CN115707794A - Surface-binding agent and method for treating substrate surface - Google Patents

Abstract

A surface binding agent includes a triazole compound and an imidazole compound. The surface binding agent of the present invention forms an organic layer on the surface of the substrate, effectively improving the adhesion between the surface of the substrate that has not been roughened in advance and the coating material, such as photoresist, ink and to-be-added Metal layer (formed by sputtering, vapor deposition, etc.), so that the coating material can be prevented from peeling off from the surface of the substrate.

Description

Surface binder and method for treating substrate surface

technical field

The present invention relates to a kind of surface binding agent and the method for using it to treat the substrate surface, especially relate to a kind of surface binding agent treatment non-metallic surface (such as the surface of glass, silicon crystal, polyimide (PI) film etc.) and Metal surfaces (such as the surface of copper and copper alloys, cast iron, aluminum, steel, nickel, zinc, nickel-iron alloys, etc.) to enhance the surface of the substrate and photoresist, ink or metal layer to be added (by sputtering, Evaporation, etc.) and other methods of adhesion between coating materials.

Background technique

Usually, in order to improve the adhesion between the surface of the substrate and the coating material, the method of pre-roughening the surface of the substrate is adopted, for example, forming a photoresist on the roughened copper foil of the printed circuit board, and then exposing to make the light The resist has a specific pattern shape, so that part of the surface of the copper foil is exposed, and then the exposed copper is removed by etching. After the photoresist is removed, the copper that has not been removed by etching remains, and the desired copper circuit pattern is formed on the printed circuit board.

However, if roughening is used, the rough copper surface will conform to the circuit pattern, and the signal transmission path of high-frequency and high-speed transmission usually occurs on the surface of the circuit (skin effect). If the surface of the circuit is uneven, it will generate signal bad question. Moreover, roughening treatment is usually accompanied by polluted wastewater, which also has environmental protection problems. On the other hand, as the line patterns gradually become thinner and smaller, the problem of adhesion between the roughened copper surface and the patterned photoresist becomes more serious. Therefore, in the current era of high-frequency and high-speed transmission, the industry expects to fabricate circuits in a manner that does not roughen the surface of the substrate conductor.

At present, there are known methods for pre-treating metal surfaces with surface treatment compositions. However, the surface treatment compositions described in the prior art still have the effect of excessive corrosion or uneven corrosion of the substrate surface, or adhesion enhancement effects of the surface treatment composition. Not obvious issues.

Contents of the invention

In order to solve the above problems, the present invention provides a surface binding agent for improving the surface adhesion of non-metallic substrates, the surface binding agent includes triazole compounds and imidazole compounds.

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-dimethyl At least one of kiimidazoles.

In one embodiment, the surface binding agent further includes a pyridine compound, and in another embodiment, the pyridine compound includes at least one selected from 2-picoline and 2-mercaptopyridine.

In one embodiment, the concentration of each of the triazole compound, imidazole compound and pyridine compound is between 0.05 g/L and 50 g/L.

In one embodiment, the surface binding agent further includes dimethylacetamide as a catalyst, and in another embodiment, the concentration of dimethylacetamide is between 5 mL/L and 100 mL/L.

In one embodiment, the surface binding agent does not include acidic compounds.

In one embodiment, the surface bonding agent can further be used to improve the surface adhesion of the metal substrate, and in another embodiment, the surface bonding agent further includes 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, and phosphoric acid.

In one embodiment, the organic acid compound comprises a compound 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, butanedioic acid 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, amine At least one selected from the group consisting of sulfonic acid, β-chloropropionic acid, nicotinic acid, ascorbic acid, hydroxytrimethylacetic acid, and levulinic acid.

In one embodiment, the surface binding agent further includes at least one member selected from the group consisting of ethanolamine, diethylene glycol monobutyl ether, and dimethoxyethane.

The present invention also provides a method for treating the surface of a substrate, comprising contacting the surface bonding agent of the present invention with the surface of the substrate to enhance the adhesion between the surface of the substrate and a layer covering the surface of the substrate. Concentrating on, wherein, the substrate is a metal substrate or a non-metal substrate, and the layer covering the surface of the substrate 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 member selected from the group consisting of copper, aluminum, nickel, zinc, iron, chromium and alloys thereof. In one embodiment, the material of the non-metal substrate and the non-metal layer is glass, polyimide film, prepreg, imageable dielectric, imageable resin, solder mask, etch photoresist or silicon crystals.

