CN100400620C - Treatment method of reused liquid crystal material - Google Patents
Treatment method of reused liquid crystal material Download PDFInfo
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- CN100400620C CN100400620C CNB031255809A CN03125580A CN100400620C CN 100400620 C CN100400620 C CN 100400620C CN B031255809 A CNB031255809 A CN B031255809A CN 03125580 A CN03125580 A CN 03125580A CN 100400620 C CN100400620 C CN 100400620C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
Abstract
To provide a treating method for recovering and reusing a liquid crystal material having purity and physical properties reusable as a liquid crystal panel from a used liquid crystal panel. This treating method to reuse the liquid crystal material comprises (1) a process of taking out the liquid crystal material from the liquid crystal panel, (2) a process of purifying the taken out liquid crystal material, (3) a process of measuring the physical properties of the purified liquid crystal material and (4) a process of adjusting the physical properties of the liquid crystal material.
Description
Technical field
The present invention relates to be used for to utilize again the treatment process of the liquid crystal material that uses in the liquid crystal board that uses in the depleted liquid crystal display device on bad plate that liquid crystal board manufacturing process discharges or the market.
Background technology
Liquid crystal display device is as the linkage interface of people and computer etc. and be used for various uses, and the usage quantity in its output and market sharply increases.
Because recent Environmental awareness improves, therefore do not studying the discarded method that generation is loaded to environment or utilizing method again.
But even in resembling the computer big indicating meter such with liquid crystal display device, contained liquid crystal material also only has a small amount of about 1g in the liquid crystal board.And, because liquid crystal material is clipped in inner face and is coated with in the glass of organic membrane such as alignment films, and seals with sheet materials such as Resins, epoxy, so the development efficiency height, can utilize again easily and under the situation of non-involvement impurity, extract, and the treatment process of the economy that can reuse is difficult.
In the treatment process of useless liquid crystal board, the method of the recycling of liquid crystal material has been proposed, the treatment process of utilizing again that is used for liquid crystal material is wherein disclosed, comprise with organic solvents such as acetone or Virahols and will wash out in the liquid crystal slave plate, perhaps by liquid crystal being scraped off the recovery liquid crystal material, and in this liquid crystal that composition changes takes place by this recovery, add and mix the low molecular compound that may be removed at recovery process, come the liquid crystal composition that reclaims is adjusted (referring to patent documentation 1,2 and 3).
But, because the liquid crystal material purity that obtains by disclosed method in the above-mentioned document is very low, cause the physical parameter generation not normal owing to reclaim, it is difficult therefore it directly being utilized as liquid crystal material again.
In addition, though also disclose the method (referring to Patent Document 4) that liquid crystal material reclaims with supercutical fluid, the method (referring to Patent Document 5) that reclaims with hot water etc. are for utilization again, must adjust again many physical parameters, and treatment technology like this is not established as yet.
Patent documentation 1
The spy opens 2001-305501 communique (page 3, paragraph numbering 0017 and 0018)
Patent documentation 2
The spy opens 2001-305502 communique (page 3, paragraph numbering 0014 and 0015)
Patent documentation 3
The spy opens 2001-337305 communique (page 3, paragraph numbering 0020 and 0021)
Patent documentation 4
The spy opens 2002-126688 communique (page 2, paragraph numbering 0010)
Patent documentation 5
The spy opens 2002-166259 communique (page 2)
Summary of the invention
Problem of the present invention provides a kind of treatment process that is had the liquid crystal material of the purity that can be used further in the liquid crystal board and physical parameter by the recycling of exhausted liquid crystal board.
Present inventors are in order to solve above-mentioned problem, and to extract liquid crystal material from liquid crystal board, the result that the treatment process of utilizing again studies in great detail is the invention below having made.
Be that the present invention is the treatment process that is used for utilizing again liquid crystal material, it is characterized in that, comprising:
1) operation that liquid crystal material is extracted, the 2) operation of refining this liquid crystal material that extracts, 3) measure the operation of the physical parameter of this liquid crystal material of purified from liquid crystal board, and 4) adjust the operation of the physical parameter of this liquid crystal material.
If only liquid crystal material is extracted from liquid crystal board,, will be necessary as second operation therefore as the refining step that limits and remove them as far as possible of next process owing to sneak into impurity or ionic impurity from the component parts of liquid crystal board.In ensuing operation, be refined to which kind of degree and the processing passing through to be carried out and refiningly will remove which kind of composition, must before and after refining, compare.At this moment, in order finally to re-use, must measure the physical parameter of the liquid crystal material of MIN necessity as liquid crystal board.Adjust by necessary MIN physical parameter to the physical parameter of the liquid crystal that obtains by this operation and when re-using, make it suitable, thereby can re-use the liquid crystal material of recovery.
The working of an invention scheme
Below will be described in detail every operation of the present invention.
(1) operation that liquid crystal material is extracted from liquid crystal board
(a) plate is cut off
2 glass substrates enclosing liquid crystal material are bonding by sheet material.When plate cuts off, cut off in the sheet material inboard, contain 2 blocks of glass and wherein in the open system of the liquid crystal material of clamping, make it not contain sheet material what obtain by cut-out.Sheet material normally is made of Resins, epoxy or acrylate resin, is not contained in the liquid crystal material but importantly do not make by the resin-lint that cuts off the sheet material generation.Resin material sneaking in liquid crystal material can be removed by filtering liquid crystal material.But, because liquid crystal material contacts with resin-lint, the feasible liquid crystal purity drop that from liquid crystal, extract such as contained solidifying agent, additive in the resin.Particularly, ionic impurity because that it shows will cause re-using of liquid crystal material the time is bad, therefore must be avoided contacting of sheet material and liquid crystal.
(b) liquid crystal material is extracted from 2 blocks of glass
(b-1) method with an organic solvent
By using the organic solvent dissolution liquid crystal material, liquid crystal material can be washed out between 2 glass substrates.From the organic solvent solution of the liquid crystal material that obtains thus, adopt method such as distillation that organic solvent is heated up in a steamer, obtain liquid crystal material.
