CN115707794A - Surface-binding agent and method for treating substrate surface - Google Patents
Surface-binding agent and method for treating substrate surface Download PDFInfo
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- CN115707794A CN115707794A CN202111615347.3A CN202111615347A CN115707794A CN 115707794 A CN115707794 A CN 115707794A CN 202111615347 A CN202111615347 A CN 202111615347A CN 115707794 A CN115707794 A CN 115707794A
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Abstract
A surface binding agent comprises a triazole compound and an imidazole compound. The surface bonding agent forms an organic layer on the surface of the base material, so that the adhesive force between the surface of the base material which is not subjected to roughening treatment in advance and a coating material, such as photoresist, ink and a metal layer to be added (formed in a sputtering mode, an evaporation mode and the like), is effectively improved, and the coating material can be prevented from being stripped from the surface of the base material.
Description
Technical Field
The present invention relates to a surface bonding agent and a method for processing a substrate surface using the same, and more particularly, to a method for processing a non-metal surface (e.g., a surface of glass, silicon crystal, polyimide (PI) film, etc.) and a metal surface (e.g., a surface of copper and copper alloy, iron casting, aluminum, steel, nickel, zinc, nickel-iron alloy, etc.) using a surface bonding agent to improve adhesion between the surface of a substrate and a coating material such as a photoresist, an ink, or a metal layer to be added (formed by sputtering, vapor deposition, etc.).
Background
Generally, in order to improve the adhesion between the substrate surface and the coating material, a method of roughening the substrate surface in advance is used, for example, a photoresist is formed on a roughened copper foil of a printed circuit board, then, the photoresist is exposed to have a specific pattern shape to expose a portion of the copper foil surface, then, the exposed copper is removed by etching, and after the photoresist is removed, the copper which is not removed by etching is left to form a desired copper wiring pattern on the printed circuit board.
However, if roughening treatment is applied, the roughened copper surface will be conformal to the circuit pattern, and the signal transmission path for high frequency and high speed transmission usually occurs on the circuit surface (skin effect), and if the circuit surface is not flat, the problem of poor signal will occur. Moreover, the roughening treatment is usually accompanied by pollution of waste water, and has an environmental problem. On the other hand, as the line pattern is gradually thinned and shrunk, the adhesion problem between the roughened copper surface and the patterned photoresist becomes more serious. Therefore, in the current high-frequency and high-speed transmission era, it is desired to manufacture the circuit without roughening the surface of the substrate conductor.
At present, methods for pretreating metal surfaces using surface treatment compositions are known, but the surface treatment compositions described in the prior art still have the problems of excessive corrosion or uneven corrosion of the substrate surface, or insignificant adhesion promotion effect.
Disclosure of Invention
In order to solve the above problems, the present invention provides a surface bonding agent for improving the surface adhesion of a non-metal substrate, wherein the surface bonding agent comprises a triazole compound and an imidazole compound.
In one embodiment, the triazole compound includes at least one selected from benzotriazole and 5-methylbenzotriazole, and the imidazole compound includes at least one selected from imidazole, dihydroimidazole, and 1, 2-dimethylimidazole.
In one embodiment, the surface binding agent further comprises a pyridine compound, and in another embodiment, the pyridine compound comprises at least one selected from the group consisting of 2-methylpyridine and 2-mercaptopyridine.
In one embodiment, the concentration of each of the triazole compound, imidazole compound, and pyridine compound is between 0.05g/L and 50 g/L.
In one embodiment, the surface binding agent further comprises dimethylacetamide as a catalyst, and in another embodiment, the concentration of dimethylacetamide is between 5mL/L to 100 mL/L.
In one embodiment, the surface binding agent does not include an acid compound.
In one embodiment, the surface bonding agent may further serve to promote surface adhesion of the metal substrate, and in another embodiment, the surface bonding agent further comprises at least one of an inorganic acid compound and an organic acid compound.
In one embodiment, the inorganic acid compound includes at least one selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid.
In one embodiment, the organic acid compound includes at least one selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oxalic acid, acrylic acid, crotonic acid, methacrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, benzoic acid, phthalic acid, cinnamic acid, glycolic acid, lactic acid, malic acid, salicylic acid, glycine, tartaric acid, citric acid, sulfamic acid, beta-chloropropionic acid, nicotinic acid, ascorbic acid, hydroxytrimethylacetic acid and levulinic acid.
