CN113025116A - Printing ink, printed circuit board inner layer circuit, manufacturing method of printed circuit board inner layer circuit and printed circuit board - Google Patents
Printing ink, printed circuit board inner layer circuit, manufacturing method of printed circuit board inner layer circuit and printed circuit board Download PDFInfo
- Publication number
- CN113025116A CN113025116A CN202010175052.8A CN202010175052A CN113025116A CN 113025116 A CN113025116 A CN 113025116A CN 202010175052 A CN202010175052 A CN 202010175052A CN 113025116 A CN113025116 A CN 113025116A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- circuit board
- printed circuit
- ink
- inner layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
-
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
-
- 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
- H05K3/06—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 chemically or electrolytically, e.g. by photo-etch process
- H05K3/061—Etching masks
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Emergency Medicine (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of electronic materials, and particularly relates to ink, an inner layer circuit of a printed circuit board, a manufacturing method of the inner layer circuit and the printed circuit board. The invention uses unsaturated carboxylic acid modified epoxy resin, curing agent, active diluent, photoinitiator, filler and auxiliary agent as raw materials to prepare ink, the ink is coated on a substrate and cured to form an etching-resistant coating, the part except the circuit on the etching-resistant coating is removed by a laser engraving method, and the manufacture of the inner layer circuit of the printed circuit board is completed by etching the circuit and pressing. The ink disclosed by the invention is solvent-free environment-friendly ink, and has the advantages of strong bonding force with a prepreg and good heat resistance, so that an inner layer circuit can be manufactured by a simple laser engraving method without adopting a traditional exposure and development method, and the manufactured inner layer circuit has high density and high resolution, and the yield is remarkably improved.
Description
Technical Field
The invention belongs to the technical field of electronic materials, and particularly relates to ink, an inner layer circuit of a printed circuit board, a manufacturing method of the inner layer circuit and the printed circuit board.
Background
With the development of Printed Circuit Board (PCB) technology, the circuit pattern of the circuit board becomes finer and finer. At present, for manufacturing an inner layer circuit which is mainly used for signal transmission of full-page high-density high-resolution (line width and line distance is less than 75 mu m/75 mu m), the yield of the traditional exposure and development manufacturing method of the printed circuit board is lower than 50%.
In addition, the printed circuit board processing industry is a high pollution industry, and a large amount of waste water and waste gas are generated in the production process. With the improvement of environmental awareness of people, the national requirements on environmental protection are more and more strict, the labor cost is higher and more, and how to realize the green manufacturing of the printed circuit board is the direction of the effort of the PCB of our generation. The traditional printed circuit board inner layer circuit is made of two kinds of etching-proof coating materials, one is a dry film which is photosensitive and etching-proof, and the other is photosensitive and etching-proof circuit ink (wet film). The two processes are basically consistent: pasting a dry film (or printing a wet film), hot pressing (or drying), pasting a film, exposing, developing, etching a circuit, removing the film, and hot pressing PP (next layer process). Wherein, dry film manufacturers need to discharge a large amount of volatile solvents for manufacturing dry films, and the circuit printing ink also contains several tens percent of volatile solvents, which all cause a large amount of VOC emission. Meanwhile, a large amount of wastewater is generated during the development and film stripping of the manufacturing process.
Disclosure of Invention
The invention aims to provide ink, an inner layer circuit of a printed circuit board, a manufacturing method of the inner layer circuit and the printed circuit board, and aims to solve the technical problems of complicated steps, generation of a large amount of waste gas and waste water and the like in the manufacturing of the inner layer circuit of the traditional printed circuit board.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the invention provides ink which comprises the following components in percentage by weight, based on the total weight of the ink as 100 percent:
wherein the structural formula of the unsaturated carboxylic acid modified epoxy resin is shown as the formula (I):
formula (I) wherein x ═ 1/4) n- (2/3) n, n ═ 2, 3, or 4, y ═ n-x; r is any structure except epoxy; r' is any structure except carboxyl; r' is-CH3Or H.
In a preferred embodiment of the present invention, the unsaturated carboxylic acid-modified epoxy resin is obtained by ring-opening polymerization of an epoxy resin and an unsaturated monocarboxylic acid.
In a further preferred embodiment of the present invention, the epoxy resin is at least one selected from the group consisting of bisphenol a epoxy resin, bisphenol F epoxy resin, liquid novolac epoxy resin, hydrogenated bisphenol a epoxy resin, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, triglycidyl-p-aminophenol and pentaerythritol tetraglycidyl ether.
In a further preferred embodiment of the present invention, the unsaturated monocarboxylic acid is at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, and β -carboxyethyl (meth) acrylate.
As a preferred technical scheme of the invention, the ring-opening polymerization reaction is carried out under the catalysis of an esterification catalyst.
In a preferred embodiment of the present invention, the ring-opening polymerization reaction is performed under the catalysis of an esterification catalyst, and the esterification catalyst is at least one selected from a tertiary amine esterification catalyst, a quaternary ammonium salt esterification catalyst, and a phosphine esterification catalyst.
In a preferred embodiment of the present invention, the epoxy resin is selected from the group consisting of dicyclopentadiene phenol type epoxy resin, biphenyl phenol type epoxy resin, bisphenol a type novolac epoxy resin, condensed ring naphthalene type epoxy resin, 4 '-methylenebis (N, N' -diglycidylaniline), tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether methane, triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, tetraglycidyl-1, 3-bisaminomethylcyclohexane, silicone-modified epoxy resin, polyamide-modified epoxy resin, benzoxazine-modified epoxy resin, bisphenol a epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol a epoxy resin, 4, 5-epoxycyclohexane-1, 2-dimethyldiglycidyl ester, hydrogenated bisphenol F epoxy resin, and mixtures thereof, 2- (3, 4-epoxycyclohexyl) -5, 5-spiro (3, 4-epoxycyclohexyl) -1, 3-dioxane homopolymer, 1, 4-cyclohexanedimethanol bis (3, 4-epoxycyclohexanecarboxylic acid) ester, bis ((3, 4-epoxycyclohexyl) methyl) adipate, and at least one of triglycidyl p-aminophenol.
In a preferred embodiment of the present invention, the curing agent is at least one selected from the group consisting of amine curing agents, acid anhydride curing agents, imidazole curing agents, and blocked isocyanates.
