magnetron sputtering, and pumping the vacuum degree of the cavity to 1.0 multiplied by 10-3Pa～1.0×10-5Pa, adjusting the distance between the substrate and the target to be 45-95 mm, introducing inert gas, wherein the flow of the inert gas is 10-35 sccm, the pressure of the inert gas is 0.2-4 Pa, and depositing in holes and/or on the surface of the porous mica sheet by magnetron sputtering to obtain a metal compound.
In an embodiment of the present invention, a metal compound is deposited in the pores and/or on the surface of the porous mica sheet by a Physical Vapor Deposition (PVD) method, and the metal compound is present in the form of a thin film having a thickness of a nanometer order. Optionally, the thin film has a thickness of 10nm to 100 nm.
In the embodiment of the present invention, in the step (1), the sintering temperature is 1450 ℃.
In the embodiment of the present invention, in the step (1), the size of the target to be formed is Φ 50 × 2 mm.
In the embodiment of the present invention, in the step (2), the vacuum degree of the chamber is 5.0 × 10-4Pa。
In an embodiment of the present invention, in the step (2), a distance between the substrate and the target is adjusted to be 60 mm.
In an embodiment of the present invention, in the step (2), the inert gas includes argon; optionally, the inert gas is introduced at a flow rate of 25sccm and the pressure of the inert gas is 2.0 Pa.
In the embodiment of the invention, the porous mica sheet deposited with the metal compound is crushed to obtain the porous mica particles and the metal compound filled in the pores of the porous mica particles and/or loaded on the surfaces of the porous mica particles. Optionally, the average particle size of the crushed porous mica particles is from 0.5 μm to 50 μm.
In the embodiment of the invention, the ball milling operation is as follows: according to the weight parts, 100 parts of an active main body, 30-70 parts of epoxy resin, 30-80 parts of an organic solvent and 1-5 parts of an auxiliary agent are added into a planetary ball mill, then ceramic microspheres or glass microspheres are added, after ball milling is carried out for 1.5-3 hours, the ceramic microspheres or the glass microspheres are filtered and removed, and after drying, the laser activator is obtained. Alternatively, the ball milling time is 2 h.
In the embodiment of the present invention, the epoxy resin is 50 parts.
In the embodiment of the present invention, the amount of the organic solvent is 50 parts. Alternatively, the organic solvent includes, but is not limited to, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, ketone solvents, ester solvents. Further optionally, the organic solvent is one or more of xylene, cyclohexane, butanone, methyl isobutyl ketone, and ethyl acetate.
In an embodiment of the present invention, the auxiliary agent includes at least one of an adhesion promoter, a coupling agent, a substrate wetting agent, and a dispersing agent. The addition of the aid aids in ball milling. The adhesion promoter is used for improving the bonding force between the base material and the coating, the coupling agent is used for improving the compatibility of the inorganic filler and the main resin in the composition, the base material wetting agent is used for reducing the surface tension of the liquid composition and improving the spreading capacity of the liquid composition on the base material, and the dispersing agent is used for preventing the inorganic filler in the composition from agglomerating and improving the dispersibility of the inorganic filler, and the time and the energy required for completing the dispersing process. Alternatively, the adhesion promoter may be a specially modified polyester compound (e.g., BYK-4500, BYK-4510, WoodbenceL LTW), the coupling agent may be a phthalate-based coupling agent (e.g., TMC-210, TMC-311, available from KenreQi Inc.), the substrate wetting agent may be a modified silicone (e.g., BYK-310, BYK-331, BYK-378, available from BYK), and the dispersant may be a low molecular weight wax (e.g., C-963, CERACOL39, CERACOL79, BYK110 available from Corning).
In the embodiment of the invention, the adding amount of the ceramic beads or the glass beads is 1.5-4 times of the weight of the active main body. Optionally, the addition amount of the ceramic beads or the glass beads is 2-3 times of the weight of the active main body. Further optionally, the ceramic or glass beads are added in an amount of 2.4 times the weight of the active host. Optionally, the ceramic or glass beads have a diameter of 1 mm.
In the embodiment of the invention, the drying method after ball milling is a spray drying method.