In one embodiment, the surface binding agent further comprises at least one selected from the group consisting of ethanolamine, diethylene glycol monobutyl ether, dimethoxyethane.
The invention also provides a method for treating the surface of a base material, which comprises the step of contacting the surface bonding agent with the surface of the base material to improve the adhesive force between the surface of the base material and a layer coated on the surface of the base material, wherein the base material is a metal base material or a non-metal base material, and the layer coated on the surface of the base material is a metal layer or a non-metal layer.
In one embodiment, the material of the metal substrate and the metal layer includes at least one selected from the group consisting of copper, aluminum, nickel, zinc, iron, chromium, and alloys thereof. In one embodiment, the non-metallic substrate and the non-metallic layer are made of glass, polyimide film, prepreg, imageable dielectric, imageable resin, solder resist, etch resist, or silicon crystal.
In one embodiment, the surface-binding agent is contacted with the surface of the substrate by spin coating, soaking, or spraying.
In one embodiment, the reaction temperature is between 20 ℃ and 60 ℃ when the surface binding agent is brought into contact with the surface of the substrate.
In one embodiment, the reaction time is between 30 seconds and 900 seconds when the surface binding agent is contacted with the surface of the substrate.
In one embodiment, the surface of the substrate is a surface that has not been previously roughened.
In one embodiment, the surface-binding agent is pre-diluted to 10% to 20% prior to contact with the surface of the substrate.
In one embodiment, the method of treating the surface of a substrate according to the present invention further comprises washing the surface of the substrate with water after the surface-binding agent is contacted with the surface of the substrate, and then drying the substrate by heat drying.
The surface bonding agent of the invention has the following characteristics:
1. the surface bonding agent is applied to the surface of the base material to form an organic layer, so that the adhesive force between the surface of the base material which is not subjected to roughening treatment in advance and the material coated on the surface is effectively improved, and the material coated on the surface is prevented from falling off and peeling;
2. because the process of roughening treatment (such as brushing, sand blasting, micro etching and the like) can be eliminated, the generation of wastes for roughening treatment (heavy metal wastewater, corrosive strong acid and the like) is avoided, and simultaneously, the surface of the substrate has better flatness;
3. the substrate and the layer formed thereon are widely used, and include glass, polyimide film, prepreg, imageable dielectric, imageable resin, solder resist, etching resist, non-metals such as silicon crystal, and metals such as copper, aluminum, nickel, zinc, iron, chromium, and alloys thereof;
4. an organic layer formed by the surface bonding agent is transparent and colorless, the color of the surface of the base material cannot be changed, and when copper is used as the base material, the copper surface color difference cannot occur, so that automatic-Optical Inspection (AOI) detection is facilitated;
5. the surface bonding agent has reworkability, and the surface bonding agent has excellent effect after being repeatedly used;
6. the organic layer formed after the surface of the base material is treated by the surface bonding agent has hydrophobicity, and the problem of ink hole blowing generated by the subsequent coating of the solder mask ink in the via hole can be solved when copper is used as the base material.
Drawings
Fig. 1 to 3 are test results of comparative examples 3 to 5.
Fig. 4 to 6 are test results of examples 17 to 19 of the surface binding agent of the present invention.
Detailed Description
It should be understood that any ratio or any other adjustment of the scale in the specification should still fall within the scope of the technical contents described in the present invention without affecting the function of the present invention and the purpose achieved. Meanwhile, the terms such as "above" and the like in the present specification are used for clarity of description only, and are not used to limit the scope of the present invention, and changes or adjustments of the relative relationship thereof may be regarded as the scope of the present invention without substantial changes in the technical contents.
The surface-binding agent of the present invention includes a triazole compound and an imidazole compound.
The triazole compound and the imidazole compound are main components for improving the adhesion between the surface of the base material and the coating material, and form an organic layer on the surface of the base material. Examples of the triazole compound include benzotriazole and 5-methylbenzotriazole, and examples of the imidazole compound include imidazole, dihydroimidazole and 1, 2-dimethylimidazole. The triazole compound and the imidazole compound can be used as bridging ligands, and N-1 and N-3 are used as coordination atoms and are respectively connected to atoms on the surface of the substrate and atoms of the coating material to form bonding, so that the effect of bridging the surface of the substrate and the coating material is achieved.