In a preferred embodiment of the present invention, the reactive diluent is selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl methacrylate, OXE-10, OXE-30, vinyl alicyclic epoxy resin, alicyclic epoxy acrylate, alicyclic epoxy methacrylate, p-tert-butylphenyl glycidyl ether, o-tolyl glycidyl ether, phenyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, dipropylene glycol glycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, 1, 2-dihexylene diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and mixtures thereof, At least one of resorcinol diglycidyl ether, glycerol polyglycidyl ether, glycidyl versatate, dimer acid diglycidyl ester, and adipic acid diglycidyl ester.
As a preferable technical solution of the present invention, the photoinitiator is at least one selected from an acylphosphine oxide photoinitiator, a benzoin photoinitiator, an aminoalkyl benzophenone photoinitiator, a benzophenone, a thioxanthone photoinitiator, and an iron arene photoinitiator.
In a preferred embodiment of the present invention, the filler is at least one selected from the group consisting of barium sulfate, talc, crystalline silica, fused silica, amorphous silica, nano silica, alumina, and fine silica powder.
As a preferable technical solution of the present invention, the auxiliary agent includes at least one of a dispersant, a leveling agent, and a defoaming agent.
The invention also provides a manufacturing method of the inner layer circuit of the printed circuit board, which comprises the following steps:
providing ink;
coating the printing ink on a substrate, and carrying out curing reaction to form an etching-resistant coating;
according to the circuit diagram, removing a part needing to be removed on the anti-etching coating by a laser engraving method;
and etching the circuit, and pressing to complete the manufacture of the inner layer circuit of the printed circuit board.
As a preferable technical scheme of the invention, the pulse duration of the laser emission of the laser engraving method reaches the level of picoseconds/nanoseconds/femtoseconds.
As a preferable technical scheme of the invention, the laser light source of the laser engraving method comprises an ultraviolet laser, an infrared laser and CO2At least one of a laser.
In a preferred embodiment of the present invention, the laser engraving method has a laser intensity of 5kw to 15 kw.
As a preferable technical scheme of the invention, the engraving speed of the laser engraving method is 1mm/s-10 mm/s.
In a preferred embodiment of the present invention, the curing reaction includes a photo-curing reaction and a thermal curing reaction.
In another aspect, the invention provides an inner layer circuit of a printed circuit board, which is manufactured by the manufacturing method of the inner layer circuit of the printed circuit board.
The invention also provides a printed circuit board, wherein an etching-proof coating is arranged on the printed circuit board, and the etching-proof coating is obtained by coating the printing ink on the printed circuit board and curing.
The invention also provides another printed circuit board which comprises the inner layer circuit of the printed circuit board.
The unsaturated carboxylic acid modified epoxy resin in the ink enables the obtained ink to have a cyclic structure with good heat resistance, provides a plurality of active groups for the photocuring reaction and the thermocuring reaction of the obtained ink, and is beneficial to the ink to form an anti-etching coating; secondly, the unsaturated carboxylic acid modified epoxy resin, the curing agent, the reactive diluent, the photoinitiator, the filler and the auxiliary agent are used as raw materials, the obtained printing ink does not contain VOC (volatile organic compound) components, is environment-friendly, has good heat resistance, can meet the laminating requirement, has strong bonding force with a copper layer and a prepreg, and does not have the problems of delamination and falling off during thermal shock and reflow soldering.
According to the manufacturing method of the inner layer circuit of the printed circuit board, the anti-etching coating is formed by using the printing ink, the traditional film sticking, exposure, development and other processes can be omitted, and the laser engraving method is directly used for engraving on the anti-etching coating, so that the manufacturing process of the printed circuit board is shortened, and management and control are facilitated; meanwhile, the manufacturing method of laser engraving also avoids the problem of discharge of waste water and waste gas, and is more environment-friendly; most importantly, the manufacturing method of the inner layer circuit of the printed circuit board can improve the processing capability of high density and high resolution with the line width/line distance of less than 75 mu m/75 mu m, and has good application prospect and value. Correspondingly, the inner layer circuit of the printed circuit board manufactured by the manufacturing method has higher precise patterns, and the yield is obviously improved.
The printed circuit board of the invention has the advantages of good heat resistance, strong bonding force and lamination because of the anti-etching coating formed by curing the printing ink.
The other printed circuit board of the invention also has the advantages of functionalization and integration because the inner layer circuit of the printed circuit board comprises the inner layer circuit of the printed circuit board and the inner layer circuit has higher precise patterns.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and the embodiments described below are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention. Those whose specific conditions are not specified in the examples are carried out according to conventional conditions or conditions recommended by the manufacturer; the reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be understood that the weight of the related components mentioned in the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, it is within the scope of the disclosure that the content of the related components is scaled up or down according to the embodiments of the present invention. Specifically, the weight described in the embodiments of the present invention may be a unit of mass known in the chemical field such as μ g, mg, g, kg, etc.
In the description of the invention, an expression of a word in the singular should be understood to include the plural of the word, unless the context clearly dictates otherwise. The terms "comprises" or "comprising" are intended to specify the presence of stated features, quantities, steps, operations, elements, portions, or combinations thereof, but are not intended to preclude the presence or addition of one or more other features, quantities, steps, operations, elements, portions, or combinations thereof.
In the description of the present invention, when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present.
In this specification, "lower" or "upper" is not an absolute concept, but may be a relative concept that can be explained by replacing "upper" or "lower", respectively, according to the viewpoint of the observer.
The embodiment of the invention provides ink, which comprises the following components in percentage by weight, based on the total weight of the ink as 100 percent:
wherein the structural formula of the unsaturated carboxylic acid modified epoxy resin is shown as the formula (I):
formula (I) wherein x ═ 1/4) n- (2/3) n, n ═ 2, 3, or 4, y ═ n-x; r is any structure except epoxy; r' is any structure except carboxyl; r' is-CH3Or H.
The unsaturated carboxylic acid modified epoxy resin in the ink has a plurality of active groups which enable the obtained ink to carry out photocuring reaction and thermocuring reaction and a cyclic structure which enables the obtained ink to have good heat resistance; secondly, the unsaturated carboxylic acid modified epoxy resin, the curing agent, the reactive diluent, the photoinitiator, the filler and the auxiliary agent are used as raw materials, the obtained printing ink does not contain VOC (volatile organic compound) components, is environment-friendly, has good heat resistance, can meet the laminating requirement, has strong bonding force with a copper layer and a prepreg, and does not have the problems of delamination and falling off during thermal shock and reflow soldering.
