TW201114888A - Aqueous detergent composition - Google Patents

Abstract

Disclosed is an aqueous detergent composition containing no alkaline compound, which includes based on total weight of the composition, 0.1 to 15 wt% of a C1 to C5 lower alcohol, 0.1 to 15 wt% of a water-soluble glycol ether compound, and 0.01 to 10 wt% of one or more selected from among organic phosphoric acids and salts thereof, with the remainder being water.

Description

[Technical Field] [0001] The present invention relates to a water-based detergent composition for use in a semiconductor, a display device, or the like. More specifically, it is a substrate water-based detergent composition used before and after the rubbing operation of the liquid crystal alignment film in the liquid crystal cell (ce 11) manufacturing process of the liquid crystal display device. [0002] [Prior Art] Generally, in the liquid crystal cell fabrication process, in order to have two patterned pattern substrates having an electric pattern, the function of the alignment film and the insulating film is first applied to the polycrystalline film. After the amine (polyimide), after a mating film is formed in a certain direction to form a alignment film, in order to form a container of the liquid crystal cell and control the thickness of the liquid crystal cell, the spacer 〇 [0003] (spacer) and the sealing adhesive are disposed. It is placed between the two substrates to join the two substrates to each other. At this time, if there is residual contaminant on the alignment film substrate which is injected into the liquid crystal, not only a clear picture cannot be displayed, but also a bad situation is often caused in the packaging process, and it is necessary to remove the residual residue on the substrate by washing. Contaminants. ' ' >ί'f; κ心. ί': When manufacturing liquid crystal cells of a liquid crystal display device, the source of contamination of the substrate may include performing a friction engineering process t before bonding two polyimide substrates (PI). Foreign matter or polyimine particles that have been rubbed off the rubbing cloth can cause undesirable conditions when these contaminants are attached to the substrate. [0004] In order to remove such contaminants which occur during the process, the most common method now is to use a solvent such as isopropyl alcohol, an aqueous solution of isopropyl alcohol or pure water. However, if the solvent is used for washing, the solvent will remain on the substrate. 099120711 Form No. A0101 Page 3 of 16 0993376168-0 201114888 Poor situation. In addition to this, there are problems with chemical stability such as safety and flammability. Moreover, after entering the era of high oil prices, as the price of raw materials rises, the cost of manufacturing engineering also rises. Moreover, in the case of pure water, it is impossible to thoroughly clean up the pollutants, which causes a problem of a decrease in manufacturing yield. Further, a detergent containing a basic compound therein may cause damage to a polyimide film (PI). [0006] In order to solve the aforementioned problems, many manufacturers are currently working on water-based cleaning systems that have operational safety and are improved in washing power and flexibility by adding various surfactants. SUMMARY OF THE INVENTION [0007] In order to solve the aforementioned problems, the main object of the present invention is to provide a water-based detergent composition characterized by having excellent moisturizing and soaking effects, so that it can be thoroughly The contaminant on the alignment film substrate is washed to obtain an excellent cleaning effect. In addition, it does not cause damage to the alignment film, and it is safe and environmentally friendly because it has no ignition and low foaming. [0008] The present invention is a water-based detergent composition which does not contain a basic compound, and more specifically, provides a lower alcohol, a water-soluble glycol ether compound containing C1 to C5, and one or more selected from organic A component of phosphoric acid and an organic phosphate, and a water-based detergent composition. Further, the present invention provides a liquid crystal display device comprising a liquid crystal cell of an alignment film washed with the above-described water-based detergent composition. [0010] The water-based detergent composition of the present invention has excellent wetting and soaking effects 099120711 Form No. A0101 Page 4 / Total 16 Page 0993376168-0 201114888 [0011] ο [0012] ❹ [0013], so The contaminant on the alignment film substrate can be thoroughly washed to obtain an excellent washing effect. In addition, there is no damage to the alignment film, and it is safe and environmentally friendly due to lack of ignitability and low bubble. In this way, in the liquid crystal cell manufacturing process of the liquid crystal display device, the water-based detergent composition of the present invention can be excellent in the substrate cleaning process performed before and after the rubbing operation of the liquid crystal alignment film. effect. [Embodiment] The cleaning liquid composition of the present invention is a water-based detergent composition containing no basic compound therein, and the water-based detergent composition contains C-C5 low-grade alcohol, a water-soluble glycol ether compound, One or more components selected from the group consisting of organic phosphoric acid and organic acid salt, and water-based detergent composition. In general, basic compounds are often used to remove contaminants or organic matter from the atmosphere, but if used in liquid crystal cell manufacturing of display devices, it is easy to cause polyimide (PI) alignment. The condition of the membrane being damaged. Since the cleaning liquid composition of the present invention does not contain an alkali compound, it is possible to prevent the polyimide film (PI) from being damaged. Further, the water-based detergent composition of the present invention is a combination of a Cb C5 lower alcohol, a water-soluble glycol ether compound, and one or more components selected from the group consisting of organic phosphoric acid and an organic phosphate, and thus is in a display device. In the cell manufacturing process, when used in the cleaning operation before and after the rubbing of the liquid crystal alignment film, excellent cleaning effect of the pollutants can be obtained, and since it is not igniting and low bubble, it is safe and environmentally friendly. . Especially in the washing of polyimine (PI, polyimide) 099120711 Form No. A0101 Page 5 / 16 pages 0993376168-0 201114888 Alignment film 'has played a very good detergent cleaning effect. [0014] The low-grade alcohol of Cl~C5, the water-soluble glycol mystery compound, one or more components selected from the group consisting of organic phosphoric acid and organic phosphate, and the preferred content of water in the water-based detergent composition are The total weight of the substance is based on the weight of the C5 C5 lower alcohol, 1·1 weight by weight, and the water-soluble diol mystery compound is 1. 1% by weight (wt%) to 15% by weight (wt%), one or more selected from The composition of the organic phosphoric acid and the organic phosphate is 〇. 〇1% by weight (wt%) to 10% by weight (wt%), and the remaining amount is water. [0015] The above-mentioned C1 to C5 low-grade alcohol enhances the wettability and the permeation force of the cleaning liquid to the substrate, and at the same time prevents the contaminant from re-sticking back, and as a result, the contaminant on the substrate can be easily removed. [0016] The type of the lower alcohol of the above-mentioned C1 to C5 is not particularly limited. However, in consideration of physical properties such as water solubility, it is recommended to use a lower alcohol such as decyl alcohol, for example, decyl alcohol, ethanol, or n-propanol. , isopropanol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, glycerol, hydrazine , a low-grade alcohol such as 2, 4-butanetriol, and the salty component may be used alone or in combination of two or more components. The weight ratio of the above-mentioned low-grade alcohol is preferably 0.1% by weight (% by weight) to 15% by weight, and the optimum ratio is 〇. 5重量% ( Wt%) to 1〇 weight. If the content of the lower alcohol is less than 0.1% by weight (wt%), the surface tension cannot be lowered and the wettability is not easily obtained, and if it exceeds 15% by weight, the lower alcohol remains on the substrate. Causes bad. 099120711