The surface bonding agent of the present invention further comprises a pyridine compound as a secondary component for enhancing adhesion between the surface of the substrate and the coating material. Examples of the pyridine compound include 2-methylpyridine and 2-mercaptopyridine.
In the surface binding agent, the concentration of each of the triazole compound, imidazole compound, and pyridine compound is between 0.05g/L and 50g/L, 0.1g/L and 40g/L, 0.25g/L and 30g/L, 0.5g/L and 25g/L, or 1g/L and 25g/L, the concentration may be, for example, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50g/L, but is not limited thereto.
<xnotran> 0.05g/L 200g/L , 0.1g/L 200g/L , 1g/L 150g/L , 10g/L 100g/L , 25g/L 100g/L , 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200g/L, . </xnotran>
A triazole compound, an imidazole compound, and a pyridine compound are dissolved in a solvent to formulate a surface-binding agent. The type of the solvent is not limited as long as it can dissolve the compound at an appropriate concentration. In one embodiment the solvent is water, in other embodiments the solvent may be other organic solvents, and the solvent may also include both organic solvents and water.
Examples of the solvent include aromatic solvents such as benzene, toluene, xylene, ethylbenzene, cresol, and chlorobenzene; aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, n-hexanol, and cyclohexanol; glycols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; glycerol; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, and cyclohexanone; ethers such as diethyl ether, dipropyl ether, dibutyl ether, dihexyl ether, benzyl methyl ether, benzyl ethyl ether, and tetrahydrofuran; glycol monoethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, and diethylene glycol monophenyl ether; glycol diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol dipropyl ether; glycol monoacetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate; monoether monoacetates of glycols such as diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, and 4-methyl-4-methoxypentyl acetate; esters such as methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, ethyl-3-propoxypropionate, propyl-3-methoxypropionate, isopropyl-3-methoxypropionate, ethoxyethyl acetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, and γ -butyrolactone; aprotic polar organic solvents such as N, N, N ', N' -tetramethylurea, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, hexamethylphosphoramide, 1, 3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide. In one embodiment, solvents such as water and diethylene glycol monobutyl ether.
The surface-binding agent of the present invention may further include a catalyst, and the type of the catalyst is not limited, and specifically, dimethylacetamide may be exemplified. The catalyst accelerates the action between the surface binding agent and the surface of the base material, can shorten the treatment time and is beneficial to the control of the manufacturing process. The concentration of the catalyst may be between 5mL/L and 100mL/L, for example, a concentration of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100mL/L, but is not limited thereto.
The pH of the surface binding agent of the present invention may generally be between 7 and 8, but is not limited thereto. The pH value may be, for example, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0. The pH of the surface-binding agent is measured without the acid compound, i.e., the surface-binding agent of the present invention may not contain an inorganic acid and/or an organic acid. However, in other embodiments, the surface bonding agent of the present invention may further include an inorganic acid compound, which can adjust the pH of the surface bonding agent, and on the other hand, the inorganic acid compound may also have a micro-etching effect, so as to form a very fine corrosion trace on the surface of the substrate, thereby increasing the contact area with the coating material and improving the adhesion.
The kind of the inorganic acid compound is not particularly limited, and may be at least one selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, for example, and when a mixture of inorganic acids is used, the respective acids may be combined in any appropriate ratio. In one embodiment, the surface-binding agent comprises sulfuric acid.
The concentration of the inorganic acid compound may be between 50g/L and 400g/L, such as, but not limited to, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400 g/L.
In other embodiments, the surface bonding agent of the present invention may further include an organic acid compound, which can adjust the pH of the surface bonding agent as the inorganic acid compound, and on the other hand, the organic acid compound may also have a microetching effect, so as to form a very fine corrosion trace on the surface of the substrate, thereby increasing the contact area with the coating material and enhancing the adhesion.
