TWI801608B - Composition for surface treatment, film comprising the same, and method for surface treatment using the same - Google Patents

Abstract

This application relates to a composition for surface treatment, a film comprising the same, and a method for surface treatment using the same.

Description

Composition for surface treatment, film comprising same and use Its method of surface treatment

This application relates to a composition for surface treatment and a method for using it for surface treatment.

Since electronic devices including semiconductors are required to have high performance and multi-functionality, miniaturization and thinning of electronic devices has become a basic requirement for improving mounting efficiency per unit volume.

In recent years, the development of mobile devices and communication technologies has led the development of rigid substrates to flexible substrates, surface mount components to embedded components, multilayer substrates to high density multilayer substrates (HDI), thin films to coreless Substrate development, micro-processing to micro-processing and heat dissipation, eco-friendly materials to low-loss and eco-friendly materials, etc. In addition, improvement in adhesion between layers is evaluated as an important factor for ensuring high reliability and achieving low roughness microfabricated circuits of substrates.

At present, the main use on the surface of the material is to form the physical surface roughness (for example, CZ treatment and UV treatment) to improve adhesion, but the material will be damaged. Therefore, a chemical method for surface treatment that does not damage the material and has high adhesion is attracting attention.

Common methods of forming surface roughness to improve adhesion include a method of forming a silane coupling agent by CVD, a method of forming an oxide film by UV treatment, and after breaking polymer surface bonds by ion beam treatment Methods of changing to a hydrophilic surface, etc.

In Korean Patent Publication No. 10-2004-0087534, a surface treatment agent is disclosed which is coated using a coating liquid containing a silicone compound.

The present invention solves the problems associated with conventional methods of providing surface roughness (eg, damage to materials and additional processing costs) and provides a method of increasing the surface energy of a substrate and increasing adhesion to metal layers.

The present invention provides a composition comprising: polydopamine (poly-dopamine) for surface modification, polydopamine is the smallest single molecule having both catechol and amine; Adhesive glutamine (glutamine), which has the highest adhesiveness among amine-based organic additives; and tris(hydroxymethyl)aminomethane, which is most suitable for this, In order to obtain conditions for improving the adhesion between the substrate and the electroless copper plating layer.

According to one aspect, a composition for surface treatment is provided, the The composition includes polydopamine, glutamine and tris(hydroxymethyl)aminomethane.

According to one embodiment, the composition for surface treatment may comprise, based on the total composition, 0.5 to 3 milligrams/milliliter (mg/mL) of polydopamine, 1 to 2 mg/mL of glutamine, and 20 to 100 millimoles per liter (mM) of tris(hydroxymethyl)aminomethane.

According to one embodiment, the composition for surface treatment may contain 1.5 to 2 mg/ml of glutamine based on the total composition.

According to one embodiment, the pH of the composition may be 7.5 to 9.5.

According to another aspect, there is provided a film comprising the composition for surface treatment of the present invention.

According to one embodiment, the composition for surface treatment may be coated to have a thickness of 10 nm to 40 nm.

According to an embodiment, the film may have a contact angle (θ) of 10 to 25 degrees.

According to another aspect, there is provided a method for surface treatment, the method comprising applying the composition for surface treatment of the present invention to the surface of a substrate to be treated.

According to one embodiment, said applying step may comprise soaking for 12 hours to 30 hours.

According to an embodiment, the method for performing surface treatment may further include immersing in deionized (DI) water for 12 hours to 36 hours for stabilization.

According to an embodiment, the substrate may be a build-up film or a liquid crystal polymer film.

According to an embodiment, the film may have a coating thickness of 10 nm to 40 nm.

According to one embodiment, a polydopamine coating composition comprising glutamine and tris(hydroxymethyl)aminomethane can be used to increase the surface energy of the substrate and form a uniform coating for improved adhesion to the metal layer without Damage to surface-treated substrates.

According to one embodiment, there is provided an excellent method for surface treatment to improve the adhesion to an electroless copper layer by performing a glutamine-containing polydopamine coating on the surface of a substrate, wherein the method utilizes Uniform coating on the surface of the substrate is provided by controlling the coating solution, coating time, and concentration of the organic solvent.

According to one embodiment, the polydopamine coating process is extremely simple, does not require additional equipment, and is performed at low cost without damaging the substrate.

According to one embodiment, when a surface treatment process is performed using the composition for surface treatment described in this application, the adhesion of the substrate (eg, non-roughened insulating material) to metal can be improved. The composition for surface treatment described herein can be used not only for laminated films but also for all kinds of substrates requiring interlayer adhesion regardless of the purpose.