Usually at the inner face of 2 glass substrates, be formed with organic membrane or SiO such as polyimide
2Deng mineral membrane.As mentioned above, when flowing out, make sneaking into of impurity be inferior limit, require as far as possible with a small amount of organic solvent dissolution liquid crystal simultaneously and wash from these organic membrane and mineral membrane with organic solvent.
(organic solvent)
Viewpoint thus is as the preferred hexane of organic solvent, varsol that the toluene isopolarity is low.Alcoholic solvents such as methyl alcohol, ethanol, Virahol, acetone, methylethylketone equal solvent polarity height particularly have the shortcoming high to the solvability of ionic impurity.Therefore, if adopt the high solvent of polarity to carry out reclaimer operation, can be from organic membrane and mineral membrane stripping impurity, the foreign matter content in the liquid crystal material solution of recovery increases, and is therefore not preferred.
Also have, the ratio resistance of alcohols self is low, contains large quantity of moisture and ionic impurity in the solvent, and the result has reduced the resistance of the liquid crystal material that takes out from liquid crystal board, therefore is not suitable as extraction solvent.And alcoholic solvent is not high for the solvability of liquid crystal material, when therefore using alcoholic solvent, has to cause situation about separating out in liquid crystal material, so be not preferred.
Varsol such as hexane, toluene is difficult to stripping polarity macromolecule component or oligopolymer composition from organic membrane and mineral membrane and sheet material.And the ratio resistance of solvent self is 10
14Ω cm, very high, be preferred therefore.
(b-2) method by blowing
As the method that liquid crystal material is extracted, do not use solvent, the method that liquid crystal material is extracted by blow gas (blowing) from 2 blocks of glass from 2 blocks of glass.
Can use air as the gas that blows, but, preferably use rare gas elementes such as nitrogen or argon gas in order to suppress the oxidative degradation of liquid crystal material.
Method as air-supply can be used following method.
A. in advance separately, the method that reclaims by blow gas attached to the liquid crystal material on each glass substrate with 2 glass substrates
B. the method for blow gas between 2 glass substrates
C. with 2 strippable substrates, utilize liquid crystal to pass through surface tension simultaneously and, add blowing of gas in the effect that the direction of delaminate of two substrates is concentrated, extract the method for liquid crystal material effectively
The method of A is separated substrate in advance, therefore has the high characteristics of air-supply efficient.But, owing to contact, cause oxidative degradation easily with air, therefore preferably blow rare gas element.
Oxidative degradation takes place in short being difficult for of the method for B and the duration of contact of air, but between 2 substrates in several microns the gap liquid crystal material of clamping to overcome surface tension, must carry out brute force and blow, so efficient is low.
The method of C is used rare gas element simultaneously from being difficult to cause that it is more preferred that oxidative degradation and organic efficiency two aspects have both consideration, is particularly preferred.
(air supply method)
In order to be limited in minimum as far as possible from the sneaking into of impurity of organic membrane that contacts with liquid crystal material and mineral membrane, carry out the recovery of liquid crystal material effectively, plate is tilted, by air-supply liquid crystal material is concentrated in one direction.By from the air-supply mouth front end with the wire blow gas, as air-brush the method for liquid crystal material in a direction set is fit to.
Scrape in the method for getting at physics such as scrapers, can't avoid organic membrane and mineral membrane generation physical friction, therefore be difficult to avoid sneak into impurity from these films.
(b-3) utilize the method for centrifugal force
Secondly, as the method for not using solvent, can enumerate the method for utilizing centrifugal force.As mentioned above, with 2 glass substrates separately, after being formed on the state that adheres to liquid crystal material on the glass substrate, it is arranged in the separating centrifuge, liquid crystal material is separated from substrate by centrifugal force.With respect to liquid crystal material is separated from glass substrate, act on effectively in order to make centrifugal force, glass substrate preferably is set.In addition, in order to reclaim isolating liquid crystal material effectively, the liquid crystal material container is set preferably.
Be suitable for adopting recovery method of the present invention plate so long as liquid crystal board just be not particularly limited, but because very little plate yield is also few, so the diagonal angle is that the above plate of 140mm is preferred, the diagonal angle is that the above plate of 200mm is more preferred.
(2) operation of the refining liquid crystal material that extracts
(a) make with extra care by distillation
As mentioned above, sneak in the liquid crystal material from low molecular compound and macromolecular compound organic membrane that forms on the sheet material of the component parts of the liquid crystal board of enclosing liquid crystal material or the glass substrate and mineral membrane, that contain as impurity, therefore these must be removed from liquid crystal material.Under the discrepant situation of boiling point of the boiling point of liquid crystal material and impurity, it is useful removing impurity by distillation, distills more preferred under the air pressure that forces down than atmosphere.
(molecular distillation)
So-called molecular distillation is in high vacuum (10
-1Pa is following) under, in than the short distance of the mean free path of the molecule that evaporates by hot face, dispose condenser, the distillating method that carries out.In this method, can not apply high temperature to liquid crystal material and distill, the liquid crystal material of higher also can be made with extra care.At this moment, 10
-1～10
-2Carry out under the pressure of Pa, alleviated the temperature load of liquid crystal material, the rate of recovery of low molecular weight liquid crystal material improves, and is preferred therefore.
In addition, under than the high slightly pressure of molecule distillation, (surpass 10
-1Pa), the casual labourer's preface distillation than configuration condenser in the long slightly distance of the mean free path of molecule also is useful.This method is compared with molecular distillation, be wanting at temperature load, but the distillation efficiency height is preferred under the big situation of treatment capacity.
