TW201920642A - Mask cleaning solution composition - Google Patents

Abstract

The present invention provides a mask cleaning liquid composition characterized by comprising the amide compound represented by the following chemical formula 1, wherein R1 and R2 are each independently a methyl group or an ethyl group; R3 is hydrogen or a C1 to C4 saturated or unsaturated hydrocarbon group substituted or un-substituted with a C1 to C4 alkoxy group, wherein, when R1 and R2 are a methyl group, R3 is a saturated hydrocarbon group of C2 to C4 or an unsaturated hydrocarbon group of C2 to C4 substituted or un-substituted by a C1-C4 alkoxy group. The mask cleaning liquid composition of the present invention has an advantage of exhibiting a good cleaning power and facilitating an easier operable process even without using any environmentally controlled substance such as NMP.

Description

Mask cleaning liquid composition

The present invention relates to a mask cleaning liquid composition, and more particularly, to a mask cleaning liquid composition for removing various organic matters from a mask used in a vacuum evaporation process.

Flat panel displays (FPDs) have attracted attention as display devices. Among them, liquid crystal display devices and Organic Light Emitting Diodes (OLEDs) have become the focus of attention.

At present, the most commonly used liquid crystal display devices as displays have advantages such as lighter weight, smaller size, and lower power consumption than conventional cathode ray tubes (CRT). However, there are disadvantages: since it is not self-emissive, a backlight needs to be used, and the viewing angle is limited due to the use of liquid crystal.

In contrast, OLED elements have the advantages of low driving voltage, high luminous efficiency, wide viewing angle, and fast response speed. Especially since they are self-luminous, they have the advantage of not requiring a backlight. Such an OLED element emits light by using a self-luminous light-emitting organic substance so that electrons and holes supplied from a cathode and an anode are recombined.

For semiconductor devices such as OLEDs or flat panel displays, in order to form various organic layers such as light emitting layers, hole injection layers, hole transport layers, electron transport layers, and electron injection layers in the manufacturing process, a mask is used to An organic substance is vapor-deposited. At this time, the organic matter is also attached to the surface of the mask. Due to the organic matter thus adhered, the shape of the pattern formed by the mask may be deformed. This will lead to a decrease in the efficiency of the evaporation process and may affect the performance of the manufactured semiconductor device or flat panel display. Therefore, it is necessary to remove the organic substances deposited on the mask.

Korean Laid-Open Patent No. 2011-0095814 relates to a cleaning material composition for a vapor deposition material and a cleaning method using the cleaning material composition for a vapor deposition material, and discloses a method containing N-methyl-2-pyrrolidone (N-Methyl- 2-pyrrolidone), and 1,3-Dimethyl-2-imidazolidinone (1,3-Dimethyl-2-imidazolidinone) vapor deposition material cleaning solution composition.

Korean Laid-Open Patent No. 1388283 relates to a mask cleaning device, which discloses a mask cleaning device having the following characteristics, that is, an ultrasonic cleaning unit that generates an ultrasonic wave and cleans a mask immersed in a cleaning solution. ; The cleaning liquid loop part for discharging and supplying the cleaning liquid of the ultrasonic cleaning part, the frequency of the ultrasonic wave in the ultrasonic cleaning part is 75KHz to 90KHz, the intensity is 800W to 1100W, and the cleaning liquid is N -N-Methyl Pyrrolidinone (NMP) mixture.

However, N-methyl-2-pyrrolidone (NMP) used in conventional mask cleaning liquids is a toxic substance. Specifically, according to Korean National Institute of Environmental Sciences No. 2014-25, it is contained at a content of 0.3% by weight or more. Substances classified as toxic. When using a mask cleaning solution containing NMP, it is not only harmful to the human body, but also environmentally unsound.

In addition, the mask cleaning process determines the operating time according to the process conditions, so performance degradation should not occur after long-term storage in the atmospheric state. In particular, due to exposure to the atmosphere, performance degradation should not occur due to moisture absorption.

