KR101954274B1 - Aluminum Surface Treatment Method for Polymer Bonding - Google Patents

Abstract

The present invention relates to an aluminum surface treatment method for bonding polymeric resins capable of enhancing adhesion to a polymer resin by treating the surface of aluminum using an etching and anodizing process using an acid or a base. (A) pre-treating the aluminum substrate by degreasing, etching and dismounting; (b) anodizing the pretreated aluminum substrate by immersing the pretreated aluminum substrate in an electrolytic solution; And (c) bonding the polymer resin to the anodized aluminum, the method comprising the steps of: (a) providing a polymer resin joint for alternately performing etching using an acid and etching using a base, The present invention provides a method for treating an aluminum surface.

Description

[0001] The present invention relates to an aluminum surface treatment method for polymer resin bonding,

The present invention relates to a method for treating an aluminum surface for bonding a polymer resin, and more particularly, to a method for treating an aluminum surface by using an etching and an anodizing process using an acid or a base, To an aluminum surface treatment method for bonding.

Generally, bonding of aluminum and a polymer resin is mostly carried out using an adhesive. However, since most of the adhesives used for bonding the polymer resin are chemically melted and then bonded, it is not applied to aluminum, so physical adhesives are often used for bonding the polymer resin and aluminum.

The physical adhesive is an adhesive that physically bonds two materials using friction force and van der Waals force while being positioned between two materials. It can be used for various materials and has less damage to the material, but has a lower adhesive strength than a chemical adhesive It has disadvantages.

Therefore, in order to overcome the disadvantages of such a physical adhesive, although the composition of the adhesive is different and the adhesive optimized according to each material and the use environment is used, it has a disadvantage that it is difficult to provide each kind of adhesive.

In order to improve this, a method of modifying the surface of aluminum has been used. In the case of modifying the surface of aluminum, the surface activity and friction of aluminum are increased, so that a high adhesive force can be obtained even when an adhesive for general- It is not necessary to use an adhesive, and the amount of adhesive used can be minimized.

Korean Patent Laid-Open No. 10-2015-0098911 discloses a method for producing a heterogeneous material conjugate. In the present invention, the surface modifying material and the medium gas are mixed and then thermally decomposed or photolyzed, and the surface of the high-molecular substance is modified by using the pyrolyzed or photodegraded gas. However, the surface is modified by using pyrolyzed gas under high temperature conditions Therefore, it has a disadvantage that it can not be applied to a polymer resin which is weak in heat.

Korean Patent No. 10-1606567 discloses a method for producing an aluminum-polymer goosene bonded body and an aluminum-polymer resin bonded body produced thereby. In this invention, the aluminum base is acid-etched and the electrochemical coating method is used to improve the adhesion with the polymer resin while securing the airtightness of aluminum. However, since the nanopore of aluminum is permeated and adhered to the polymer, It is difficult to apply it to a high-viscosity polymer resin.

In order to solve the above-mentioned problems, the present invention provides an aluminum surface treatment method for bonding a polymer resin capable of enhancing adhesion to a polymer resin by treating an aluminum intervening surface using an etching and anodizing process using an acid or a base .

In order to solve the above-mentioned problems, the present invention provides a method for manufacturing a semiconductor device, comprising the steps of: (a) pre-treating an aluminum substrate by degreasing, etching and dismounting; (b) anodizing the pretreated aluminum substrate by immersing the pretreated aluminum substrate in an electrolytic solution; And (c) bonding the polymer resin to the anodized aluminum, the method comprising the steps of: (a) providing a polymer resin joint for alternately performing etching using an acid and etching using a base, The present invention provides a method for treating an aluminum surface.

The degreasing may be carried out in the presence of an anhydrous sodium carbonate, sodium phosphate monobasic, potassium monophosphate, ammonium phosphate monobasic, dibasic sodium phosphate, dibasic potassium phosphate, dibasic ammonium phosphate, sodium tertiary phosphate, potassium tertiary phosphate, Wherein the aqueous solution contains at least one selected from the group consisting of sodium polyphosphate, potassium pyrophosphate, sodium pyrophosphate, sodium pyrophosphate, sodium hexametaphosphate, sodium tartrate, potassium tartrate, sodium nitrate, potassium nitrate, sodium citrate and potassium citrate Degreasing agent.