(b) make with extra care by sorbing material
The liquid crystal material that extracts from liquid crystal board contains ionic impurity.These ionic impurities except the deterioration by liquid crystal material self generate, also contain from the sheet material of liquid crystal board component parts or the extract of organic membrane on the glass substrate and mineral membrane as mentioned above.Usually, these ionic impurity adsorbed ion compounds by handling with the sorbing material that does not adsorb liquid crystal material basically, can separate the deionizing compound from liquid crystal material.For this purpose, sorbing material is preferably selected from: alumina, silica gel, silicon-dioxide alumina class, zeolite and ion exchange resin, more preferably alumina, silica gel, silicon-dioxide alumina class.These sorbing materials can mix different types of sorbent material to be used.As judging the isolating method of ionic impurity, can estimate by the method for analyzing with ion chromatograph etc., and estimate by the liquid crystal material after refining is measured following ratio resistance, current value and ion density.
As the method for the liquid crystal material that reclaims with sorbent treatment, can enumerate, method, the method for directly in liquid crystal material, adding that sorbent material is used as chromatographic column, be dissolved in the solvent after, the method for adding sorbing material.In order to improve adsorption efficiency, liquid crystal material is dissolved in becomes solution state in the solvent, and to wherein adding sorbing material, the method that improves the contact efficiency of ionic impurity and sorbing material by modes such as stirrings is fit to.In order after liquid crystal material is refining, to remove sorbing material fully, use membrane filter etc., it is preferred removing sorbing material by filtering separation.
(3) operation of the physical parameter of mensuration purified liquid crystal material
By aforesaid method, the liquid crystal material that from liquid crystal board, extracts, obtain through refining step, the composition when being injected into liquid crystal board is different.And, no matter be used for the situation of the purposes same use that is removed with the liquid crystal material that reclaims once more, perhaps be used for the situation of other purposes, must grasp the characteristic of the liquid crystal material that reclaims.Evaluation rerum natura as liquid crystal material can be enumerated various rerum naturas, but measure following physical parameter, and grasps this value, is favourable when utilizing again.When utilizing, the rerum natura of important liquid crystal material is nematic liquid crystal phase-isotropic phase transition temperature, specific refractory power anisotropy, dielectric constant anisotropy, the spontaneous pitch of liquid crystal material and compare resistance again.This can be measured by current value, ion density mensuration and conservation rate than resistance value and replace.
(nematic liquid crystal phase-isotropic phase transition temperature)
When using liquid crystal material, owing to must present the nematic liquid crystal phase in the upper limit of the use temperature of used liquid crystal board, therefore the mensuration of the nematic liquid crystal phase-isotropic phase transition temperature (Tni) of the liquid crystal material of specific recovery is important as liquid crystal board.The mensuration of Tni can be used common measuring method.Just, can enumerate the method estimated by polarizing microscope and by the DCS method for measuring.
In the above-mentioned refining step, the low-molecular weight compound in the liquid crystal material is removed by distillation fraction, and high-molecular weight compounds does not carry out part distillation the possibility that is removed is also arranged, when therefore make with extra care by distillation, and mensuration Tni particularly important.
(specific refractory power anisotropy)
When using the use liquid crystal material as liquid crystal board, specific refractory power anisotropy (Δ n) long-pending that constitutes distance between 2 substrates of plate and used liquid crystal material is necessary rerum natura in the optical design of liquid crystal board, and therefore the mensuration of the Δ n of specific recovery is important.Mensuration can be with common measuring method.Just, can enumerate with the method for Abb and with the method for little refractometer.
(dielectric constant anisotropy)
Can when using liquid crystal material, drive liquid crystal material with driving voltage as liquid crystal board, obtain necessary rerum natura in the optical design of sufficient contrast gradient, therefore the mensuration of the dielectric constant anisotropy (Δ ε) of the liquid crystal material of specific recovery be important.
Use in the refining step of above-mentioned sorbent material, the possibility that the compound that the liquid crystal material Semi-polarity is high has part absorption to be removed, when therefore in refining step, using sorbent material, the mensuration particularly important of Δ ε.
In addition, the mensuration of Δ ε can be measured voltage-light transmission rate with being injected in the standard liquid crystal board, confirms that threshold voltage or saturation voltage replace.
(spontaneous pitch)
Usually in the liquid crystal material that in liquid crystal board, uses,, add optically active compound, give liquid crystal material spontaneous pitch (P for making it to show the hank knotting structure; μ m).If spontaneous pitch reduces, it is bad that orientation then takes place, and can not satisfy electrooptics characteristics such as the contrast gradient of design or speed of answer, is necessary rerum natura therefore.Mensuration can be measured with webge slot.
By above-mentioned distillation when method for refining is carried out in method for refining and absorption, the part of high-molecular weight optically active compound is lost with distillment, or by optionally being adsorbed in the sorbing material, addition becomes and lacks than originally addition, and therefore the mensuration of the spontaneous pitch of specific recovery liquid crystal material is important.
(than the mensuration of resistance, current value, ion density and voltage retention)
Self-evident, when being driven, and when being driven, all require to obtain the ratio resistance value of high liquid crystal material by inert element by activeleg.But the liquid crystal material of recovery contains above-mentioned ionic impurity, and is more than the situation of injecting in liquid crystal board than resistance low about 1/100.By the influence that ionic impurity produces,, can estimate by measuring current value, ion density and voltage retention except than the resistance measurement.
(4) operation of the physical parameter of adjustment liquid crystal material
The physical parameter that is used for the liquid crystal material of liquid crystal board can be adjusted by the liquid crystalline cpd that mixes its constituent.
(adjustment of nematic liquid crystal phase-isotropic phase transition temperature (Tni))
In refining step, by distillation or sorbent material, when Tni originally changed, in order to readjust, it was useful adding liquid crystalline cpd.Tni sets up because the addition rule is basic when the mixing of compound and composition, therefore can calculate the ratio of adding material by following formula.
