JP2020532642A - A cleaning composition for cleaning glass articles and a method for cleaning a glass substrate using the same. - Google Patents

Abstract

A cleaning composition for cleaning a glass article and a method for cleaning a glass substrate using the same are provided. The cleaning composition comprises an alkali in the range of about 1% by mass to about 20% by mass, a surfactant in the range of about 0.1% by mass to about 10% by mass, and about 10% by mass, based on 100% by mass of the cleaning composition. A chelating agent in the range of 0.1% by mass to about 10% by mass, an organic solvent in the range of about 0.1% by mass to about 10% by mass, and a dispersion stable in the range of about 0.1% by mass to about 10% by mass. The dispersion stabilizer contains an agent and has the structure of the following formula (1). The cleaning composition can be used to effectively remove particle and organic pollutants on the surface of the glass substrate. [Chemical 1]

Description

priority

This application is under Article 119 of the US Code, Vol. 35, No. 10-2017-0109487, Korean Patent Application No. 10-2017-0109487, filed on August 29, 2017, on which its contents are relied upon and cited in its entirety. It claims the benefits of priority.

One or more embodiments relate to a cleaning composition for cleaning a glass article and a method of cleaning the glass substrate using the cleaning composition, and more particularly, particle contaminants and organic contaminants on the surface of the glass substrate. The present invention relates to a cleaning composition for cleaning a glass article, which can be effectively removed, and a method for cleaning a glass substrate using the same.

Various cleaning processes are used, including physical and chemical methods, to manufacture glass substrates used in flat panel displays and the like. In order to remove particle and organic pollutants on the glass substrate, a cleaning composition with further improved cleaning capacity is still needed.

One or more embodiments include a cleaning composition for cleaning glass articles and a glass substrate using the same, which can effectively remove particle and organic pollutants on the surface of the glass substrate. Includes cleaning methods.

Additional embodiments are described, in part, in the description below, and some will be apparent from the description or will be apparent by the implementation of the embodiments presented.

According to one or more embodiments, the cleaning composition for cleaning the glass article is an alkali in the range of about 1% to about 20% by weight, about 0% by weight, based on 100% by weight of the cleaning composition. .1% by weight to about 10% by weight surfactant, about 0.1% to about 10% by weight chelating agent, about 0.1% to about 10% by weight organic solvent, And a dispersion stabilizer in the range of about 0.1% by mass to about 10% by mass, the dispersion stabilizer has the structure of the following formula (1).

(Where "n" is 5,000 integer from 10, ^{"M +"} is an alkali metal or alkaline earth metal cation, "R ^-" is O ^- or COO ^- with is there)

In some embodiments, the cleaning composition is an alkali in the range of about 5% to about 20% by weight, in the range of about 2% to about 5% by weight, based on 100% by weight of the cleaning composition. Surfactants, chelating agents in the range of about 3% to about 8% by weight, organic solvents in the range of about 3% to about 8% by weight, and about 0.1% by weight to about 3% by weight. Contains dispersion stabilizer.

In this case, the dispersion stabilizer may have the structure of the following formula (1-1).

(In the formula, "n" is an integer from 50 to 1,000 and "M" is sodium or potassium)

The surfactants include polyoxyalkylene alkylphenol ether, polyoxyalkylenearylphenol ether, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene alkylamine, sorbitan fatty acid ester, polyalkyl glucoside, and alkyl alcohol. It may contain at least one selected from the group consisting of amines and aryl alcohol amines.

In some embodiments, the surfactant may have the structure of formula (2) below.

(In the formula, the portion represented by "CS" is a linear hydrocarbon having 10 to 14 carbon atoms, and the portion represented by "EOS" is ethylene oxide, which is represented by "POS". The moieties are propylene oxide, where EOS and POS each form blocks or alternate with each other, a: b from 7: 3 to 9.5: 0.5).

Specifically, the portion represented by CS may be a linear hydrocarbon having 12 carbons, and a: b is from about 8.5: 1.5 to about 9.3: 0.7. Sometimes.

The alkalis are sodium hydroxide (NaOH), potassium hydroxide (KOH), magnesium hydroxide (Mg (OH) ₂ ), calcium hydroxide (Ca (OH) ₂ ), ammonia (NH ₃ ), and hydroxide. At least selected from the group consisting of tetraethylammonium, tetramethylammonium hydroxide, aminoethoxyethanol, triethanolamine, diethanolamine, monoethanolamine, ammonium hydroxide, tetrapropylammonium hydroxide, butylammonium hydroxide, and choline hydroxide. May include one.

The chelating agent includes potassium pyrophosphate, calcium carbonate, sodium carbonate, sodium silicate, sodium gluconate, citric acid, salicylic acid, malonic acid, succinic acid, glutaric acid, pyrophosphate, polyphosphate, benzotriazole, sorbitol, glucose, etc. It may contain at least one selected from the group consisting of benzotriazole carboxylate and triltriazole. In some embodiments, the chelating agent is nitrilo-2,2', 2 "-acetic acid (NTA), diethylenetriaminepentacetic acid (DTPA), ethylenediaminetrilotetraacetic acid (EDTA), or a metal salt thereof. May include, the metal salt of which may include a potassium salt or a sodium salt, in which case the chelating agent ranges from about 2% by weight to about 7% by weight based on 100% by weight of the cleaning composition. NTA metal salts and DTPA metal salts in the range of about 1% to about 6% by weight may be included.