In some embodiments, the unsaturated carboxylic acid-modified epoxy resin is obtained by ring-opening polymerization of an epoxy resin and an unsaturated monocarboxylic acid, wherein the epoxy group is in excess during the reaction.
In some embodiments, the epoxy resin is selected from at least one of bisphenol a epoxy resin, bisphenol F epoxy resin, liquid novolac epoxy resin, hydrogenated bisphenol a epoxy resin, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, triglycidyl p-aminophenol, and pentaerythritol tetraglycidyl ether, so as to provide a cyclic structure and a plurality of active groups for the obtained unsaturated carboxylic acid modified epoxy resin, facilitate the photo-curing and thermal-curing reactions, and improve the heat resistance of the ink.
In some embodiments, the unsaturated monocarboxylic acid is selected from at least one of acrylic acid, methacrylic acid, itaconic acid, and beta-carboxyethyl (meth) acrylate. These unsaturated monocarboxylic acids can provide carboxyl groups to the resulting unsaturated carboxylic acid-modified epoxy resin to further enhance its reactivity in the curing reaction.
In order to lower the activation energy of the reaction and increase the reaction rate, in some embodiments, the ring-opening polymerization reaction is catalyzed by an esterification catalyst; preferably, the addition mass of the catalyst accounts for 0.01-0.1% of the total mass of the reactants. Wherein the esterification catalyst is at least one of tertiary amine esterification catalyst, quaternary ammonium salt esterification catalyst and phosphine esterification catalyst.
Preferably, the tertiary amine esterification catalyst is selected from at least one of triethylamine, N-dimethylbenzylamine and N, N-dimethylaniline; the quaternary ammonium salt esterification catalyst is at least one selected from trimethyl benzyl ammonium chloride, methyl triethyl ammonium chloride and hexadecyl trimethyl ammonium bromide; the phosphine esterification catalyst is at least one selected from triphenylphosphine, tributylphosphine, triethylphosphine, tri-o-toluyl phosphine, tri-m-toluyl phosphine, tri-p-phenyl-formyl phosphine and tri (p-methoxyphenyl) phosphine.
In some embodiments, the ring-opening polymerization of the epoxy resin with the unsaturated monocarboxylic acid is conducted in the absence of a solvent. And (3) measuring the acid value in the reaction process, terminating the reaction when the acid value is less than or equal to 1, cooling and discharging to obtain the unsaturated carboxylic acid modified epoxy resin. The temperature and the reaction time of the ring-opening polymerization reaction are not particularly required, and the temperature and the reaction time can be adjusted according to the conventional ring-opening polymerization reaction temperature and time in the field and the actual conditions.
Furthermore, when the epoxy resin and the unsaturated monocarboxylic acid are mixed for ring-opening polymerization reaction to synthesize the unsaturated carboxylic acid modified epoxy resin, a polymerization inhibitor is added to prevent the unsaturated bond from self-polymerization and influence the reaction efficiency. Preferably, the addition mass of the polymerization inhibitor accounts for 0.1-0.5% of the total mass of the reactants. Optionally, the polymerization inhibitor is at least one selected from Hydroquinone (HQ), p-benzoquinone (PBQ), methyl hydroquinone (THQ), p-Hydroxyanisole (HQMME), 2-tert-butylhydroquinone (MTBHQ), 2, 5-di-tert-butylhydroquinone (2,5-DTBHQ), and p-Hydroxyanisole (HEMQ). The role of the unsaturated carboxylic acid-modified epoxy resin in the ink of the present invention is as described above, and will not be described herein. If the addition amount of the unsaturated carboxylic acid modified epoxy resin is too large, the viscosity of the ink may increase, which is not favorable for construction application, and then the UV curing ratio increases, the thermosetting ratio decreases, which results in decrease of interlayer adhesion and heat resistance; when the amount of the unsaturated carboxylic acid-modified epoxy resin added is too small, surface dryness during UV curing becomes insufficient. Therefore, the weight percentage of the unsaturated carboxylic acid modified epoxy resin in the ink is controlled to be 10% -20% in the embodiment of the invention. Specifically, the unsaturated carboxylic acid-modified epoxy resin typically comprises, but is not limited to, the following weight percentages: 10%, 12%, 14%, 15%, 16%, 18%, 20%.
The epoxy resin is a main material of thermosetting reaction, and the epoxy resin and the curing agent are subjected to crosslinking reaction when heated, so that the heat resistance and the interlayer adhesion of the film layer are improved. In some embodiments, the epoxy resin is selected from the group consisting of dicyclopentadiene phenol type epoxy resin, biphenyl phenol type epoxy resin, bisphenol a type novolac epoxy resin, fused ring naphthalene type epoxy resin, 4 '-methylenebis (N, N' -diglycidylaniline), tetraphenylglycidylethane, triphenylglycidylether methane, triglycidyl isocyanurate, tetraglycidyldiaminodiphenylmethane, tetraglycidyl-1, 3-bisaminomethylcyclohexane, silicone modified epoxy resin, polyamide modified epoxy resin, benzoxazine modified epoxy resin, bisphenol a epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol a epoxy resin, 4, 5-epoxycyclohexane-1, 2-dimethyldiglycidyl ester, 2- (3, 4-epoxycyclohexyl) -5, 5-spiro (3, 4-epoxycyclohexyl) -1, 3-dioxane homopolymer, 1, 4-cyclohexanedimethanol bis (3, 4-epoxycyclohexanecarboxylic acid) ester, bis ((3, 4-epoxycyclohexyl) methyl) adipate, and at least one of triglycidyl p-aminophenol. The weight percentage of the epoxy resin in the ink is 35-55%. Specifically, the epoxy resin typically, but not by way of limitation, comprises in weight percent: 35%, 40%, 45%, 50%, 55%.