Formula (A):
The Tni of required liquid crystal material (℃): Tr
The Tni of the compound that adds (℃): Tx
The Tni of refining back liquid crystal material (℃): Tc
The ratio of component (%) of the compound that adds: X
For example, in the time of the Tni=90 of required liquid crystal material ℃, Tni=85 ℃ of refining back liquid crystal material, Tni=177 ℃ of the liquid crystalline cpd (P) that adds,, can calculate the ratio of the compound of interpolation by with in each value substitution formula (A).That is, if by the liquid crystal material after refining: 94.6%, the ratio of liquid crystalline cpd (P) 5.4% is added liquid crystalline cpd (P), then can obtain Tni=90 ℃ liquid crystal material.The calculated value that obtains by this method and the difference of measured value are usually in 1～2 ℃.
In that above-mentioned mixing is actual when carrying out, obtain 90.4 ℃ liquid crystal material.
Common refining in, be subjected to adsorbing the long influence that divides the big compound of subconstiuent equimolecular quantity etc., situation about diminishing than originally containing ratio is many.Therefore, in order to adjust Tni, 3 rings or 4 cyclic cpdss represented by general formula (I) are preferred.
(in the formula, R
1And R
2The carbonatoms of representing available fluorine replacement independently of one another is 1～16 alkyl, carbonatoms is 1～16 alkoxyl group, carbonatoms is 2～16 alkenyl, perhaps carbonatoms is 3～16 alkenyloxy, A, B and C represent 1 independently of one another, the 4-phenylene, 2-or 3-fluoro-1, the 4-phenylene, 2,3-two fluoro-1,4-phenylene, 3,5-two fluoro-1, the 4-phenylene, 2-or 3-chloro-1, the 4-phenylene, 2,3-two chloro-1, the 4-phenylene, 3,5-two chloro-1, the 4-phenylene, the 2-methyl isophthalic acid, the 4-phenylene, the 3-methyl isophthalic acid, the 4-phenylene, naphthalene-2,6-two bases, luxuriant and rich with fragrance-2,7-two bases, fluorenes-2,7-two bases, instead-1,4-cyclohexalene base, 1,2,3,4-tetraline-2,6-two bases, naphthane-2,6-two bases, instead-1,3-diox-2,5-two bases, pyridine-2,5-two bases, pyrimidine-2,5-two bases, pyrazine-2,5-two bases or pyridazine-2,5-two bases, also available 1～3 fluorine atom of these groups replaces, m represents 1 or 2, Z
1And Z
2Represent independently of one another singly-bound ,-CH
2H
2-,-(CH
2)
4-,-OCH
2-,-CH
2O-,-COO-,-CH=CH-,-CF=CF-,-CH=N-N=CH-or-C ≡ C-.But m is 2 o'clock, 2 Z
2And C is independent separately, can be identical, or different.)
In these liquid crystalline cpds, in order not to be vulnerable to the influence of other characteristic, and can adjust effectively, Tni is that 120～300 ℃ compound is preferred.If Tni is than 120 ℃ of little compounds, then in order to adjust, addition must be many, therefore influence other characteristic, and the solubleness deficiency might be separated out, and is therefore not preferred.In addition, adopt than 300 ℃ of high compounds, addition tails off, and it is big therefore to adjust error, is unfavorable for adjusting effectively.
As the compound of general formula (I) expression, A, B and C are 1,4-phenylene or anti--1, and 4-cyclohexalene base is preferred.Particularly, A and B are instead-1, and the bicyclohexane compound of 4-cyclohexalene base is therefore little with respect to the influence of liquid crystal material Δ n and Δ ε because Δ n is little, Δ ε is little, Tni is high, can adjust Tni, so be preferred.
R
1And R
2Be preferably the alkyl of carbonatoms 1～5.Z
1And Z
2Be preferably singly-bound ,-CH
2CH
2-or-COO-.Singly-bound is because chemical stability is good, and therefore by adding, the chemical stability of liquid crystal material is difficult to impaired.In addition ,-COO-is because the solvability height, so addition is high and be difficult to separate out, so preferably.
In addition, when adjusting, liquid crystalline cpd not only, and have the liquid-crystal composition of adjusting necessary Tni and be fine by similarly adding to adjust also.
(adjustment of specific refractory power anisotropy (Δ n))
The Δ n of refining back liquid crystal material, the influence that only is subjected to the compound by treatment losses changes.Identical with the adjustment of Tni, by adding liquid crystalline cpd adjustment again, can adjust to required Δ n according to following formula (B).
Formula (B):
The Δ n:Nr of required liquid crystal material
The Δ n:Ny of the compound that adds
The Δ n:Nc of refining back liquid crystal material
The ratio of component (%) of the compound that adds: Y
In order to adjust effectively by a small amount of the interpolation, the compound that Δ n is big is useful.As the scope of the Δ n of the compound of preferred interpolation, 0.15～0.30th, preferred.As these compounds, the compound that has the compound of biphenyl structural or have a tolane structure is preferred.
In addition, during inching Δ n, the smaller compound of Δ n is useful.As preferred Δ n, can enumerate Δ n and be 0.03～0.07 compound.As compound, has the compound of bicyclohexane structure, because its Δ n is little, Tni is high, so be preferred with this kind Δ n.
Identical with the adjustment of Tni, when adjusting the Δ n of the liquid crystal material after making with extra care, also can be not only liquid crystalline cpd, and be to have the liquid-crystal composition of adjusting necessary Tni by same interpolation adjustment.
(adjustment of dielectric constant anisotropy (Δ ε))
The compound that Δ ε is big is by one of compound of refining easily loss.The Δ ε of the liquid crystal material after refining only is subjected to changing by the influence of the compound of treatment losses.Identical with the adjustment of Tni, by adding liquid crystalline cpd adjustment again, can adjust required Δ ε according to following formula (C).