In some embodiments, the chelate composition may further comprise a bleach, phase stabilizer, or buffer.

According to one or more embodiments, the cleaning composition for cleaning the glass article is an alkali in the range of about 5% to about 20% by weight, about 2% by weight, based on 100% by weight of the cleaning composition. Surfactants ranging from% to about 5% by weight, chelating agents ranging from about 3% to about 8% by weight, organic solvents ranging from about 3% to about 8% by weight, and about 0.1% by weight. It contains a dispersion stabilizer in the range of% to about 3% by mass, and the surfactant has the structure of the above formula (2).

According to one or more embodiments, the method of cleaning the glass substrate is the step of supplying the cleaning composition onto the glass substrate; using a friction cleaning unit, the cleaning composition is brought into contact with the glass substrate. It comprises a step of cleaning the surface of the glass substrate; and a step of removing the cleaning composition from the glass substrate. The cleaning composition contains an alkali in the range of about 5% by mass to about 20% by mass, a surfactant in the range of about 2% by mass to about 5% by mass, and about 3% by mass, based on 100% by mass of the cleaning composition. May contain chelating agents in the range of% to about 8% by weight, organic solvents in the range of about 3% to about 8% by weight, and dispersion stabilizers in the range of about 0.1% to about 3% by weight. ..

The dispersion stabilizer may have the structure of the above formula (1). In addition, the surfactant may have the structure of the above formula (2).

When the cleaning composition is used, particle and organic pollutants on the surface of the glass substrate will be effectively removed.

These and / or other aspects will become apparent and more easily recognized from the following description of embodiments when interpreted with the accompanying drawings.
A graph showing changes in the contact angle before and after cleaning using the cleaning compositions of Example 1, Comparative Example 1, and Comparative Example 2. A graph showing the average glass particle removal rate when cleaning is performed by using the cleaning compositions of Example 1, Comparative Example 1, and Comparative Example 2. A graph showing changes over time in the number of particles before and after application of the cleaning composition of Example 1 and after reapplication of the conventional cleaning composition. Graph showing continuous change in the number of particles during application of the cleaning composition of Example 1 (indicated by the shaded area).

Here, we will refer in detail to embodiments where similar reference numbers refer to elements as well, examples of which are shown in the accompanying drawings throughout. In this regard, the embodiments may have different embodiments and should not be construed as being limited to the description set forth herein. Accordingly, embodiments are only described below by reference to the drawings to illustrate aspects of this description. As used herein, the term "and / or" includes any and all combinations of one or more of the related listed items.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, this disclosure may be embodied in many different forms and should not be construed as limited to the embodiments described below. The embodiments will be construed as provided to fully explain the disclosure to those skilled in the art. Throughout, similar reference numbers indicate similar elements. Also, the various elements and areas in the drawings are shown as schematics. Therefore, the present disclosure is not limited by the relative size or distance shown in the accompanying drawings.

The terminology used herein is for the sole purpose of describing a particular embodiment and is not intended to limit this disclosure. As used herein, nouns are intended to refer to multiple objects unless the context explicitly indicates otherwise. Terms such as "consisting of", "including", and "having", when used herein, refer to the existence of the features, integers, processes, operations, elements, components, or combinations thereof described in 1. It should be understood that it does not preclude the existence or addition of one or more other features, integers, processes, operations, elements, components, or combinations thereof.

Unless otherwise stated, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by those skilled in the art. Also, terms such as those defined in commonly used dictionaries should be construed as having a meaning consistent with their meaning in the context of the relevant technology and are ideal unless explicitly defined here. It should be understood that it is not interpreted in a formal or overly formal sense.

If a particular embodiment is performed differently, then the particular process sequence may differ from the order described. For example, two consecutively described processes may occur at substantially the same time or in the reverse order of the described order.

In the accompanying drawings, differences from the illustrated shapes may be predicted, for example, as a result of manufacturing techniques and / or tolerances. Therefore, embodiments should not be construed as being limited to the particular shape of the region shown herein and may include, for example, shape deviations resulting from the manufacturing process. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed components. Further, the term "board" used herein may refer to the board itself, or a laminated structure including the board and a layer or film formed on the board. Further, the term "board surface" used herein may refer to an exposed surface of the substrate itself or an outer surface of a layer or film formed on the substrate.

One embodiment provides a cleaning composition comprising an alkali, a surfactant, a chelating agent, an organic solvent, and a dispersion stabilizer. The cleaning composition comprises an alkali in the range of about 1% by mass to about 20% by mass, a surfactant in the range of about 0.1% by mass to about 10% by mass, and about 10% by mass, based on 100% by mass of the cleaning composition. A chelating agent in the range of 0.1% by mass to about 10% by mass, an organic solvent in the range of about 0.1% by mass to about 10% by mass, and a dispersion stable in the range of about 0.1% by mass to about 10% by mass. May contain agents. The rest of the cleaning composition may include water, such as deionized water (DIW).

In some embodiments, the cleaning composition is an alkali in the range of about 5% to about 20% by weight, in the range of about 2% to about 5% by weight, based on 100% by weight of the cleaning composition. Surfactants, chelating agents in the range of about 3% to about 8% by weight, organic solvents in the range of about 3% to about 8% by weight, and about 0.1% by weight to about 3% by weight. Contains dispersion stabilizer.