In one embodiment, the surface bonding agent is contacted with the surface of the substrate by spin coating, dipping or spraying.

In one embodiment, the reaction temperature is between 20°C and 60°C when the surface binding agent is brought into contact with the surface of the substrate.

In one embodiment, the surface-binding agent is brought into contact with the surface of the substrate for a reaction time of between 30 seconds and 900 seconds.

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% before contacting the surface of the substrate.

In one embodiment, the method for treating the surface of the substrate of the present invention further comprises washing the excess surface bonding agent with water after the surface bonding agent is in contact with the surface of the substrate, and then drying the substrate with heat.

Surface binding agent of the present invention has the following characteristics:

1. The surface binding agent is applied on the surface of the substrate to form an organic layer, which can effectively improve the adhesion between the surface of the substrate that has not been pre-roughened and the material covering it, and prevent the material covering it from falling off and peeling off ;

2. Since the roughening treatment (such as brushing, sandblasting, micro-etching, etc.) process can be eliminated, waste for roughening treatment (heavy metal wastewater, corrosive strong acid, etc.) can be avoided. At the same time, the surface of the substrate has better flatness sex;

3. A wide range of applicable substrates and layers on them, including glass, polyimide film, prepreg, imageable dielectric, imageable resin, solder mask, etch lithography Nonmetals such as rubber and silicon crystals, and metals such as copper, aluminum, nickel, zinc, iron, chromium and their alloys;

4. The organic layer formed by the surface binder is transparent and colorless, and will not change the color of the substrate surface. When copper is used as the substrate, there will be no color difference on the copper surface, which is conducive to automatic optical inspection (Auto-Optical Inspection) , AOI) detection;

5. The surface binding agent has reworkability, and the repeated use of the surface binding agent of the present invention still has excellent effects;

6. The organic layer formed after the surface of the substrate is treated with a surface binder is hydrophobic, and when copper is used as the substrate, it can improve the problem of ink blowing caused by subsequent coating of solder resist ink in the via hole.

Description of drawings

1 to 3 are the test results of Comparative Examples 3 to 5.

Fig. 4 to Fig. 6 are test results of examples 17 to 19 of the surface binding agent of the present invention.

Detailed ways

It should be noted that any change in the proportional relationship or adjustment of the size in this specification should still fall within the scope covered by the technical content described in the present invention without affecting the effects and goals that can be achieved by the present invention. Inside. At the same time, terms such as "above" quoted in this specification are only for the convenience of description, and are not used to limit the scope of the present invention. , should also be regarded as the scope where the present invention can be implemented.

The surface binding agent of the present invention includes triazole compounds and imidazole compounds.

The triazole compound and the imidazole compound are the main components to enhance the adhesion between the surface of the substrate and the coating material, and form an organic layer on the surface of the substrate. Examples of triazole compounds include benzotriazole and 5-methylbenzotriazole, and examples of imidazole compounds include imidazole, dihydroimidazole, and 1,2-dimethylimidazole. Triazole compounds and imidazole compounds can be used as bridging ligands, which use N-1 and N-3 as coordinating atoms, respectively connected to the atoms on the surface of the substrate and the atoms of the coating material to form bonds, so as to achieve the bridging group The effect of the material surface and the coating material.

The surface-binding agent of the present invention further includes a pyridine compound as a secondary component for enhancing the adhesion between the surface of the substrate and the coating material. Pyridine compounds include, for example, 2-picoline, 2-mercaptopyridine, and the like.

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, between 0.1g/L and 40g/L, between 0.25g/L and 30g /L, between 0.5g/L and 25g/L, or between 1g/L and 25g/L, the concentration can be 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 not limited thereto.

The total concentration of the adhesion promoting compound can be between 0.05g/L and 200g/L, between 0.1g/L and 200g/L, between 1g/L and 150g/L, between 10g/L and 100g/L Between, or between 25g/L and 100g/L, the concentration can 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, 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, but not limited thereto.