The kind of the organic acid compound is not particularly limited, and may be at least one selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oxalic acid, acrylic acid, crotonic acid, methacrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, benzoic acid, phthalic acid, cinnamic acid, glycolic acid, lactic acid, malic acid, salicylic acid, glycine, tartaric acid, citric acid, sulfamic acid, β -chloropropionic acid, nicotinic acid, ascorbic acid, hydroxytrimethylacetic acid and levulinic acid, and when an organic acid mixture is used, the respective acids may be combined in any appropriate ratio. In one embodiment, the surface binding agent comprises acetic acid.
The concentration of the organic acid compound may be between 5g/L and 100g/L, for example, and is not limited to, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 g/L.
In the case where an acid compound such as an organic acid compound or an inorganic acid compound is added, the pH of the surface-binding agent of the present invention is greatly lowered, for example, to a pH of less than 4, less than 3, or less than 2, but is not limited thereto. Specifically, the pH of the surface-binding agent when the organic acid and/or the inorganic acid is added may be 3.9, 3.8, 3.7, 3.6, 3.5, 3.4, 3.3, 3.2, 3.1, 3.0, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0. When the surface-binding agents of the present invention do not include acid compounds, they are generally more suitable for use on non-metallic substrate surfaces; when the surface binding agent of the present invention comprises an acid compound, it is generally suitable for use on the surface of a metal substrate, but is not limited thereto.
The surface binding agent of the present invention may further include at least one other component selected from the group consisting of ethanolamine, diethylene glycol monobutyl ether, dimethoxyethane. Various additives may be added without impairing the object of the present invention, and examples thereof include a pH adjuster, a dispersant, a surfactant, a preservative, a viscosity adjuster, an antioxidant, an ultraviolet absorber, a stabilizer, and a colorant.
The present invention provides a method of treating a surface of a substrate, comprising cleaning the surface of the substrate; contacting a surface binding agent with the surface of the substrate; optionally washing excess surface binder with water; and performing thermal drying or photocuring to form an organic layer on the surface of the substrate. The surface of the base material is treated by the surface bonding agent to improve the adhesive force between the base material and the material on the surface of the base material.
The surface of the substrate can be cleaned by using an organic solvent or an acidic cleaning agent, and specifically, for example, a solution of sulfuric acid, phosphoric acid, or the like, or isopropyl alcohol can be used, but not limited thereto.
After the surface of the substrate is cleaned, the surface bonding agent is brought into contact with the surface of the substrate. The contact method is not particularly limited, and a method such as sputtering, evaporation, immersion or immersion, spin coating, or spraying can be used, and a suitable contact method can be optionally selected. From the viewpoint of forming a uniform organic layer, a dipping or dipping treatment may be preferably used.
The surface bonding agent of the invention can be applied to a wide variety of substrates, such as metal substrates or non-metal substrates, and a wide variety of layers subsequently coated on the surface of the substrate, such as metal layers or non-metal layers. The metal substrate and the metal layer are made of copper, aluminum, nickel, zinc, iron, chromium, or an alloy thereof, and the non-metal substrate and the non-metal layer are made of glass, polyimide film, prepreg, imageable dielectric material, imageable resin, solder resist, etching resist, silicon crystal, or the like. Since the surface adhesion of the base material is greatly enhanced by using the surface-bonding agent, the surface of the base material may be a surface that has not been previously roughened.
When the impregnation treatment is used, the temperature of the surface-binding agent is preferably between 20 ℃ and 60 ℃, more preferably between 30 ℃ and 50 ℃; the immersion time is preferably between 60 seconds and 900 seconds, more preferably between 60 seconds and 600 seconds. A water washing step is optionally carried out after the impregnation treatment, and finally a drying step is carried out.
When a spray treatment is used, the temperature of the surface-binding agent is preferably also between 20 ℃ and 60 ℃, more preferably between 30 ℃ and 50 ℃. The treatment is preferably carried out under a spray pressure of between 0.01MPa and 0.3MPa and a spray time of between 15 and 600 seconds, more preferably under a spray pressure of between 0.05MPa and 0.2MPa and a spray time of between 30 and 300 seconds. A water washing step is optionally performed after the dipping process to wash away excess surface binder, and finally a thermal drying or photo-curing step is performed to allow the surface binder to form an organic layer on the surface of the substrate.