Formula (C):
The Δ ε of required liquid crystal material: Er
The Δ ε of the compound that adds: Ez
The Δ ε of refining back liquid crystal material: Ec
The ratio of component (%) of the compound that adds: Z
In order to adjust effectively by a small amount of the interpolation, the compound that Δ ε is big is useful.As the scope of the Δ ε of the compound of preferred interpolation, Δ ε is 5～40th, and is preferred.As these compounds, preferably have the compound and compound of cyano group end group with F end group.Compound with cyano group end group because Δ ε is big, therefore can be adjusted Δ ε by a small amount of interpolation.On the other hand, has the compound of F end group, because Δ ε is little, be suitable for inching Δ ε, and because the compound with F end group is not easy to be subjected to the pollution of ionic species etc., be difficult to raise by the refining ratio resistance value of improving, therefore be suitable for as the adjustment liquid crystal material.Particularly, contain 3,4, the compound of 5-trifluoro-benzene structure is suitable especially.As being used for the suitable big compound of Δ ε of the present invention, can enumerate the compound of general formula (II) expression.
(in the formula, R
3The carbonatoms that expression can replace with fluorine is 1～16 alkyl, carbonatoms is 1～16 alkoxyl group, carbonatoms is 2～16 alkenyl, perhaps carbonatoms is 3～16 alkenyloxy, and D and E represent 1 independently of one another, the 4-phenylene, 2-or 3-fluoro-1, the 4-phenylene, 2,3-two fluoro-1,4-phenylene, 3,5-two fluoro-1, the 4-phenylene, 2-or 3-chloro-1, the 4-phenylene, 2,3-two chloro-1, the 4-phenylene, 3,5-two chloro-1, the 4-phenylene, the 2-methyl isophthalic acid, the 4-phenylene, the 3-methyl isophthalic acid, the 4-phenylene, naphthalene-2,6-two bases, luxuriant and rich with fragrance-2,7-two bases, fluorenes-2,7-two bases, instead-1,4-cyclohexalene base, 1,2,3,4-tetraline-2,6-two bases, naphthane-2,6-two bases, instead-1,3-dioxane-2,5-two bases, pyridine-2,5-two bases, pyrimidine-2,5-two bases, pyrazine-2,5-two bases or pyridazine-2,5-two bases, also available 1～3 fluorine atom of these groups replaces, n represents 0,1 or 2, Z
3And Z
4Represent independently of one another singly-bound ,-CH
2CH
2-,-(CH
2)
4-,-OCH
2-,-CH
2O-,-COO-,-CH=CH-,-CF=CF-,-CH=N-N=CH-or-C ≡ C-, Y represents cyano group, fluorine atom, chlorine atom, trifluoromethoxy, trifluoromethyl, difluoro-methoxy, hydrogen atom or 3,3,3-trifluoro ethoxy, X
1, X
2Expression hydrogen atom, fluorine atom or chlorine atom.But n is 2 o'clock, 2 Z
3And E is independent separately, can be identical, or different.)
As the compound of general formula (II) expression, preferred D and E are 1,4-phenylene or anti--1,4-cyclohexalene base.And then D and E are instead-1, and the bicyclohexane compound of 4-cyclohexalene base is therefore little with respect to the influence of the Δ n of liquid crystal material or Tni because Δ n is little, Tni is high, can carry out the adjustment of Δ ε, is preferred.
R
3Be preferably the alkane Z of carbonatoms 1～5
3And Z
4Be preferably singly-bound ,-CH
2CH
2-or-COO-.Singly-bound and-CH
2CH
2-because chemical stability is good, therefore be difficult to impaired by the chemical stability of adding liquid crystal material.In addition ,-COO-is because the solvability height, so addition can increase, and is difficult for simultaneously separating out, so be preferred.
X
1And X
2Preferably at least one is F, and two compounds that are F are more preferred.Y is preferably F or CN, and when paying attention to chemical stability, F is preferred, Δ ε is being transferred when big, and CN is preferred.Specifically, have 3,4, the compound of 5-trifluorophenyl or have 4-cyano group-3, the compound of 5-difluorophenyl is preferred.
And, when adjusting, can be not only liquid crystalline cpd by similarly adding to adjust, and be to have the liquid-crystal composition of adjusting necessary Δ ε.
(a plurality of physical parameter time adjust)
Nematic liquid crystal phase-isotropic phase transition temperature (Tni), specific refractory power anisotropy (Δ n) and dielectric constant anisotropy (Δ ε) are when adjusting simultaneously, by calculating X, Y and the Z of three formulas that satisfy formula (D), formula (E) and formula (F) expression simultaneously, can obtain the ratio of three kinds of materials of interpolation.
Formula (D):
(Tx-Tc)X+(Ty-Tc)Y+(Tz-Tc)Z＝(Tr-Tc)×100
Formula (E):
(Nx-Nc)X+(Ny-Nc)Y+(Nz-Nc)Z＝(Nr-Nc)×100
Formula (F):
(Ex-Ec)X+(Ey-Ec)Y+(Ez-Ec)Z＝(Er-Ec)×100
The Tni of required liquid crystal material (℃): Tr
The Δ n:Nr of required liquid crystal material
The Δ ε of required liquid crystal material: Er
The Tni of refining back liquid crystal material (℃): Tc
The Δ n:Nc of refining back liquid crystal material
The Δ ε of refining back liquid crystal material: Ec
The ratio of component of the compound that adds in order to adjust Tni (%): X
The Tni of compound (℃): Tx
The Δ n:Nx of the compound that adds
The Δ ε of the compound that adds: Ex
The ratio of component (%) of the compound that adds in order to adjust Δ n: Y
The Tni of compound (℃): Ty
The Δ n:Ny of the compound that adds
The Δ ε of the compound that adds: Ey
The ratio of component (%) of the compound that adds in order to adjust Δ ε: Z
The Tni of compound (℃): Tz
The Δ n:Nz of the compound that adds
The Δ ε of the compound that adds: Ez
According to the value that aforementioned calculation goes out, add to adjust and use compound, but the physical parameter that needn't once just achieve the goal carries out but can divide for several times.At this moment, in order to improve the cryopreservation of composition, it also is preferred using other compound.
In addition, under the situation of the physical parameter of failing once to obtain purpose, can carry out the said determination operation repeatedly and adjust operation.