Form No. A010I Page 6 of 16 0993376168-0 201114888 [0018] ❹ [0019] 〇

In the above aqueous detergent composition, the water-soluble glycol ether compound can remove the oil component on the surface of the friction substrate which is difficult to remove using a low-grade aqueous alcohol solution, and at the same time, improve the solubility in water. Among the above water-soluble glycol ether compounds, a water-soluble glycol ether of Cl-C10 is suggested. Preferred examples of the water-soluble glycol ether of C1 to C10 are 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 A component such as BTG, propylene glycol monomethyl ether (MFG) or dipropylene glycol monoterpene (MFDG) may be used alone or in combination of two or more components. 3^^ 隐转丨丨 The above water-soluble glycol ether compound is determined by the total weight of the washing liquid. It is recommended to use 0.1% by weight (%) to 15% by weight (^%), wherein The optimum content is from 0.5 wt% (wt%) to 10 wt% (wt%). If the content is less than 0.1% by weight (wt%), it is not easy to remove the oil component on the surface of the friction substrate, and if it exceeds 15% by weight (wt%), the viscosity of the detergent composition rises. The problem of the wettability of the substrate to be cleaned is reduced. V

[0020] In the above-mentioned water-based washing composition, a component selected from the group consisting of organic light or organic Wei salt prevents the contamination between the various scorpions, and can also enhance the cleaning process. The dampening power of the detergent on the substrate improves the cleaning effect. [0021] The kind of the above organic phosphoric acid is not particularly limited to use aminotri(methylsulfonic acid), ethylenediyldicarboxylic acid, for example, 099120711 1,1-diphosphoric acid, hydroxypropylidene-1, Form No. A0101 Page 7 of 16 1-Hydroxyethylidene - Di-disc acid, 1-hydroxybutyrene 0993376168-0 201114888 Base-1,1-diphosphoric acid, ethylamino-di(methylene phosphate), 1,2-propylene diamine tetra (methylene phosphate), dodecylamino-bis (methylene phosphate), nitrotri(methylene phosphate), ethylene diamine-bis (methylene phosphate) , ethylenediaminetetrakis (phosphinic acid), hexene diamine tetrakis(phosphonium phosphate), diethylenetriamine pentadecylphosphoric acid, cyclohexanediamine tetra(phosphonium phosphate), hydroxyphosphonium acetic acid An organic phosphoric acid such as 2-phosphono-butane-1,2,4-tricarboxylic acid. Among them, 1-hydroxyethylidene 1,1-diphosphate, hydroxyphosphonium acetate, aminotris(arylenephosphoric acid), 2-phosphonium-butane-1,2,4-tricarboxylic acid and the like are preferably used. Further, as the above organic phosphate, a sodium salt or a potassium salt of the above-mentioned organic phosphoric acid can be used. [0022] Among the above-mentioned constituents, the content of one or more components selected from the group consisting of organic phosphoric acid and organic phosphate is based on the total weight of the cleaning liquid, and it is recommended to use 0.01 weight% /» (wt%) to 10% by weight ( The content of the above-mentioned one or more selected from the group consisting of the organic phosphoric acid and the organophosphate is less than 0.10. 01% by weight (wt%) to 5% by weight (wt ° / 〇. In the case of % by weight (wt%), it is not easy to increase the wettability of the surface of the substrate after rubbing, and if the content exceeds 10% by weight/e (wt%), the component remains on the substrate to cause an adverse effect. [0023] The water component in the water-based detergent composition is not particularly limited, but it is recommended to use water for semiconductor engineering and have a specific resistance value of more than 18 ΜΩ/αη. The water content may be based on other constituents. [0024] In order to improve the cleaning performance, the water-based detergent composition of the present invention may be supplemented with additives commonly used in the industry, such as preservatives, wet penetrants, dispersants, surface modifiers, etc. 