A triazole compound, an imidazole compound, and a pyridine compound are dissolved in a solvent to formulate a surface-binding agent. The type of solvent is not limited as long as it can be dissolved at an appropriate concentration. In one embodiment, the solvent is water, and in other embodiments, the solvent can be other organic solvents, and the solvent can also contain both organic solvents and water.

As solvents, for example, aromatics such as benzene, toluene, xylene, ethylbenzene, cresol, and chlorobenzene; methanol, ethanol, n-propanol, isopropanol, n-butanol, n-hexanol, and cyclohexanol can be used Aliphatic alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; glycerol; acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl Ketones such as isobutyl ketone and cyclohexanone; ethers such as diethyl ether, dipropyl ether, dibutyl ether, dihexyl ether, benzyl methyl ether, benzyl ethyl ether, and tetrahydrofuran; ethylene glycol mono Methyl 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 Ethers: 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 di Glycol diethers such as methyl ether, diethylene glycol diethyl ether and diethylene glycol dipropyl ether; 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 mono Diol monoacetate such as ethyl ether acetate; 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-methyl-3-methoxybutyl acetate, 3-ethyl-3-methyl Oxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate ester, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxy Monoether monoacetates of diols such as amyl acetate, 3-methyl-4-methoxypentyl acetate and 4-methyl-4-methoxypentyl acetate; Methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl, methyl-3- Methoxypropionate, Ethyl-3-methoxypropionate, Ethyl-3-ethoxypropionate, Ethyl-3-propoxypropionate, Propyl-3-methoxy propionate, isopropyl-3-methoxypropionate, ethyl ethoxyacetate, 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 and other esters; N,N, N',N'-tetramethylurea, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphoramide, 1,3- Aprotic polar organic solvents such as dimethyl-2-imidazolinone and dimethyl sulfoxide. In one embodiment, solvents such as water and diethylene glycol monobutyl ether.

The surface binding agent of the present invention may also include a catalyst, and the type of the catalyst is not limited, specifically, dimethylacetamide may be exemplified. The catalyst accelerates the interaction between the surface binder and the surface of the substrate, which can shorten the processing time and facilitate the control of the process. The catalyst concentration can be between 5mL/L and 100mL/L, such as 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 not limited thereto.

The pH value of the surface binding agent of the present invention can generally be between 7 and 8, but is not limited thereto. The pH can 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 value of the above-mentioned surface binding agent is measured when no acid compound is contained, that is, the surface binding agent of the present invention may not contain inorganic acid and/or organic acid. However, in other embodiments, the surface binding agent of the present invention may also include an inorganic acid compound, which can adjust the pH value of the surface binding agent. On the other hand, the inorganic acid compound may also have a microetching effect, making the substrate Microscopic corrosion traces are formed on the surface, thereby increasing the contact area with the coating material and improving adhesion.

The type of the inorganic acid compound is not particularly limited. For example, it may be at least one selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid. When using an inorganic acid mixture, each acid may be combined in any appropriate ratio. In one embodiment, sulfuric acid is included in the surface binding agent.

The concentration of the mineral acid compound may be between 50 g/L and 400 g/L, such as 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, 400g/L, but not limited thereto.

In other embodiments, the surface binding agent of the present invention can also include an organic acid compound, which can adjust the pH value of the surface binding agent like the above-mentioned inorganic acid compound. On the other hand, the organic acid compound can also have a micro-etching effect, Form very fine corrosion traces on the surface of the substrate, thereby increasing the contact area with the coating material and improving adhesion.

The type of the organic acid compound is not particularly limited, for example, it may be selected from formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic 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. When using an organic acid mixture, the acids can be combined in any appropriate ratio. In one embodiment, acetic acid is included in the surface binding agent.

The concentration of the organic acid compound can be between 5 g/L and 100 g/L, such as 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, 100g/L, but not limited thereto.