According to one embodiment, the polydopamine composition for surface treatment described herein is environmentally friendly and harmless to the human body.

FIG. 1 illustrates a surface treatment method using a composition for surface treatment according to an embodiment of the present application.

(a) of FIG. 2 is an image showing the color of the composition for surface treatment according to an embodiment of the present application after preparation.

(b) of FIG. 2 is an image showing the color of the composition for surface treatment according to an embodiment of the present application after a certain period of time after being prepared.

(c) of FIG. 2 is an image showing the surface of the substrate before surface treatment of the substrate (ABF) with the composition for surface treatment according to an embodiment of the present application.

(d) of FIG. 2 is an image showing the surface of the substrate after the substrate (ABF) is surface-treated with the composition for surface treatment according to an embodiment of the present application.

FIG. 3A is a graph showing C1s peaks from X-ray photoelectron spectroscopy (XPS) and focused ion beam analysis (FIB), which are used to determine the The surface treatment result of the composition for surface treatment of Example 1.

FIG. 3B is a graph showing O1s peaks from X-ray photoelectron spectroscopy (XPS) and focused ion beam analysis (FIB), which are used to judge whether the surface treatment was carried out using the compositions for surface treatment of Comparative Example 1 and Example 1. Result after surface treatment.

FIG. 3C is a graph showing N1s peaks from X-ray photoelectron spectroscopy (XPS) and focused ion beam analysis (FIB), which are used to judge whether the surface treatment was carried out using the compositions for surface treatment of Comparative Example 1 and Example 1. Result after surface treatment.

FIG. 3D is a graph showing Si2p peaks from X-ray photoelectron spectroscopy (XPS) and focused ion beam analysis (FIB), which are used to judge whether the surface treatment was carried out using the compositions for surface treatment of Comparative Example 1 and Example 1. Result after surface treatment.

Figure 3E is a graph showing the results from X-ray photoelectron spectroscopy (XPS) and focused ion beam analysis. The graph of Cu2p peak of analysis (FIB), which is used to judge the results after surface treatment using the composition for surface treatment of Comparative Example 1 and Example 1.

FIG. 4A is an image showing a cross-section of a substrate of Comparative Example 1. FIG.

FIG. 4B is an image showing a cross-section of a substrate of Comparative Example 3. FIG.

FIG. 4C is an image showing a cross-section of the substrate of Example 1. FIG.

FIG. 5 shows contact angles and SEM images according to the treatment time of the composition for surface treatment according to an embodiment of the present application.

FIG. 6 shows the results of a cross cut test according to whether glutamine is added to the composition for surface treatment according to an embodiment of the present application.

FIG. 7 shows results after surface treatment of a substrate (ABF) using the compositions for surface treatment of Comparative Example 1, Comparative Example 3, and Example 1 and then electroless copper plating on the result.

8 shows the results of a cross-hatch test for evaluating cross-hatch image, contact angle, and adhesiveness according to the concentration of glutamine in the composition for surface treatment of Comparative Example 4 and Examples 1 to 3.

9A shows whether or not tris(hydroxymethyl)aminomethane and the concentration of tris(hydroxymethyl)aminomethane are added in the composition for surface treatment of Comparative Example 1, Comparative Example 5 and Example 1, Focused ion beam analysis (FIB) results.

FIG. 9B shows the results of focused ion beam analysis (FIB) and cross-cut test results according to the concentration of tris(hydroxymethyl)aminomethane in the compositions for surface treatment of Comparative Example 5 and Example 1. FIG.

Although the present disclosure has been described with reference to specific embodiments, it should be understood that those skilled in the art can make Various changes and modifications.

The terminology used in the description is intended to describe certain embodiments only and does not limit the disclosure in any way. Expressions in the singular include the plural unless explicitly used otherwise. In this description, expressions such as "comprising" or "consisting of" are intended to designate features, numbers, steps, operations, elements, parts or combinations thereof and should not be construed as Any existence or possibility of one or more other characteristics, numbers, steps, operations, elements, parts or combinations thereof is excluded.

Throughout the description of the present disclosure, when the description of a certain technology is determined to avoid the main points of the present disclosure, the relevant detailed description will be omitted.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In order to facilitate a thorough understanding of the present invention, the same reference numerals are used for the same components regardless of the figure number.

1. Composition for surface treatment

The composition for surface treatment of the present invention is used for surface treatment of Ajinomoto Build up Film (ABF). The use of the composition for surface treatment enables uniform surface treatment regardless of the kind of substrate by controlling the coating (treatment) time, the concentration of the components, and the like.