In the embodiment of the present invention, the average particle diameter of the laser activator is 0.5 to 70 μm.
In the second aspect of the invention, the active main body is prepared by adopting a PVD method, the preparation method is simple and easy to operate, and the process is easy to control. And performing ball milling on the active main body and epoxy resin to obtain the laser activator.
In a third aspect, the present invention provides a slurry containing a laser activator, comprising, by weight: 100 parts of main resin, 5-20 parts of curing agent, 30-120 parts of organic solvent and 2.5-75 parts of laser activator as described in the first aspect.
In the embodiment of the invention, the slurry containing the laser activator comprises the following components in parts by weight: 100 parts of main resin, 10-20 parts of curing agent, 50-120 parts of organic solvent and 20-25 parts of laser activator as described in the first aspect.
In an embodiment of the present invention, the host resin includes at least one of an acrylic resin, an epoxy resin, an alkyd resin, and a polyester resin, and the curing agent includes at least one of an amino resin and an isocyanate.
In the embodiment of the invention, the mass fraction of the solid content of the slurry containing the laser activator is 2-40%, and the preferable range is 8-30%.
In the embodiment of the invention, the slurry containing the laser activator further comprises 1-7 parts of an auxiliary agent, wherein the auxiliary agent comprises at least one of a leveling agent, an adhesion promoter, a base material wetting agent and a dispersing agent.
In the embodiment of the invention, the leveling agent is used for promoting the coating to form a flat, smooth and uniform coating film in the drying film-forming process, the adhesion promoter is used for improving the bonding force between the base material and the coating, the base material wetting agent is used for reducing the surface tension of the liquid composition and improving the spreading capability of the liquid composition on the base material, the defoaming agent is used for preventing and eliminating air bubbles in the liquid composition and improving the workability of the liquid composition, and the dispersing agent is used for preventing inorganic fillers in the composition from agglomerating and improving the dispersibility of the inorganic fillers. Preferably, the leveling agent can be a silicone-based oligomer (e.g., BYK300, BYK302, BYK306, BYK341, etc.), the adhesion promoter can be a specially modified polyester compound (e.g., WoDegussa LTW, Tego addid900, BYK-4500, BYK-4510), and the substrate wetting agent can be a modified silicone ether (e.g., TEGO WET, DisperbYK-160, DisperbYK-168, DisperbYK-171, DisperbYK-112, etc.).
In the embodiment of the invention, the organic solvent is obtained by mixing xylene and methyl isobutyl ketone according to the volume ratio of 1: 3. The solvent has better solubility and volatility, so that the binding force of organic matters and inorganic matters in the slurry is better.
The third aspect of the invention provides a slurry containing a laser activator, which can be used for preparing a flexible circuit board.
In a fourth aspect, a method of preparing a slurry containing a laser activator comprises:
mixing 100 parts by weight of main body resin, 5-20 parts by weight of curing agent, 30-120 parts by weight of organic solvent and 2.5-75 parts by weight of the laser activator in the first aspect, stirring for 20-50 minutes, and ball-milling for 1-4 hours to obtain slurry containing the laser activator.
In the embodiment of the invention, the stirring speed is 3000 rpm-5000 rpm.
In the embodiment of the invention, ceramic beads or glass beads are added in the ball milling process.
In the embodiment of the invention, the adding amount of the ceramic beads or the glass beads is 0.5-2 times of the mass of the slurry.
In the embodiment of the present invention, the diameter of the ceramic beads or the glass beads is 1 mm.
The preparation method of the slurry containing the laser activator provided by the fourth aspect of the invention is simple and easy to operate.
Fig. 1 is a schematic diagram of a manufacturing process of a flexible circuit board according to an embodiment of the present invention. As shown in fig. 1, in a fifth aspect, a method for manufacturing a flexible circuit board includes:
s01, as shown in figure 1(a), coating or printing the slurry containing the laser activator in the third aspect on the surface of a base material 110, and curing at 80-150 ℃ for 0.5-3 h to obtain a coating 120;
s02, as shown in fig. 1(b), performing selective laser ablation activation on the coating to form a circuit pattern layer 130;
s03, as shown in fig. 1(c), the circuit pattern layer 130 is subjected to electroless plating treatment to form a metal plating layer 140 at the laser-ablated position in the circuit pattern layer, thereby obtaining the flexible circuit board.
