Background technology
Liquid crystal panel has the low advantage of current consumption, has been used for showing multiple image, for example in the fields such as panel of products such as computer terminal indicating meter, TV screen and mobile phone.
In typical liquid crystal panel technology, make two sheet glass substrates at a distance of the predetermined distance below 10 microns, and, make and wherein form a hollow space with bonding two plate bases of solid, then liquid crystal material is enclosed in this hollow space.Above-mentioned two sheet glass substrate inside are provided with the electrode that display text and image are used, and it is made of transparent conductive film, and when applying control thereon and using electrical signal, i.e. the demonstration of may command literal and image.
In the technology of above-mentioned liquid crystal panel, the outside of the connection portion of two plate bases can stay micron-sized little width unavoidably, and space of unavoidable generation.Therefore, when liquid crystal material was injected hollow space between two sheet glass substrates, liquid crystal material can be invaded in this space because of wicking action.Because the pollutent in the atmosphere can be dissolved in the liquid crystal material space in, and these spaces are positioned at just and apply the position of electrical signal to transparency electrode, can cause the problem of insulativity deterioration.Therefore, the liquid crystal material in the intrusion space must be cleaned and remove.
Because the substrate of gap is very narrow at interval below 10 microns.So as desiring to remove fully the liquid crystal material of intrusion, employed sanitising agent must have the clean ability of height.In the prior art available clean-out system, effect preferably is a fluothane, trichloroethane, and trieline, zellon and methylene dichloride etc. contains the organic solvent of halogen.But, owing to the control to halogen-containing organic solvent is a ring very important in world's environmental protection scheme, so greatly limited in the use.
Substitute in development under the demand of clean-out system, some can replace the novel detergent of aforementioned halogen-containing organic solvent to be developed.Be mainly the solvent of hydrocarbon, or the mixed component of hydrocarbon cosolvent and polyglycol ether, open flat 10-25495 as the spy and disclose a kind of clean-out system that can effectively clean the dirt of liquid crystal cell, the boiling point that this clean-out system contains 5-95 weight % 160-280 ℃ representative examples of saturated aliphatic hydrocarbon polymer and/or saturated alicyclic hydrocarbon (as, decane or cyclododecatriene), with the glycol ether of 5-95 weight %, its chemical general formula is R1-(O-C
nH
2n)
m(wherein, R1 and R2 are H to-O-R2, and alkyl or acyl group, the total number of carbon atoms of R1 and R2 are 1-20, and n is 2 or 3; M is the integer among the 1-3) (as, the vinyl glycol dimethyl ether).But the clean ability of this class clean-out system is relatively poor relatively, and flammable high.
In addition, in the production technique of liquid crystal panel, the mother metal glass cutting must be become the glass substrate of fritter usually, and meeting produces a large amount of powder in cutting process, these powder can be attached to the surface of electrode terminal, and greatly hinders packaging process subsequently, removes so must clean.The Superficial Foreign Body of glass powder and so on usually with Intermolecular Forces attached to the liquid crystal panel surface, but also might make wedding agent with liquid crystal material, and closely attached on the liquid crystal panel, the clean-out system that therefore can remove the panel surface foreign matter must have higher clearing power.The clean-out system that is used for glass powder of prior art, open as the spy that disclosed clean-out system is an alkaline cleaner in flat 5-271699 and the flat 7-305093 of Te Kai and the special Japanese patent application of opening 2001-181699, not only easily liquid crystal panel is caused damage, and can not effectively clean and make wedding agent and the glass powder of close attachment on liquid crystal panel with liquid crystal material.
Along with the densification Progress in technique of liquid crystal panel in recent years, void pitch between described base plate of liquid crystal panel is narrower again, add will going of demand that promotes production capacity and the production qualification rate that improving liquid crystal panel, required clean-out system must have the clean ability of height of ablution crystal panel at short notice.Not only need to clean the liquid crystal material of invading the gap, but also will possess the ability of cleaning the electrode terminal Superficial Foreign Body simultaneously.In addition, used stn liquid crystal material mostly is that to have with cyano group be the substituent aromatics of representative, and the TFT liquid crystal material is the substituent aromatic compound of representative for having with the cyanogen atom.Because the molecular structure of stn liquid crystal material and TFT liquid crystal material is different with physical properties, also need a large amount of various types to clean composition applicable to the different plurality of liquid crystals material of molecular structure transitivity.Disclose a kind of liquid crystal panel use liquid cleaner composition as CN1451731A, said composition comprises that carbon number is the hydrocarbon polymer of 8-20, and content is 5-50 weight %; Anion surfactant, content are 1-20 weight %; General formula is R
4O (BO)
0R
5Compound, content is 1-40 weight %; Methyl-sulphoxide, content are 1-20 weight %, and a certain amount of water, wherein, and R
4For carbon number is alkyl or alkenyl, the phenyl of 4-11, or phenmethyl, R
5For hydrogen atom or carbon number are the alkyl of 1-4, BO is that carbon number is the oxyalkylene group of 2-3, and 0 is 1-6.R as described
4O (BO)
0R
5Compound can be glycol ether compounds such as Diethylene Glycol single-butyl ether, Diethylene Glycol dibutyl ether.The disclosed liquid crystal cleaning agent composition of CN1451731A is the aq. type clean-out system, make the combustibility of clean-out system reduce greatly though contain water in the aq. type clean-out system, but on cleaning performance than leaning solvent difference, and the component of said composition is more, it is complicated to form, therefore, the cost height and the preparation process complexity that cause this clean-out system.