In one embodiment, the surface-binding agent of the present invention may be diluted to a diluted concentration of 10% to 20% prior to contacting the surface of the substrate.
After the surface bonding agent disclosed by the invention contacts the surface of the base material, an organic layer is formed on the surface of the base material, the organic layer is transparent and hydrophobic, and is extremely thin and difficult to distinguish by naked eyes, so that whether the organic layer is successfully formed can be determined by dropping water on the surface of the base material and observing whether the water has a large contact angle with the surface and is in a water drop shape.
Specifically, the surface-bonding agent of the present invention may be contacted with the surface of a metal substrate such as a copper plate, a copper foil substrate, or the like, for example, by immersing the substrate such as a copper plate, a copper foil substrate, or the like in a bath containing the surface-bonding agent of the present invention to form an organic layer on the surface of the substrate, and then forming a polymer coating material such as a photoresist on the organic layer so that the organic layer is interposed between the coating material and the substrate. Alternatively, the surface bonding agent may be contacted with the surface of a non-metal substrate such as glass or polyimide film to form an organic layer, and then a metal layer such as nickel, chromium, or copper may be plated so that the organic layer is interposed between the metal layer and the substrate.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the description of the present specification.
Test example 1
The surface-binding agent of example 1 includes compounds such as benzotriazole, imidazole, and dihydroimidazole that promote adhesion. The copper plate without roughening treatment was immersed in the surface-bonding agent of example 1 for 15 minutes at room temperature to allow the surface-bonding agent to treat the copper surface, followed by washing with water, drying, and then coating/pressing a film of dry film photoresist (dry film photoresist E9500, available from changxing materials industries ltd.) on the copper surface. Using 3 percent of NaOH solution as stripping solution, soaking the copper plate coated with the photoresist in the stripping solution, controlling the operating temperature to be 50 ℃, observing the stripping condition of the photoresist from the copper surface, and recording the time when the stripping area of the photoresist reaches 30 percent.
Examples 2 to 7 were tested in the same procedure as in example 1, except that the composition of the surface-binding agent, the soaking time of the surface-binding agent, and other parameters were adjusted as shown in table 1 below. In comparative example 1, the surface bonding agent was not immersed, and the copper plate without roughening treatment was directly immersed in the stripping solution.
The surface bonding agent compositions, the surface bonding agent soaking times, and the photoresist stripping times of examples 1 to 7 and comparative example 1 are shown in table 1 below. In the composition of the surface binding agent stock solution, the concentration of benzotriazole is between 3g/L and 30g/L, the concentration of imidazole is between 0.5g/L and 5g/L, the concentration of dihydroimidazole is between 0.5g/L and 5g/L, the concentration of 2-methylpyridine is between 3g/L and 30g/L, the concentration of 5-methylbenzotriazole is between 0.5g/L and 5g/L, the concentration of 1, 2-dimethylimidazole is between 0.5g/L and 5g/L, the concentration of 2-mercaptopyridine is between 0.5g/L and 5g/L, and the concentration of dimethylacetamide is between 5mL/L and 50 mL/L. Before the surface of the base material is treated by the surface binding agent, the stock solution is diluted to 20 percent by water and then treated.
TABLE 1
From the results in table 1 above, it is known that the copper surface can be treated with the surface bonding agent of example 1 to slow the time for stripping the photoresist from the copper surface, which is prolonged from 1 min 01 s to 2 min 02 s, showing that the surface bonding agent of example 1 can effectively improve the adhesion between the copper surface and the photoresist. On the other hand, as the kinds of compounds for promoting adhesion in the surface bonding agent increase, the adhesion promotion effect between the copper surface and the photoresist becomes more remarkable, and the results of example 6 show that the time for stripping the photoresist from the copper surface is greatly prolonged to 3 minutes and 29 seconds, and even if the soaking time of the surface bonding agent is reduced to 3 minutes, as shown in example 7, the time for stripping the photoresist from the copper surface can be maintained at 3 minutes and 18 seconds, which is far better than that of comparative example 1 without using the surface bonding agent.