According to an aspect of the present invention, the composition for surface treatment may include polydopamine, glutamine and tris(hydroxymethyl)aminomethane.

polydopamine

The surface treatment layer of poly-dopamine (poly-dopamine, PDA) formed by the oxidation reaction of catechol and the like exhibits excellent adhesive properties, and in addition, the catechol and amine functional groups contained in polydopamine participate in the surface treatment layer. modified. In addition, the surface treatment layer can be easily bonded to any surface to provide excellent adhesion regardless of the type of substrate.

As shown in Scheme 1 below, polydopamine can be formed by oxidation, cyclization and polymerization, but it is not limited thereto. The structure of dopamine can be represented by Formula 1 below.

Specifically, polydopamine can be obtained by self-polymerization of dopamine. Here, the spontaneous oxidation of dopamine in the initial stage is carried out by oxygen dissolved in a weak base conditioned solution, and by spontaneous intramolecular nucleophilic cyclization polymerization (spontaneous intramolecular nucleophilic cyclization polymerization) dopamine-quinone (dopamine-quinone) is converted into 5,6-dihydroxyindole (5,6-dihydroxyindole, DHI) to be coated on the surface of the substrate.

The coating thickness can be adjusted by adjusting the concentration of polydopamine. Using about 0.5 mg/ml of polydopamine gives a coating thickness of about 20 nm, using about 1 mg/ml of polydopamine gives a coating thickness of about 25 nm, and using about 2 mg/ml of polydopamine A coating thickness of about 25 nm to 40 nm will be obtained. However, when the concentration of polydopamine was about 3 mg/ml or greater than 3 mg/ml, there was no significant difference in coating thickness.

In order to obtain a suitable coating thickness, the concentration of polydopamine in the composition for surface treatment may be 0.5 to 3 mg/ml. When the concentration of polydopamine is less than 0.5 mg/ml, the thickness of the surface treatment (coating) is too thin to achieve the desired effect. On the other hand, when the concentration was greater than 3 mg/ml, there was no significant difference in effect.

Glutamine

Glutamine (glutamic acid) is an amino acid that is a monoamide of glutamic acid.

According to one embodiment of the present invention, glutamine is an important factor affecting surface energy. As the surface energy becomes higher, the adhesion becomes better. As the concentration of glutamine increased from 0.5 mg/ml, the contact angle gradually decreased and then started to increase from a glutamine concentration of 1.5 mg/ml. This means that the surface energy and adhesion force increase as the concentration of glutamine increases from 0.5 mg/ml to 1.5 mg/ml, and then decreases from 1.5 mg/ml.

Therefore, in order to obtain the desired high adhesion in the present invention, the surface A suitable concentration of glutamine in the treated composition is, but not limited to, 1 to 2 mg/ml, preferably 1.5 to 2 mg/ml. When the concentration of glutamine is less than 1 mg/ml or exceeds 2 mg/ml, the surface energy may decrease, the contact angle may increase, and the adhesion to the metal plating required in the present invention may be significantly decreased.

For example, the structure of glutamine may be represented by Formula 2 below.

Tris(hydroxymethyl)aminomethane

Tris(hydroxymethyl)aminomethane (also known as Tris) contains primary amine groups and is used to prepare basic buffer solutions.

When tris(hydroxymethyl)aminomethane is included in the composition for surface treatment, tris(hydroxymethyl)aminomethane enables uniform coating on the metal surface during surface treatment. Therefore, if the concentration of tris(hydroxymethyl)aminomethane is too low, coating may be uneven. The coating at a concentration of tris(hydroxymethyl)aminomethane of 50 mmol/L was more uniform than that at a concentration of tris(hydroxymethyl)aminomethane of 10 mmol/L. It should therefore be noted that a suitable concentration of tris(hydroxymethyl)aminomethane may be between 20 and 100 mmol/L in order to maintain the desired uniform coating. When the concentration of tris(hydroxymethyl)aminomethane is less than 20 mmol/liter, the surface treatment may be uneven. On the other hand, when the concentration exceeds Over 100 mmol/L, there was no significant difference in effect.

The pH of the tris(hydroxymethyl)aminomethane-containing composition may be alkaline, preferably 7.5 to 9.5. However, it is not limited to this.

For example, the structure of tris(hydroxymethyl)aminomethane may be represented by Formula 3 below.

other additives

The composition for surface treatment of the present invention may further include a pH regulator to control the coating thickness. Examples of the pH adjuster include strong acids such as hydrochloric acid (HCl), sulfuric acid (H ₂ SO ₄ ) or nitric acid (HNO ₃ ), preferably hydrochloric acid (HCl).