In one embodiment of the present invention, the substrate includes, but is not limited to, one of a PI (polyimide) film, a PET (polyethylene terephthalate) film and a PEN (polyethylene naphthalate) film, and the thickness of the substrate is 5 to 250 μm, preferably 18 to 150 μm.
In an embodiment of the present invention, in the step S01, the coating method includes bar coating, spin coating, spray coating, blade coating, or roll coating. The laser activator-containing paste can also be applied to the substrate by various printing methods, such as screen printing, gravure printing, offset printing, and flexographic printing. The specific coating process or printing process is not particularly specified, and may be a process that is conventional in the art. Optionally, the thickness of the coating is 2-100 μm. Optionally 10-50 μm; further optionally 10-30 μm.
In the embodiment of the invention, in the step S02, the laser wavelength range of the laser ablation activation is 193-1064 nm, and the laser scanning speed is 50-8000 mm/S.
The invention carries out selective laser ablation activation on the coating, thereby forming a groove in the coating and further obtaining a circuit pattern; and reducing the metal compound in the laser activator activated by laser ablation into a metal simple substance, and then carrying out chemical plating treatment on the circuit pattern subjected to laser ablation, wherein the metal simple substance is used as a catalyst for chemical plating, a metal plating layer is catalytically grown at the position subjected to laser ablation, and a metal circuit is formed on the surface of the base material to obtain the flexible circuit board.
In an embodiment of the present invention, in the step S03, the metal plating layer includes at least one of a copper plating layer, a nickel plating layer, and a gold plating layer. Optionally, the thickness of the metal coating is 5-20 μm. Alternatively, the electroless plating process is selected from the conventional techniques in the art, and is not particularly limited herein.
The invention can design the circuit according to the needs by a computer, then carry out laser activation on the part of the surface of the coating layer needing to prepare the circuit, release metal crystal nuclei by selective laser irradiation activation, and easily carry out a chemical plating process, thereby forming a metal plating layer and obtaining the flexible circuit board.
The metal compound in the slurry containing the laser activator can form a catalytic center of a metal coating after subsequent reduction, the porous mica particles are used as a carrier of the metal compound, the catalytic effect can be improved, and the binding force between the coating and the coating is strong.
Compared with the traditional chemical etching process, the preparation method of the flexible circuit board provided by the fifth aspect of the invention can omit processes of printing photoresist, exposure, development, etching and the like for manufacturing circuit patterns, has short and simple process flow, reduces the production cost and the equipment investment cost, can obviously reduce the size of the flexible circuit board, and can realize automatic continuous production of whole rolls of materials.
Example 1:
a method of manufacturing a flexible circuit board, comprising:
1. preparing a laser activator:
(1) preparing a target material: 100g of zinc oxide powder is weighed, sintered at 1450 ℃, and then pressed into a target material with phi of 50 multiplied by 2 mm.
(2) Putting the target material in the step (1) into a cavity of a coating device and a mica sheet as a substrate, and pumping the vacuum degree of the cavity to 5.0 multiplied by 10 by a mechanical pump and a molecular pump-4Pa；
(3) Adjusting technological parameters: the distance between the base targets is 60mm, argon is introduced as working gas, the gas flow is 25sccm, the pressure is 2.0Pa, and the obtained zinc oxide-doped mica sheet is the active main body.
(4) And (4) crushing the mica sheets doped with zinc oxide obtained in the step (3), placing the crushed mica sheets in a ball milling tank, adding epoxy resin and an organic solvent, adding ceramic beads, placing the mixture in a planetary ball mill, and carrying out ball milling for 2 hours. Wherein the weight parts of the components are as follows:
100 portions of doped zinc oxide mica powder
50 parts of epoxy resin
50 portions of organic solvent
0.5 part of base material wetting agent and 2 parts of dispersing agent
The addition amount of the ceramic beads is 240 parts.
(5) And (4) filtering the sample obtained in the step (4) to separate ceramic beads, drying by adopting a spray drying method, and screening to obtain the required dried laser activator A, wherein the average particle size of the laser activator A powder is 3 microns.