099120711 Form No. Α0101 Page 8 / Total 16 pages 099: 201114888 [0025] [0028] The constituent components contained in the water-based detergent composition of the present invention can be produced according to a general method, but it is recommended to use semiconductor engineering. Further, the present invention relates to a liquid crystal cell comprising an alignment film cleaned with the aqueous detergent composition, and a liquid crystal display device comprising the liquid crystal cell. The water-based detergent composition of the present invention is used. The residual contaminant on the alignment film substrate can be completely removed, and thus the liquid crystal cell having such an alignment film exhibits excellent quality. In addition, the liquid crystal display device including such a liquid crystal cell can provide a clear display surface. There is no particular limitation on the method of cleaning the water-based detergent composition of the present invention, and for example, a soaking method, a shaking method, an ultrasonic cleaning method, a jet cleaning method, a mud cleaning method, or the like can be used. Various cleaning methods such as brush cleaning method. The cleaning liquid composition of the present invention is used in a liquid crystal cell manufacturing process of a liquid crystal display device, and the liquid crystal alignment film is rubbed. (rubbing) a detergent on a substrate before and after the operation, the cleaning liquid not only has excellent safety, but also completely removes contaminants such as particles remaining on the alignment film substrate. In addition, the present invention The cleaning liquid composition does not generate a residue of the cleaning liquid, and can prevent the contaminants such as particles from re-adhering back to the substrate. The surface of the alignment film is not damaged by the cleaning operation. In addition, the cleaning system which is safe and stable can be provided. In addition, the water-based detergent composition of the present invention has low bubble characteristics, so that the work product caused by the air bubbles is prevented during the use of the spray engineering. 099120711 Form No. A0101 Page 9 of 16 Page 0993376168-0 [0029] 201114888 The situation of quality reduction. [0030] 膏 Μ 1 1 1 1 1 1 1 1 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 In the mixing tank, after the mixture was stirred at 500 rpm for 1 hour at normal temperature, the composition of the cleaning liquid was completed. Test Example: Detergency and Orientation Film Quotation Evaluation [0032] 1. Detergency Evaluation [0033] The cleaning liquid compositions prepared in the above Examples 1 to 13 and Comparative Example 4 were placed in 100 ml. After a beaker of a capacity of 250, the substrate (5x5x0. 7 cm) after rubbing with a polyimide (PI, polyiraide) alignment film was immersed, and then subjected to ultrasonic washing (40 kHz, 20 ° C) for 1 minute. Clean homework. Thus, the substrate taken after a certain period of cleaning operation was rinsed with ultrapure water for 30 seconds. Next, the liquid on the surface of the substrate was removed with nitrogen, placed in an oven, and dried at 170 ° C for 5 minutes. Finally, after the substrate was inspected using a scanning electron microscope (SEM: Hitachi, model S-4700), the cleaning power was judged by the number of foreign particles remaining on the surface of the substrate. The comparison results are shown in Table 1, Figure 1, and Figure 2 below. [0034] 2. Polyacetamide alignment film exaggeration evaluation [0035] After the cleaning solution 100 prepared in the above Example 13 and Comparative Examples 1 to 4 was placed in a beaker of a capacity of 250, A glass substrate on which the polyimide film was formed was immersed in a beaker for 30 minutes for washing. Next, the substrate is taken out from the cleaning liquid composition, and after rinsing with water, the liquid on the surface of the substrate is removed by nitrogen to be dried. 099120711 Form No. A0101 Page 10 of 16

