KR102377875B1 - Cleaner composition for glass substrate - Google Patents

Abstract

The present invention relates to a cleaning liquid composition for glass substrates, comprising a fluorinated compound, a polyhydric alcohol, and water, wherein the polyhydric alcohol includes a first polyhydric alcohol having an unsaturated bond and a second polyhydric alcohol not having an unsaturated bond characterized in that The cleaning liquid composition of the present invention can effectively suppress stains on the glass surface while having excellent cleaning power.

Description

Glass substrate cleaning liquid composition {CLEANER COMPOSITION FOR GLASS SUBSTRATE}

The present invention relates to a cleaning solution composition that can effectively remove glass particles generated in the glass cutting (chamfering) process of a glass substrate for a display device, and specifically, has excellent cleaning power and can effectively suppress the occurrence of stains on the glass surface It relates to a cleaning solution composition.

In general, a flat panel display (FPD) such as an organic light emitting diode (OLED), a plasma display panel (PDP), a liquid crystal display panel (LCD), etc. is manufactured by performing various processes on a glass substrate.

For example, organic light emitting diodes (OLEDs) are attracting attention as next-generation display devices because they have a wide viewing angle, excellent contrast, and fast response speed.

In general, an organic light emitting display device has a stacked structure in which a light emitting layer is inserted between an anode and a cathode so that a color can be realized by recombination of holes and electrons injected from an anode and a cathode in the light emitting layer to emit light. However, since it is difficult to obtain high-efficiency light emission with this structure, an intermediate layer containing organic or inorganic materials such as an electron injection layer, an electron transport layer, a hole transport layer and a hole injection layer is selectively inserted between each electrode and the light emitting layer. are doing

Flat panel displays including OLED are generally manufactured through processes such as a pattern forming process, a thin film deposition process, an encapsulation process, a chamfering process, and a module assembly process. Contaminants such as organic or inorganic particles adsorbed on the surface of the glass substrate during the manufacturing process through the above process greatly affect the performance and yield of the finished product. It is necessary to reduce contamination as much as possible by washing. Therefore, a lot of research has been done on the cleaning solution required between each process.

For example, Korean Patent Application No. 10-2010-0090847 discloses a composition for cleaning glass substrates including a fluorine-based compound, a water-soluble organic solvent, a carboxylic acid-based copolymer, and water, and additionally organic phosphoric acid. However, the composition has a problem of staining due to corrosion on the glass surface during the OLED manufacturing process as a polishing debris cleaner of SiO ₂ component, and organic phosphoric acid used as an additional component has a problem of wastewater treatment due to eutrophication of the phosphorus compound.

In particular, it is urgent to develop a cleaning composition that does not cause stains on the glass substrate because poor staining of the glass substrate in the OLED having a bottom light emitting structure has a weak effect on the luminance.

An object of the present invention is to provide a cleaning solution composition that does not cause stains while effectively removing glass particles generated in the glass cutting (chamfering) process of a substrate manufacturing process for a display device.

The present invention in order to solve the above technical problem,

It provides a cleaning liquid composition for a glass substrate, comprising a fluorinated compound, a polyhydric alcohol, and water, wherein the polyhydric alcohol includes a first polyhydric alcohol having an unsaturated bond and a second polyhydric alcohol not having an unsaturated bond.

The cleaning liquid composition of the present invention has excellent cleaning power against glass particles generated in the glass cutting (chamfering) process and can effectively suppress stains on the glass surface. It can be usefully used in manufacturing.

1 is a flowchart schematically illustrating a glass etch rate measurement experiment process according to Experimental Example 1. Referring to FIG.
2 is an SEM image of the glass surface before cleaning.
3 is an SEM image of a glass surface cleaned using the cleaning solution of Example 4. FIG.
4 is an SEM image of a glass surface cleaned using the cleaning solution of Comparative Example 2.
The left side of FIG. 5 is an SEM image of the OLED TFT substrate before cleaning, and the right side is a 130 times magnified image of the left image.
6 is a SEM image of the OLED TFT substrate cleaned using the cleaning solution of Example 4.

Hereinafter, the present invention will be described in detail. The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

According to the present invention, a cleaning liquid for glass substrates comprising a fluorinated compound, a polyhydric alcohol, and water, wherein the polyhydric alcohol includes a first polyhydric alcohol having an unsaturated bond and a second polyhydric alcohol not having an unsaturated bond. A composition is provided.

According to one embodiment, the cleaning solution composition may include 0.1 to 30 parts by weight of the fluorinated compound and 1 to 60 parts by weight of the polyhydric alcohol.