Therefore, it is required to develop a mask cleaning liquid that is excellent in cleaning power even if it does not contain environmentally controlled substances such as NMP, does not cause degradation in performance due to moisture absorption, and is easy to handle.

Prior art literature

Patent literature

Korean Published Patent No. 2011-0095814 (2011.08.25.)

Korean Published Patent No. 1388283 (2014.04.16.)

Problems to be solved

An object of the present invention is to provide a cleaning liquid composition that exhibits a good cleaning power even without containing an environmentally controlled substance.

Another object of the present invention is to provide a cleaning liquid composition that does not require ultrasonic and electrolytic cleaning and is excellent in stability and easy to process.

Problem solving

The cleaning liquid composition of the present invention for achieving the above-mentioned object is characterized by including a sulfonamide-based compound represented by the following Chemical Formula 1.

[Chemical Formula 1]

In the above Chemical Formula 1,

R1 and R2 are each independently methyl or ethyl, R3 is hydrogen, or C1 ~ C4 saturated or unsaturated hydrocarbon group substituted or unsubstituted by C1 ~ C4 alkoxy group, wherein when R1 and R2 are methyl In this case, R3 is a saturated hydrocarbon group of C2 to C4 or an unsaturated hydrocarbon group of C2 to C4 substituted or unsubstituted by an alkoxy group of C1 to C4.

Invention effect

The mask cleaning liquid composition of the present invention has the advantages of exhibiting good cleaning power even when it does not contain environmentally controlled substances such as NMP, and is easy to process.

In addition, the mask cleaning liquid composition of the present invention has an advantage of suppressing a decrease in performance due to moisture absorption.

In addition, when the mask is cleaned with the mask cleaning liquid composition of the present invention, there is an advantage that ultrasonic waves and electrolytic cleaning are not required.

Hereinafter, the present invention will be described in more detail.

In the present invention, when it is pointed out that a certain component is "on" another component, it includes not only the case where a certain component is in contact with another component, but also the case where other components are present between the two components.

In the present invention, when a certain part “contains” a certain constituent element, it means that as long as there is no particularly contrary description, other constituent elements may be further included instead of excluding other constituent elements.

One aspect of the present invention relates to a mask cleaning solution composition containing a fluorene-based compound represented by the following Chemical Formula 1.

[Chemical Formula 1]

In the above Chemical Formula 1,

R1 and R2 are each independently methyl or ethyl, R3 is hydrogen, or C1 ~ C4 saturated or unsaturated hydrocarbon group substituted or unsubstituted by C1 ~ C4 alkoxy group, wherein when R1 and R2 are methyl In this case, R3 is a saturated hydrocarbon group of C2 to C4 or an unsaturated hydrocarbon group of C2 to C4 substituted or unsubstituted by an alkoxy group of C1 to C4.

In the present invention, the alkoxy group may be a linear, branched or cyclic chain. Although the number of carbon atoms of the alkoxy group is not particularly limited, the number of carbon atoms is preferably 1 to 4. Specific examples include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, and sec-butoxy. .

In the present invention, the saturated hydrocarbon group may be any of a straight chain, a branched chain, and a cyclic ring that satisfy the above-mentioned number of carbon atoms.

Examples of the linear or branched saturated hydrocarbon group include linear alkyl groups such as methyl, ethyl, propyl, and butyl; branched alkyl groups such as isopropyl and isobutyl; and the like. The saturated hydrocarbon group preferably has 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms. However, when R1 and R2 are both methyl groups, the carbon number of the saturated hydrocarbon group is 2 to 4.

Examples of the cyclic saturated hydrocarbon group include a cyclopropyl group and a cyclobutyl group.

In the present invention, the unsaturated hydrocarbon group has an unsaturated group at the terminal, which may be a linear aliphatic unsaturated hydrocarbon group having a carbon number of 2 to 4, or a branched aliphatic unsaturated hydrocarbon group. Examples of the linear aliphatic unsaturated hydrocarbon group include vinyl, propenyl (allyl), and butenyl, and examples of the branched unsaturated hydrocarbon group include 1-methacryl, 2 -Methacryl and the like, but not limited thereto.