The curing agent is a substance which promotes or controls the curing reaction, and by adding the curing agent, the resin can be subjected to a photo-curing reaction and a thermal curing reaction, and the heat resistance and the stability of the obtained ink are remarkably influenced. In some embodiments, the curing agent is selected from at least one of amine curing agents, anhydride curing agents, imidazole curing agents, blocked isocyanates. The addition amount of the curing agent is too much, so that the flexibility of an anti-etching coating formed on the printed circuit board by the printing ink is easily reduced, and the problems of cracking and the like occur; if the amount of the curing agent added is too low, problems such as incomplete curing reaction, and a decrease in the hardness and thermal stability of the resist layer formed on the printed wiring board by the ink may occur. Thus, the present examples control the percent by weight of curing agent in the ink to be between 5% and 10%. Specifically, typical, but not limiting, amounts of the curing agent are as follows: 5%, 6%, 7%, 8%, 9%, 10%.
Preferably, the amine curing agent is selected from at least one of diaminodiphenyl sulfone (DDS), diaminodiphenylmethane (DDM); the acid anhydride curing agent is at least one selected from phthalic anhydride, Benzophenone Tetracarboxylic Dianhydride (BTDA), diphenyl sulfone tetracarboxylic dianhydride (DSDA), tetrahydrophthalic anhydride (THPA), NA, and methylcyclohexenyl tetracarboxylic dianhydride (MCTC); the imidazole curing agent is selected from PN-23, PN-31, PN-40, PN-50, PN-H, 2-undecylimidazole, 2-heptadecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2-methylimidazole isocyanurate, 2-phenylimidazole isocyanurate, 2, 4-diamino-6- (2-methylimidazole-1-ethyl) -S-triazine, 2, 4-diamino-6- (2-ethyl-4-methylimidazole-1-ethyl) -S-triazine, N-methyl-phenyl-imidazole, N-methyl-1-ethyl) -S-triazine, N-methyl-N-phenyl-imidazole, N-methyl-1-ethyl-S, 2, 4-diamino-6- (2-undecylimidazole-1-ethyl) -S-triazine, 2-phenyl-4, 5-dimethyloimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4, 5-bis (cyanoethoxymethylene) imidazole, 1-dodecyl-2-methyl-3-benzylimidazole chloride, 1, 3-dibenzyl-2-methylimidazole chloride, boron trifluoride-amine complex (BF3-MEA, BF3-BZA, BF 3-DMA); cationic initiator: at least one of aromatic diazonium salt, bis (4-dodecylbenzene) iodonium hexafluoroantimonate, (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, mixed sulfonium hexafluoroantimonate, (5-p-toluenesulfonyloxyimine-5H-thiophen-2-ylidene) - (4-methoxyphenyl) -acetonitrile).
The reactive diluent can participate in the curing reaction of the unsaturated carboxylic acid modified epoxy resin, becomes a part of the cross-linked network structure of a cured product, and can reduce the viscosity of the system. In some embodiments, the reactive diluent is selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl methacrylate, OXE-10, OXE-30, vinyl cycloaliphatic epoxy resins, cycloaliphatic epoxy acrylates, cycloaliphatic epoxy methacrylates, p-tert-butylphenyl glycidyl ether, o-tolyl glycidyl ether, phenyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, dipropylene glycol glycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, 1, 2-dihexylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, a, At least one of glycerol polyglycidyl ether, glycidyl versatate, dimer acid diglycidyl ester and adipic acid diglycidyl ester. If the addition amount of the reactive diluent is too large, the curing reaction rate is easily reduced, and the reaction time is prolonged; the addition amount of the reactive diluent is too small, and the viscosity of the obtained ink is possibly too high, so that the ink is not favorable for being coated on the surface of a substrate to form an etching-resistant coating. Thus, the present examples control the weight percent of reactive diluent in the ink to between 5% and 10%. In particular, typical, but not limiting, amounts of reactive diluents are as follows by weight percent: 5%, 6%, 7%, 8%, 9%, 10%.
The photoinitiator can absorb energy in an ultraviolet light region or a visible light region to generate free radicals or cations, so that the polymerization, crosslinking and curing reaction of the monomers is initiated. In some embodiments, the photoinitiator is selected from at least one of acylphosphine oxide based photoinitiators, benzoin based photoinitiators, aminoalkyl phenone based photoinitiators, benzophenones, thioxanthone based photoinitiators, and iron arene based photoinitiators. The problems that the anti-etching coating formed on the printed circuit board by the ink is too thick and the like are easily caused by excessive addition of the photoinitiator, and the addition of other components is correspondingly reduced to influence the performance of the anti-etching coating; if the amount of the photoinitiator is too small, the photocuring reaction may be incomplete, and the properties such as the bonding force and the heat resistance of the obtained etching resist coating may be affected. Thus, the present examples control the weight percent of photoinitiator in the ink to between 1% and 5%. In particular, typical, but not limiting, amounts of photoinitiator in weight percent are: 1%, 2%, 3%, 4%, 5%.
Preferably, the acylphosphine oxide photoinitiator is selected from 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, diethyl 2,4, 6-trimethylbenzoylphosphonate, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) - (4 ', 4' -dimethyloctyl-2) phosphine oxide; the benzoin photoinitiator is at least one selected from benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; the amino alkyl benzophenone photoinitiator is selected from at least one of diphenylethanedione, alpha-dimethoxy-alpha-phenylacetophenone, alpha-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy-cyclohexyl benzophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone and 2-phenylbenzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone; the thioxanthone photoinitiator is at least one selected from 2-chlorothianthrone, isopropyl thioxanthone and 2, 4-diethylthioxanthone.
The filler has low cost, can further improve the heat resistance, the adsorption force, the insulativity and other properties of the anti-etching coating formed by the ink, and can also reduce the production cost. In some embodiments, the filler is selected from at least one of barium sulfate, talc, crystalline silica, fused silica, amorphous silica, nanosilica, alumina, microsilica. The addition amount of the filler is too much, and the content of other components is reduced correspondingly, so that the original performance of the anti-etching coating is influenced; if the addition amount of the filler is too small, the production cost is high, and the large-scale production is not facilitated. Thus, the present examples control the weight percent of filler in the ink to be between 20% and 40%. In particular, typical, but not limiting, amounts of fillers are in percent by weight: 20%, 25%, 30%, 35%, 40%.
The auxiliary agent mainly plays an auxiliary role in the ink, and can be a wetting dispersant for improving the dispersibility of the filler and at least one of a leveling agent and a defoaming agent which do not influence recoating. The addition amount of the auxiliary agent is too much, and problems such as dripping, vortex eye and the like can occur; the addition amount of the auxiliary agent is too small, and the flatness and the smoothness of the obtained etching-resistant coating are not enough. Thus, the inventive examples controlled the weight percent of the adjuvant in the ink to be between 0% and 1%.