The fluoride compound effectively removes glass particles generated in the chamfering (glass cutting) process through micro-etching of the glass surface.

The fluorinated compound is ammonium bifluoride (NH ₄ HF ₂ ), hydrofluoric acid (HF), ammonium fluoride (NH ₄ F), tetramethyl ammonium fluoride ((CH ₃ ) ₄ NF), tetraethyl ammonium fluoride ((CH ₃ CH ₂ ) ₄ NF), may be selected from the group consisting of fluoroboric acid and fluorobenzene, but is not limited thereto.

The content of the fluorinated compound may be 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the total weight of the composition. If the content is less than 0.1 parts by weight, it may not be possible to expect an increase in the solubility for contaminants due to the glass component of the cleaning composition, and if it exceeds 30 parts by weight, a problem of changing the surface smoothness of the glass substrate may occur due to excessive glass etching effect. can

The polyhydric alcohol serves to suppress damage to the glass surface and defective stains that may occur during micro-etching of the glass surface using a fluorinated compound. The content of the polyhydric alcohol may be 1 to 60 parts by weight based on 100 parts by weight of the total weight of the composition.

The first polyhydric alcohol may be a compound of two or more hydroxyl groups having a double bond or a triple bond, and may be a nonionic surfactant.

Preferably, it may be a polyhydric alcohol having an acetylene bond, for example, an acetylene glycol-based compound. Commercially Surfynol 104, 420, 440, 465, 485, 504, 61, DF-110D, DF-210, DF-37, DF-58, DF-75, SF-F, TG, GA, CT -111, CT-136, CT-151, PSA-204, PSA-216, PSA-336, OP-340, OP-350, 104S, and DF-110S.

The first polyhydric alcohol may be contained in an amount of 1 to 30 parts by weight, preferably 5 to 30 parts by weight, and more preferably 10 to 20 parts by weight based on 100 parts by weight of the total weight of the composition.

The second polyhydric alcohol is a compound that does not have an unsaturated bond, unlike the first polyhydric alcohol, and may be a polyhydric alcohol having 2 to 10 carbon atoms, preferably a compound having 2 or more and 10 or less hydroxyl groups.

For example, it may be selected from the group consisting of glycerol, ethylene glycol, erythritol, arabitol, ribitol, xylitol, mannitol, sorbitol, galactitol, idetol, mannose, galactose and glucose.

The second polyhydric alcohol may be contained in an amount of 1 to 40 parts by weight, preferably 5 to 40 parts by weight, and more preferably 10 to 30 parts by weight based on 100 parts by weight of the total weight of the composition.

According to one embodiment, the cleaning liquid composition of the present invention may be provided as a concentrate intended to be diluted with an appropriate amount of water before use, and in this case, each component is present in the cleaning liquid composition in an amount falling within the aforementioned appropriate range. may be included to For example, the concentrate may be used by diluting the cleaning solution composition 2 to 100 times, for example 5 to 50 times.

Even when used in dilution, the relative weight ratio of the fluorine compound and the polyhydric alcohol or the relative weight ratio of the first polyhydric alcohol and the second polyhydric alcohol may be selected within the above range. Specifically, the composition according to an embodiment of the present invention may contain 1 to 30 parts by weight and 1 to 40 parts by weight of the first polyhydric alcohol and the second polyhydric alcohol. In consideration of the glass surface damage and stain-preventing effect, the weight ratio of the first polyhydric alcohol to the second polyhydric alcohol may be 1: 0.5 to 3, preferably 1: 1 to 2. When the weight ratio is less than 1: 0.5, if the content of the second polyhydric alcohol is low, there is a risk that the glass surface protection effect may be reduced, and if it is 1: 3 or more, the viscosity in the concentrate increases, so it may not be easy to manage the cleaning liquid .

According to one embodiment, it is preferable that the cleaning liquid composition according to the present invention does not contain an organic alkali, an organic acid, or an organic phosphoric acid. Organic alkalis have insufficient cleaning power due to poor etching ability on glass particles or glass surfaces, and when used with ammonium fluoride, organic acids are undesirable because they may cause non-uniform etching on the glass surface. There is a problem with wastewater treatment.

The cleaning liquid composition according to the invention contains a significant amount of water. As the water, deionized water or ultrapure water with reduced impurities generally used for semiconductor processing may be used. For example, the water used may have a purity of 18 MΩ/cm or more, and the content of the remaining amount may be included with respect to the composition of the composition based on 100 parts by weight of the total amount of the cleaning composition.