With improvement keeping quality at low temperatures is purpose, even when needs reduce the addition of same material, similarly also can increase into mark.
(spontaneous pitch)
Chipal compounds also can be described as by one of compound of refining easily loss.Because the loss of chipal compounds, the spontaneous pitch (p) of the liquid crystal material after making with extra care become big (promptly extending).The value of the spontaneous pitch of liquid crystal material has very big influence to the threshold voltage of liquid crystal display device or orientation stability etc.
The spontaneous pitch of liquid crystal material, represent by formula (G):
HTP＝1/(p×0.01C)
(in the formula, C represents the addition (quality %) of optically active compound, and p represents spontaneous pitch (μ m)), long-pending being inversely proportional to of the concentration (quality %) of the chipal compounds of the spiral torsion of the chipal compounds of interpolation: HTP (1/ μ m) and interpolation.In order to adjust by a small amount of interpolation, the chipal compounds that torsion is big is effectively, if but torsion is excessive, then inching difficulty, and therefore the torsion of used chipal compounds is that 3～30 (with absolute value representations) are preferred.
The inverse of the spontaneous pitch when in addition, torsion can be by the chipal compounds that adds 1 quality % in liquid crystal material is tried to achieve.Parent that this value is added changes, and therefore adjusts in order to be used for, and adds 1 quality % in the liquid crystal material after refining, try to achieve torsion after, be preferred by calculating the addition of determining chipal compounds in proportion.
As preferred chipal compounds, can enumerate the following compound except that cholesterol derivatives such as cholesterol ester in the ninth of the ten Heavenly Stems.
(in various, R and R
1The expression carbonatoms is that 1～16 alkyl, carbonatoms are that 1～16 alkoxyl group, carbonatoms are that 2～16 alkenyl or carbonatoms are 3～16 alkenyl.)
The treatment in accordance with the present invention method, can reclaim have with reclaim before the liquid-crystal composition of the original identical physical parameter of liquid crystal material.
Also have, can also carry out recirculation having the liquid-crystal composition different with the physical parameter of original liquid-crystal composition.That is, because liquid-crystal display will design to very tiny characteristic, therefore be not no matter under which kind of situation, all recirculation is returned in the original liquid-crystal composition fully.Be difficult to make the regressive identically situation such as frequency interdependence, temperature dependency, response of threshold voltage also a lot.Which kind of degree is this difficulty become contaminated to the liquid crystal material of supplying with recirculation much relations.To depollute in order removing, and to have to carry out the purification operations of some operations, if its operation is many, grow, then the variation with the characteristic of original liquid-crystal composition will become big.
At this moment, differ surely and to reply to having the liquid-crystal composition of original physical parameter,, preferably adjust in order to offer the purposes with the liquid crystal material of the characteristic of recycling different requirements.
By the liquid crystal material that treatment process of the present invention is utilized again, preferred active indicating meter liquid crystal material.
Embodiment
Below, exemplify embodiment, the present invention will be described in more detail, but the present invention is not limited to these embodiment.
Method by regulation is made liquid crystal material (A).The composition of liquid crystal material (A) and rerum natura are by following expression.
Tni＝90℃
Δn＝0.095
Δε＝7.5
p＝85μm
Than resistance=5.8 * 10
12Ω cm
Making 200 distances that have between 20 square centimeters of surface-area, 2 glass substrates is 90 ° of TN liquid-crystal displays of 10 μ m, and vacuum is injected liquid crystal material (A) in this indicating meter.The Vth of the liquid-crystal display that obtains is 1.69V, and voltage retention is 98%.This indicating meter was placed 500 hours in 80 ℃ of thermostatic baths.
(operation that liquid crystal material is extracted from liquid-crystal display)
Inboard at the sheet material of bonding 2 substrates cuts off, and obtains being clipped in 2 liquid crystal materials in the glass substrate.In order not sneak into impurity, when carefully taking off, peel 2 substrates lentamente from sheet material or alignment films.With the liquid crystal material that adheres on the nitrogen purging substrate, in the A of liquid crystal pond, collect liquid crystal simultaneously.If no longer can collect liquid crystal as mentioned above, just wash substrate with normal hexane, in the B of liquid crystal pond, collect liquid crystal again.200 liquid-crystal displays are carried out this operation, and the normal hexane of liquid crystal pond B obtains reclaiming liquid crystal material after removing with the vaporizer distillation.Distillation is added up except that the recovery liquid crystal material that desolvates and from the liquid crystal material that liquid crystal pond A reclaims, obtain 6g and reclaim liquid crystal material (R1).
(operation of the refining liquid crystal material that takes out)
The liquid crystal material that mensuration reclaims from liquid crystal pond A and with the gas-chromatography of the liquid crystal material of liquid crystal pond B recovery.Consequently, the containing ratio at the peak of removing the liquid crystal material that reclaims with liquid crystal pond A from the liquid crystal material that liquid crystal pond B reclaims is below 1%, therefore will merge from the liquid crystal material of liquid crystal pond B recovery and with the liquid crystal material that liquid crystal pond A reclaims, carry out following refining step (surpass at 1% o'clock, carry out following refining step respectively).Ratio resistance before the liquid crystal material that obtains is refining is 6.8 * 10
11Ω cm.
The liquid crystal material that extracts is 10
-1Make with extra care by molecular distillation under the vacuum tightness of Pa, obtain 5.2g and reclaim liquid crystal material (R2).
To reclaim liquid crystal material (R2) and in normal hexane, dissolve, after ion-exchange water washing 2 times, carry out refining with adsorbents with 0.1% silica gel with respect to liquid crystal material.With method same as described above the liquid crystal material that obtains reclaiming (R3) is removed in the hexane distillation.
(measuring the operation of the physical parameter of purified liquid crystal material)
Tni, Δ n, Δ ε and the spontaneous pitch of the recovery liquid crystal material (R3) that mensuration obtains.