The preparation method of the ink can comprise the following steps:
s1, providing unsaturated carboxylic acid modified epoxy resin (A), epoxy resin (B), curing agent (C), reactive diluent (D), photoinitiator (E), filler (F) and auxiliary agent (G);
s2, adding unsaturated carboxylic acid modified epoxy resin (A), epoxy resin (B), curing agent (C), photoinitiator (E), auxiliary agent (G), filler (F) and active diluent (D) in sequence while stirring, dispersing at high speed for 15-20 min (the temperature is controlled to be less than 50 ℃), grinding to the fineness of less than 10 mu m, and then adjusting the viscosity to 100 +/-20 dPa.s by using a small amount of active diluent (D);
and S3, filtering and packaging to obtain the finished product material of the ink.
The ink finished product material is preserved at the temperature below 5 ℃ before use, and is thawed at room temperature for 8 hours when used.
Based on the ink, the embodiment of the invention provides a method for manufacturing an inner layer circuit of a printed circuit board, which comprises the following steps:
s01, providing ink;
s02, coating the ink on the substrate, and carrying out curing reaction to form an etching-resistant coating;
s03, according to the circuit diagram, removing the parts except the circuit on the anti-etching coating by a laser engraving method;
and S04, etching the circuit, and pressing to complete the manufacture of the inner layer circuit of the printed circuit board.
Firstly, the method for manufacturing the inner layer circuit of the printed circuit board forms the etching-resistant coating by using the printing ink, can directly engrave on the etching-resistant coating by using a laser engraving method without adopting the traditional film sticking, exposure, development and other processes, shortens the manufacturing flow of the printed circuit board and is beneficial to management and control; secondly, the manufacturing method of the laser engraving also avoids the problem of discharge of waste water and waste gas, and is more environment-friendly; finally and most importantly, the method for manufacturing the inner layer circuit of the printed circuit board can improve the processing capability of high density and high resolution with the line width/line distance of less than 75 mu m/75 mu m.
In S01, the ink is the ink described above and is not described herein for brevity.
In S02, the ink is applied by a method including, but not limited to, screen printing or roll coating.
In some embodiments, the curing reaction includes a photo-curing reaction and a thermal curing reaction. Because the printed circuit board is vertically arranged in the heat curing and manufacturing processes, the light curing reaction with the shaping function is firstly carried out to avoid the ink sagging. After the photocuring reaction, the coating is thermally cured for 15min to 60min at the temperature of 100 ℃ to 200 ℃ to form the etching-resistant coating. Specifically, typical but not limiting thermal curing temperatures are 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃; typical, but not limiting, thermal curing times are 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60 min.
In S03, the laser engraving method engraves the coating on the portion to be etched away from the substrate according to the pattern of the wiring pattern, and the engraving accuracy affects the accuracy of the inner layer wiring. Thus, in some embodiments, the laser engraving process laser emission pulse duration is on the order of picoseconds/nanoseconds/femtoseconds to meet the accuracy requirements of the inner layer lines actually fabricated.
The laser source has a certain influence on the precision of the inner layer circuit, and in some embodiments, the laser source adopted by the laser engraving method can be an ultraviolet laser, an infrared laser, or CO2At least one of a laser.
In the laser engraving process, the laser energy absorbed by the material is a key element for achieving the corresponding engraving precision. The laser energy is affected by the intensity of the laser engraving and the engraving speed. Thus, in some embodiments, the intensity of the laser engraving is set to 5kw to 15kw, and the engraving speed of the laser engraving is set to 1mm/s to 10 mm/s. In particular, typical, but not limiting, laser engraving intensities are 5kw, 6kw, 7kw, 8kw, 9kw, 10kw, 11kw, 12kw, 13kw, 14kw, 15 kw; typical, but not limiting, laser engraving speeds are 1mm/s, 2mm/s, 3mm/s, 4mm/s, 5mm/s, 6mm/s, 7mm/s, 8mm/s, 9mm/s, 10 mm/s.
The pressing in S04 is obviously different from the conventional method. In the traditional method, because a dry film (or a printed wet film) needs to be pasted before exposure and development, after a circuit is etched, a laminating step can be carried out only by removing the film; the anti-etching coating formed by the ink can be directly laminated after the circuit is etched without film stripping. The anti-etching coating formed by the ink has excellent heat resistance and laminating performance, has good bonding force with a substrate (copper layer and the like) and a prepreg, and does not have the problem of delamination and falling off when the anti-etching coating is subjected to thermal shock during lamination.
Accordingly, the embodiment of the invention provides an inner layer circuit of a printed circuit board, which is manufactured by the manufacturing method of the inner layer circuit. Because the inner layer circuit of the printed circuit board is carved by adopting a laser carving method, the requirements of the inner layer circuit with signal transmission as a main part on high density and high resolution of the line width/line distance of less than 75 mu m/75 mu m can be met, and the yield is also obviously improved.
Accordingly, the embodiment of the invention provides a printed circuit board, which comprises an etching-resistant coating formed by curing the ink. The printed circuit board of the present invention also has the advantages of good heat resistance, strong bonding force and lamination capability due to the advantages of the etching-resistant coating.
Correspondingly, the embodiment of the invention also provides another printed circuit board which comprises the inner-layer circuit of the printed circuit board. Because the inner layer circuit has a higher precise pattern, the printed circuit board obtained by the invention also has the advantages of functionalization and integration.
In order to clearly understand the details and operation of the above embodiments of the present invention for those skilled in the art, and to obviously show the advanced performance of the ink, the inner layer circuit of the printed circuit board, the manufacturing method thereof, and the printed circuit board of the embodiments of the present invention, the above technical solutions are exemplified by a plurality of embodiments.