Embodiment
According to liquid crystal cleaning agent composition provided by the invention, gross weight with said composition is a benchmark, the content of described hydrocarbon polymer is 60-98 weight %, be preferably 75-98 weight %, the content of glycol ether compound is 1-20 weight %, be preferably 1-15 weight %, the content of nonionogenic tenside is 1-20 weight %, is preferably 1-15 weight %.
According to the present invention, described nonionogenic tenside is selected from one or more in polyoxyethylene glycol bisgallic acid ester, the fatty alcohol-polyoxyethylene ether, and preferred nonionogenic tenside is a polyoxyethylene glycol bisgallic acid ester.
Described polyoxyethylene glycol bisgallic acid ester has following chemical general formula:
R
1COO-(CH
2-CH
2-O-CH
2-CH
2-O)
n-OC-R
2
In the formula, R
1, R
2Identical or different, for carbonatoms is the alkyl or alkenyl of 3-10, under the preferable case, described R
1And R
2Identical, be selected from a kind of in amyl group, hexyl, heptyl, octyl group or pentenyl, hexenyl, heptenyl, the octenyl; N is 1-16, is preferably the integer of 1-12.Polyoxyethylene glycol bisgallic acid ester can be selected from one or more in dimerization ethylene glycol bis amyl group acid esters, trimerization ethylene glycol bis heptyl acid esters, trimerization ethylene glycol bis octyl group acid esters, the two hexyl acid esters of ten polyoxyethylene glycol, the two hexenyl acid esters of four polyoxyethylene glycol, the two octenyl acid esters of six polyoxyethylene glycol as described.
Described fatty alcohol-polyoxyethylene ether has following chemical general formula:
RO-(CH
2-CH
2-O)
n-H
In the formula, R is that carbonatoms is the alkyl or alkenyl of 2-20, R can be selected from a kind of in amyl group, octyl group, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl or octenyl, decene base, hendecene base, laurylene base, tridecylene base, tetradecene base, ten pentaene bases, hexadecylene base, 17 thiazolinyls, the octadecylene base as described, and n is the integer of 2-10.
According to the present invention, described fatty alcohol-polyoxyethylene ether can be selected from one or more in octyl group alcohol three polyoxy Vinyl Ethers, decyl alcohol eight Soxylat A 25-7s, dodecyl alcohol six Soxylat A 25-7s, tridecyl alcohol ten Soxylat A 25-7s, pentadecyl alcohol six Soxylat A 25-7s, hexadecyl alcohol eight Soxylat A 25-7s, hendecene base alcohol six Soxylat A 25-7s, laurylene base alcohol ten Soxylat A 25-7s, the Brij, more preferably Brij.Described Brij has following chemical general formula:
CH
3(CH
2)
7CH=CH(CH
2)
8O(CH
2CH
2O)
n-H
Described hydrocarbon polymer is that carbonatoms is the alkane of 6-20 and/or in the unsaturated hydrocarbon one or more.Hydrocarbon polymer can be selected from one or more in octane, positive nonane, n-decane, n-dodecane, n-tetradecane, n-hexadecane, Octadecane, octane-iso, Permethyl 99A., isohexadecane, hexanaphthene, dodecyl hexanaphthene, tetradecene basic ring hexane, decene, laurylene, tetradecene, the undecyl tetrahydrobenzene, the more preferably mixture of one or more in n-undecane, n-dodecane, n-tridecane, laurylene, dodecyl hexanaphthene, the undecyl tetrahydrobenzene as described.
Described glycol ether compound has following chemical general formula:
R
1-O-(CH
2CH
2O)
n-R′-O-(CH
2CH
2O)
n-R
2
In the formula, R
1, R
2Identical or different, for carbonatoms is the alkyl or alkenyl of 1-20, under the preferable case, R
1And R
2Identical, be selected from a kind of in ethyl, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, tridecyl, hexenyl, heptenyl, octenyl, nonene base, the decene base; Described R ' is the alkylidene group of 1-16 or a kind of group in the aryl or aralkyl for carbonatoms, as is selected from a kind of in methylene radical, ethylidene, propylidene, butylidene, phenyl, naphthyl, phenmethyl, the styroyl; N is 1-6, is preferably the integer of 2-5.