When acid compounds such as organic acid compounds and inorganic acid compounds are added, the pH value of the surface binding agent of the present invention is greatly reduced, for example, the pH is less than 4, less than 3, or less than 2, but not limited thereto. Specifically, the pH value of the surface binding agent when adding organic acid and/or inorganic acid can 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 agent of the present invention does not include acid compounds, it is generally more suitable for use on the surface of non-metallic substrates; when the surface binding agent of the present invention includes acid compounds, it is generally more suitable for use on the surface of metal substrates on, but not limited to.

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, and dimethoxyethane. In the case where the object of the present invention is not hindered, various additives may be added, for example, pH adjusters, dispersants, surfactants, preservatives, viscosity adjusters, antioxidants, ultraviolet absorbers, stabilizers and colorants agent etc.

The invention provides a method for treating the surface of a substrate, comprising cleaning the surface of the substrate; contacting a surface bonding agent with the surface of the substrate; optionally cleaning the excess surface bonding agent with water; and performing thermal drying or photocuring An organic layer is formed on the surface of the substrate. The surface of the substrate is treated with a surface binding agent to promote adhesion between the substrate and materials overlying the surface of the substrate.

Cleaning the surface of the substrate can be achieved by using an organic solvent or an acidic cleaner, specifically, sulfuric acid, phosphoric acid and other solutions, isopropyl ketone, but not limited thereto.

After cleaning the surface of the substrate, the surface bonding agent is brought into contact with the surface of the substrate. The method of contact is not particularly limited, methods such as sputtering, vapor deposition, soaking or immersion, spin coating, or spraying can be used, and an appropriate contact method can be optionally selected. From the viewpoint of forming a uniform organic layer, soaking or immersion treatment is preferably used.

The surface bonding agent of the present invention can be applied to a wide range of substrates, which can be metal substrates or non-metal substrates, and the types of layers subsequently coated on the surface of the substrate are also wide, which can be metal layers or non-metal layers. . Materials of metal substrates and metal layers such as copper, aluminum, nickel, zinc, iron, chromium and their alloys, etc. Materials of non-metal substrates and non-metal layers such as glass, polyimide film, prepreg, imageable Dielectrics, imageable resins, solder resists, etch photoresists and silicon crystals. Since the use of the surface binding agent greatly strengthens the surface adhesion of the substrate, the surface of the substrate may be a surface that has not been roughened in advance.

When dipping is used, the temperature of the surface binding agent is preferably between 20°C and 60°C, more preferably between 30°C and 50°C; the dipping time is preferably between 60 seconds and 900 seconds, more preferably between Between 60 seconds and 600 seconds. Typically, the dipping treatment is optionally followed by a water washing step and finally a drying step.

When spraying is used, the temperature of the surface binding agent is also preferably between 20°C and 60°C, more preferably between 30°C and 50°C. The spray pressure is preferably between 0.01MPa to 0.3MPa and the spray time is between 15 to 600 seconds, more preferably the spray pressure is between 0.05MPa to 0.2MPa and the spray time is between 30 to 300 seconds processed below. Usually, a water washing step is optionally performed after the dipping treatment to remove excess surface binder, and finally a heat drying or photocuring 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 concentration of 10% to 20% before contacting the surface of the substrate.

After the surface-binding agent of the present invention contacts the surface of the substrate, an organic layer is formed on the surface of the substrate. The organic layer is transparent and hydrophobic. Since the organic layer is extremely thin and difficult to see with the naked eye, it can be absorbed by dripping water. On the surface of the substrate, it is observed whether the water has a large contact angle with the surface in a drop shape to determine whether the organic layer is successfully formed.

Specifically, the surface bonding agent of the present invention can be in contact with the surface of metal substrates such as copper plates and copper foil substrates, for example, substrates such as copper plates and copper foil substrates are immersed in a bath containing the surface bonding agent of the present invention to An organic layer is formed on the surface of the substrate, and then a polymer coating material such as photoresist is formed on the organic layer so that the organic layer is interposed between the coating material and the substrate. On the other hand, the surface bonding agent can also be contacted with the surface of non-metallic substrates such as glass and polyimide film to form an organic layer, and then plated with metal layers such as nickel, chromium, and copper to make the organic layer intersect. between the metal layer and the substrate.