Tni＝88℃
Δn＝0.094
Δε＝7.0
p＝90μm
Than resistance=4.6 * 10
12Ω cm
By refining step, be improved than resistance, find that promptly being used in active indicating meter also can obtain very high ratio resistance value.But, finding that Tni is low 2 ℃, Δ n is low 0.001, and Δ ε is little 0.5, and p has grown 5 μ m.
In order to utilize liquid crystal material again, may not be returned to original characteristic, at this, attempt reproducing this and test the characteristic of all liquid crystal materials (A).
Because Tni descends, so the compound of adding type (A-1) expression
(Tni=168 ℃, Δ n=0.095, Δ ε=0.8), owing to Δ ε diminishes, so the compound of adding type (A-2) expression
(Tni＝94℃，Δn＝0.09，Δε＝12)。Also have, spontaneous pitch is extended, and therefore adds as chipal compounds, and in (III-1), R is C
6H
13O-, R
1Be C
6H
13The compound of formula (A-3) expression of compound.
Addition with the compound of formula (A-1) expression is X%, is Z% with the addition of the compound of formula (A-2) expression, for making Tni=90 ℃ of liquid crystal material after the interpolation, Δ n=0.095 and Δ ε=7.5, calculates with above-mentioned formula (D) with (F).
If should be worth in the substitution formula (D), then can derive following formula.
(168-88)X+(94-88)Z＝(90-88)×100
80X+6Z＝200
If continue to be worth in the substitution formula (F), then can derive following formula.
(0.8-7)X+(12-7)Z＝(7.5-7)×100
-6.2X+5Z＝50
Separate this company cube journey, calculate X=1.6%, Z=11.8%.
By being worth in the substitution formula (E), can be in the hope of adjusted Δ n this moment.
Δn＝(0.094×0.866)+(0.090×0.016)+(0.095×0.118)＝0.094
In order to adjust spontaneous pitch, the addition of the compound of formula (A-3) expression is determined according to following method.
By in refining parent, adding the compound of 1 quality % formula (A-3) expression, measure the spiral torsion (HTP) of the compound of this liquid crystal material Chinese style (A-3) expression, obtain HTP=10.0 this moment.By above-mentioned formula (G), tried to achieve the concentration of the chipal compounds that should add by 1/85-1/90=10 Δ C: Δ C obtains Δ C=0.01%.
Based on above calculated value, with the liquid crystal material 86.6% after refining, formula (A-1) 1.6% and formula (A-2) 11.8% are mixed, and sneak into formula (A-3) 0.01% in this mixture 99.99%, carry out the adjustment again of physical parameter.Physical parameter to this liquid-crystal composition is measured, and Tni=89.7 ℃ of this moment, Δ n=0.095, Δ ε=7.6, p=84 μ m are very consistent with calculated value, obtain required recycling recovery liquid crystal material.
The recovery liquid crystal material vacuum that obtains is injected in the original T N liquid-crystal display, measures characteristic.
Vth=1.67V, voltage retention is 98%, can obtain and use before the substantially the same characteristic of liquid-crystal display.
In this specification sheets and claims, all % all represent quality %.
The effect of invention
By treatment process of the present invention, can make and think originally that reclaim in the used liquid crystal board of difficulty could The liquid crystal material of recycling becomes possibility.
Claims (20)
1. a treatment process that is used for utilizing again liquid crystal material is characterized in that, comprises following operation:
1) operation that liquid crystal material is extracted, the 2) operation of refining this liquid crystal material that extracts, 3) measure the operation of the physical parameter of this liquid crystal material of purified from liquid crystal board, and 4) adjust the operation of the physical parameter of this liquid crystal material.
2. according to the treatment process of claim 1 record, wherein, the operation that liquid crystal material is extracted from liquid crystal board is by hydrocarbon organic solvent dissolving liquid crystal material, after extracting in the liquid crystal material slave plate, to distill the operation of removing organic solvent.
3. according to claim 1 record and treatment process, wherein, the operation that liquid crystal material is extracted from liquid crystal board is, by blow gas with the operation of extracting in the liquid crystal material slave plate.
4. according to the treatment process of claim 1 record, wherein, the operation of refining liquid crystal material is a molecular distillation.
5. according to the treatment process of claim 4 record, wherein, the decompression degree of molecular distillation is 10
-1Pa～10
-2Pa.
6. according to the treatment process of claim 1 record, wherein, the operation of refining liquid crystal material is to use at least a operation that is selected from alumina, silica gel, silicon-dioxide alumina class, zeolite and ion exchange resin.
7. according to the treatment process of claim 1 record, wherein, the operation of measuring the liquid crystal material physical parameter is, measures the nematic liquid crystal phase-isotropic phase transition temperature, specific refractory power anisotropy, dielectric constant anisotropy, spontaneous pitch of liquid crystal material at least and than a kind of operation in the resistance.
8. according to the treatment process of claim 1 record, wherein, the operation of adjusting the liquid crystal material physical parameter is that adding nematic liquid crystal phase-isotropic phase transition temperature is 120 ℃～300 ℃ the liquid crystalline cpd or the operation of liquid-crystal composition.
According to Claim 8 the record treatment process, wherein, nematic liquid crystal phase-isotropic phase transition temperature is that 120 ℃～300 ℃ liquid crystalline cpd or composition is liquid crystalline cpd or the composition with dicyclohexyl benzene structure.
10. according to the treatment process of claim 1 record, wherein, the operation of adjusting the liquid crystal material physical parameter is, adds dielectric constant anisotropy and be 5～40 the liquid crystalline cpd or the operation of liquid-crystal composition.
11. according to the treatment process of claim 10 record, wherein, dielectric constant anisotropy is that 5～40 liquid crystalline cpd or composition are to have 3,4, the liquid crystalline cpd or the composition of 5-trifluoro-benzene structure.
12. according to the treatment process of claim 1 record, wherein, the operation of adjusting the liquid crystal material physical parameter is, adds the specific refractory power anisotropy and be 0.03～0.07 the liquid crystalline cpd or the operation of liquid-crystal composition.