Test example 2
Examples 8 to 15 were prepared by preparing a copper foil substrate (FR-4, available from south asia plastic industries, ltd.) having a thickness of 1oz, cleaning the surface of the copper foil with an acidic cleaner, and then immersing the copper foil substrate in a surface-bonding agent at room temperature, wherein the surface-bonding agent includes a surface-adhesion-promoting compound such as benzotriazole, imidazole, dihydroimidazole, 2-methylpyridine, 5-methylbenzotriazole, 1, 2-dimethylimidazole, and 2-mercaptopyridine, and dimethylacetamide, and each component of the surface-bonding agent stock solution is as described in test example 1; then washing and drying; coating/pressing a film of dry film photoresist (dry film photoresist E9500, available from Changxing materials industries, ltd.) on the surface of the copper foil to form photoresist with the thickness of 25 μm; exposing the photoresist in 100 dot patterns of 10 × 10 in total, wherein each dot pattern has a diameter of 50 μm and a pitch of each dot is 50 μm; subsequently, taking a sodium carbonate solution with the concentration of 1% (namely 10 g/L) as a developing solution, developing the photoresist in a spraying mode, controlling the temperature to be 30 ℃, setting the pressure to be 30psi, spraying for 60 seconds, then washing and drying; and finally, observing the retention condition of the dot pattern of the photoresist. In comparative example 2, the surface bonding agent was not immersed, and the copper foil substrate was directly coated with a photoresist, exposed, developed, washed with water, and dried. The parameters and results of examples 8 to 15 and comparative example 2 are shown in table 2 below.
TABLE 2
The higher the ratio of dot number remaining, the better the adhesion between the copper foil surface and the photoresist. In the results of table 2, the number of the complete dots of comparative example 2 without using the surface bonding agent was only 71, while the number of the complete dots of examples 8 to 15 using the surface bonding agent was more than 92, and the number of the complete dots was more than 100 with the increase of the soaking time and the increase of the dilution concentration, which provides excellent yield.
Test example 3
The surface of the glass substrate was treated by spraying a surface-binding agent, which includes compounds for promoting surface adhesion such as benzotriazole, imidazole, dihydroimidazole, 2-methylpyridine, 5-methylbenzotriazole, 1, 2-dimethylimidazole, and 2-mercaptopyridine, and dimethylacetamide as example 16, wherein the surface-binding agent stock solution was used in an amount of 20% by dilution with water as compared with the example 1. Then, a plurality of strips of photoresist strips arranged in parallel and having a width of 2 μm and a thickness of 20 μm were designed and formed on the surface of the glass substrate (pressing parameters: pressing temperature 90 ℃, pressing pressure 3kg, pressing speed 2 m/min), and exposure and development were performed under the conditions of test example 2. The result shows that the photoresist after development does not float and fall off, namely the surface bonding agent can also effectively improve the adhesive force between the glass surface and the photoresist.
Test example 4
The polyimide film was treated with isopropyl alcohol (IPA) for 5 minutes, then washed with water and dried, and then a chromium layer was sputtered on the surface of the polyimide film to a thickness of 100nm, and a copper layer was further sputtered on the surface of the polyimide film to a thickness of 500nm, as comparative examples 3 to 5. And then attaching a 3M #610 adhesive tape to the surface of the plating layer, removing bubbles between the adhesive tape and the plating layer, quickly tearing the adhesive tape from the surface of the plating layer in a 90-degree vertical pulling mode within 1 minute after attaching the adhesive tape at a speed of less than 3 seconds, and observing the peeling condition of the plating layer. Wherein, the initial stickiness of the 3M #600 and 3M610 tapes was 32oz/inch, which was about 357g/cm.
The method is applicable to: CID A-A-113, type 1, class B,3M Brand Premium Transmission Film Tape 600,3M Brand Premium cell Tape 610
According to the following: IPC-TM-650Number 2.4.1/2.4.1.1/2.4.1.3/2.4.1.4/2.4.28/2.4.28.1
The results of fig. 1 to 3 show that the peeling area of the metal plating layer under the tape reaches 70 to 99% without using the surface bonding agent, indicating that the adhesion between the polyimide film and the metal plating layer is insufficient and the peeling force of the tape cannot be resisted.