The etching may be carried out using one or more acids selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, and acetic acid or one kind selected from the group of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, lithium hydroxide, aluminum hydroxide, Or more can be used.

In step (b), sulfuric acid is used as an electrolyte, and anodizing can be performed at 30 to 60 ° C for 1 to 30 minutes and at a voltage of 5 to 30 V using a DC rectifier.

The aluminum may be aluminum 5052, and the polymer resin may be polybutylene terephthalate (PBT).

The etching and dismutting steps of step (a) may be repeated 2 to 10 times.

The etching can alternately perform etching using an acid and etching using a base.

The dismut may be performed using sulfuric acid.

The joining step may be a step of melting or pressurizing and joining.

The method of aluminum surface treatment for polymer resin bonding according to the present invention enables strong bonding with a polymer resin since the surface of aluminum is etched and then anodizing is performed to increase the activity and frictional force of the surface, It can be widely used in the manufacture of home appliances, airplanes, automobiles, etc., which must be mixed and used.

Hereinafter, preferred embodiments of the present invention will be described in detail. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. Throughout the specification, when an element is referred to as " including " an element, it means that it can include other elements, not excluding other elements, unless specifically stated otherwise.

In addition, in adding reference numerals to the constituent elements of the drawings, it is to be noted that the same constituent elements are denoted by the same reference numerals even though they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected or connected to the other component, Quot; may be "connected," "coupled, " or" connected. &Quot;

(A) pre-treating the aluminum substrate by degreasing, etching and dismounting; (b) anodizing the pretreated aluminum substrate by immersing the pretreated aluminum substrate in an electrolytic solution; And (c) bonding the polymer resin to the anodized aluminum, the method comprising the steps of: (a) providing a polymer resin joint for alternately performing etching using an acid and etching using a base, The present invention provides a method for treating an aluminum surface.

Aluminum which can be surface-treated in the present invention can be used not only for aluminum used in the past but also for all aluminum surfaces requiring adhesion with a polymer resin, but it is preferable to use a surface treatment such as 1085, 1080, 1070, 1050, 1100, 1200, 2014, 2017, More preferably at least one selected from the group consisting of SEQ ID NOs: 2219, 2024, 3033, 3203, 3004, 3014, 3005, 3105, 5005, 5052, 5652, 5154, 5254, 5082, 5182, 5083, 5086, 6160, 7075, 1N00, 1N30, 5052 surface treatment is possible.

The step (a) is a step of pretreating the surface of the aluminum base material, and is roughly divided into a degreasing step, an etching step and a desmutting step.

The degreasing step is a step of removing impurities and oil on the surface of the aluminum substrate. The degreasing step may be carried out without limitation as long as it is a degreasing agent capable of removing contaminants present on the aluminum surface. Preferably, Sodium phosphate, potassium phosphate, sodium polyphosphate, potassium pyrophosphate, potassium phosphate, sodium phosphate, potassium phosphate monobasic, ammonium phosphate monobasic, sodium bisphosphate, potassium diphosphate, ammonium diphosphate, sodium dihydrogen phosphate, A degreasing agent containing at least one selected from the group consisting of sodium pyrophosphate, sodium pyrophosphate, sodium hexametaphosphate, sodium tartrate, potassium tartrate, sodium nitrate, potassium nitrate, sodium citrate and potassium citrate, more preferably anhydrous sodium carbonate And sodium tertiary phosphate can be used.