I 201114888. Finally, the degree of damage of the substrate was examined using a scanning electron microscope (SEM··Hitachi, model S-4700) and visual inspection. The results of the inspection are as follows: Table 1 [0036] [Table 1] [0037] 〇 成分 成分 低 低 酒精 酒精 酒精 酒精 酒精 P P P P P P P P P P P P P P P P P P P P P P P P P wt wt wt %) Type t (wt%) Example 1 A-1 5 Bl Cl 2 戎* 〇 No Example 2 A-1 5 Bl 5 C-2 2 Residual ◎ No Example 3 Ai 10 Bl 5 ττ- 5 Residual amount ◎ No Example 4 A-1 5 B-2 5 Cl 2 Residual stage 〇 No Example 5 A-1 5 B-2 i- C-2 5 Residual amount ◎ Example 6 A-1 5 B- 2 10 03 2 Residual kettle ◎ None Example 7 A-1 5 B-3 5 C-2 2 Play ◎ No Example 8 A-2 5 Bl 5 Cl 2 Residual * 〇 No Example 9 A-2 5 B_2 5 Cl 2 Residual amount 〇 No Example 10 A-2 5 B-3 5 C-2 2 Residual ◎ No example Π A-3 5 Bl 5 C-2 2 Residue ◎ No Example 12 A-3 5 B-2 5 C-2 2 Residual kettle ◎ No example A-3 5 B-3 5 C-2 2 Residual amount ◎ No comparative example i ΤΜΑΗ 1 Residual Dong ◎ Deviation from comparative example η R.? ( 2ft Residual Quantity Δ h Comparative Example 3 C-2 5 Several quantities X No comparison example _4 100 wt% X None

