KR20190026385A - Aluminum Surface Treatment Method for Polymer Bonding - Google Patents

Abstract

The present invention relates to an aluminum surface treatment method for silicone resin bonding, which can increase an adhesive force with silicone resin by treating an aluminum surface with an etching and anodizing process by using an acid or a base. The present invention provides an aluminum surface treatment method for silicone resin bonding, which comprises the following steps of: (a) pretreating an aluminum substrate by defatting, etching, and desmutting; (b) immersing the pretreated aluminum substrate in an electrolyte perform plasma electrolytic oxidation (PEO); and bonding silicone resin to aluminum that is plasma electrolytic oxidized.

Description

TECHNICAL FIELD The present invention relates to an aluminum surface treatment method for bonding a silicon resin,

The present invention relates to a method of treating an aluminum surface for bonding a silicone resin, and more particularly, to a method for treating an aluminum surface by using an acid or an alkaline base and an anodizing process, 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. The present invention improves the adhesion with the polymer resin while securing the airtightness of the aluminum using the acid nickname and the electrochemical coating method of the aluminum base. However, since the nanopore of the aluminum permeates and adheres the polymer, the high molecular weight polymer or It is difficult to apply it to a high-viscosity polymer resin.

In order to solve the above-described problems, the present invention provides an aluminum surface treatment method for silicone resin bonding, which can improve adhesion to a silicone resin by treating an aluminum intervening surface using nicking and anodizing 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, (b) dipping the pretreated aluminum substrate in an electrolytic solution to perform plasma electrolytic oxidation (PEO); And (c) bonding the silicon resin to the plasma electrolytically oxidized aluminum.

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.

Wherein the nickname includes 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 of the base may be used.

The step (b) uses an aqueous solution of sodium silicate (Na ₂ SiO ₃ ) and potassium hydroxide (KOH) as an electrolytic solution at a temperature of 0 to 50 ° C. for 1 to 30 minutes using a DC rectifier at a voltage of 100 to 300 V Can be performed.

The aluminum may be aluminum 5052.

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

The nicknames can be alternated with nicknames using an acid and nicknames 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 aluminum surface treatment method for bonding the silicone resin according to the present invention alters the surface of aluminum and then performs anodizing to increase the activity and frictional force of the surface so that strong bonding with the silicone resin is enabled, 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, nicking and dismounting; (b) dipping the pretreated aluminum substrate in an electrolytic solution to perform plasma electrolytic oxidation (PEO); And (c) bonding the silicon resin to the plasma electrolytically oxidized aluminum.

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 divided into degreasing, nicking and desmutting steps.

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 nickname is a step of chemically etching the surface of the aluminum. The nickname includes at least one acid selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, and acetic acid, or an inorganic acid such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, And at least one base selected from the group consisting of aluminum hydroxide and ammonium hydroxide. Particularly, when an acid is used as a nicking solution, 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, and the nitric acid is used in an amount of 200 to 500 g / L, preferably 300 to 350 g / , 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, nicking does not occur. When it is contained in an amount exceeding 500 g / L, excessive nicking may occur and the surface may be damaged.

When a base is used as the nicking solution, sodium hydroxide may 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, no nicking occurs. When it is contained in an amount exceeding 200 g / L, excessive nicking may occur and damage to the surface may occur.

The desmut may be performed using sulfuric acid as a step of removing the oxide generated on the aluminum surface by the nickname. 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 nicking and desmutting steps may be performed once after the degreasing step, but may preferably be 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. In addition, when repeating the nickname and the dismut as described above, the nickname using the acid and the nickname using the base can be alternately repeated, and preferably, the base nickname after the nickname can be performed.

Each treatment (degreasing, nicking, 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.