[Dispersion stabilizer]
The dispersion stabilizer may have the structure of the following formula (1).

(Where "n" is 5,000 integer from 10, ^{"M +"} is an alkali metal alkaline earth metal cation, "R ^-" is O ^- or COO ^- is )

In some embodiments, the dispersion stabilizer may have the structure of formula (1-1) below.

(In the formula, "n" is an integer from 50 to 1,000 and "M" is sodium or potassium)

More specifically, the dispersion stabilizer may contain at least one of the structures listed in formula (1-2) below.

It is presumed that the dispersion stabilizer removes the particles by adhering to the particles at the −R ⁻ M ⁺ site. That is, it is assumed that the −R ⁻ M ⁺ site will adhere to the particles and that the particles will be easily removed from the surface of the glass article. However, this disclosure is not limited by this theory.

When cleaning compositions are used to clean glass articles, too low a dispersion stabilizer content lacks the ability to prevent particles from reattaching to glass articles such as glass substrates. Sometimes. On the other hand, too much dispersion stabilizer content would be economically inconvenient.

[Surfactant]
Surfactants include polyoxyalkylene alkylphenol ethers, polyoxyalkylenearylphenol ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene alkylamines, sorbitan fatty acid esters, polyalkyl glucosides, alkyl alcohol amines, and It may contain at least one selected from the group consisting of aryl alcohol amines.

In some embodiments, the surfactant may have the structure of formula (2) below.

(In the formula, the portion represented by "CS" is a linear hydrocarbon having 10 to 14 carbon atoms, the portion represented by "EOS" is ethylene oxide, and the portion represented by "POS". Is a propylene oxide, each of EOS and POS forming blocks or alternating with each other, a: b from 7: 3 to 9.5: 0.5)

Here, the ethylene oxide portion represents a repeating unit derived from ethylene oxide, and the propylene oxide portion represents a repeating unit derived from propylene oxide.

In the surfactant of formula (2), CS may be any one of decyl, undecylic, lauryl, tridecylic, and tetradecyl. In some embodiments, in the surfactant of formula (2), CS may have 11 to 13 carbon atoms, which is, for example, a linear hydrocarbon having 12 carbon atoms. There is.

In formula (2), EOS and POS are represented as forming their respective blocks, but EOS and POS do not need to form their respective blocks. _{Thus, - (EOS) 2 - (} POS) - (EOS) 5 - (POS) 2 -, - (EOS) - (POS) 2 - (EOS) 6 - (POS) -, and - _{(EOS) 9} - With respect to the-(EOS) _a- (POS) _b symbol in formula (2) such as (POS)-(EOS)-(POS)-, one or more POS may be placed between two EOS. One or more EOS may be placed between two POS.

Here, "a" and "b" represent the number of corresponding repeating units, which may form a predetermined ratio, where a: b is, for example, 7: 3 to 9.5: 0. It can be .5, or 8.5: 1.5 to 9.3: 0.7. If a: b is too small (ie, the ratio of POS to EOS to POS is too high), the phase inversion temperature (PIT) may decrease and therefore the detergency may deteriorate. On the other hand, if a: b is too large (ie, the ratio of POS to EOS to POS is too low), excessive bubbles may be generated during the cleaning process.

[alkali]
The alkali is, for example, but not limited to, sodium hydroxide (NaOH), potassium hydroxide (KOH), magnesium hydroxide (Mg (OH) ₂ ), calcium hydroxide (Ca (OH) ₂ ), ammonia ( Consists of NH ₃ ), tetraethylammonium hydroxide, tetramethylammonium hydroxide, aminoethoxyethanol, triethanolamine, diethanolamine, monoethanolamine, ammonium hydroxide, tetrapropylammonium hydroxide, butylammonium hydroxide, and choline hydroxide. It may contain at least one selected from the group.

The hydroxy groups of the alkali may break down the organic chains for efficient removal. Also, when the glass particles should be removed, the hydroxy group finely etches the contact area between the glass particles and the glass substrate so that the glass particles are easily separated (ie, silicic acid in the silicon dioxide state). It may change to a state). Therefore, if the alkali content is too low, the detergency may be insufficient. On the other hand, too much alkali content would be harmful to the environment.

[Chelating agent]
The chelating agent will remove metallic materials among the contaminants; however, it is not limited to this disclosure.

Chelating agents include potassium pyrophosphate, calcium carbonate, sodium carbonate, sodium silicate, sodium gluconate, citric acid, salicylic acid, malonic acid, succinic acid, glutaric acid, pyrophosphate, polyphosphate, benzotriazole, sorbitol, glucose, and carboxylic acid. It may contain at least one selected from the group consisting of benzotriazole acid and triltriazole.

In some embodiments, the chelating agent is diethylenetriaminetetraacetic acid (DTPA) (CAS number 67-43-6), nitrilo-2,2', 2 "-triacetic acid (NTA) (CAS number 139-13-). 9), ethylenediaminetetraacetic acid (EDTA) (CAS No. 60-00-4), or a metal salt thereof, which may contain a potassium salt or a sodium salt.

The chelating agent may be used alone or together. For example, a mixture of about 2% to about 7% by weight NTA and about 1% to about 6% by weight DTPA may be used as the chelating agent with respect to 100% by weight of the cleaning composition.