Example 1
An ink, the preparation method comprises the following steps:
(1) 240g of bisphenol A epoxy resin, 0.1g of hydroquinone, 0.05g of MEHQ and 0.6g of triphenylphosphine are added into a reaction kettle, stirred and heated to 80 ℃, and then 60g of acrylic acid is added. When the temperature rises to 85 ℃, stopping heating, naturally raising the temperature, and when the temperature is stable and does not rise any more, heating to ensure that the material temperature is stabilized at about 106 ℃. After 6h of reaction, measuring the acid value once every half an hour, stopping heating when AV is less than or equal to 1, and discharging when the temperature is lower than 80 ℃ to obtain unsaturated carboxylic acid modified epoxy resin (A1);
(2) adding unsaturated carboxylic acid modified epoxy resin (A1), epoxy resin (B), curing agent (C), photoinitiator (E), filler (F), auxiliary agent (G), filler (F) and active diluent (D) in turn while stirring, dispersing at high speed for 15-20 min (the temperature is controlled to be less than 50 ℃), grinding for at least 3 times by three-roll until the fineness is less than 10 mu m, and then adjusting the viscosity to 100 +/-20 dPa.s by using the active diluent (D);
(3) and filtering and packaging to obtain the finished product material of the printing ink.
In step (2), the specific selection and amounts of each component are detailed in table 1.
Example 2
The ink preparation method in this example is the same as example 1, except that the selection and amounts of the other components used in preparing the ink are as specified in Table 1.
Example 3
The ink preparation method in this example is the same as example 1, except that the selection of other components and the amounts of the components are different in preparing the ink, as detailed in table 1.
Example 4
An ink, the preparation method comprises the following steps:
(1) 240g of bisphenol A epoxy resin, 0.1g of hydroquinone, 0.05g of MEHQ and 0.6g of triphenylphosphine are added into a reaction kettle, stirred and heated to 80 ℃, and 72g of methacrylic acid is added. When the temperature rises to 85 ℃, stopping heating, naturally raising the temperature, and when the temperature is stable and does not rise any more, heating to ensure that the material temperature is stabilized at about 106 ℃. After 6h of reaction, measuring the acid value once every half an hour, stopping heating when AV is less than or equal to 1, and discharging when the temperature is lower than 80 ℃ to obtain unsaturated carboxylic acid modified epoxy resin (A2);
(2) adding unsaturated carboxylic acid modified epoxy resin (A2), epoxy resin (B), curing agent (C), photoinitiator (E), filler (F), auxiliary agent (G), filler (F) and active diluent (D) in turn while stirring, dispersing at high speed for 15-20 min (the temperature is controlled to be less than 50 ℃), grinding for at least 3 times by three-roll until the fineness is less than 10 mu m, and then adjusting the viscosity to 100 +/-20 dPa.s by using the active diluent (D);
(3) and filtering and packaging to obtain the finished product material of the printing ink.
In step (2), the specific selection and amounts of each component are detailed in table 1.
Example 5
The inks of this example were prepared as in example 4, except that the selection and amounts of the other components used to prepare the inks were as specified in Table 1.
Example 6
The ink preparation method in this example is the same as example 4, except that the selection of other components and the amounts of the components are different in preparing the ink, as detailed in table 1.
Example 7
An ink, the preparation method comprises the following steps:
(1) 247g of trimethylolpropane triglycidyl ether, 0.12g of hydroquinone, 0.08g of MEHQ and 1.2g of triphenylphosphine were added to the reaction vessel, stirred and heated to 80 ℃ and 115g of methacrylic acid was added. When the temperature rises to 85 ℃, stopping heating, naturally raising the temperature, and when the temperature is stable and does not rise any more, heating to ensure that the material temperature is stabilized at about 106 ℃. After 6h of reaction, 0.04g of MEHQ is added, then the acid value is measured every half hour, the heating is stopped when the AV is less than or equal to 1, and the material is discharged when the temperature is lower than 80 ℃, so that the unsaturated carboxylic acid modified epoxy resin (A3) is obtained;
(2) adding unsaturated carboxylic acid modified epoxy resin (A3), epoxy resin (B), curing agent (C), photoinitiator (E), filler (F), auxiliary agent (G), filler (F) and active diluent (D) in turn while stirring, dispersing at high speed for 15-20 min (the temperature is controlled to be less than 50 ℃), grinding for at least 3 times by three-roll until the fineness is less than 10 mu m, and then adjusting the viscosity to 100 +/-20 dPa.s by using the active diluent (D);
(3) and filtering and packaging to obtain the finished product material of the printing ink.
In step (2), the specific selection and amounts of each component are detailed in table 1.
Example 8
The inks of this example were prepared as in example 7, except that other components were selected and used in the preparation of the inks, as detailed in Table 1.
Example 9
The ink preparation method in this example is the same as example 7, except that the selection of other components and the amounts of the components are different in preparing the ink, as detailed in Table 1.
TABLE 1 selection of ink ingredients and amounts (% by weight) of examples 1-9
The inks obtained in examples 1 to 9 were applied to a copper plate by screen printing or roll coating, cured by UV curing and heat curing (100 ℃, 30min), then the exposed copper surface was engraved by laser engraving of the coating over the part to be etched, after etching the lines according to the conventional method, PP was pressed with the etch-resistant coating remaining, and the fabrication of the inner layer lines was completed.
And testing the inner layer circuit made of the etching-resistant coating, wherein the test standard is as follows:
1. line width/line pitch: the laser design engraves a line with a line width and a line distance of 30 μm, and the actual line width/line distance range is observed under a high power microscope.
2. The yield of the etched circuit is as follows: after etching, the circuit is observed by a high power microscope to see whether the circuit is open or short-circuited, and if not, the circuit is determined to be qualified.
3. And (3) testing the adhesive force: and (4) respectively scribing 11 scribing lines on the surface of the anti-etching coating layer vertically and horizontally by using a hundred-grid cutter, wherein the length of the scribing line is about 20mm, and the depth is preferably the depth for scratching the paint layer. And slowly and flatly pasting one end of the 3M adhesive tape on the louver from the most edge of the louver, flatly pressing, waiting for 90 +/-30 seconds, then pressing the substrate (or the product) with the left hand, pinching the free end of the adhesive tape with the right hand, and quickly tearing off the 3M adhesive tape at about 180 degrees in the opposite direction. And carefully checking the falling condition of the etching-resistant coating on the grids by using a magnifying glass, judging that the adhesion is OK if the falling area of the etching-resistant coating is below 5%, and judging that the adhesion is NG if the falling area of the etching-resistant coating is not more than 5%.