2. Membrane

The composition of the present invention can be used in various known substrates capable of surface treatment, but not limited thereto, and can be used to produce films.

The use of the composition for surface treatment according to the invention enables the production of films in a simple process which is environmentally friendly and which has significantly improved adhesion to metal coatings.

The film may be, but not limited to, a laminated film or a liquid crystal polymer film such as ABF or LCP.

Films with a coating thickness of 10 nm to 40 nm can be easily prepared using the composition of the present invention.

The films can be easily processed at contact angles (θ) of 10 to 25 degrees.

The film can be readily used to produce low roughness micromachined circuit substrates or flexible substrates.

The ABF film has high processing efficiency and easy handling, and the thickness of the conductor can be adjusted freely, so that it can be beneficial to the etching process in the panel plating method. Furthermore, no additional removal steps are required, which is a further advantage.

3. The method of surface treatment

The surface treatment method of the present invention may include applying the composition for surface treatment of the present invention to the surface of a substrate. The applying step may include, but is not limited to, immersing the substrate in the composition for surface treatment.

The contact angle varies depending on the immersion time of the substrate in the composition for surface treatment, and thus the degree of adhesion can be determined. The time of immersion in the composition for surface treatment is not particularly limited, but is 12 hours to 30 hours, preferably 20 hours to 30 hours. If the immersion time is less than 12 hours, surface treatment (coating) may be insufficient. On the other hand, if the immersion time is longer than 30 hours, the difference in surface treatment effect may not be significant.

The method of performing surface treatment of the present invention may further comprise stabilizing the impregnated substrate in DI water. Such stabilization can enhance the stability of the coating. The stabilization time is not limited thereto, but is 12 hours to 36 hours, preferably 20 hours to 30 hours. If the stabilization time is less than 12 hours, surface treatment may not be easily performed. On the other hand, if the stabilization time is greater than 36 hours, the difference in the effect of the surface treatment may not be significant. big.

The surface treatment method of the present application is extremely simple, and provides an environmentally friendly coating that is harmless to the human body at low cost without damaging the substrate.

Preferred embodiments of the present invention will be described in detail below. The following examples are intended to illustrate the invention, but the scope of the invention should not be construed as being limited to these examples. In the following examples, only examples using specific compounds are illustrated. However, it will be apparent to those skilled in the art that equivalents to similar compounds may be used.

example

Preparation of compositions for surface treatment

A composition for surface treatment comprising polydopamine, glutamine and tris(hydroxymethyl)aminomethane was prepared.

The composition for surface treatment of the present invention and the composition of the comparative example were prepared using the components in Table 1 below. Tris(hydroxymethyl)aminomethane was quantified and dissolved in deionized water, and adjusted to a weak base state of 8.5 using a pH regulator. Polydopamine and glutamine were added to the prepared tris(hydroxymethyl)aminomethane solution, and stirred to react with oxygen in the solution. When the color of the reaction mixture started to change to beige, the substrate (ABF) was dipped therein for surface treatment. The composition used for the surface treatment was initially light brown in color but gradually changed to dark brown over time. After a period of time, there is no more color change and a thin film is formed on the surface of the substrate.

Substrates were subjected to surface treatment using the composition for surface treatment of the present application for 24 hours, washed and immersed in DI water for 24 hours or more stabilization. The surface of the substrate (ABF) after surface treatment becomes darker than before treatment. The surface treatment can be confirmed visually (see Figure 1 and Figure 2).

Determination of coating and adhesion

Surface analysis was performed using X-ray photoelectron spectroscopy (XPS) and cross-sectional analysis was performed using focused ion beam equipment (FIB) to confirm whether surface treatment was performed. The contact angle ( θ ) indicative of the surface energy is measured in order to derive the contribution of the components in the composition used for the surface treatment.

Cross cut tests were performed to study the adhesion to the coated surface metal.

Based on the above results, the functions of each composition and its process conditions were obtained.

Experimental example

Using X-ray Photoelectron Spectroscopy (XPS) and Focused Ion Beam Analysis (FIB) to analyze

The results of surface treatment using the compositions of Comparative Examples 1 to 5 and Examples 1 to 6 were analyzed by X-ray photoelectron spectroscopy (XPS) and focused ion beam equipment (FIB). The results of the analysis are summarized in Figures 3A to 3E. As shown in Table 2, it was confirmed that the N1s peak increased, indicating that the surface treatment layer was formed on the surface of the ABF substrate.