If the chelating agent content is too low, metal contaminants may be removed inadequately. On the other hand, if the chelating agent content is too high, the cleaning phase will be unstable, the manufacturing cost will increase, the TN value will increase, and therefore there may be environmental problems.

[Organic solvent]
Organic solvents such as alcohols, alcohol amines, ketones, esters, and amides may be used as organic solvents; however, the present disclosure is not limited thereto.

Alcohols used as organic solvents are ethanol, propanol, butanol, hexanol, heptanol, octanol, decanol, isopropanol, isohexanol, isooctanol, isodecanol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol methyl ether, diethylene glycol methyl ether. , Triethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, triethylene glycol ethyl ether, ethylene glycol monopropyl ether, diethylene glycol monopropyl ether, triethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, tri Contains at least one selected from the group consisting of ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol dibutyl ether, triethylene glycol dibutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, and triethylene glycol monohexyl ether. Sometimes.

Alcohol amines used as organic solvents consist of the group consisting of monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), N-ethyldiethanolamine, N, N-diethylethanolamine, and triisopropanolamine. It may contain at least one selected.

The ketone used as the organic solvent is at least one selected from the group consisting of acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, and cyclohexanone. May include one.

The esters used as organic solvents are ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate. , Methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, methylpropyl 2-oxypropionate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2-methyl Ethyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-methoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoic acid Includes at least one selected from the group consisting of methyl, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl carbitol acetate, butyl carbitol acetate, and γ-butyrolactone. Sometimes.

The amide used as the organic solvent may contain at least one selected from the group consisting of N, N-dimethylformamide, N-methylpyrrolidone, and N, N-dimethylacetamide.

In some embodiments, the organic solvent may include a mixture of TEA and MEA. In this case, the mass ratio of TEA to MEA may be from about 7: 3 to about 9: 1. If the mass ratio of TEA to MEA is out of the above range, the cleaning composition may discolor if left for a long period of time.

[Other ingredients]
According to embodiments, the cleaning composition may further contain phase stabilizers, buffers, and bleach in addition to the ingredients.

(1) Phase stabilizer A fatty acid or a metal salt thereof may be used as a phase stabilizer. For example, sodium or potassium salts of fatty acids having 5 to 15 carbon atoms may be used. However, the present disclosure is not limited thereto.

The content of the phase stabilizer may be in the range of about 2% by weight to about 8% by weight with respect to 100% by weight of the cleaning composition. If the content of the phase stabilizer is too low, the phase stabilizer may not act to prevent phase separation. Further, if the content of the phase stabilizer is too large, the detergency of the cleaning composition may be weakened.

(2) Bleach For example, NaOCl may be used as a bleach; however, the present disclosure is not limited thereto.

The content of bleach may range from about 0.1% to about 1% by weight with respect to 100% by weight of the cleaning composition. If the content of bleach is too low, the efficiency of removing organic substances may decrease. Also, if the content of bleach is too high, the amount of active oxygen may increase and therefore the detergency may be weakened.

(3) buffering agents such as buffering agents, K ₂ CO ₃ are sometimes used; however, the present disclosure is not limited thereto.

The content of the buffer may be in the range of about 0.2% by weight to about 2% by weight with respect to 100% by weight of the cleaning composition. If the content of the buffer is too low, the pH of the cleaning composition may become unstable. Also, if the content of the buffer is too high, it may be out of the pH range suitable for cleaning.

Hereinafter, the embodiments and effects of the present disclosure will be described in more detail with reference to specific embodiments and comparative examples; however, these embodiments are solely for the purpose of providing a clearer understanding of the present disclosure. There is no intention to limit the range.

[Example 1-Production of cleaning composition]
A cleaning composition having the following composition was produced (% by mass is based on the total mass of the cleaning composition).

(1) 10% by mass alkali (5% by mass KOH5, 5% by mass NaOH)
(2) 3 wt% of a surfactant _{(C12- (EOS) 9 - (} POS) 1)
(3) 5% by mass chelating agent (2% by mass calcium carbonate, 3% by mass sodium carbonate)
(4) 5% by mass organic solvent (2% by mass diethylene glycol, 3% by mass triethylene glycol)
(5) 1% by mass dispersion stabilizer (in formula (1), n = 150 and -COONa are used as -R ^- M ⁺ )
(6) The remaining amount of deionized water

After measuring the mass of each component and providing the above composition, these components were mixed at room temperature to prepare a washing composition.

[Comparative Example 1 and Comparative Example 2]
Performance was compared by using two commercially available cleaning compositions (LGL200, Parker225X) currently used for cleaning glass substrates.

[Organic substance removability test 1]
First, in order to produce a glass substrate sample having a surface contaminated with an organic substance, an adhesive tape was attached to the surface of the glass substrate sample (100 mm × 100 mm), and after 1 hour, the surface of the glass substrate sample was coated. The adhesive tape was peeled off by applying a vertical force. In this way, 60 glass substrate samples having a surface contaminated with an organic adhesive component were prepared.

Then, by using the cleaning composition of Example 1, the contact angles of 20 glass substrate samples before and after cleaning were measured. For each glass substrate sample, the contact angle of water droplets was measured, the glass substrate sample was washed with the cleaning composition, and then the contact angle was measured again. The average contact angle before cleaning was calculated, and the average contact angle after cleaning was calculated.