According to the present invention, described glycol ether compound can be selected from one or more in the two butyl ethers of three polyoxy ethene ethylidene, three polyoxy ethene, the two Octyl Ether of three polyoxy ethene ethylidene, three polyoxy ethene, the two butyl ethers of oxozone Ethenylbenzene methyl oxozone ethene, the two hexene ethers of oxozone ethene butylidene oxozone ethene.
Preparation method according to liquid crystal cleaning agent composition provided by the invention, this method comprises hydrocarbon polymer, glycol ether compound and nonionogenic tenside is mixed, wherein, described nonionogenic tenside is selected from one or more in polyoxyethylene glycol bisgallic acid ester, the fatty alcohol-polyoxyethylene ether.
Preparation method according to liquid crystal cleaning agent composition provided by the invention, the preferable amount of each component makes in the liquid crystal cleaning agent composition that obtains and contains, gross weight with said composition is a benchmark, content is the hydrocarbon polymer of 75-98 weight %, content is the glycol ether compound of 1-15 weight %, and content is the nonionogenic tenside of 1-15 weight %.
Described mixing is preferably under agitation to be carried out, and described blended temperature is preferably room temperature.
According to the present invention, the method for liquid crystal material being cleaned with described cleansing composition can adopt and well known to a person skilled in the art that any means cleans.Described method comprises liquid crystal material to be cleaned such as liquid crystal cell is contacted with cleansing composition that the temperature of described contact is 30-80 ℃, is preferably 45-65 ℃; The time of contact is 5-45 minute, is preferably 10-35 minute.Under the preferable case, described contact is for to be immersed in liquid crystal cell in the described cleansing composition, and described contact is preferably in ultrasonic wave to be carried out.
According to the present invention, after with described clean-out system liquid crystal cell being cleaned, described purging method also comprises the step of washing liquid crystal cell, and described washing is the basic solution washing of 0.1-5 weight % with concentration for elder generation, as potassium hydroxide or sodium hydroxide, and then use distilled water wash.The step that also comprises oven dry after the washing, the condition of described oven dry and method are conventionally known to one of skill in the art.
Below will the invention will be further described by embodiment.
Embodiment 1
Present embodiment illustrates preparation and the purposes with cleansing composition of the present invention.
The two n-butyl ether of 3 weight part oleyl alcohol, six Soxylat A 25-7s, 2 weight parts, three polyoxy ethene ethylidene, three polyoxy ethene and 65 weight part n-undecanes, 30 weight part n-dodecanes are mixed obtain cleansing composition A1.
The above-mentioned clean-out system that configures is heated to 50 ℃, 50 liquid crystal cells (it is 280A that BYD company produces the trade mark) are immersed in the above-mentioned detergent solution, concussion was taken out after 10 minutes in ultrasonic wave, use the potassium hydroxide solution of 1 weight % and distilled water with the liquid crystal cell washes clean respectively, dried the liquid crystal cell after obtaining cleaning 2 hours for 100 ℃.
Embodiment 2
Present embodiment illustrates preparation and the purposes with cleansing composition of the present invention.
The two n-butyl ether of the oxozone Ethenylbenzene methyl oxozone ethene of 5 weight part trimerization ethylene glycol bis n-heptyl acid esters and 5 weight part trimerization ethylene glycol bis n-octyl acid esters, 10 weight parts and 80 weight part dodecyl hexanaphthenes are mixed obtain cleansing composition A2.
The above-mentioned clean-out system that configures is heated to 50 ℃, 50 liquid crystal cells (it is 280A that BYD company produces the trade mark) are immersed in the above-mentioned detergent solution, concussion was taken out after 15 minutes in ultrasonic wave, use the potassium hydroxide solution of 1 weight % and distilled water with the liquid crystal cell washes clean respectively, dried the liquid crystal cell after obtaining cleaning 2 hours for 100 ℃.
Embodiment 3
Present embodiment illustrates preparation and the purposes with cleansing composition of the present invention.
5 weight part n-tridecane bases alcohol, ten Soxylat A 25-7s, the two n-butyl ether of 5 weight part oxozone Ethenylbenzene methyl oxozone ethene and 90 weight part n-undecanes are mixed obtain cleansing composition A3.
The above-mentioned clean-out system that configures is heated to 60 ℃, 50 liquid crystal cells (it is 280A that BYD company produces the trade mark) are immersed in the above-mentioned detergent solution, concussion was taken out after 25 minutes in ultrasonic wave, use the potassium hydroxide solution of 1 weight % and distilled water with the liquid crystal cell washes clean respectively, dried the liquid crystal cell after obtaining cleaning 2 hours for 100 ℃.