The mask cleaning liquid composition of the present invention may be in a neat (pure) state of the amidoamine compound represented by the above Chemical Formula 1. For example, the mask cleaning liquid composition of the present invention can be formed from a fluorene-based compound represented by the aforementioned Chemical Formula 1.

In one embodiment of the present invention, the amidamine-based compound represented by the above Chemical Formula 1 may be selected from the group consisting of N, N-dimethylpropanamide, N, N-dimethylisobutylamidine, and N, N-diamine. Methacrylamide, N, N-dimethylmethacrylamine, N, N-diethylmethaneamine, N, N-diethylacetamide, N, N-diethylpropylamine Amine, N, N-diethylisobutylamidine, N, N-diethylacrylamidine, N, N-diethylmethacrylamidine, 3-methoxy-N, N-dimethylformamide One or more of the group consisting of propylpropylamine and 3-butoxy-N, N-dimethylpropylamine, for example, can be used alone or in combination of two or more.

Since the mask cleaning liquid composition of the present invention contains a fluorene-based compound represented by the above Chemical Formula 1, it has excellent mask cleaning power, and does not affect masks such as SUS, Invar, etc. that form a mask. The material has the advantages of damage, and because it can replace environmentally harmful substances such as NMP, it has the advantages of being excellent in the environment and easy in the process. Specifically, the mask cleaning liquid composition of the present invention includes a non-expandable steel material mask that is not used for patterning organic light-emitting elements, and a stainless steel (SUS 304, 316, 420, etc.) that supports the mask. The base material has the advantage of causing damage such as corrosion.

For example, the mask cleaning liquid composition of this invention is excellent in the cleaning power with respect to the various organic substances adhering to the said mask.

The organic substance may be, for example, a substance that forms a red, green, and / or blue light emitting layer, a hole transport layer (HTL), a hole injection layer (HIL), and the like. The light emitting layer may emit red, green, and / or blue light, and may be formed of a phosphorescent substance or a fluorescent substance. At this time, as the light-emitting host material, (carbazole-9-yl) biphenyl (Ccarbazole-9-yl) biphenyl (CBP) or 1,3-bis (carbazole-9-yl) benzene (1 , 3-bis (carbazol-9-yl) benzene, mCP), but it is not limited to this.

As the red light-emitting dopant, bis (1-phenylisoquinoline) acetylacetonato iridium (PIQIr (acac)), bis (1-phenylquinoline) acetamidine can be used. Acetone iridium (bis (1-phenylquinoline) acetylacetonato iridium (PQIr (acac)), tris (1-phenylquinoline) iridium (PQIr), octaethylporphyrin platinum Phosphorescent substances such as PtOEP), or fluorescent substances such as tris- (8-hydroxyquinoline) aluminum (Alq3).

As the green light-emitting dopant, a phosphorescent substance such as fac tris (2-phenylpyridine) iridium (Ir (ppy) ₃ ) or tris (8-hydroxyquine) can be used. (Fluoroline) aluminum (tris- (8-hydroxyquinoline) aluminum, Alq3), but it is not limited to this.

As the blue light-emitting dopant, a phosphorescent substance such as (4,6-F ₂ ppy) ₂ Irpic, or spiro-DPVBi, spiro-6P, distyrylbenzene (DSB), distyryl Fluorescent substances such as aromatic (DSA), PFO-based polymers, and PPV-based polymers are not limited thereto.