The degreasing agent may be used by mixing the anhydrous sodium carbonate at a ratio of 10 to 30 g / L, preferably 15 to 25 g / L, and most preferably 20 g / L. When the anhydrous sodium carbonate is contained in an amount less than 10 g / L, the concentration is low and it is difficult to expect a degreasing effect. When the anhydrous sodium carbonate is contained in an amount exceeding 30 g / L, the anhydrous sodium carbonate is adsorbed on the aluminum surface, have. The sodium tertiary phosphate may contain 3 to 10 g / L, preferably 5 to 7 g / L, and most preferably 6.6 g / L. When the concentration of sodium tertiary phosphate is less than 3 g / L, the concentration is low and it is difficult to expect a degreasing effect. When the concentration of sodium tertiary phosphate is more than 10 g / L, the dispersing power of the degreasing agent may become strong.

The etching is a step of chemically etching the surface of the aluminum. The etching includes at least one acid selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, and acetic acid or an acid selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, And at least one base selected from the group consisting of aluminum hydroxide and ammonium hydroxide. In particular, when an acid is used as an etchant, it is possible to use a water-in-water mixture in which nitric acid and hydrochloric acid are mixed in a ratio of 3: 1. The nitric acid is used in an amount of 200 to 500 g / L, preferably 300 to 350 g / Concentration, and nitric acid and hydrochloric acid may be mixed at a ratio of 3: 1. At this time, when nitric acid is contained in an amount less than 200 g / L, etching does not occur. When it is contained in an amount exceeding 500 g / L, excessive etching may occur to cause damage to the surface.

When a base is used as an etching solution, sodium hydroxide can be used. The sodium hydroxide may be mixed at a ratio of 100 to 200 g / L, preferably 130 to 170 g / L, and most preferably 150 g / L. When sodium hydroxide is used in an amount less than 100 g / L, etching does not occur. When it is contained in an amount exceeding 200 g / L, excessive etching may occur to cause damage to the surface.

Further, it is preferable that the etching is performed alternately by etching using an acid and etching using a base. The etching using an acid and the etching using a base differ in the surface treatment effect and the surface activity after the etching, so that the adhesion of the polymer resin can be maximized by alternately using the acid and the base for etching. In addition, it is preferable that the acid etching and the base etching are performed after acid etching.

The desmut may be performed using sulfuric acid as a step of removing the oxide generated on the aluminum surface by the etching. The sulfuric acid may be used in a mixture of 100 to 300 g / L, preferably 150 to 250 g / L, and most preferably 200 g / L. When the sulfuric acid is mixed at less than 100 g / L, the desmut effect is lowered. When the sulfuric acid is mixed at more than 300 g / L, there may be aluminum corrosion due to the sulfur phase.

The etching and desmutting steps may be performed once after the degreasing step, but preferably repeated 2 to 10 times, most preferably twice. If the repetition exceeds 10 times, corrosion of the surface becomes excessive and surface damage may occur.

Each treatment (degreasing, etching, and desmutting) in the step (a) may be performed at 40 to 80 ° C for 10 seconds to 20 minutes. If it is carried out at less than 40 ° C or less than 10 seconds, the pretreatment effect of each step is lowered. If it is carried out at more than 80 ° C or more than 20 minutes, aluminum may be damaged.

In the step (b), anodizing of the surface-treated aluminum substrate may be carried out using sulfuric acid as an electrolyte, and anodizing may be performed at 30 to 60 ° C for 1 to 30 minutes and at a voltage of 5 to 30 V using a DC rectifier have. The anodizing process is a process in which an oxide film is formed on the surface of the aluminum by electro-oxidizing the surface of the aluminum, and the oxide film has porosity, so that bonding with the polymer resin can be further strengthened. Further, after the anodizing, it is also possible to inject the dye into the oxide film so that the aluminum substrate has a certain color.

After the anodizing is completed, the substrate is washed to remove liquid and impurities remaining on the surface, and then dried and bonded to the polymer resin. The polymer resin may be any polymeric resin that can be bonded to the aluminum base material, but polybutylene terephthalate (PBT) may be preferably used. The bonding of the aluminum base material and the polymer resin is preferably performed by melting the polymer resin and then bonding or merely applying a pressure.

Hereinafter, the present invention will be described in detail with reference to examples.