2. Preparing a coating containing a laser activator:
100 parts of acrylic resin (BS101, manufactured by Jiangsu Sanxylo chemical industry), 15 parts of isocyanate (N75, manufactured by Bayer materials), 80 parts of mixed solvent (wherein the volume ratio of xylene to methyl isobutyl ketone is 1:3), 20 parts of laser activator A (self-made), 2 parts of adhesion promoter (Tego addid900, manufactured by winning industry group), 0.8 part of dispersant (BYK110, manufactured by Germany Bikk chemical industry), 1 part of leveling agent (BYK300, manufactured by Bikk chemical company) are added into a grinding tank, then stirred for 30 minutes at 3000 r/min by a stirrer and uniformly mixed, then 100 parts of ceramic microspheres (diameter is 1mm) are added, and after grinding is carried out for 2 hours at the stirring speed of 3000 r/min in the grinding tank, the ceramic microspheres are filtered out to obtain the required slurry containing the laser activator.
Using a 30 μm KD coating bar, a slurry containing a laser activator was applied to the surface of a PI film having a thickness of 50 μm. Then baked in an oven at 100 ℃ for 3h to obtain a coating with a thickness of 30 μm.
3. And (3) carrying out laser treatment on the coating and then electroplating to form the flexible circuit board:
and (3) performing laser ablation on the surface of the cured coating by adopting a laser, wherein the laser wavelength is 1064nm, and the laser power is as follows: 20W, laser frequency: 15KHz, scanning speed: 500 mm/s.
And carrying out chemical copper plating treatment on the ablated circuit to obtain the circuit meeting the design requirement.
Example 2:
a method of manufacturing a flexible circuit board, comprising:
1. preparing a laser activator:
(1) preparing a target material: 100g of silver oxide powder is weighed, sintered at 900 ℃, and pressed into a target material with phi of 50 multiplied by 2 mm.
(2) Putting the target material in the step (1) into a cavity of a coating device and a mica sheet as a substrate, and pumping the vacuum degree of the cavity to 1.0 multiplied by 10 by a mechanical pump and a molecular pump-3Pa；
(3) Adjusting technological parameters: the distance between the base targets is 70mm, argon is introduced as working gas, the gas flow is 25sccm, the pressure is 3.0Pa, and the obtained silver oxide-doped mica sheet is the active main body.
(4) And (4) crushing the silver oxide-doped mica sheet obtained in the step (3), placing the crushed mica sheet into a ball milling tank, adding epoxy resin and an organic solvent, adding ceramic beads, placing the mixture into a planetary ball mill, and carrying out ball milling for 2 hours. Wherein the weight parts of the components are as follows:
100 parts of silver oxide-doped mica powder
30 parts of epoxy resin
30 portions of organic solvent
0.2 part of base material wetting agent and 3 parts of dispersing agent
The addition amount of the ceramic beads is 200 parts.
(5) And (4) filtering the sample obtained in the step (4) to separate ceramic beads, drying by adopting a spray drying method, and screening to obtain the required dried laser activator B, wherein the average particle size of the laser activator B powder is 15 microns.
2. Preparing a coating containing a laser activator:
100 parts of epoxy resin (R140, produced by Mitsui chemical Co., Ltd.), 10 parts of amino resin (CYMEL303, produced by CyatoTechnological Co., Ltd.), 120 parts of a mixed solvent (wherein the volume ratio of xylene to methyl isobutyl ketone is 1:3), 25 parts of a laser activator B (self-made), 3 parts of an adhesion promoter (Tego addid900, produced by Wogojian Industrial group Co., Ltd.), 0.5 part of a dispersant (BYK110, produced by Germany Bick chemical Co., Ltd.), 1 part of a leveling agent (BYK302, produced by Bick Chemicals Co., Ltd.) were added to a grinding pot, and then stirred at 3000 rpm for 30 minutes by a stirrer, mixed uniformly, 100 parts of glass beads were added, and after grinding was carried out in the grinding pot at a stirring speed of 3000 rpm for 1 hour, ceramic beads (diameter: 1mm) were filtered out to obtain a desired slurry containing the laser activator.