The hole transport layer may be selected from N, N′-bis (1-naphthyl) -N, N′-diphenyl- (1,1′-biphenyl) -4,4′-diamine (N , N′-Di (1-naphthyl) -N, N′-diphenyl- (1,1′-biphenyl) -4,4′-diamine (NPD), N, N′-bis (3-methylphenyl) ) -N, N'-bis (phenyl) -benzidine (N, N'-bis- (3-methylphenyl) -N, N'-bis- (phenyl) -benzidine (TPD)), s-TAD and 4 , 4 ', 4 "-Tri (N-3-methylphenyl-N-phenyl-amino) -triphenylamine (4,4', 4"-Tris (N-3-methylphenyl-N-phenyl-amino ) -triphenylamine (MTDATA) is formed in any one or more groups, but is not limited thereto. For example, as the hole transport layer material, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolinone derivatives, Phenylenediamine derivative, arylamine derivative, amino substituted chalcone derivative, oxazole derivative, styrylanthracene derivative, fluorenone derivative, fluorene derivative, stilbene derivative, silazane derivative , Polysilane-based, aniline-based copolymers, conductive polymer oligomers (especially thiophene oligomers), and the like.

In addition, an oxadiazole derivative or a triazole derivative, a phenanthroline derivative, a 2,9-dimethyl-4,7-diphenyl- As a material for the hole injection layer, 1,10-phenanthroline (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), aluminum complex, etc.) can be selected from copper phthalocyanine ( one or more of the group consisting of copper phthalocyanine (CuPc), poly (3,4-ethylene dioxythiophene) (Pod (3,4-ethylene dioxythiophene), PEDOT), polyaniline (PANI), and NPD .

In another embodiment of the present invention, the mask cleaning liquid composition may further include a water-soluble polar solvent.

In another embodiment of the present invention, the water-soluble polar solvent may include one or more members selected from the group consisting of a protic polar solvent and an aprotic polar solvent.

Specifically, the water-soluble polar solvent of the present invention includes a protic polar solvent and an aprotic polar solvent, and these may be used alone or in combination.

Examples of the protic polar solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, and diethylene glycol monomethyl ether. , Diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol Alcohol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol mono Alkylene glycol monoalkyl ethers such as methyl ether; and tetrahydrofurfuryl alcohol, etc., and also include 4-hydroxymethyl-1,3-dioxolane, 4-hydroxymethyl-2,2-di Methyl-1,3-dioxolane, 4-hydroxyethyl-2,2-dimethyl-1,3-dioxolane, 4-hydroxypropyl-2,2-dimethyl-1 , 3-dioxolane, 4-hydroxybutyl-2,2-dimethyl-1,3-dioxolane, 4-hydroxymethyl-2,2-diethyl-1,3-di Oxypentane, 4-hydroxymethyl-2-methyl-2-ethyl-1,3-dioxolane and other hydroxydioxolane-based compounds may be used alone or in combination of two or more. Not limited to this Commonly used in the art may be used, protic polar solvent does not inhibit the object of the present invention.

Examples of the above-mentioned aprotic polar solvent include lactone compounds such as γ-butyrolactone; osmium compounds such as dimethylsulfinium (DMSO) and cyclobutane; triethyl phosphate and tributyl phosphate And other phosphate compounds; carbonate compounds such as dimethyl carbonate, ethylene carbonate, and propylene carbonate, which can be used alone or as a mixture of two or more, but are not limited thereto.

The water-soluble polar solvent works together with the amidoamine compound represented by the above Chemical Formula 1 to dissolve the organic material remaining in the mask, and can also play a role in that it can be easily removed by water during the rinse process of deionized water after washing The cleaning liquid can minimize re-adsorption / re-adhesion of the removed organic material or improve the removal force of the specific organic material.

The water-soluble polar solvent can be selected according to the performance required in the subsequent cleaning process. For proper cleaning power and stable operation of the process, the boiling point of the water-soluble polar solvent is preferably not low. For example, it is preferred to have a boiling point of 150 to 290 ° C. When a water-soluble polar solvent having a boiling point within the above range is used, environmental considerations and manufacturing process considerations are preferred.