Further, by using the cleaning composition of Comparative Example 1 for the other 20 glass substrate samples and further using the cleaning composition of Comparative Example 2 for the other 20 glass substrate samples, before / after cleaning. The average contact angle was calculated in the same way.

FIG. 1 is a graph showing changes in the contact angle before and after cleaning using the cleaning compositions of Example 1, Comparative Example 1, and Comparative Example 2.

Referring to FIG. 1, the average contact angles before cleaning with the cleaning compositions of Comparative Examples 1 and 2 were 69 ° and 76 °, respectively, and the average contact angles after cleaning were 30 ° and 30 °, respectively. It was 29 °. That is, the degree of decrease in the average contact angle before and after cleaning was 39 ° and 47 °, respectively.

On the other hand, the average contact angle before cleaning using the cleaning composition of Example 1 was 75 °, and the average contact angle after cleaning was 21 °. That is, the degree of decrease in the average contact angle before and after cleaning was 54 °.

That is, since the degree of change in the average contact angle was remarkably large, it can be seen that the cleaning composition of Example 1 showed excellent organic substance removability.

[Glass particle removability test 1]
First, in order to produce a glass substrate sample having a surface contaminated with glass particles, fine glass particles were applied to the surface of the glass substrate sample (100 mm × 100 mm). For this purpose, the fine glass particles were dispersed in ethanol and then coated on the surface of the glass substrate sample by a rotary coating method. After that, it was dried to sufficiently remove ethanol. In this way, 60 glass substrate samples having a surface contaminated with glass particles were prepared.

Then, by using the cleaning composition of Example 1, the glass particle removal rate of 20 glass substrate samples before / after cleaning was measured. The glass particle removal rate was measured for 9 points of each glass substrate sample, and the average value was defined as the glass particle removal rate of the glass substrate sample. The glass particle removal rate was measured for each of the 20 glass substrate samples, and then the average value was defined as the glass particle removal rate of the cleaning composition of Example 1.

Further, by using the cleaning composition of Comparative Example 1 for the other 20 glass substrate samples and using the cleaning composition of Comparative Example 2 for the remaining 20 glass substrate samples, before / after cleaning. The average glass particle removal rate was calculated in the same way.

FIG. 2 is a graph showing the average glass particle removal rate when cleaning is performed by using the cleaning compositions of Example 1, Comparative Example 1, and Comparative Example 2.

Referring to FIG. 2, when the cleaning compositions of Comparative Examples 1 and 2 were used, the glass particle removal rates were 8.60% (Comparative Example 1) and 14.77% (Comparative Example 2).

On the other hand, when the cleaning composition of Example 1 was used, the glass particle removal rate was 17.07%.

Therefore, since the glass particle removal rate was relatively high, it can be seen that the cleaning composition of Example 1 showed excellent glass particle removal possibility.

[Line application test 1]
The change in the number of particles when the cleaning composition of Example 1 was applied to the production line was measured. That is shown in FIG. FIG. 3 shows the time course of the number of particles before and after the application of the cleaning composition of Example 1 and after the reapplication of the conventional cleaning composition. Here, the number of particles refers to the number of particles having a diameter of 0.3 micrometer (μm) or more.

Referring to FIG. 3, the average number of particles when the cleaning composition of Example 1 is applied is compared with the average number of particles when the cleaning composition of Comparative Example 1 is applied (indicated by a horizontal broken line). The numbers (indicated by the horizontal dashed line) were reduced by about 16%.

Therefore, it will be found that the number of particles will be effectively reduced in the actual process when the cleaning composition is applied.

[Line application test 2]
The change in the number of particles when the cleaning composition of Example 1 was applied to the production line was continuously measured. That is shown in FIG. FIG. 4 shows the continuous change over time in the number of particles during application (shadow portion) of the cleaning composition of Example 1.

In FIG. 4, the continuous graph shows the result of the 100% inspection of the number of particles in all articles, and the square dots represent the result of the sample inspection of the number of particles in the article at the corresponding time points. Since the results of the sample inspection and the results of the 100% inspection during the period of applying the cleaning composition of Example 1 (shaded areas) show substantially the same tendency, the inspection of the number of particles is performed substantially accurately. It is judged that it is.

In addition, as a result of calculating the total average, from the result of sample inspection (square dots), the number of particles when the cleaning composition of Example 1 was used was the same as when the conventional cleaning composition was used. In comparison, it can be seen that there was a decrease of about 15%. In addition, from the result of 100% inspection (black line), the number of particles when the cleaning composition of Example 1 was used was reduced by about 17% as compared with the case where the conventional cleaning composition was used. I understand.

Therefore, it will be found that when the cleaning composition is applied, the number of particles will also be effectively reduced in the actual process.

[Comparative Example 3]
A cleaning composition was produced in the same manner as in Example 1 except that a material having the structure of the following formula (3) was used as the dispersion stabilizer.

[Example 2]
A cleaning composition was produced in the same manner as in Example 1 except that a material having the structure of the following formula (1-3) was used as the dispersion stabilizer.

[Glass particle removability test 2]
The removability test of glass particles was carried out by using the cleaning compositions of Example 1, Example 2, and Comparative Example 3. The test method was the same as in the glass particle removability test 1.