The slurry containing the laser activator was applied to the surface of the PET film with a thickness of 38 μm using a 40 μm KD coating bar. Then baked in an oven at 120 ℃ for 1h to obtain a coating with a thickness of 30 μm.
3. And (3) carrying out laser treatment on the coating and then electroplating to form the flexible circuit board:
and (3) performing laser ablation on the surface of the cured coating by adopting a laser, wherein the laser wavelength is 514nm, and the laser power is as follows: 20W, laser frequency: 20KHz, scanning speed: 1000 mm/s.
And carrying out chemical copper plating treatment on the ablated circuit to obtain the circuit meeting the design requirement.
Example 3:
a method of manufacturing a flexible circuit board, comprising:
1. preparing a laser activator:
(1) preparing a target material: 100g of magnesium oxide powder is taken, sintered at 1800 ℃ and then pressed into a target material with phi of 50 multiplied by 2 mm.
(2) Putting the target material in the step (1) into a cavity of a coating device and a mica sheet as a substrate, and pumping the vacuum degree of the cavity to 1.0 multiplied by 10 by a mechanical pump and a molecular pump-5Pa；
(3) Adjusting technological parameters: the distance between the base targets is 90mm, argon is introduced as working gas, the gas flow is 35sccm, the pressure is 4Pa, and the obtained magnesium oxide-doped mica sheet is the active main body.
(4) And (3) crushing the mica sheet doped with the metal oxide obtained in the step (3), placing the crushed mica sheet into a ball milling tank, adding epoxy resin and an organic solvent, adding ceramic beads, placing the mixture into a planetary ball mill, and carrying out ball milling for 3 hours. Wherein the weight parts of the components are as follows:
100 portions of magnesium oxide-doped mica powder
Epoxy resin 70 parts
30 portions of organic solvent
5 parts of assistant, 0.5 part of flatting agent, 2 parts of adhesion promoter, 1.5 parts of base material wetting agent and 1 part of dispersing agent
The addition amount of the ceramic beads is 150 parts.
(5) And (4) filtering and separating the ceramic beads from the sample obtained in the step (4), drying by adopting a spray drying method, and then screening to obtain a dried laser activator C, wherein the average particle size of the laser activator C powder is 25 microns.
2. Preparing a coating containing a laser activator:
100 parts of alkyd resin (AN950/70X, manufactured by Cytex chemical Co., Ltd.), 18 parts of amino resin (CYMEL303, manufactured by Cytex chemical Co., Ltd.), 50 parts of mixed solvent (xylene: methyl isobutyl ketone ═ 1:3), 30 parts of laser activator C (self-made), 3 parts of adhesion promoter (Tego addid900, manufactured by winning industry group), 0.5 part of dispersant (CERACOL39, manufactured by Pickery chemical Co., Ltd.), 2 parts of leveling agent (BYK306, manufactured by Pickery chemical Co., Ltd.) were added to a grinding pot, and then stirred at 3000 rpm for 30 minutes by a stirrer, mixed uniformly, then 100 parts of glass beads (diameter 1mm) were added, and after 2 hours of grinding at 3000 rpm in the grinding pot, the glass beads were filtered to obtain a slurry containing the laser activator.
The slurry containing the laser activator was applied to the surface of a PEN film having a thickness of 38 μm using a 50 μm KD coating bar. Then baked in an oven at 150 ℃ for 0.5h to obtain a coating with a thickness of 50 μm.
3. And (3) carrying out laser treatment on the coating and then electroplating to form the flexible circuit board:
and (3) performing laser ablation on the surface of the cured coating by using a laser, wherein the laser wavelength is 193nm, and the laser power is as follows: 5W, laser frequency: 25KHz, scanning speed: 2000 mm/s.