In the case where the water-soluble solvent has a low boiling point, the amount used in the process is increased due to volatilization in the cleaning process, which may adversely affect the operating environment. Therefore, it is preferable to use a water-soluble polar solvent having a boiling point within the above range.

In another embodiment of the present invention, the content of the water-soluble polar solvent may be 1 to 50 parts by weight, preferably 5 to 40 parts by weight, and more preferably 5 to 100 parts by weight with respect to the entire cleaning solution composition. 30 parts by weight. When the content of the water-soluble polar solvent is within the above range, there is an advantage that it is possible to produce a cleaning liquid composition having excellent cleaning power and easy removal in a rinse process of deionized water after cleaning, so it is preferable.

Since the cleaning liquid composition of the present invention contains an amidine-based compound represented by the above Chemical Formula 1 and has excellent cleaning power, it has the advantage that ultrasonic waves, electrolytic cleaning, and the like are not required.

Hereinafter, in order to specifically describe this specification, examples will be described in detail. However, the embodiments in this specification can be modified into various other forms, and should not be construed as the scope of this specification is limited by the following examples. The examples in this specification are intended to be more complete for those with ordinary knowledge in the field. Provided. In addition, hereinafter, "%" and "parts" indicating content are based on weight unless otherwise mentioned.

Examples and Comparative Examples: Production of Cleaning Liquid Composition

The cleaning liquid compositions of Examples and Comparative Examples were produced according to the structures and compositions of Table 1 below.

[Table 1]

Experimental example 1: Evaluation of cleaning ability of organic material adsorption mask

In order to confirm the cleaning effect of the mask cleaning liquid compositions of the examples and comparative examples, five types of masks were attached to each of the substances used as the light-emitting layer and the electron / hole transporting layer included in the organic light-emitting element according to a general method. (Material: Non-swelling steel) We performed a cleaning power evaluation. After the manufactured mask cleaning liquid composition was heated to 50 ° C. in a constant temperature bath, the mask cleaning liquid composition (reagent) was stirred. After immersing and cutting the mask with an organic material attached to the mask cleaning solution composition under stirring to a size of 2 × 2 cm, the mask was washed with deionized water for 1 minute, and determined by SEM (scanning microscope, Hitachi-4800). Whether there is any organic material on the surface of the mask to evaluate the cleaning power. The mask cleaning liquid immersion time was performed in units of 5 minutes, and the time during which the residue did not remain on the mask surface was indicated to evaluate the cleaning power. The results are shown in Table 2 below.

[Table 2]

Referring to Table 2, it can be confirmed that in the examples in which the amidine-based compound, the amidine-based compound, and the water-soluble polar solvent shown in Chemical Formula 1 are mixed, the masks 1 to 5 can be cleaned within 25 minutes.

However, in the case of the comparative example, in addition to the comparative example 1 containing an environmentally controlled substance, it was confirmed that one or more masks in each comparative example were 30 minutes or more, and the cleaning power fell.

In Comparative Examples 2 to 4 in which the amidine-based substance in which R1 and R2 were not methyl or ethyl in Chemical Formula 1 was used, it was confirmed that the cleaning power of the mask 2 and the mask 3 was decreased.

In addition, in Comparative Example 5 of the amine-based substance in which R3 exceeds C4 in Chemical Formula 1, it was confirmed that the cleaning power of the masks for all masks 1 to 5 is decreased. When R1 and R2 are methyl groups, and R3 is hydrogen or C1 Next, it can be confirmed that the removal force decreases with respect to the masks 2 and 3.

In addition, in Comparative Examples 8, 9, 10, and 11 that did not include the amidamine-based compound represented by Chemical Formula 1 and only contained a water-soluble polar solvent, it was also confirmed that the mask cleaning power was decreased, and it was not included in the amidamine-based compound of Chemical Formula 1. In Comparative Examples 12 and 13 of a mixture with a polar solvent, it was also confirmed that the cleaning power was decreased.