Example  One

A specimen of 1.2 cm in width, 4 cm in length, and 0.3 cm in thickness made of aluminum 5052 was prepared and then subjected to pretreatment through degreasing, etching and dismutting steps. The solutions used in the pretreatment steps are shown in Table 1 below.

Degreasing Anhydrous sodium carbonate (20 g / L),
Sodium tertiary phosphate (6.6 g / L) etching (330 g / l), hydrochloric acid (110 g / l) Dismute Sulfuric acid (200 g / l)

1 L of each solution of each step was prepared, and then the aluminum specimen was immersed at a temperature of 60 캜 for 1 minute each for pretreatment.

The pretreated aluminum specimen was subjected to anodizing at a voltage of 5 V using a DC rectifier at 45 ° C for 5 minutes with sulfuric acid (50 g / l) as an electrolyte.

The anodized specimen was attached to PBT to have a bonding area of 0.6 cm < 2 >.

Example 2

In the same manner as in Example 1, except that sodium hydroxide (150 g / l) was used as an etchant.

Example 3

The same procedure was followed except that the dismutation step in Example 1 was followed by further etching using sodium hydroxide (150 g / l) as an etchant followed by a further dismutation step using the same medicament as in Example 1 .

Experimental Example

The bonding strengths of the samples of Examples 1 to 3 were measured, and the results are shown in Table 2 below.

Example 1 Example 2 Example 3 One 22.4 29.7 32.4 2 23.8 27.6 29.8 3 24.7 26.8 33.7 4 27.6 21.7 33.4 5 21.4 26.9 30.1 6 23.5 26.5 32.5 7 19.2 24.9 32.0 8 24.2 26.5 33.1 9 17.2 25.0 32.4 10 22.0 27.5 33.2 11 26.3 31.4 31.2 12 22.6 29.5 31.4 13 24.5 27.6 31.1 14 24.6 30.9 33.6 15 23.8 32.3 33.1 16 24.0 33.8 28.8 17 26.2 33.1 34.0 18 27.1 30.2 33.2 19 18.4 33.1 29.9 20 23.41 33.9 28.1 Average 23.3 28.9 31.8

As a result of conducting experiments using 20 specimens per each embodiment, as shown in Table 2, the adhesive strength of the etching solution of Example 2 was higher than that of Example 1, which was etched using an acid on the average, , Etching with an acid, and etching with a base showed the highest adhesive strength.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereto will be. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (8)

(a) Pretreatment by degreasing, etching, and dismuting the aluminum substrate
(b) anodizing the pretreated aluminum substrate by immersing the pretreated aluminum substrate in an electrolytic solution; And
(c) bonding the polymer resin to the anodized aluminum;
A method of aluminum surface treatment for polymer resin bonding comprising:
Wherein the etching is performed using a mixed solution of nitric acid and hydrochloric acid, and then etching is performed using sodium hydroxide. The method according to claim 1,
The degreasing may be carried out in the presence of an anhydrous sodium carbonate, sodium phosphate monobasic, potassium monophosphate, ammonium phosphate monobasic, sodium bisphosphate, potassium diphosphate, ammonium diphosphate, sodium phosphate dibasic, potassium diphosphate, Wherein the aqueous solution contains at least one selected from the group consisting of sodium polyphosphate, potassium pyrophosphate, sodium pyrophosphate, sodium pyrophosphate, sodium hexametaphosphate, sodium tartrate, potassium tartrate, sodium nitrate, potassium nitrate, sodium citrate and potassium citrate An aluminum surface treatment method performed with a degreasing agent. delete The method according to claim 1,
Wherein the anodizing is performed at 30 to 60 ° C for 1 to 30 minutes and at a voltage of 5 to 30 V using a DC rectifier using sulfuric acid as the electrolyte solution. The method of claim 1, wherein
Wherein the aluminum is aluminum 5052, and the polymer resin is polybutylene terephthalate (PBT). delete The method according to claim 1,
Wherein the dismut is performed using sulfuric acid. The method according to claim 1,
Wherein the step of bonding is a step of melting or pressing to join the aluminum surface.