As a result, when the cleaning composition of Comparative Example 3 was used, the glass particle removal rate was 11.91%, whereas when the cleaning composition of Example 1 was used, the glass particle removal rate was 18. It was 11%, and it can be seen that the glass particle removal rate was 16.53% when the cleaning composition of Example 2 was used.

Therefore, it can be seen that it is convenient to use the dispersion stabilizers of the present disclosure in which the -COO ^- Na ⁺ group is directly attached to the main chain to remove the glass particles. It will also be seen that the dispersion stabilizer of Example 1 has a higher glass particle removal rate than the dispersion stabilizer of Example 2.

[Example 3]
A cleaning composition was produced in the same manner as in Example 1, except that a: b in the surfactant was adjusted to 7.5: 2.5.

[Example 4]
A cleaning composition was produced in the same manner as in Example 1, except that a: b in the surfactant was adjusted to 7: 3.

[Comparative Example 4]
A cleaning composition was produced in the same manner as in Example 1, except that a: b in the surfactant was adjusted to 6.5: 3.5.

[Organic substance removal power test 2]
By using the cleaning compositions of Example 1, Example 3, Example 4, and Comparative Example 4, the change in contact angle was measured in the same manner as in the organic substance removability test 1. The measurement results are shown in Table 1 below.

With reference to Table 1, it can be seen that the contact angle reducing effect of the cleaning compositions of Examples 1, 3 and 4 is greater than the contact angle reducing effect of the cleaning compositions of Comparative Example 4. In other words, it can be seen that the organic substance removing effect of the cleaning compositions of Examples 1, 3 and 4 is larger than the organic substance removing effect of the cleaning composition of Comparative Example 4.

In addition, it can be seen that the organic substance removing effect of the cleaning composition of Example 1 is greater than the organic substance removing effect of the cleaning compositions of Examples 3 and 4.

[Example 5]
Example 1 and the chelating agent, except that 2% by weight of NTA Na salt and 3% by weight of DTPA Na salt were used instead of 2% by weight calcium carbonate and 3% by weight sodium carbonate. Similarly, a cleaning composition was produced.

[Example 6]
As a surfactant, 3 wt% of _{C12- (EOS) 9 - (POS} ) instead of _one, except using 3 mass% of polyoxymethylene ethylphenol ether, as in Example 1, A cleaning composition was produced.

[Example 7]
The cleaning composition was the same as in Example 1, except that 4% by weight TEA and 1% by weight MEA were used as the organic solvent instead of 2% by weight diethylene glycol and 3% by weight triethylene glycol. Manufactured a thing.

[Example 8]
As in Example 1, except that 2% by weight potassium pyrophosphate and 3% by weight sorbitol were used as the chelating agent instead of 2% by weight calcium carbonate and 3% by weight sodium carbonate. A cleaning composition was produced.

[Example 9]
As a surfactant, 3 wt% of C12- _(EOS) 9 - instead of _{(POS) 1,} except for using 3 wt% of poly propyl glucoside, as in Example 1, the cleaning compositions Manufactured.

Although the embodiments of the present disclosure have been described in detail above, those skilled in the art may make various changes herein without departing from their spirit and scope as defined in the following claims. Will be understood.

It should be understood that the embodiments described herein should be considered only for the purpose of explanation, not for limited purposes. Descriptions of features or embodiments within each embodiment should typically be considered available for other similar features or embodiments in other embodiments.

Although one or more embodiments have been described with reference to the drawings, various modifications of the embodiments and details may be made without departing from the spirit and scope of the present disclosure as defined in the following claims. Those skilled in the art will understand that.

Hereinafter, preferred embodiments of the present invention will be described in terms of terms.

Embodiment 1
In a cleaning composition for cleaning glass articles, with respect to 100% by mass of the cleaning composition,
Alkali in the range of about 1% by weight to about 20% by weight,
Surfactants in the range of about 0.1% by weight to about 10% by weight,
Chelating agents in the range of about 0.1% by weight to about 10% by weight,
Organic solvents in the range of about 0.1% to about 10% by weight, and dispersion stabilizers in the range of about 0.1% to about 10% by weight.
Including
The dispersion stabilizer has the structure of the following formula (1) and has a structure of the following formula (1).

Where "n" is 5,000 integer from 10, ^{"M +"} is an alkali metal or alkaline earth metal cation, "R ^-" is O ^- or COO ^- is , Cleaning composition.

Embodiment 2
The cleaning composition is based on 100% by mass of the cleaning composition.
Alkali in the range of about 5% by weight to about 20% by weight,
Surfactants in the range of about 2% by weight to about 5% by weight,
Chelating agents in the range of about 3% by weight to about 8% by weight,
Organic solvents in the range of about 3% by weight to about 8% by weight, and dispersion stabilizers in the range of about 0.1% by weight to about 3% by weight.
The cleaning composition according to the first embodiment.

Embodiment 3
The dispersion stabilizer has the structure of the following formula (1-1) and has a structure of the following formula (1-1).

The cleaning composition according to embodiment 1, wherein "n" is an integer of 50 to 1,000 and "M" is sodium or potassium.

Embodiment 4
The surfactants are polyoxyalkylene alkylphenol ether, polyoxyalkylenearylphenol ether, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene alkylamine, sorbitan fatty acid ester, polyalkyl glucoside, alkyl alcohol amine, The cleaning composition according to embodiment 1, which comprises at least one selected from the group consisting of and arylalcohol amines.

