TWI540206B - Detergent composition,liquid crystal cell and liquid crystal display - Google Patents

Description

Cleaning agent composition, liquid crystal unit and liquid crystal display

The present invention relates to a cleaning composition.

The present application claims the benefit of the Korean Patent Application No. 10-2010-005563, filed on Jun.

Generally, in the manufacture of a liquid crystal cell, polyimine (PI) is coated on two patterned substrates having an electrode pattern so as to be imparted with a function of an alignment layer and an insulating layer, and an upper surface thereof is subjected to friction in a predetermined direction. Thereby forming an alignment layer. Thereafter, a sealing adhesive and a separator for controlling the thickness of the liquid crystal cell are disposed between the substrates, and then the two substrates are bonded to each other. Accordingly, if contaminants remain on the alignment layer substrate, liquid crystal is injected thereon, it is difficult to obtain a clear display screen, and packaging defects may be undesirably generated. Therefore, a cleaning process is required to remove contaminants from the substrate.

When manufacturing liquid crystal cells of liquid crystal displays (LCDs), the source of contaminants of the substrate may include impurities separated in a rubbing cloth used in a rubbing process before bonding two PI substrates or PI particles together, and may adhere to the substrate. Undesirably causing defects. The removal of such contaminants produced in the process is conventionally accomplished with a solvent such as an aqueous solution of isopropanol or isopropanol, or pure water. However, the use of solvent cleaning is disadvantageous because the solvent may remain behind the substrate and may also be undesirably problematic in terms of environmental safety and chemical stability including flammability. In addition, with the advent of the high oil price era, the use of solvent cleaning may result in increased process costs that are proportional to the increase in the price of raw materials. Moreover, cleaning with pure water did not show sufficient cleaning ability to remove contaminants, and thus accompanied by a decrease in production yield.

Further, a cleaning agent containing a basic compound may undesirably damage the PI alignment layer.

Further, Japanese Patent Laid-Open No. Hei 3-62018 discloses a method of ultrasonically cleaning a friction substrate using pure water to stably form a high pretilt angle. However, it is not easy to introduce ultrasonic waves into the process of manufacturing a display, and cleaning with pure water cannot satisfy the performance of the cleaning agent required recently. Japanese Patent Publication No. Hei 3-81730 discloses a method of cleaning a surface of a friction substrate using a brush, but since secondary contaminants and contaminants from the brush are again attached to the substrate, it is impossible to expect an ideal cleaning effect.

In the above Japanese Patent, the use of a device for imparting physical cleaning ability in the cleaning process undesirably increases the cost of the cleaning process, and is inevitably problematic, including the use of isopropyl alcohol or pure water. The solvent is left on the substrate, the rinsing is poor, the particles are reattached, and the like.

Therefore, in order to solve the above-mentioned problems, research on various aqueous cleaning systems superior in human safety and work safety and capable of exhibiting high cleaning ability and rinsing characteristics by the addition of various surfactants has been continuously conducted.

Accordingly, the present invention is directed to providing a cleaning composition which has superior wetting and permeation effects, whereby removal of contaminants from the upper surface of the alignment layer substrate is very effective.

Furthermore, the present invention is directed to providing a cleaning composition that does not damage the alignment layer.

Further, the present invention is directed to providing a cleaning composition which is nonflammable, is therefore safe and environmentally friendly, and has low foaming properties.

Furthermore, the present invention is directed to providing a cleaning composition that does not attack a metal layer comprising copper and a metal layer comprising aluminum.

One aspect of the present invention provides a cleaning composition containing no basic compound, comprising 0.1 to 15% by weight of a C1 to C5 lower alcohol, 0.1 to 15% by weight of a water-soluble B based on the total weight of the composition. A glycol ether compound, 0.01 to 10% by weight of an organic phosphoric acid, 0.001 to 10% by weight of a pyrrolyl compound, and the remainder being water.

Another aspect of the present invention provides a liquid crystal cell comprising an alignment layer washed with the above cleaning agent composition.

A still further aspect of the invention provides an LCD comprising the above liquid crystal cell.