4. Acid and alkali resistance: 25 ℃ 10 vol% H2SO4And 10 wt% in NaOH for 30min, and the acid and alkali resistance test is passed and is regarded as OK, otherwise NG.
5. And (3) heat resistance test: and (3) coating the rosin type soldering flux on the surface of the laminated PCB, immersing the PCB in a 288 ℃ lead-tin furnace for 10s, cooling, repeating for a plurality of times until the layering phenomenon appears, and judging the PCB to be qualified if the number of times is at least more than 6.
The results are shown in Table 2.
TABLE 2 results of performance tests of etching resists and inner layer wiring formed by the inks obtained in examples 1 to 9
As can be seen from the performance test results in Table 2, the anti-etching coating obtained by curing the ink on the printed circuit board has good adhesion, and the heat resistance, the solvent resistance, the acid resistance and the alkali resistance all accord with the IPC industrial standard; the line width of the inner layer circuit obtained by the manufacturing method of the inner layer circuit is 20-30 mu m; the line distance is 30-40 μm, the high-density and high-resolution circuit has the advantages of high density and high resolution, and the yield of the etched circuit reaches 100%.
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 (10)
1. The ink is characterized by comprising the following components in percentage by weight based on the total weight of the ink as 100 percent:
wherein the structural formula of the unsaturated carboxylic acid modified epoxy resin is shown as the formula (I):
formula (I) wherein x ═ 1/4) n- (2/3) n, n ═ 2, 3, or 4, y ═ n-x; r is any structure except epoxy; r' is any structure except carboxyl; r' is-CH3Or H.
2. The ink according to claim 1, wherein the unsaturated carboxylic acid-modified epoxy resin is obtained by ring-opening polymerization of an epoxy resin and an unsaturated monocarboxylic acid.
3. The ink of claim 2, wherein the epoxy-based resin is selected from at least one of bisphenol a epoxy resin, bisphenol F epoxy resin, liquid novolac epoxy resin, hydrogenated bisphenol a epoxy resin, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, triglycidyl-p-aminophenol, pentaerythritol tetraglycidyl ether; and/or
The unsaturated monocarboxylic acid is at least one selected from acrylic acid, methacrylic acid, itaconic acid and beta-carboxyethyl (methyl) acrylate; and/or
The ring-opening polymerization reaction is carried out under the catalysis of an esterification catalyst; and/or
The ring-opening polymerization reaction is carried out under the catalysis of an esterification catalyst, and the esterification catalyst is selected from at least one of tertiary amine esterification catalysts, quaternary ammonium salt esterification catalysts and phosphine esterification catalysts.
4. The ink according to claim 1, wherein the epoxy resin is selected from the group consisting of dicyclopentadiene phenol type epoxy resin, biphenyl phenol type epoxy resin, bisphenol a type novolac epoxy resin, condensed ring naphthalene type epoxy resin, 4 '-methylenebis (N, N' -diglycidylaniline), tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether methane, triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, tetraglycidyl-1, 3-bisaminomethylcyclohexane, silicone modified epoxy resin, polyamide modified epoxy resin, benzoxazine modified epoxy resin, bisphenol a epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol a epoxy resin, 4, 5-epoxycyclohexane-1, 2-dimethyldiglycidyl ester, hydrogenated bisphenol F epoxy resin, 4, 5-epoxycyclohexane-1, 2-dimethyldiglycidyl ester, hydrogenated bisphenol a epoxy resin, and mixtures thereof, 2- (3, 4-epoxycyclohexyl) -5, 5-spiro (3, 4-epoxycyclohexyl) -1, 3-dioxane homopolymer, 1, 4-cyclohexanedimethanol bis (3, 4-epoxycyclohexanecarboxylic acid) ester, bis ((3, 4-epoxycyclohexyl) methyl) adipate, and at least one of triglycidyl p-aminophenol.
5. The ink according to any one of claims 1 to 4, wherein the curing agent is at least one selected from the group consisting of amine curing agents, acid anhydride curing agents, imidazole curing agents, and blocked isocyanates; and/or
The reactive diluent is selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl methacrylate, OXE-10, OXE-30, vinyl alicyclic epoxy resin, alicyclic epoxy acrylate, alicyclic epoxy methacrylate, p-tert-butylphenyl glycidyl ether, o-tolyl glycidyl ether, phenyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, dipropylene glycol glycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, 1, 2-dihexylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, a, At least one of glycerol polyglycidyl ether, glycidyl versatate, dimer acid diglycidyl ester and adipic acid diglycidyl ester; and/or
The photoinitiator is selected from at least one of acyl phosphine oxide photoinitiators, benzoin photoinitiators, amino alkyl benzophenones photoinitiators, benzophenones, thioxanthones photoinitiators and iron arene photoinitiators; and/or
The filler is at least one selected from barium sulfate, talcum powder, crystalline silica, fused silica, amorphous silica, nano-silica, alumina and silica micropowder; and/or
The auxiliary agent comprises at least one of a dispersing agent, a flatting agent and a defoaming agent.
6. A method for manufacturing an inner layer circuit of a printed circuit board is characterized by comprising the following steps:
providing an ink according to any one of claims 1 to 5;
coating the printing ink on a substrate, and carrying out curing reaction to form an etching-resistant coating;
according to the circuit diagram, removing the parts except the circuit on the etching-proof coating by a laser engraving method;
and etching the circuit, and pressing to complete the manufacture of the inner layer circuit of the printed circuit board.
7. The method for manufacturing the inner layer circuit of the printed circuit board as claimed in claim 6, wherein the pulse duration of the laser emission of the laser engraving method reaches the level of picoseconds/nanoseconds/femtoseconds; and/or
The laser source of the laser engraving method comprises an ultraviolet laser, an infrared laser and CO2At least one of a laser; and/or
The laser intensity of the laser engraving method is 5-15 kw; and/or
The engraving speed of the laser engraving method is 1-10 mm/s.
8. The method for manufacturing inner layer circuit of printed circuit board as claimed in claim 6, wherein the curing reaction comprises photo curing reaction and thermal curing reaction.
9. An inner layer circuit of a printed circuit board, characterized by being manufactured by the manufacturing method of any one of claims 6 to 8.