On the other hand, the polyimide film is treated with a surfactant for 5 minutes and then washed with water; then soaking the polyimide film in a surface binding agent for 5 minutes, washing and drying the polyimide film to enable the surface binding agent to treat the surface of the polyimide film, wherein the surface binding agent comprises compounds for improving surface adhesion such as benzotriazole, imidazole, dihydroimidazole, 2-methylpyridine, 5-methylbenzotriazole, 1, 2-dimethylimidazole, 2-mercaptopyridine and the like, and dimethylacetamide, the raw solution of the surface binding agent is used in a ratio of 20% by diluting the raw solution with water as described in test example 1; then washing and drying; next, DC sputtering (power 600W) was used to sputter 100nm thick chromium layer and 500nm thick copper layer as metal plating layers as examples 17 to 19. Finally, a 3M610 tape was attached to the metal plating layer to test the peeling of the metal plating layer in the manner described above.
The results of fig. 4 to 6 show that the peeling area of the metal plating layer under the tape was less than 1% after the surface of the polyimide film was treated with the surface bonding agent, which indicates that the surface of the polyimide film could achieve excellent bonding with the metal layer after the surface bonding agent treatment, and could resist the peeling force of the tape.
Therefore, the surface binding agent can treat the surface of the base material to form an organic layer on the surface of the base material, so that the adhesive force between the surface of the base material which is not subjected to roughening treatment in advance and the coating material is effectively improved, and the coating material is prevented from falling off and peeling. The method can eliminate the roughening treatment process, reduce the process cost, avoid generating wastes (heavy metal wastewater, corrosive strong acid and the like) for roughening treatment, and has wide variety of applicable base materials and coating materials and reworkability, so that the surface bonding agent has excellent effect after being repeatedly used.
The above embodiments are provided to illustrate the principles and efficacy of the present invention, and not to limit the invention. Any person skilled in the art can modify the above-described embodiments without departing from the spirit and scope of the present invention. Therefore, the scope of the invention is to be determined by the claims that follow.
It should be understood that within the scope of the technical content described in the present invention, the technical features (such as described in the embodiments and examples) can be freely combined with each other to form a new or more preferable technical solution, and for the sake of brevity, the detailed description is omitted. Moreover, the numerical ranges recited herein are intended to be inclusive of the ranges recited herein, as long as the numerical values fall between the upper and lower ends, and the subranges associated with the endpoints or other numerical values are also intended to be encompassed within the ranges recited herein.
Claims (23)
1. A surface bonding agent for improving the surface adhesion of a non-metal base material is characterized by comprising a triazole compound and an imidazole compound.
2. The surface binding agent according to claim 1, wherein the triazole compound comprises at least one selected from benzotriazole and 5-methylbenzotriazole, and the imidazole compound comprises at least one selected from imidazole, dihydroimidazole and 1, 2-dimethylimidazole.
3. The surface binding agent of claim 1, further comprising a pyridine compound.
4. The surface binding agent of claim 3, wherein the pyridine compound comprises at least one selected from the group consisting of 2-methylpyridine and 2-mercaptopyridine.
5. The surface binding agent of claim 1, wherein the concentration of the triazole compound and the imidazole compound is each between 0.05g/L and 50 g/L.
6. The surface binding agent of claim 3, wherein the pyridine compound is present at a concentration of between 0.05g/L and 50 g/L.
7. The surface binding agent of claim 1, further comprising dimethylacetamide.
8. The surface binding agent of claim 7, wherein the concentration of dimethylacetamide is between 5mL/L and 100 mL/L.
9. The surface binding agent according to claim 1, wherein the surface binding agent does not comprise an acid compound.
10. The surface bonding agent of claim 1, further used for improving the surface adhesion of a metal substrate.
11. The surface binding agent of claim 10, further comprising at least one of an inorganic acid compound and an organic acid compound.
12. The surface binding agent of claim 11, wherein the inorganic acid compound comprises at least one selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid.
13. The surface binding agent of claim 11, wherein the organic acid compound comprises at least one selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oxalic acid, acrylic acid, crotonic acid, methacrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, benzoic acid, phthalic acid, cinnamic acid, glycolic acid, lactic acid, malic acid, salicylic acid, glycine, tartaric acid, citric acid, sulfamic acid, beta-chloropropionic acid, nicotinic acid, ascorbic acid, hydroxytrimethylacetic acid and levulinic acid.