A detailed description of the invention is given below.

The detergent composition containing no basic compound according to the present invention contains a C1 to C5 lower alcohol, a water-soluble glycol ether compound, an organic phosphoric acid, a pyrrolyl compound, and water.

Typically, basic compounds are used to remove contaminants or organic matter from the air. However, in the case where an alkaline compound is used in the process of manufacturing a liquid crystal cell of an LCDs, the liquid crystal alignment layer, particularly, the PI alignment layer may be damaged. Therefore, the cleaning composition according to the present invention does not contain such a basic compound, thereby preventing damage to the liquid crystal alignment layer.

Further, the cleaning composition according to the present invention is advantageous because of the combination of a C1 to C5 lower alcohol, a water-soluble glycol ether compound, and an organic phosphoric acid, thereby exhibiting superiority in removing contaminants and preventing damage of the alignment layer. The effect, and in the process of manufacturing the liquid crystal cell of the display, when the substrate is cleaned before or after rubbing the liquid crystal alignment layer, exhibits incombustibility and low foaming. Sex. Moreover, the composition is very effective for removing contaminants in cleaning the liquid crystal alignment layer, particularly, the PI alignment layer. Moreover, due to the pyrrolyl compound, the cleaning composition according to the present invention does not damage the metal layer containing Cu and the metal layer containing Al, so that the electrode or the wire located at the uncovered portion of the liquid crystal alignment layer is not corroded.

The C1 to C5 lower alcohol contained in the cleaning composition according to the present invention enhances the wetting and penetrating ability of the cleaning agent to the substrate, and improves the ability to prevent the contaminants from being reattached, thereby easily removing the contamination from the substrate. Things.

The lower alcohol may be used in an amount of 0.1 to 15% by weight based on the total weight of the composition, and preferably 0.5 to 10% by weight. If the amount of the lower alcohol is less than 0.1% by weight, the surface tension is not lowered, making it difficult to exhibit wettability and penetration ability. On the contrary, if the amount of the lower alcohol exceeds 15% by weight, the lower alcohol may remain behind the substrate, undesirably causing defects.

The type of the C1-C5 lower alcohol is not particularly limited, but is preferably a C1-C4 lower alcohol, for example, methanol, ethanol, n-propanol, isopropanol, ethylene glycol, 1, based on the characteristics including water solubility. 2-propanediol, 1,3-propanediol, 1,2 butanediol, 1,3 butanediol, 1,4-butanediol, glycerol, and 1,2,4-butanetriol, can be used alone Alternatively, a mixture of two or more may be used.

The water-soluble glycol ether compound contained in the detergent composition plays a role in removing the oil component and improving the solubility in water, and the oil component is considered to be difficult to rub from friction only by using a lower alcohol aqueous solution. The surface of the substrate is removed.

The water-soluble glycol ether compound can be used in an amount of 0.1 to 15% by weight, based on the total weight of the composition, and preferably 0.5 to 10% by weight. If the amount of the water-soluble glycol ether compound is less than 0.1% by weight, it is difficult to remove the oil component from the surface of the friction substrate. Conversely, if the amount of water-soluble glycol ether compound More than 15% by weight, the resulting cleaning agent may become very viscous, so that its ability to wet and penetrate the substrate may be deteriorated in the cleaning process.

The water-soluble glycol ether compound is preferably a water-soluble glycol ether of C1 to C10. Examples of the water-soluble glycol ether of C1 to C10 may include ethylene glycol monomethyl ether (MG), diethylene glycol monomethyl ether (MDG), triethylene glycol monomethyl ether (MTG), polyethylene glycol. Monomethyl ether (MPG), ethylene glycol monoethyl ether (EG), diethylene glycol monoethyl ether (EDG), ethylene glycol monobutyl ether (BG), diethylene glycol monobutyl ether (BDG), triethylene Alcohol monobutyl ether (BTG), propylene glycol monomethyl ether (MFG), dipropylene glycol monomethyl ether (MFDG), which may be used singly or in combination of two or more.