According to one embodiment, the detergent composition according to the present invention minimizes the generation of bubbles and increases the cleaning power of the detergent, and may also optionally include a nonionic surfactant that can serve to solubilize components in the detergent that are poorly soluble in water. may be Nonionic surfactants that can be preferably used are those of low foaming, methyl or ethyl endcaps of ethylene oxide-propylene oxide-ethylene oxide copolymers, saturated or unsaturated aliphatic alcohols and aromatic alcohol ethoxylates, saturated or unsaturated ethylene oxide-propyleneoxide adducts of aliphatic alcohols and aromatic alcohols, acetylene glycol diol alkoxylates, alkyl polyglucosides having an alkyl group having 4 or less carbon atoms, and mixtures thereof. The nonionic surfactant may be contained in an amount of 0.01 to 2 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total weight of the composition. If the content of the nonionic surfactant is less than 0.01 parts by weight, the desired cleaning power may not be satisfied.

The composition according to the invention is preferred as a cleaning liquid for display substrates, in particular for OLED display substrates.

The display substrate has a generally rectangular shape and is made of a glass material. Therefore, corner cutting for four corners (corners) of the board, and short edge machining (Edge Cut) and long edge machining (Edge Cut) for the edges of the short and long sides of the board, that is, the corner and side of the board chamfering for chamfering is performed.

The cleaning solution composition of the present invention having the above composition can effectively remove the glass particles generated in the glass cutting (chamfering) process and improve the OLED stain defect problem that occurs during the process. is preferable to

The composition for cleaning a glass substrate according to the present invention can be prepared by a conventionally known method, and it is preferable to have a purity for a semiconductor process. The cleaning method to which the composition for cleaning glass substrates according to the present invention is applied is not particularly limited, and it can be applied to methods such as immersion cleaning method, shaking cleaning method, ultrasonic cleaning method, shower/spray cleaning method, puddle cleaning method, brush cleaning method, stirring cleaning method, etc. In the present invention, an immersion cleaning method or an ultrasonic cleaning method is particularly preferable.

Hereinafter, embodiments of the present invention will be described in more detail so that those of ordinary skill in the art can easily carry out the present invention. However, these Examples only illustrate the present invention, and the content of the present invention is not limited to the following Examples.

<Examples 1 to 6 and Comparative Examples 1 to 3> Preparation of cleaning solution composition

Compositions of Examples 1 to 9 and Comparative Examples 1 to 3 according to the present invention were prepared by mixing each component at the component content shown in Table 1 below. The content of each component is indicated in parentheses and is in wt% unless otherwise specified. The remaining amount of deionized water was added to bring the total weight of the composition to 100%.

division 1st polyhydric alcohol Dissension
compound Second polyhydric alcohol organic solvent polymer organic phosphoric acid Example 1 Surfynol
(16) ABF
(4) glycerol
(20) - - - Example 2 Surfynol
(16) ABF
(6) glycerol
(20) - - - Example 3 Surfynol
(16) ABF
(8) glycerol
(20) - - - Example 4 Surfynol
(16) ABF
(12) glycerol
(20) - - - Example 5 Surfynol
(16) ABF
(16) glycerol
(20) - - - Example 6 Surfynol
(16) ABF
(16) glycerol
(30) - - - Example 7 Surfynol
(16) ABF
(16) ethylene glycol
(30) - - - Example 8 Surfynol
(16) ABF
(16) xylitol
(30) - - - Example 9 Surfynol
(16) ABF
(16) sorbitol
(30) - - - Comparative Example 1 Surfynol
(16) ABF
(8) - MEA
(14) - - Comparative Example 2 Surfynol
(16) ABF
(16) - - - - Comparative Example 3 - ABF
(One) - MTG
(One) PAA
(One) HEDP
(One)

The abbreviations used in the table above are as follows.

Surfynol: Surfynol 465, Acetylene Glycol

ABF: Ammonium Bifluoride (NH ₄ HF ₂ )

MEA: Monoethanolamine

MTG: Triethyleneglycol monoethyl ether

PAA: Polyacrylic acid: HS-DISPERSANT 5801 (Sannovco Korea)

HEDP: 1-Hydroxyethane-1,1-diphosphonic acid

< Experimental example 1 to 2> Glass by cleaning solution etching Rate and time to spotting

The compositions of Examples 1 to 9 and Comparative Examples 1 and 2 were further diluted 20-fold, and Comparative Example 3 was used without further dilution.

As shown in FIG. 1, a specimen having a photoresist piece attached to it was prepared on a glass substrate. 2 is an SEM image of the glass surface before cleaning.

The cleaning solution was sprayed on the specimen for 1 minute at room temperature to measure the step according to the etching as shown in FIG. 1 , and the staining time was measured.