14. The surface binding agent according to claim 1, further comprising at least one member selected from the group consisting of ethanolamine, diethylene glycol monobutyl ether, and dimethoxyethane.
15. A method of treating a surface of a substrate comprising contacting the surface-binding agent of any one of claims 1 to 14 with the surface of the substrate to promote adhesion to a layer overlying the surface of the substrate, wherein the substrate is a metal substrate or a non-metal substrate and the layer overlying the surface of the substrate is a metal layer or a non-metal layer.
16. The method of claim 15, wherein the metal substrate and the metal layer are formed of a material including at least one selected from the group consisting of copper, aluminum, nickel, zinc, iron, chromium, and alloys thereof.
17. The method of claim 15, wherein the non-metallic substrate and the non-metallic layer are formed from glass, polyimide film, prepreg, imageable dielectric, imageable resin, solder resist, etch resist, or silicon crystal.
18. The method of claim 15, wherein the surface binding agent is contacted with the surface of the substrate by spin coating, dipping, or spraying.
19. The method of claim 15, wherein the surface binding agent is contacted with the surface of the substrate at a reaction temperature of between 20 ℃ and 60 ℃.
20. The method of claim 15, wherein the surface binding agent is contacted with the surface of the substrate for a reaction time of between 30 seconds and 900 seconds.
21. The method of claim 15, wherein the surface of the substrate is a surface that has not been previously roughened.
22. The method as claimed in claim 15, wherein the surface binding agent is pre-diluted to 10% to 20% prior to contacting the surface of the substrate.
23. The method of claim 15, further comprising washing excess surface binder after the surface binder contacts the surface of the substrate, and then heat drying the substrate.
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| TW110130897 | 2021-08-20 | ||
| TW110130897A TWI795879B (en) | 2021-08-20 | 2021-08-20 | Surface binding agent and method of treating substrate surface |
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| CN116607136A (en) * | 2023-06-01 | 2023-08-18 | 武汉创新特科技有限公司 | Bonding agent for circuit board surface treatment and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4428987A (en) * | 1982-04-28 | 1984-01-31 | Shell Oil Company | Process for improving copper-epoxy adhesion |
| JPH07113154B2 (en) * | 1984-04-12 | 1995-12-06 | 電気化学工業株式会社 | Surface treatment method |
| JPS61266241A (en) * | 1985-05-21 | 1986-11-25 | 株式会社日立製作所 | Surface treating method of copper |
| JPH04318192A (en) * | 1991-04-15 | 1992-11-09 | Nikko Kyodo Co Ltd | Surface treating solution and surface treating method |
| JP4008605B2 (en) * | 1999-01-13 | 2007-11-14 | 日本ペイント株式会社 | Non-chromium coating agent for metal surfaces |
| JP4318192B2 (en) | 1999-08-04 | 2009-08-19 | 道夫 永坂 | Vegetation waterway |
| JP4309602B2 (en) * | 2001-04-25 | 2009-08-05 | メック株式会社 | Method for improving adhesion between copper or copper alloy and resin, and laminate |
| US8088246B2 (en) * | 2009-01-08 | 2012-01-03 | Cordani Jr John L | Process for improving the adhesion of polymeric materials to metal surfaces |
| CN106663504A (en) * | 2014-07-14 | 2017-05-10 | 户田工业株式会社 | Method for producing conductive coating film, and conductive coating film |
| JP6560976B2 (en) * | 2014-12-19 | 2019-08-14 | 四国化成工業株式会社 | Surface treatment liquid for inorganic material or resin material, surface treatment method and use thereof |
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| CN116607136A (en) * | 2023-06-01 | 2023-08-18 | 武汉创新特科技有限公司 | Bonding agent for circuit board surface treatment and preparation method thereof |
| CN116607136B (en) * | 2023-06-01 | 2024-01-05 | 武汉创新特科技有限公司 | Bonding agent for circuit board surface treatment and preparation method thereof |
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| TWI795879B (en) | 2023-03-11 |
| TW202309342A (en) | 2023-03-01 |
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| JP2023029271A (en) | 2023-03-03 |
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