Embodiments of the present invention are described below through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the content described in this specification.

test case 1

The surface binding agent in Example 1 includes compounds that can improve adhesion, such as benzotriazole, imidazole, and dihydroimidazole. At room temperature, soak the unroughened copper plate in the surface bonding agent of Example 1 for 15 minutes, so that the surface bonding agent treats the copper surface, then wash with water, dry, and then apply/press a dry film on the copper surface Photoresist (dry film photoresist E9500, purchased from Eternal Materials Industry Co., Ltd.). Use 3% NaOH solution as the film removal solution, and soak the copper plate coated with photoresist in the film removal solution at an operating temperature of 50°C. Observe the peeling of the photoresist from the copper surface. The time is recorded when the area reaches 30%.

Examples 2 to 7 were tested in the same steps as in Example 1, but parameters such as the composition of the surface binding agent and the soaking time of the surface binding agent were adjusted as shown in Table 1 below. In Comparative Example 1, the surface binding agent was not soaked, and the unroughened copper plate was directly soaked in the film-removing solution.

The surface binding agent composition, surface binding agent soaking time and photoresist stripping time 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, and the concentration of dihydroimidazole is between 0.5g /L to 5g/L, the concentration of 2-picoline 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, the concentration of dimethylacetamide Between 5mL/L and 50mL/L. Before treating the surface of the substrate with the surface binding agent, the stock solution is diluted to 20% with water and then treated.

Table 1

As can be seen from the results in Table 1 above, the copper surface treated with the surface bonding agent of Example 1 can slow down the time for the photoresist to peel off from the copper surface, extending from 1 minute 01 seconds to 2 minutes 02 seconds, showing that the surface bonding agent of Example 1 The agent can effectively improve the adhesion between the copper surface and the photoresist. On the other hand, as the types of compounds that improve the adhesion in the surface binder increase, the effect of improving the adhesion between the copper surface and the photoresist is more significant. The results of Example 6 show that the time for the photoresist to peel off from the copper surface It has been significantly extended 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 the photoresist to be peeled off from the copper surface can still be maintained at 3 minutes and 18 seconds, which is far from It is better than Comparative Example 1 which does not use surface binding agent.

test case 2

Embodiments 8 to 15 are to prepare a copper foil substrate (FR-4, purchased from Nan Ya Plastic Industry Co., Ltd.) with a thickness of 1 oz, and clean the surface of the copper foil with an acidic cleaner, and then soak the copper foil substrate on the surface at room temperature In the binding agent, wherein the surface binding agent includes benzotriazole, imidazole, dihydroimidazole, 2-picoline, 5-methylbenzotriazole, 1,2-dimethylimidazole and 2-mercaptopyridine Compounds and dimethylacetamide that improve surface adhesion, and the ratio of the components of the surface binder stock solution are as described in Test Example 1; then washed with water and dried; then coated/laminated dry film photolithography on the surface of copper foil Glue (dry film photoresist E9500, purchased from Changxing Materials Industry Co., Ltd.) to form a photoresist with a thickness of 25 μm; a total of 100 dot patterns of 10*10 are used to expose the photoresist, wherein each dot pattern The diameter is 50 μm, and the distance between each dot is 50 μm; subsequently, the sodium carbonate solution with a concentration of 1% (ie 10g/L) is used as the developing solution to develop the photoresist by spraying, the temperature is controlled at 30°C, the pressure The setting is 30psi, the spraying treatment time is 60 seconds, then washed with water and dried; finally observe the retention of the dot pattern of the photoresist. In Comparative Example 2, the surface bonding agent was not soaked, and the copper foil substrate was directly coated with photoresist and then 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 dots remaining, the better the adhesion between the copper foil surface and the photoresist. In the results of Table 2, the number of complete dots in Comparative Example 2 that did not use the surface binding agent was only 71, while the number of complete dots in Examples 8 to 15 that used the surface binding agent reached more than 92, and as the immersion With the increase of time and the increase of dilution concentration, the number of complete dots can reach 100, with excellent yield.