The organic phosphoric acid contained in the cleaning agent composition according to the present invention functions to disperse the contaminant particles so as not to aggregate, and also functions to improve the wetting and permeating ability of the substrate in the cleaning process, thereby improving the cleaning. effect. Further, the organic phosphoric acid can effectively remove the metal particles, and can also prevent corrosion of the metal layer containing Cu and the metal layer containing Al.

The organic phosphoric acid may be used in an amount of 0.01 to 10% by weight, based on the total weight of the composition, and preferably 0.1 to 5% by weight. If the amount of the organic phosphoric acid is less than 0.01% by weight, the wetting and penetration ability to the surface of the substrate to be rubbed cannot be increased. On the contrary, if the amount of the organic phosphoric acid exceeds 10% by weight, this component may remain behind the substrate, undesirably causing defects.

Examples of the organic phosphoric acid are not particularly limited, and include aminotrimethylenephosphonic acid, ethylene diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and 1-hydroxypropylidene-1,1-di. Phosphonic acid, 1-hydroxybutylidene-1,1-diphosphonic acid, ethylaminodimethylenephosphonic acid, 1,2-propylenediaminetetramethylenephosphonic acid, dodecylaminodimethylene Phosphonic acid, nitrotris (methylenephosphonic acid), ethylenediamine dimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, hexene Diamine tetramethylene phosphonic acid, diethylenetriamine penta methylene phosphonic acid, cyclohexanediamine tetramethylene phosphonic acid, hydroxyphosphonium acetic acid and 2-phosphonic acid-butane-1,2,4- Tricarboxylic acid. Particularly useful are 1-hydroxyethylidene-1,1-diphosphonic acid, hydroxyphosphonium acetic acid, aminotrimethylenephosphonic acid or 2-phosphonic acid-butane-1,2,4-tricarboxylic acid.

The pyrrolyl compound contained in the cleaning composition according to the present invention minimizes corrosion of the metal layer containing Cu and the metal layer containing Al.

The pyrrolyl compound can be used in an amount of from 0.001 to 10% by weight, based on the total weight of the composition, and preferably from 0.01 to 3% by weight. When the amount of the component falls within the above range, the damage to the metal layer containing Cu and the metal layer containing Al, that is, the corrosion thereof can be minimized, and economical efficiency can be obtained.

A pyrrolyl compound represented by the following Formula 1 is preferred.

In the formula 1, R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a halogen atom, a C1 to C6 alkyl group, a C3 to C6 cycloalkyl group, an allyl group, an aryl group, an amino group, a C1 to C6 alkylamino group. , nitro, cyano, mercapto group, C1 to C6 alkyl fluorenyl, hydroxy, C1 to C6 hydroxyalkyl, carboxyl, C1 to C6 carboxyalkyl, decyl, C1 to C6 alkoxy, or heterocyclic The unit price of the group.

The pyrrolyl compound represented by the formula 1 may be selected from N-[(benzotriazole)methyl]diethanolamine, N-[(methyl-1H-benzotriazol-1-yl)methyl]dimethanol. Amine, N-[(ethyl-1H-benzotriazol-1-yl)methyl]diethanolamine, N-[(methyl-1H-benzotriazol-1-yl)methyl]dipropanol Amine, 2,2'-[[(methyl) -1H-benzotriazol-1-yl)methyl]imino]dicarboxylic acid, 2,2'-[[(methyl-1H-benzotriazol-1-yl)methyl]imino] A group consisting of dimethylamine and N-[(amine-1H-benzotriazol-1-yl)methyl]diethanolamine.

Further, the water contained in the detergent composition according to the present invention is not particularly limited, but may include deionized water suitable for a semiconductor process, and has at least 18 MΩ. The resistivity of cm. The amount of water can be adjusted according to the amount of other components. Water was added as a residue based on the total weight of the composition such that the total weight percentage of the composition was 100.

The absence of an organic acid in the cleaning composition according to the invention is preferred. The reason is that when the cleaning agent composition containing organic acid is used after rubbing the alignment layer in the manufacture of LCDs, the metal particles can be effectively removed from the surface of the alignment layer, particularly the PI alignment layer, but the corrosion of the metal electrode or the wire It may also be accelerated.