10. A printed circuit board, wherein an etching-resistant coating is arranged on the printed circuit board, and the etching-resistant coating is obtained by coating the ink of any one of claims 1-5 on the printed circuit board and curing; and/or
The printed circuit board includes the printed circuit board inner layer wiring of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010175052.8A CN113025116A (en) | 2020-03-13 | 2020-03-13 | Printing ink, printed circuit board inner layer circuit, manufacturing method of printed circuit board inner layer circuit and printed circuit board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010175052.8A CN113025116A (en) | 2020-03-13 | 2020-03-13 | Printing ink, printed circuit board inner layer circuit, manufacturing method of printed circuit board inner layer circuit and printed circuit board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113025116A true CN113025116A (en) | 2021-06-25 |
Family
ID=76458880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010175052.8A Pending CN113025116A (en) | 2020-03-13 | 2020-03-13 | Printing ink, printed circuit board inner layer circuit, manufacturing method of printed circuit board inner layer circuit and printed circuit board |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113025116A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114773905A (en) * | 2022-04-15 | 2022-07-22 | 华南理工大学 | A kind of white UV/heat dual curing FPC inkjet character ink and preparation method thereof |
| CN115060853A (en) * | 2022-06-30 | 2022-09-16 | 珠海中京电子电路有限公司 | Etching uniformity detection method, device and equipment of etching machine and storage medium |
| CN115236936A (en) * | 2022-09-22 | 2022-10-25 | 之江实验室 | Femtosecond laser cured and crosslinked polyamic acid photoresist and preparation method, use method and application thereof |
| CN115612040A (en) * | 2022-09-23 | 2023-01-17 | 共享新材料(山东)有限公司 | Photosensitive resin and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1408764A (en) * | 2001-09-27 | 2003-04-09 | 山荣化学株式会社 | Light solidified and heat solidified resin composition and method for producing printed circuit board |
| CN108219589A (en) * | 2017-12-06 | 2018-06-29 | 中山大学 | A kind of UV-LED inkjet printings welding resistance ink and its preparation method and application |
-
2020
- 2020-03-13 CN CN202010175052.8A patent/CN113025116A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1408764A (en) * | 2001-09-27 | 2003-04-09 | 山荣化学株式会社 | Light solidified and heat solidified resin composition and method for producing printed circuit board |
| CN108219589A (en) * | 2017-12-06 | 2018-06-29 | 中山大学 | A kind of UV-LED inkjet printings welding resistance ink and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 姜培安: "《印制电路板的可制造性设计》", vol. 1, 30 September 2007, 中国电力出版社, pages: 170 * |
| 邵念勤等: "《机械制造基础》", vol. 1, 西安地图出版社, pages: 317 - 318 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114773905A (en) * | 2022-04-15 | 2022-07-22 | 华南理工大学 | A kind of white UV/heat dual curing FPC inkjet character ink and preparation method thereof |
| CN115060853A (en) * | 2022-06-30 | 2022-09-16 | 珠海中京电子电路有限公司 | Etching uniformity detection method, device and equipment of etching machine and storage medium |
| CN115236936A (en) * | 2022-09-22 | 2022-10-25 | 之江实验室 | Femtosecond laser cured and crosslinked polyamic acid photoresist and preparation method, use method and application thereof |
| CN115236936B (en) * | 2022-09-22 | 2022-12-06 | 之江实验室 | Femtosecond laser cured and crosslinked polyamic acid photoresist and preparation method, use method and application thereof |
| CN115612040A (en) * | 2022-09-23 | 2023-01-17 | 共享新材料(山东)有限公司 | Photosensitive resin and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113025116A (en) | Printing ink, printed circuit board inner layer circuit, manufacturing method of printed circuit board inner layer circuit and printed circuit board | |
| JP6203874B2 (en) | White curable resin composition, cured product thereof, printed wiring board having the cured product, and reflector for light-emitting element comprising the cured product | |
| DE69208106T2 (en) | AN ADHESIVE POLYMERIZABLE ADHESIVE, COATING AGENT AND METHOD FOR THE PRODUCTION THEREOF | |
| EP2738226B1 (en) | Photocurable ink jet ink and electronic circuit board | |
| KR20110106237A (en) | Resin composition which has photocurability and thermosetting, and dry film soldering resist | |
| CN113024773A (en) | Modified acrylate resin, preparation method thereof, solder resist ink and printed circuit board | |
| JP2009239181A (en) | Resin composition for printed circuit board, dry film, and printed circuit board | |
| JP2019174824A (en) | Curable resin composition, dry film, cured product and printed wiring board | |
| KR20180089286A (en) | Reactive polycarboxylic acid compound, active energy ray curable resin composition using same and cured product thereof, and use thereof | |
| CN109897509A (en) | A kind of UV photocureable coating for aluminum-based copper-clad plate | |
| JP5137823B2 (en) | Reactive carboxylate compound, curable resin composition using the same, and use thereof | |
| CN113025114A (en) | Drilling ink and application thereof | |
| WO2000040632A1 (en) | Curable resin composition, modified copolymer and resin composition, and alkali development type photocurable glass paste | |
| JP6556735B2 (en) | Reactive polyester compound and active energy ray-curable resin composition using the same | |
| KR20100058450A (en) | Reactive carboxylate compound, curable resin composition using the same, and use of the same | |
| WO2013172009A1 (en) | Reactive polyester compound and active energy ray-curable resin composition | |
| JP2009227848A (en) | Epoxycarboxylate compound with little chlorine content, derivative thereof, active energy ray-curable resin composition containing the same, and cured product thereof | |
| CN102766375B (en) | Method for preparing low viscosity ultraviolet (UV) curing solder resist ink | |
| CN107298753B (en) | Reactive epoxy carboxylate compound, reactive polycarboxylic acid compound resin composition, cured product and article | |
| JP2009249607A (en) | Photosensitive resin composition and cured product of the same | |
| CN109679402B (en) | Hole plugging ink composition special for hole plugging and filling and printed circuit board | |
| JP2007153933A (en) | Bonding method and adhesive | |
| TWI726131B (en) | Epoxy carboxylate compound, polycarboxylic acid-based compound, energy beam curable resin composition containing the same and its cured product | |
| CN103819616A (en) | Photosensitive acrylic AED resin and negative photoresist composition comprising same, and preparation method thereof | |
| CN105968001B (en) | Carboxyl group-containing reactive compound, curable resin composition and cured product using the compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210625 |
|
| RJ01 | Rejection of invention patent application after publication |