Embodiment 5
The surfactant has the structure of the following formula (2) and has a structure of the following formula (2).

In the formula, the portion represented by "CS" is a linear hydrocarbon having 10 to 14 carbon atoms, the portion represented by "EOS" is ethylene oxide, and the portion represented by "POS". Is a propylene oxide, EOS and POS each form blocks or alternate with each other, a: b from 7: 3 to 9.5: 0.5, according to embodiment 1. Composition.

Embodiment 6
In the fifth embodiment, the portion represented by CS is a linear hydrocarbon having 12 carbon atoms, and a: b is from about 8.5: 1.5 to about 9.3: 0.7. The cleaning composition described.

Embodiment 7
The alkalis are sodium hydroxide (NaOH), potassium hydroxide (KOH), magnesium hydroxide (Mg (OH) ₂ ), calcium hydroxide (Ca (OH) ₂ ), ammonia (NH ₃ ), tetraethylammonium hydroxide. , At least one selected from the group consisting of tetramethylammonium hydroxide, aminoethoxyethanol, triethanolamine, diethanolamine, monoethanolamine, ammonium hydroxide, tetrapropylammonium hydroxide, butylammonium hydroxide, and choline hydroxide. The cleaning composition according to the first embodiment.

8th Embodiment
The chelating agent
Potassium pyrophosphate, calcium carbonate, sodium carbonate, sodium silicate, sodium gluconate, citric acid, salicylic acid, malonic acid, succinic acid, glutaric acid, pyrophosphate, polyphosphate, benzotriazole, sorbitol, glucose, benzotriazole carboxylate, And at least one selected from the group consisting of triltriazole; or nitrilo-2,2', 2 "-triacetic acid (NTA), diethylenetriaminepentacetic acid (DTPA), ethylenediaminetrilotetraacetic acid (EDTA), or a metal thereof. salt;
Including
The cleaning composition according to the first embodiment, wherein the metal salt contains a potassium salt or a sodium salt.

Embodiment 9
The chelating agent is a metal salt of NTA in the range of about 2% by mass to about 7% by mass and a metal salt of DTPA in the range of about 1% by mass to about 6% by mass with respect to the cleaning composition of 100% by mass. The cleaning composition according to the eighth embodiment.

Embodiment 10
In a cleaning composition for cleaning glass articles, with respect to 100% by mass of the cleaning composition,
Alkali in the range of about 5% by weight to about 20% by weight,
Surfactants in the range of about 2% by weight to about 5% by weight,
Chelating agents in the range of about 3% by weight to about 8% by weight,
Organic solvents in the range of about 3% by weight to about 8% by weight, and dispersion stabilizers in the range of about 0.1% by weight to about 3% by weight.
Including
The surfactant has the structure of the following formula (2) and has a structure of the following formula (2).

In the formula, the portion represented by "CS" is a linear hydrocarbon having 10 to 14 carbon atoms, the portion represented by "EOS" is ethylene oxide, and the portion represented by "POS". Is a propylene oxide, EOS and POS each forming blocks or alternating with each other, a: b being 7: 3 to 9.5: 0.5, a cleaning composition.

Embodiment 11
In the method of cleaning the glass substrate
The process of supplying the cleaning composition onto a glass substrate,
A step of contacting the cleaning composition with the glass substrate to clean the surface of the glass substrate using a friction cleaning unit, and a step of removing the cleaning composition from the glass substrate.
Have
The cleaning composition is based on 100% by mass of the cleaning composition.
Alkali in the range of about 5% by weight to about 20% by weight,
Surfactants in the range of about 2% by weight to about 5% by weight,
Chelating agents in the range of about 3% by weight to about 8% by weight,
Organic solvents in the range of about 3% by weight to about 8% by weight, and dispersion stabilizers in the range of about 0.1% by weight to about 3% by weight.
Including methods.

Embodiment 12
The dispersion stabilizer has the structure of the following formula (1) and has a structure of the following formula (1).

Where "n" is 5,000 integer from 10, ^{"M +"} is an alkali metal or alkaline earth metal cation, "R ^-" is O ^- or COO ^- is , The method of embodiment 11.

Embodiment 13
The surfactant has the structure of the following formula (2) and has a structure of the following formula (2).

In the formula, the portion represented by "CS" is a linear hydrocarbon having 10 to 14 carbon atoms, the portion represented by "EOS" is ethylene oxide, and the portion represented by "POS". Is a propylene oxide, EOS and POS each form blocks or alternate with each other, and a: b is from 7: 3 to 9.5: 0.5, according to embodiment 11. ..

Claims (13)

In a cleaning composition for cleaning glass articles, with respect to 100% by mass of the cleaning composition,
Alkali in the range of about 1% by weight to about 20% by weight,
Surfactants in the range of about 0.1% by weight to about 10% by weight,
Chelating agents in the range of about 0.1% by weight to about 10% by weight,
Organic solvents in the range of about 0.1% to about 10% by weight, and dispersion stabilizers in the range of about 0.1% to about 10% by weight.
Including
The dispersion stabilizer has the structure of the following formula (1) and has a structure of the following formula (1).