In order to improve the cleaning performance, the cleaning composition according to the present invention may further comprise usual additives known in the art, such as corrosion inhibitors, wetting/penetrating agents, dispersing agents, surface modifiers and the like.

The components of the cleaning composition according to the present invention can be prepared by a generally known method, and preferably have a purity suitable for a semiconductor process.

Further, the present invention provides a liquid crystal cell comprising an alignment layer cleaned using the above cleaning agent composition, and further, the present invention provides an LCD comprising the above liquid crystal cell.

When the cleaning composition according to the present invention is used, the residual residue of the contaminant on the alignment layer substrate can be completely removed, whereby the liquid crystal cell containing such an alignment layer has high quality. Moreover, an LCD including such a liquid crystal cell can provide a clear display screen.

Cleaning method using the cleaning agent composition according to the present invention, Special limit. Examples thereof may include soaking, stirring, sonication, shower spraying, puddling, brushing, and the like.

The cleaning composition according to the present invention has an excellent wetting and permeation effect, so that contaminants present on the alignment layer substrate can be effectively removed. The cleaning composition according to the present invention does not damage the alignment layer included in the LCD, and therefore it is very effective to clean the substrate before or after rubbing the liquid crystal alignment layer in the process of manufacturing the liquid crystal cell of the LCD. In particular, when the cleaning composition is applied in the manufacture of an LCD process, the metal particles can be effectively removed from the upper surface of the alignment layer. Moreover, the cleaning composition according to the invention is non-combustible, thereby being safe and environmentally friendly and does not cause foaming problems. The cleaning composition according to the present invention also does not corrode a metal layer containing Cu and a metal layer containing Al.

A better understanding of the present invention can be obtained by the following examples, which are intended to be illustrative and not restrictive.

Examples 1 to 11 and Comparative Examples 1 to 8: Preparation of a detergent composition

The components shown in the following Table 1 were added in a predetermined amount to a mixing vessel equipped with a stirrer, and stirred at 500 rpm for 1 hour at room temperature, thereby preparing a detergent composition.

A-1: Ethanol

A-2: isopropanol

A-3: Glycerol

B-1: Diethylene glycol monomethyl ether (MDG)

B-2: Diethylene glycol monoethyl ether (EDG)

B-3: Diethylene glycol monobutyl ether (BDG)

C-1:1-hydroxyethylidene-1,1-diphosphonic acid (HEDP)

C-2: 2-phosphonic acid-butane-1,2,4-tricarboxylic acid (PBTC)

C-3: Hydroxyphosphoric acid (HPA)

D-1: N-[(ethyl-1H-benzotriazol-1-yl)methyl]diethanolamine

D-2: N-[(amine-1H-benzotriazol-1-yl)methyl]diethanolamine

TMAH: Tetramethylammonium hydroxide

E-1: oxalic acid

Test example: cleaning ability and evaluation of damage to the alignment layer

1. Evaluation of damage to the PI alignment layer and ability to remove particles

A substrate (5cm x 5cm x 0.7cm) whose PI alignment layer has been rubbed so that it is in the air for 24 hours, so that it is contaminated with various organic substances, inorganic substances, particles, etc., and then a spray type glass substrate cleaning device is used. Each of the cleaning compositions of Examples 1 to 11 and Comparative Examples 1 to 8 was washed at room temperature for 2 minutes. After washing, the substrate was rinsed with ultrapure water for 30 seconds and dried with nitrogen. The substrate thus obtained was observed with a scanning electron microscope (SEM) (S-4700, supplied by Hitachi, Ltd.) to evaluate whether or not the PI alignment layer was damaged and the cleaning ability was evaluated based on the number of impurity particles remaining behind the substrate.

The results are shown in Table 2 below, wherein ◎ is superior, ○ is good, Δ is medium, and X is poor. When the PI alignment layer was peeled off, the result could not be measured, and this case was represented by "-".