The step (b) is a step of plasma-electrolytic oxidation (PEO) of the surface-treated aluminum substrate, using sodium silicate (Na ₂ SiO ₃ ) and potassium hydroxide (KOH) The plasma electrolytic oxidation can be performed at a voltage of 100 to 300 V using a DC rectifier for 1 to 30 minutes. The plasma electrolytic oxidation is a process in which the surface of aluminum is oxidized by using plasma to form an oxide film on the surface of the aluminum electrode. However, since the conventional anodizing process oxidizes the aluminum itself to produce a film, processing of the wire or thin film is almost impossible. In the case of electrolytic oxidation, a silicate film is formed on the surface of an aluminum substrate, and then a film is formed by oxidizing it, so that a high strength film can be formed without damaging the aluminum substrate. In the same manner as in the anodizing, it is also possible to inject the dye into the oxide film so that the aluminum substrate has a uniform color.

After the plasma electrolytic oxidation is completed, the substrate is washed to remove liquid and impurities remaining on the surface, and then dried and bonded to the silicone resin. The silicone resin may be any silicone resin that can be bonded to the aluminum base material. The bonding of the aluminum base material and the silicone resin is preferably carried out by melting the silicone resin and then bonding or simply applying a pressure.

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

Example  One

Aluminum 5052 specimens with a width of 1.2 cm, a length of 8 cm and a thickness of 0.1 cm were prepared and then pretreated by degreasing, nicking and dismutting. 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) nickname (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 plasma electrolytic oxidation at a voltage of 200V using a sodium rectifier (Na ₂ SiO ₃ ) and potassium hydroxide (KOH) as an electrolyte at 20 ° C for 5 minutes using a DC rectifier.

The plasma electrolytically oxidized specimen was attached to the silicone resin so that the bonding area was 0.8 cm 2.

Example 2

In the same manner as in Example 1, sodium hydroxide (150 g / L) was used as the nicking solution.

Example 3

After the desmutting step in Example 1, sodium hydroxide (150 g / L) was further nicked using the nicking solution, and the same medicinal material as in Example 1 was further used to carry out the same dismutation step Respectively.

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 6.2 7.0 12.5 2 8.6 11.2 12.0 3 9.7 9.2 14.4 4 6.7 11.7 9.0 5 5.3 7.2 9.5 6 7.1 9.3 12.9 7 7.0 10.8 13.7 8 5.7 11.2 9.5 9 6.5 9.8 15.0 10 7.4 8.1 11.8 11 5.2 9.6 9.7 12 8.7 7.7 13.5 13 9.7 9.6 13.3 14 5.5 11.7 13.4 15 9.6 8.1 12.6 16 5.5 8.5 12.5 17 8.2 9.8 8.9 18 5.8 12.0 8.0 19 6.9 7.9 7.6 20 7.6 10.4 12.0 Average 7.1 9.5 11.6

As a result of conducting experiments using 20 specimens per each example, the bonding strength of the nickname Example 2 was higher than that of Example 1, which was nicknamed using an acid as shown in Table 2, using a base , And it was found that Example 3, which was nicked using an acid and nicked using a base, had 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 (9)

(a) Pretreatment by degreasing, nicking and dismuting the aluminum substrate
(b) dipping the pretreated aluminum substrate in an electrolytic solution to perform plasma electrolytic oxidation (PEO); And
(c) bonding silicon resin to the plasma electrolytically oxidized aluminum;
≪ / RTI > 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. The method according to claim 1,
Wherein the nickname includes 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 of the base. The method according to claim 1,
The step (b) uses an aqueous solution of sodium silicate (Na ₂ SiO ₃ ) and potassium hydroxide (KOH) as an electrolytic solution at a temperature of 0 to 50 ° C. for 1 to 30 minutes using a DC rectifier at a voltage of 100 to 300 V Of the aluminum surface. The method of claim 1, wherein
Wherein the aluminum is aluminum 5052. The method according to claim 1,
Wherein the nicking and desmutting steps in step (a) are performed two to ten times. The method according to claim 6,
Wherein the nicknames are alternately performed using an acid nickname and a base nickname. 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.