[Cleaning efficiency] ◎: quite good, 〇: good, △: normal, X: bad A-1: ethanol A-2: isopropyl alcohol A-3: glycerol B-1: diethylene Alcohol monomethyl ether (MDG) B-2: Diethylene glycol monoethyl ether (EDG) B-3: Diethanol monobutyl ether (BDG) C-1: Hydroxy-ethylidene-l,i-diphosphate (HEDP) 099120711 Form No. A0101 Page 11 of 16 201114888 [0040] [0041] [0042] 099120711 C-2: 2-filled-butane tricarboxylic acid (PBTC) C-3: hydroxyphosphonium Acetate (ηρα)ΤΜΑΗ·Tetramethyl ammonium hydroxide As shown in Table 1 above, the detergent compositions of Examples 1 to 13 of the present invention all exhibited excellent detergency, and Polyimine (PI, polyimide) alignment film does not cause damage. On the other hand, the cleaning liquid composition of Comparative Example 1 containing a very small amount of the test compound was not used because it completely removed the polyimide film (PI). Further, in the cleaning liquid composition of Comparative Example 2, the foreign matter was cleaned, but the trace of the organic substance remained on the substrate to cause defects. Further, in the case of the cleaning liquid composition of Comparative Example 3, although the alignment film was not damaged, the foreign matter exhibited a low cleaning power. Further, in the cleaning liquid composition of Comparative Example 4 which was composed of pure water, the polyimide film was not damaged, but the cleaning power was low and the defects were poor. The above is intended to be illustrative only and not limiting. Any equivalent modifications or alterations to the spirit and scope of the invention are intended to be included in the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a photograph of a polyimide film on a polyimide film using a scanning electron microscope (SEM) after performing a washing test using the cleaning liquid of Example 1 of the present invention. Fig. 2 is a photograph of a polyimine alignment film using the cleaning liquid of Comparative Example 4 of the present invention. [Photographing using a scanning electron microscope (SEM) to form a polyimide film. No. A0101 Page 12 of 16 201114888 Substrate Photo. [Main component symbol description] [0043]None

099120711 Form number A0101

Page 13 of 16

0993376168-0

Claims (1)

201114888 VII. Patent application scope: 1. A water-based detergent composition containing no basic compound, which comprises a C-C5 lower alcohol, a water-soluble glycol ether compound, and more than one selected from the group consisting of organic phosphoric acid and organic phosphate. Ingredients and water. 1重量%至15重量%的该重量。 The water-based detergent composition comprising 0.1% by weight to 15% by weight of the composition of the water-based cleaning liquid composition. The lower alcohol of C C5, 0.1% by weight to 15% by weight of the water-soluble glycol ether compound, 0.01% by weight to 1% by weight of the one or more selected from the group consisting of organic phosphoric acid and organic phosphate. The ingredients, and the remaining residue, are the water. 3. The water-based cleaning composition according to the first aspect of the invention, wherein in the liquid crystal display device engineering, the water-based cleaning liquid composition is used to clean the substrate before and after the friction welding process. 4. The water-based detergent composition according to claim 1, wherein the C-C5 lower alcohol comprises at least one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-l"f alcohol, 1,4-butanedipropion, glycerol and 1,2,4-butanetriol Compounds in the group formed. 5. The water-based detergent composition according to claim 1, wherein the water-soluble glycol ether compound is a water-soluble glycol mystery of c 1 to c 10 . 6. The water-based detergent composition according to claim 1, wherein the δ-water-soluble glycol ether comprises at least one selected from the group consisting of ethylene glycol monomethyl bond (μ〇) and diethylene glycol alone. Methyl 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), three 099120711 Form No. A0101 Page 14 / Total 16 pages 0993376168-0 201114888 Ethylene glycol monobutyl ether (BTG), propylene glycol monomethyl ether (MFG And a compound of the group consisting of dipropylene glycol monomethyl ether (MFDG). 7. The water-based detergent composition according to claim 1, wherein The one or more components selected from the group consisting of organic phosphoric acid and organophosphate include at least one selected from the group consisting of aminotri(methylenephosphonic acid), ethylenediphosphonic acid, 1-hydroxyethylidene-1, diphosphoric acid, and 1-hydroxyl Propyl-1,diphosphoric acid, 1-hydroxybutylidene-1,1-diphosphate, ethylamine bis(methylenephosphonic acid), 1,2-propylenediaminetetrakis(phosphonium phosphate), dodecyl Aminobis(methylenephosphonic acid), nitrotris(methylenephosphonic acid), ethylenediaminedi(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphoric acid), hexenediaminetetrakis (methylene Phosphoric acid), diethylene triamine penta methylene phosphate, cyclohexanediamine tetra (methylene phosphate), hydroxyphosphoric acid, 2-phosphoryl-butane-1,2,4-tricarboxylic acid, and a compound of the group consisting of sodium or potassium salts. A liquid crystal cell comprising an alignment film which is cleaned using the aqueous cleaning liquid composition according to any one of claims 1 to 7. A liquid crystal display device comprising the liquid crystal cell according to item 8 of the patent application. 0993376168-0 099120711 Form No. A0101 Page 15 of 16