Where "n" is 5,000 integer from 10, ^{"M +"} is an alkali metal or alkaline earth metal cation, "R ^-" is O ^- or COO ^- is , Cleaning composition. The cleaning composition is based on 100% by mass of the cleaning composition.
Alkali in the range of about 5% by weight to about 20% by weight,
Surfactants in the range of about 2% by weight to about 5% by weight,
Chelating agents in the range of about 3% by weight to about 8% by weight,
Organic solvents in the range of about 3% to about 8% by weight, and dispersion stabilizers in the range of about 0.1% to about 3% by weight.
The cleaning composition according to claim 1. The dispersion stabilizer has the structure of the following formula (1-1) and has a structure of the following formula (1-1).

The cleaning composition according to claim 1, wherein "n" is an integer of 50 to 1,000 and "M" is sodium or potassium. The surfactants are polyoxyalkylene alkylphenol ether, polyoxyalkylenearylphenol ether, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene alkylamine, sorbitan fatty acid ester, polyalkyl glucoside, alkyl alcohol amine, The cleaning composition according to claim 1, which comprises at least one selected from the group consisting of and arylalcohol amines. The surfactant has the structure of the following formula (2) and has a structure of the following formula (2).

In the formula, the portion represented by "CS" is a linear hydrocarbon having 10 to 14 carbon atoms, the portion represented by "EOS" is ethylene oxide, and the portion represented by "POS". Is a propylene oxide, EOS and POS each form blocks or alternate with each other, and a: b is from 7: 3 to 9.5: 0.5, according to claim 1. Stuff. The fifth aspect of the present invention, wherein the portion represented by CS is a linear hydrocarbon having 12 carbon atoms, and a: b is from about 8.5: 1.5 to about 9.3: 0.7. Cleaning composition. The alkalis are sodium hydroxide (NaOH), potassium hydroxide (KOH), magnesium hydroxide (Mg (OH) ₂ ), calcium hydroxide (Ca (OH) ₂ ), ammonia (NH ₃ ), tetraethylammonium hydroxide. , At least one selected from the group consisting of tetramethylammonium hydroxide, aminoethoxyethanol, triethanolamine, diethanolamine, monoethanolamine, ammonium hydroxide, tetrapropylammonium hydroxide, butylammonium hydroxide, and choline hydroxide. The cleaning composition according to claim 1. The chelating agent
Potassium pyrophosphate, calcium carbonate, sodium carbonate, sodium silicate, sodium gluconate, citric acid, salicylic acid, malonic acid, succinic acid, glutaric acid, pyrophosphate, polyphosphate, benzotriazole, sorbitol, glucose, benzotriazole carboxylate, And at least one selected from the group consisting of triltriazole; or nitrilo-2,2', 2 "-triacetic acid (NTA), diethylenetriaminepentacetic acid (DTPA), ethylenediaminetrilotetraacetic acid (EDTA), or a metal thereof. salt;
Including
The cleaning composition according to claim 1, wherein the metal salt contains a potassium salt or a sodium salt. The chelating agent is a metal salt of NTA in the range of about 2% by mass to about 7% by mass and a metal salt of DTPA in the range of about 1% by mass to about 6% by mass with respect to the cleaning composition of 100% by mass. 8. The cleaning composition according to claim 8. In a cleaning composition for cleaning glass articles, with respect to 100% by mass of the cleaning composition,
Alkali in the range of about 5% by weight to about 20% by weight,
Surfactants in the range of about 2% by weight to about 5% by weight,
Chelating agents in the range of about 3% by weight to about 8% by weight,
Organic solvents in the range of about 3% by weight to about 8% by weight, and dispersion stabilizers in the range of about 0.1% by weight to about 3% by weight.
Including
The surfactant has the structure of the following formula (2) and has a structure of the following formula (2).

In the formula, the portion represented by "CS" is a linear hydrocarbon having 10 to 14 carbon atoms, the portion represented by "EOS" is ethylene oxide, and the portion represented by "POS". Is a propylene oxide, EOS and POS each forming blocks or alternating with each other, a: b being 7: 3 to 9.5: 0.5, a cleaning composition. In the method of cleaning the glass substrate
The process of supplying the cleaning composition onto a glass substrate,
A step of contacting the cleaning composition with the glass substrate to clean the surface of the glass substrate using a friction cleaning unit, and a step of removing the cleaning composition from the glass substrate.
Have
The cleaning composition is based on 100% by mass of the cleaning composition.
Alkali in the range of about 5% by weight to about 20% by weight,
Surfactants in the range of about 2% by weight to about 5% by weight,
Chelating agents in the range of about 3% by weight to about 8% by weight,
Organic solvents in the range of about 3% by weight to about 8% by weight, and dispersion stabilizers in the range of about 0.1% by weight to about 3% by weight.
Including methods. The dispersion stabilizer has the structure of the following formula (1) and has a structure of the following formula (1).

Where "n" is 5,000 integer from 10, ^{"M +"} is an alkali metal or alkaline earth metal cation, "R ^-" is O ^- or COO ^- is , 11. Method. The surfactant has the structure of the following formula (2) and has a structure of the following formula (2).

In the formula, the portion represented by "CS" is a linear hydrocarbon having 10 to 14 carbon atoms, the portion represented by "EOS" is ethylene oxide, and the portion represented by "POS". 11 is the method of claim 11, wherein is propylene oxide, EOS and POS each form blocks or alternate with each other, and a: b is from 7: 3 to 9.5: 0.5.

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