And carrying out chemical copper plating, nickel and gold plating treatment on the ablated circuit to obtain the circuit meeting the design requirement.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A laser activator, comprising an active body and an epoxy resin coated on the surface of the active body, wherein the active body comprises a porous mica particle and a metal compound filled in the pores of the porous mica particle and/or loaded on the surface of the porous mica particle, the metal compound comprises at least one of metal oxide and metal sulfide, and the metal element in the metal compound comprises at least one of copper, bismuth, tin, zinc, silver, antimony, manganese, iron, nickel and magnesium; wherein the average particle diameter of the porous mica particles is 0.5 to 50 μm, and the porous pore diameter of the porous mica particles is 0.1 to 10 μm; the mass ratio of the epoxy resin to the metal compound is 0.5-3: 1, and the mass ratio of the metal compound to the porous mica particles is 0.1-1: 1.
2. The laser activator of claim 1, wherein the mass ratio of the active host to the epoxy resin is 1:0.3 to 0.7.
3. A method of preparing a laser activator, comprising:
taking a porous mica sheet as a substrate, depositing a metal compound in holes and/or on the surface of the porous mica sheet by a physical vapor deposition method, and then crushing the porous mica sheet deposited with the metal compound to prepare an active main body; the active body comprises porous mica particles and metal compounds filled in the pores of the porous mica particles and/or loaded on the surfaces of the porous mica particles, wherein the metal compounds comprise at least one of metal oxides and metal sulfides, and the metal elements in the metal compounds comprise at least one of copper, bismuth, tin, zinc, silver, antimony, manganese, iron, nickel and magnesium;
ball-milling the active main body and epoxy resin to enable the epoxy resin to be coated on the surface of the active main body, and drying to obtain a laser activator, wherein the laser activator comprises an active main body and the epoxy resin coated on the surface of the active main body, and the active main body comprises porous mica particles and metal compounds filled in holes of the porous mica particles and/or loaded on the surfaces of the porous mica particles; wherein the average particle diameter of the porous mica particles is 0.5 to 50 μm, and the porous pore diameter of the porous mica particles is 0.1 to 10 μm; the mass ratio of the epoxy resin to the metal compound is 0.5-3: 1, and the mass ratio of the metal compound to the porous mica particles is 0.1-1: 1.
4. The laser activator preparation method of claim 3, wherein the physical vapor deposition process comprises the specific operations of:
(1) sintering metal oxide, metal sulfide or carbonate powder containing metal elements at 900-1800 ℃ for 1-3 h, and then pressing to form a target material; the metal element comprises at least one of copper, bismuth, tin, zinc, silver, antimony, manganese, iron, nickel and magnesium;
(2) taking a porous mica sheet as a substrate, loading the porous mica sheet and the target material into a cavity for magnetron sputtering, and pumping the vacuum degree of the cavity to 1.0 multiplied by 10-3Pa～1.0×10-5Pa, adjusting the distance between the substrate and the target to be 45-95 mm, introducing inert gas, wherein the flow of the inert gas is 10-35 sccm, the pressure of the inert gas is 0.2-4 Pa, and depositing in holes and/or on the surface of the porous mica sheet by magnetron sputtering to obtain a metal compound.
5. The slurry containing the laser activator is characterized by comprising the following components in parts by weight: 100 parts of a host resin, 5 to 20 parts of a curing agent, 30 to 120 parts of an organic solvent, and 2.5 to 75 parts of the laser activator according to any one of claims 1 to 2.
6. A method for preparing a slurry containing a laser activator, comprising:
mixing 100 parts by weight of main resin, 5-20 parts by weight of curing agent, 30-120 parts by weight of organic solvent and 2.5-75 parts by weight of laser activator according to any one of claims 1-2, stirring for 20-50 minutes, and ball-milling for 1-4 hours to obtain slurry containing the laser activator.
7. A method of manufacturing a flexible circuit board, comprising:
(1) coating or printing the slurry containing the laser activator according to claim 5 on the surface of a substrate, and curing at 80-150 ℃ for 0.5-3 h to obtain a coating;
(2) carrying out selective laser ablation activation on the coating to form a circuit pattern layer;
(3) and carrying out chemical plating treatment on the circuit pattern layer, and forming a metal plating layer at the position ablated by the laser in the circuit pattern layer so as to obtain the flexible circuit board.
8. The method for preparing a flexible circuit board according to claim 7, wherein the laser wavelength range of the laser ablation activation is 193nm to 1064nm, and the laser scanning speed is 50 to 8000 mm/s.
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