Embodiment 4
Present embodiment illustrates preparation and the purposes with cleansing composition of the present invention.
5 weight part dodecyls alcohol, six Soxylat A 25-7s and 3 weight part 10-laurylene bases alcohol, ten Soxylat A 25-7s, the two 2-hexene ethers of 7 weight part oxozone ethene butylidene oxozone ethene and 60 weight part n-undecanes and 25 weight part n-tridecane are mixed obtain cleansing composition A4.
The above-mentioned clean-out system that configures is heated to 55 ℃, 50 liquid crystal cells (it is 280A that BYD company produces the trade mark) are immersed in the above-mentioned detergent solution, concussion was taken out after 12 minutes in ultrasonic wave, use the potassium hydroxide solution of 1 weight % and distilled water with the liquid crystal cell washes clean respectively, dried the liquid crystal cell after obtaining cleaning 2 hours for 100 ℃.
Embodiment 5
Present embodiment illustrates preparation and the purposes with cleansing composition of the present invention.
The two 3-hexenyl acid esters of 3 weight parts, four polyoxyethylene glycol, the two n-octyl ethers of 5 weight parts, three polyoxy ethene ethylidene, three polyoxy ethene, the two n-butyl ether of 5 weight parts, three polyoxy ethene methylene tri polyoxyethylene, the two 3-hexene ethers of 5 weight part oxozone ethene butylidene oxozone ethene and 60 weight part n-tridecane and 22 weight part n-undecane basic ring hexenes are mixed obtain cleansing composition A5.
The above-mentioned clean-out system that configures is heated to 55 ℃, 50 liquid crystal cells (it is 280A that BYD company produces the trade mark) are immersed in the above-mentioned detergent solution, concussion was taken out after 10 minutes in ultrasonic wave, use the potassium hydroxide solution of 1 weight % and distilled water with the liquid crystal cell washes clean respectively, dried the liquid crystal cell after obtaining cleaning 2 hours for 100 ℃.
Embodiment 6
Present embodiment illustrates preparation and the purposes with cleansing composition of the present invention.
10 weight part dimerization ethylene glycol bis n-pentyl acid esters and the positive decyl alcohol of 5 weight parts eight Soxylat A 25-7s, the two 4-hexene ethers of 10 weight part oxozone ethene butylidene oxozone ethene and 60 weight part n-undecanes, 10 weight part n-tridecane, 5 weight part 3-laurylenes are mixed and obtain cleansing composition A6.
The above-mentioned clean-out system that configures is heated to 55 ℃, 50 liquid crystal cells (it is 280A that BYD company produces the trade mark) are immersed in the above-mentioned detergent solution, concussion was taken out after 20 minutes in ultrasonic wave, use the potassium hydroxide solution of 1 weight % and distilled water with the liquid crystal cell washes clean respectively, dried the liquid crystal cell after obtaining cleaning 2 hours for 100 ℃.
Comparative Examples 1
This Comparative Examples explanation is cleaned liquid crystal cell with traditional leaning solvent composition.
Method according to embodiment 1 is cleaned liquid crystal cell, and different is that used clean-out system is the clean-out system of CFC113, remembers and makes B1.
Embodiment 7-12
The liquid crystal cell that the present embodiment explanation is cleaned the clean-out system A1-A6 that adopts embodiment 1-6 preparation is cleaned the rate test.
The rate of cleaning test:
Described clean rate refers to through cleaning the qualification rate of liquid crystal cell.To place microscopically to observe through the face glass of the liquid crystal cell that cleans, if the no liquid crystal in surface is residual and foreign matter is qualified product.Formula below described clean rate is available obtains: clean rate=(total number of the liquid crystal cell of qualified product number/cleaning) * 100%.
The result is as shown in table 1.
Comparative Examples 2
The liquid crystal cell that clean-out system with Comparative Examples 1 is cleaned according to the method for embodiment 7-12 is cleaned the test of rate.
The result is as shown in table 1.
Table 1
The embodiment numbering | The clean-out system numbering | The rate of cleaning |
Embodiment 7 | A1 | 94% |
Embodiment 8 | A2 | 96% |
Embodiment 9 | A3 | 98% |
Embodiment 10 | A4 | 93% |
Embodiment 11 | A5 | 93% |
Embodiment 12 | A6 | 96% |
Comparative Examples 2 | B1 | 90% |
From above clean rate result as can be seen, solvent type liquid crystal cleaning agent composition provided by the invention will significantly be better than the solvent-borne type system washing composition of biography to the cleaning function of liquid crystal cell sheet.And composition component of the present invention is simple, and preparation is simple, and cost is low.(the clean rate with the glass after traditional clean-out system CFC113 agent cleaning can only reach about 90%.)