It was confirmed by focused ion beam analysis (FIB) that for Comparative Example 3 and Example 1, a surface-treated layer with a thickness of about 24 nm or 30 nm was uniformly formed on the surface of the ABF substrate (see FIG. 4A to 4C).

Contact Angle Measurement

The contact angle ( θ ) of the substrates surface-treated with the compositions of the comparative example and the example was measured to calculate the corresponding surface energy after the surface treatment.

Perform contact angle measurement to measure the interfacial energy between solid and liquid to calculate and verify the surface energy.

Contact angle measurement was performed to confirm that Comparative Example 1 to Comparative Example 5 and Example 1 to The surface treatment results of Example 6 and determine the optimum surface treatment time. It was found that as the surface treatment time increased, the contact angle decreased, and the minimum contact angle was exhibited at a surface treatment time of 24 hours (1440 minutes). This means that it has the highest interfacial energy. However, no significant difference was observed after more than 24 hours compared to the contact angle results at a surface treatment time of 24 hours.

cross cut test

A cross-hatch test is performed to determine the adhesion between the treated surface and the metal.

Adhesion is evaluated by performing a cross-hatch test, the fastest way to measure adhesion, by cutting a surface-treated substrate into a right-angled lattice pattern and determining the resistance of the coating to separation from the substrate the appropriateness or inappropriateness of the force.

6 shows the results of a cross-cut test depending on whether glutamine was added to the compositions for surface treatment of Comparative Example 1, Comparative Example 3, and Example 1. Referring to FIG. 6, in the case where the composition for surface treatment does not contain glutamine (Comparative Example 3), since the adhesion on the substrate is significantly lower, when metal plating is performed, the coating from the substrate occurs. separation. On the other hand, in the case of the composition (Example 1), separation of the coating layer from the substrate did not occur. As shown in FIG. 7 showing surface images after surface treatment using the compositions of Comparative Example 1, Comparative Example 3, and Example 1, glutamine was identified as one of the main factors that did affect the surface energy.

As shown in FIG. 8 , it was confirmed that optimal viscosity was obtained at concentrations of glutamine corresponding to Examples 1 to 3 (i.e., 1 mg/ml to 2 mg/ml). Focus on.

According to the cross-cut test based on whether tris(hydroxymethyl)aminomethane and the concentration of tris(hydroxymethyl)aminomethane are added in the composition for surface treatment of comparative example 1, comparative example 5 and example 1 , compared with the adhesion without tris(hydroxymethyl)aminomethane, the adhesion when tris(hydroxymethyl)aminomethane is added is better, and compared with tris(hydroxymethyl)aminomethane The adhesion was even better at a concentration of 10 mmol/L of tris(hydroxymethyl)aminomethane (see Figure 9A and Figure 9B ).

Although described with reference to specific embodiments, it should be understood that those skilled in the art can do so without departing from the spirit and scope of the embodiments described herein as defined by the appended claims and equivalents thereof. Various changes and modifications may be made. Accordingly, the examples described herein are for illustration only and are not intended to limit the present disclosure. The scope of the present disclosure should be interpreted by the following patent claims, and it should be interpreted that all spirits equivalent to the following patent claims fall within the scope of the present disclosure.

Claims (11)

A composition for surface treatment, comprising polydopamine, glutamine and tris(hydroxymethyl)aminomethane, wherein said composition comprises polydopamine, 1 to 3 mg/ml based on the total composition Glutamine at 2 mg/ml and tris(hydroxymethyl)aminomethane at 20 to 100 mmol/L. The composition for surface treatment as described in claim 1 of the patent application, wherein the composition contains 1.5 to 2 mg/ml of glutamine based on the total composition. The composition for surface treatment as described in item 1 or item 2 of the patent application, wherein the pH of the composition is 7.5 to 9.5. A film comprising the composition for surface treatment as described in item 1 or item 2 of the patent application. The film according to claim 4, wherein the composition for surface treatment is coated to have a thickness of 10 nm to 40 nm. The film according to claim 4, wherein the film has a contact angle (θ) of 10 to 25 degrees. A method for surface treatment, comprising applying the composition for surface treatment described in claim 1 to the surface of a substrate to be treated. The method for surface treatment as described in claim 7, wherein the applying step includes soaking for 12 hours to 30 hours. The method for surface treatment as described in item 7 of the patent claims further includes immersing in deionized water for 12 hours to 36 hours to stabilize. The method for surface treatment as described in claim 7, wherein the substrate is a laminated film or a liquid crystal polymer film. The method for surface treatment as described in claim 10, wherein the film has a coating thickness of 10 nm to 40 nm.

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