Experimental results are shown in Table 2, Figures 3 and 4 below. 3 is an SEM image of the glass surface after cleaning with the cleaning solution of Example 4, and FIG. 4 is an SEM image of the glass surface after cleaning with the cleaning solution of Comparative Example 2.

<Experimental Example 3> Evaluation of cleaning power of glass by cleaning solution

The compositions of Examples 1 to 9 and Comparative Examples 1 and 2 were further diluted 20-fold, and Comparative Example 3 was used without further dilution.

After contaminating the prepared OLED TFT substrate with glass powder (Si particles) <100 μm) by a spin coater method, it was fired in an oven at 200° C. for 30 minutes. The fired OLED TFT substrate was cleaned at room temperature for 1 minute and the surface was observed. 5 is a SEM image of the OLED TFT substrate before cleaning, and the right side is a 130 times magnified image of the left side.

The experimental results are shown in Table 2 and FIG. 6 . 6 is an SEM image of the OLED TFT substrate cleaned using the cleaning solution of Example 4.

division Glass etch rate
(Å/s) Glass stain generation time
(minute) Si Particle Removal Example 1 1.45 10 minutes ○ Example 2 2.00 10 minutes ◎ Example 3 2.88 10 minutes ◎ Example 4 3.78 8 minutes ◎ Example 5 7.96 5 minutes ◎ Example 6 5.21 7 minutes ◎ Example 7 5.8 6.5 minutes ◎ Example 8 6.4 6 minutes ◎ Example 9 6.3 6 minutes ◎ Comparative Example 1 0.12 more than 10 minutes △ Comparative Example 2 11.10 1 min ◎ Comparative Example 3 12.40 1 min ◎

◎ : completely removed

○ : Mostly removed

△: slightly removed

X : Cannot be removed

As can be seen from Table 2 and related drawings, in the case of the cleaning agents of Examples 1 to 9 according to the present invention, the glass substrate etching rate is less than 10 Å/s, the glass stain generation time is 5 minutes or more, and the Si particle removal performance It can be seen that this is excellent.

On the other hand, in the case of Comparative Example 1, although the glass etching rate or the glass stain generation time is slow, the Si particle removal performance is poor, and in Comparative Examples 2 and 3, the Si particle removal performance is excellent, but the glass etching rate and the stain generation time are It is not desirable because it is fast.

Therefore, it can be seen that the cleaning liquid composition according to the present invention is a cleaning agent capable of effectively suppressing stains on a glass surface while having excellent cleaning power of glass particles.

As the specific part of the present invention has been described in detail above, for those of ordinary skill in the art, this specific description is only a preferred embodiment, and the scope of the present invention is not limited thereby. It will be obvious. Accordingly, it is intended that the actual scope of the present invention be defined by the appended claims and their equivalents.

Claims (9)

It contains a fluorinated compound, a polyhydric alcohol, and water, and the polyhydric alcohol includes a first polyhydric alcohol having an unsaturated bond and a second polyhydric alcohol not having an unsaturated bond,
With respect to 100 parts by weight of the total composition, the first polyhydric alcohol is 5 to 30 parts by weight, and the second polyhydric alcohol is 5 to 40 parts by weight, a cleaning solution composition for a glass substrate. According to claim 1,
A cleaning liquid composition for a glass substrate that does not contain organic alkali, organic acid or organic phosphoric acid. According to claim 1,
A cleaning solution composition for a glass substrate comprising 0.1 to 30 parts by weight of a fluorinated compound and 1 to 60 parts by weight of a polyhydric alcohol. According to claim 1,
The first polyhydric alcohol is a polyhydric alcohol having an acetylene bond, the cleaning liquid composition for a glass substrate. According to claim 1,
The second polyhydric alcohol is a polyhydric alcohol having 2 to 10 carbon atoms and 2 to 10 hydroxyl groups. A cleaning solution composition for a glass substrate. delete According to claim 1,
A cleaning solution composition for a glass substrate in which the weight ratio of the first polyhydric alcohol to the second polyhydric alcohol in the composition is 1: 0.5 to 3. According to claim 1,
The fluorinated compound is ammonium bifluoride (NH ₄ HF ₂ ), hydrofluoric acid (HF), ammonium fluoride (NH ₄ F), tetramethylammonium fluoride ((CH ₃ ) ₄ NF), tetraethylammonium fluoride ((CH ₃ CH ₂ ) ₄ NF), a cleaning solution composition for a glass substrate selected from the group consisting of fluoroboric acid and fluorobenzene. The cleaning solution composition according to any one of claims 1 to 5, 7 and 8, which is used in a cleaning process after chamfering of a display substrate.

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