Experimental example 2: Evaluation of the solubility stability of organic light-emitting elements

After the evaporation process, the organic material is separated from the mask, and then formed into a powder form using a mortar. The 0.05% organic material based on the weight of the manufactured mask cleaning solution composition is dissolved at 60 ° C for 1 hour, and then glass is used. The material is divided into 50ml transparent glass bottles, and then left at room temperature for 24 hours. For Examples 1, 2, 4, 5, 6, 8, 10 and Comparative Examples 2, 4, 6, 8, 11, 12 The stability (increased turbidity and sediment) of the mask cleaning liquid composition (reagent) was evaluated and shown in Table 3 below.

The evaluation criteria are as follows.

There is no change in the transparency of the reagent when evaluated with the naked eye: ◎

The turbidity slightly increased when evaluated by the naked eye (transparent): ○

Increase in turbidity (opaque) when evaluated with the naked eye: △

Precipitation when evaluated with the naked eye: ×

[table 3]

Referring to Table 3, in the examples in which the amidine compound of Formula 1 and the water-soluble polar solvent were mixed, the transparency of the reagent changed little after the organic material was dissolved, and it showed stability in the cleaning solution. Non-bulging steel, SUS). However, in Comparative Examples 2, 4, 6, 8, 11, and 12, after being left for 24 hours, it was confirmed that the organic materials separated from the mask 2 and the mask 3 had a decreased stability after being dissolved. From this, it was confirmed that when the number of cleanings is increased in the repeated cleaning process, re-adsorption on the substrate may cause secondary pollution.

Experimental example 3: Evaluation of absorption rate and storage stability of mask cleaning solution

In order to confirm the decrease in cleaning performance due to moisture absorption, the mask cleaning liquid composition was heated to 30 ° C in a thermostatic bath, and the mask cleaning liquid composition (reagent) was left for 48 hours, and then the moisture content was measured with a moisture analyzer Calculate the absorptivity, cut the glass with the adsorbed organic material to 2 × 4cm size, immerse (half dip) the lower glass part in the cleaning solution, wash it with deionized water for 1 minute, and then use a UV lamp (254 nm), the presence or absence of an organic material was judged with the naked eye, and the cleaning power was evaluated. The mask cleaning liquid immersion time was performed in units of 15 seconds, and the time during which the residue did not remain on the mask surface was indicated to evaluate the cleaning power. The results are shown in Table 4. Figures 1 and 2 are views of a mask viewed under a UV lamp. For example, Figure 1 is a view of an organic vapor deposited on a glass lower portion of a glass immersed in a cleaning solution, and Figure 2 is an organic vapor deposition. A figure showing that there is no substance remaining in the glass below the glass immersed in the cleaning solution.

[Table 4]

Referring to Table 4 above, the examples in which the amidine-based compound, the amidine-based compound, and the water-soluble polar solvent shown in Chemical Formula 1 were mixed showed a rapid cleaning power within 120 seconds, and the moisture content after storage stability evaluation was less than 2 % And the cleaning power has not changed.

However, in Comparative Examples 1 and 8 including NMP, the moisture content after the storage stability evaluation was 27% or more, and it was confirmed that the removal rate of a part of the organic vapor-deposited product was decreased.

no

FIG. 1 and FIG. 2 are graphs of glass based on the evaluation of the absorption rate of the mask cleaning liquid and the storage stability of the examples.

Claims (1)

A mask cleaning liquid composition comprising a fluorene-based compound and a glycol ether-based compound represented by the following Chemical Formula 1: Chemical Formula 1 In the chemical formula 1, R1 and R2 are each independently a methyl group or an ethyl group, R3 is hydrogen, or a saturated or unsaturated C1 to C4 hydrocarbon group substituted or unsubstituted with a C1 to C4 alkoxy group, where, when When R1 and R2 are methyl groups, R3 is a saturated hydrocarbon group of C2 to C4 or an unsaturated hydrocarbon group of C2 to C4 substituted or unsubstituted by an alkoxy group of C1 to C4.