2. Assessment of the ability to remove organic pollutants

A glass substrate was placed in the air for 24 hours so that it was contaminated with various organic substances, inorganic substances, particles, and the like, and then 0.5 μl of ultrapure water was added thereto, and the contact angle was measured before washing to confirm surface contamination. Specifically, 100 ml of each of the cleaning compositions of Examples 1 to 11 and Comparative Examples 1 to 8 was placed in a 250 ml beaker, and the glass substrate was immersed therein for 2 minutes at room temperature and washed. Thereafter, the substrate was washed with ultrapure water for 30 seconds and dried with nitrogen. 0.5 μl of ultrapure water droplets were applied to the glass substrate to measure the contact angle after washing.

The results are shown in Table 2 below, where the change in the contact angle after washing is 30° or more is judged as ◎, and the change in contact angle is from 15° to less than 30°. When it was judged as ○, the change in the contact angle was judged to be Δ from 5° to less than 15°, and it was judged to be X when the change in the contact angle was 5° or less.

3. Evaluation of damage to Al and Cu

In order to evaluate damage to the wires, damage to Al was evaluated using a Mo/Al/Mo wiring substrate, and damage to Cu was evaluated using a Cu/Ti wiring substrate. Specifically, 100 ml of each of the cleaning compositions of Examples 1 to 11 and Comparative Examples 1 to 8 was placed in a 250 ml beaker, and the glass substrate was immersed therein for 30 minutes at room temperature (25°) and washed. Thereafter, the substrate was washed with ultrapure water for 30 seconds and dried with nitrogen. The SEM (S-4700, supplied by Hitachi, Ltd.) was used to observe whether the Al and Cu of the substrate were damaged. The results are shown in Table 2 below.

The evaluation results of the damage of the wires are also shown in Figs.

As can be seen from Table 2, all of the cleaning compositions according to Examples 1 to 11 of the present invention showed superior cleaning ability and did not cause a PI alignment layer. Damage. Moreover, no damage to Al and Cu was observed.

However, the cleaning composition containing a small amount of the basic compound in Comparative Example 1 completely removed the PI alignment layer and damaged the metal layer containing Al and Cu, and the cleaning composition of Comparative Example 2 was effective for removing impurities, but The organic material is caused to remain behind the substrate to thereby form a stain, undesirably causing defects. The cleaning composition of Comparative Example 3 did not cause damage to the alignment layer, but had a low cleaning ability to remove impurities. The cleaning composition of Comparative Example 4 did not cause damage to the alignment layer and showed superior cleaning ability, but damaged copper; in addition to the components of the present invention, the cleaning agent combination of Comparative Example 5 further containing a basic compound The PI alignment layer was undesirably peeled off; the cleaning composition of Comparative Example 6 containing no pyrrolyl compound undesirably damaged Cu. The cleaning composition of Comparative Example 7 containing only pure water did not cause damage to the PI alignment layer but undesirably exhibited low cleaning ability, and the Comparative Example 8 detergent composition containing organic acid undesirably damaged Cu .

Meanwhile, FIG. 1 is a photograph showing a Cu surface when a Cu/Ti wiring substrate is cleaned using the cleaning composition of Example 1, and FIG. 2 is a view showing an Al surface when a Mo/Al/Mo wiring substrate is cleaned using the cleaning composition of Example 2. Photograph, FIG. 3 is a photograph showing the Al surface when the Mo/Al/Mo-wiring substrate was washed using the cleaning composition of Comparative Example 1, and FIG. 4 is a view showing the cleaning of the Cu/Ti wiring substrate using the cleaning composition of Comparative Example 1. A photo of the surface of Cu.

With respect to Figures 1 to 4, the cleaning composition of Examples 1 and 2 according to the present invention did not cause damage to the Cu/Ti wire and the Mo/Al/Mo wire. However, the cleaning composition of Comparative Example 1 damaged all of the Cu/Ti wire and the Mo/Al/Mo wire.