Test case 3

In addition, the surface of the glass substrate is sprayed with a surface binding agent, wherein the surface binding agent includes benzotriazole, imidazole, dihydroimidazole, 2-picoline, 5-methylbenzotriazole, 1,2-bis Compounds such as methylimidazole and 2-mercaptopyridine, and dimethylacetamide that promote surface adhesion, as Example 16, wherein the ratio of each component of the surface-binding agent stock solution is as described in Test Example 1, and the stock solution is diluted with water to 20 %use. Then, on the surface of the glass substrate, several long strips of photoresist with a width of 2 μm and a thickness of 20 μm are designed and formed (molding parameters: lamination temperature 90°C, lamination pressure 3kg, lamination speed 2m/min ), and carry out exposure development with the condition of test example 2. The results showed that the developed photoresist did not float off or fall off, that is, the surface binder can also effectively improve the adhesion between the glass surface and the photoresist.

Test case 4

The polyimide film was treated with isopropyl alcohol (IPA) for 5 minutes, then washed and dried with water, then a chromium layer with a thickness of 100nm was sputtered on the surface of the polyimide film, and a copper layer with a thickness of 500nm was sputtered again, as a comparison Examples 3 to 5. Then attach 3M#610 tape to the surface of the coating, remove the air bubbles between the tape and the coating, and within 1 minute after attaching the tape, pull the tape vertically at 90 degrees at a speed of less than 3 seconds to tear off the tape from the surface of the coating to observe the peeling off of the coating. Among them, the initial viscosity of 3M#600 and 3M610 adhesive tape is 32oz/inch, which is about 357g/cm.

Applicable: CID A-A-113,Type 1,Class B,3M Brand Premium Transparent FilmTape 600,3M Brand Premium Cellophane Tape 610

According to: 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 in Figures 1 to 3 show that, without the use of a surface adhesive, the peeling area of the metal plating under the tape reached 70 to 99%, indicating that the adhesion between the polyimide film and the metal plating was insufficient to resist The peel force of the tape.

On the other hand, the polyimide film is washed with water after being treated with a surfactant for 5 minutes; then soaked in the surface binding agent for 5 minutes and then washed and dried to make the surface binding agent treat the surface of the polyimide film, wherein the Surface binding agents include benzotriazole, imidazole, dihydroimidazole, 2-picoline, 5-methylbenzotriazole, 1,2-dimethylimidazole and 2-mercaptopyridine, etc. to enhance surface adhesion And dimethylacetamide, wherein, the ratio of each component of the surface-binding agent stock solution is as described in Test Example 1, and it is 20% to use the stock solution diluted with water; then wash with water and dry; then use DC sputtering (power 600W), sputtering The chromium layer plated with a thickness of 100nm and the copper layer with a thickness of 500nm are metal plating layers, as examples 17 to 19. Finally, 3M 610 adhesive tape was attached to the metal coating, and the peeling of the metal coating was tested by the aforementioned method.

The results of Fig. 4 to Fig. 6 show that after using the surface binding agent to treat the surface of the polyimide film, the peeling area of the metal coating under the adhesive tape is less than 1%, which means that the surface of the polyimide film can be bonded to the metal after the surface binding agent is processed. Excellent bond between layers, resists tape peel forces.

From the above, it can be known that the surface binding agent of the present invention can treat the surface of the substrate, form an organic layer on the surface of the substrate, effectively improve the adhesion between the surface of the substrate that has not been roughened in advance and the coating material, and avoid the coating material To fall off, to peel off. Because the roughening process can be eliminated, the cost of the process can be reduced and the waste for roughening (heavy metal wastewater, corrosive strong acid, etc.) The use of the surface binding agent of the present invention still has excellent effects.

The above-mentioned embodiments are used to illustrate the principles and effects of the present invention, but not to limit the present invention. Any person skilled in the art can modify the above-mentioned embodiments without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be listed in the following claims.

It should be understood that within the scope covered by the technical content described in the present invention, various technical features (such as those described in the embodiments and examples) can be freely combined with each other to form new or more preferred technical solutions, for For the sake of brevity, it is not repeated here. And in the numerical range composed of end values described in the present invention, as long as the numerical value falls between the upper and lower end values, it shall be included in the range described in the present invention, and it and the sub-range formed by the end points or other numerical values It should also be naturally included within the scope of the present invention.

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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