As described above, the present invention provides a cleaning composition having excellent wetting and penetration effects and is very effective in removing contaminants from the surface of the alignment layer substrate. The cleaning composition according to the present invention does not damage the alignment layer included in the LCD, and thus can exhibit superior effects in substrate cleaning performed before or after rubbing the liquid crystal alignment layer in the process of manufacturing the liquid crystal cell of the LCDs. In particular, when the cleaning composition according to the present invention is used to manufacture an LCD, its ability to remove metal particles located on the alignment layer is high. The cleaning composition according to the present invention is non-combustible and therefore safe and environmentally friendly without causing bubble problems. Moreover, the cleaning composition according to the present invention does not corrode a metal layer containing Cu and a metal layer containing Al.

While the preferred embodiment of the present invention has been disclosed for the purpose of illustration, it will be understood by those skilled in the art It is possible.

The features and advantages of the present invention will be more clearly understood from the following detailed description of the accompanying drawings in which: FIG. 1 shows the surface of Cu when the Cu/Ti wiring substrate is cleaned using the cleaning composition of Example 1; The surface of Al when the Mo/Al/Mo wiring substrate was cleaned using the cleaning composition of Example 2; FIG. 3 shows the surface of Al when the Mo/Al/Mo wiring substrate was cleaned using the cleaning composition of Comparative Example 1; And FIG. 4 shows the surface of Cu when the Cu/Ti wiring substrate was washed using the cleaning composition of Comparative Example 1.

Claims (7)

A cleaning agent composition for removing contaminants from an upper surface of an alignment layer substrate, the cleaning composition containing no basic compound and no organic acid other than organic phosphoric acid, based on the total weight of the cleaning composition, including : 5 to 10% by weight of a C1 to C5 lower alcohol; 5 to 10% by weight of a water-soluble glycol ether compound; 1 to 2% by weight of an organic phosphoric acid; 0.2 to 0.5% by weight of a pyrrolyl compound; and the remainder Water; the pyrrolyl compound is selected from N-[(benzotriazole)methyl]diethanolamine, N-[(methyl-1H-benzotriazol-1-yl)methyl]dimethanolamine , N-[(ethyl-1H-benzotriazol-1-yl)methyl]diethanolamine, N-[(methyl-1H-benzotriazol-1-yl)methyl]dipropanolamine , 2,2'-[[(methyl-1H-benzotriazol-1-yl)methyl]imino]dicarboxylic acid, 2,2'-[[(methyl-1H-benzotriazole) a group consisting of -1-yl)methyl]imino]dimethylamine and N-[(amine-1H-benzotriazol-1-yl)methyl]diethanolamine. The cleaning composition of claim 1, wherein the C1 to C5 lower alcohol is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, ethylene glycol, 1,2-propanediol, 1,3 a group consisting of propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, glycerol, and 1,2,4-butanetriol. The cleaning composition of claim 1, wherein the water-soluble glycol ether compound is a C1 to C10 water-soluble glycol ether. The cleaning composition of claim 1, wherein the water-soluble glycol ether compound is selected from the group consisting of ethylene glycol monomethyl ether, diethyl Glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, A group consisting of triethylene glycol monobutyl ether, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether. The cleaning composition of claim 1, wherein the organic phosphoric acid comprises aminotrimethylenephosphonic acid, ethylene diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, 1-hydroxybutylidene-1,1-diphosphonic acid, ethylaminodimethylenephosphonic acid, 1,2-propylenediaminetetramethylene Phosphonic acid, dodecylaminodimethylenephosphonic acid, nitrotrimethylenephosphonic acid, ethylenediamine dimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, hexenediamine tetramethylene a group consisting of phosphinic acid, diethylenetriamine penta methylene phosphonic acid, cyclohexanediamine tetramethylene phosphonic acid, hydroxyphosphonium acetic acid and 2-phosphonic acid-butane-1,2,4-tricarboxylic acid One or more selected from the group. A liquid crystal cell comprising an alignment layer which is cleaned with a cleaning composition as claimed in claim 1. A liquid crystal display comprising a liquid crystal cell as in claim 6 of the patent application.