13. according to the treatment process of claim 12 record, wherein, the specific refractory power anisotropy is that 0.03～0.07 liquid crystalline cpd or liquid-crystal composition are liquid crystalline cpd or the liquid-crystal compositions with bicyclohexane structure.
14. according to the treatment process of claim 1 record, wherein, the operation of adjusting the liquid crystal material physical parameter is that interpolation specific refractory power anisotropy is 0.15～0.30 liquid crystalline cpd or liquid-crystal composition.
15. according to the treatment process of claim 14 record, wherein, the specific refractory power anisotropy is that 0.15～0.30 liquid crystalline cpd or liquid-crystal composition are liquid crystalline cpd or the liquid-crystal compositions with biphenyl structural.
16. according to the treatment process of claim 1 record, wherein, the operation of adjusting the liquid crystal material physical parameter is to add the operation of optically active substance.
17. according to the treatment process of claim 1 record, wherein, the diagonal angle of liquid crystal board is more than the 140mm.
18. according to the treatment process of claim 1 record, wherein, the physical parameter that constitutes the liquid crystal material after physical parameter and the recovery of liquid crystal material of the liquid crystal board before reclaiming is identical.
19. according to the treatment process of claim 1 record, wherein, the physical parameter that constitutes the liquid crystal material after physical parameter and the recovery of liquid crystal material of the liquid crystal board before reclaiming is different.
20. according to the treatment process of claim 1 record, wherein, liquid crystal material is active indicating meter liquid crystal material.
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| CN100417982C (en) * | 2005-10-18 | 2008-09-10 | 比亚迪股份有限公司 | A recycled method of mixed liquid crystal reclaimed from production line |
| CN101173172B (en) * | 2006-10-30 | 2011-01-26 | 比亚迪股份有限公司 | Liquid crystal purifying method |
| CN101381604B (en) * | 2008-10-17 | 2011-08-03 | 江苏和成化学材料有限公司 | Purification method of liquid crystal monomer or liquid crystal composition |
| US8968595B2 (en) | 2011-09-02 | 2015-03-03 | Industrial Technology Research Institute | Methods for recycling liquid crystal and forming reformulated liquid crystal mixtures |
| CN102500128A (en) * | 2011-10-14 | 2012-06-20 | 合肥工业大学 | Method and system for recovering crystal liquid in abandoned liquid crystal display |
| TWI458570B (en) * | 2011-12-07 | 2014-11-01 | Ind Tech Res Inst | Method of reusing micro-encapsulated cholesteric liquid crystal |
| TWI443181B (en) | 2011-12-07 | 2014-07-01 | Ind Tech Res Inst | Method of recycling cholesteric liquid crystal |
| KR20150016133A (en) * | 2013-08-02 | 2015-02-11 | 주식회사 엘지화학 | Process for purification of photoreactive compound and photoreactive compound |
| WO2015016680A1 (en) * | 2013-08-02 | 2015-02-05 | 주식회사 엘지화학 | Method for purifying photoreactive compound and photoreactive compound |
| CN109621489A (en) * | 2018-12-29 | 2019-04-16 | 阜阳欣奕华材料科技有限公司 | A kind of method of liquid crystal purifying |
| CN114538460B (en) * | 2022-04-01 | 2023-07-28 | 合肥工业大学 | Method for preparing zeolite molecular sieve by using waste liquid crystal display panel |
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| US5540857A (en) * | 1992-12-16 | 1996-07-30 | Hitachi Chemical Co., Ltd. | Purification of liquid crystals and liquid crystal composition |
| US6056892A (en) * | 1997-03-06 | 2000-05-02 | Mitsubishi Gas Chemical Company, Inc. | Method for purifying liquid crystal |
| JP2001305502A (en) * | 2000-04-21 | 2001-10-31 | Sharp Corp | Method for treating waste liquid crystal panel |
| JP2001305501A (en) * | 2000-04-21 | 2001-10-31 | Sharp Corp | Method for treating waste liquid crystal panel |
| JP2001337305A (en) * | 2000-05-24 | 2001-12-07 | Sharp Corp | Method for treating waste liquid crystal panel |
| JP2002126688A (en) * | 2000-10-23 | 2002-05-08 | Sharp Corp | Apparatus and method for extracting liquid crystal and liquid crystal extracting system using the apparatus |
| JP2002166259A (en) * | 2000-11-30 | 2002-06-11 | Sony Corp | Recovery method of liquid crystal |
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| JP4941797B2 (en) | 2000-12-26 | 2012-05-30 | Ｄｉｃ株式会社 | Method for producing high-performance purifier |
| JP2002254059A (en) | 2001-02-28 | 2002-09-10 | Mitsubishi Materials Corp | Material recovery method from liquid crystal display panel |
-
2003
- 2003-09-09 KR KR1020030063144A patent/KR100960580B1/en active IP Right Grant
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5540857A (en) * | 1992-12-16 | 1996-07-30 | Hitachi Chemical Co., Ltd. | Purification of liquid crystals and liquid crystal composition |
| US6056892A (en) * | 1997-03-06 | 2000-05-02 | Mitsubishi Gas Chemical Company, Inc. | Method for purifying liquid crystal |
| JP2001305502A (en) * | 2000-04-21 | 2001-10-31 | Sharp Corp | Method for treating waste liquid crystal panel |
| JP2001305501A (en) * | 2000-04-21 | 2001-10-31 | Sharp Corp | Method for treating waste liquid crystal panel |
| JP2001337305A (en) * | 2000-05-24 | 2001-12-07 | Sharp Corp | Method for treating waste liquid crystal panel |
| JP2002126688A (en) * | 2000-10-23 | 2002-05-08 | Sharp Corp | Apparatus and method for extracting liquid crystal and liquid crystal extracting system using the apparatus |
| JP2002166259A (en) * | 2000-11-30 | 2002-06-11 | Sony Corp | Recovery method of liquid crystal |
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| KR20040027328A (en) | 2004-04-01 |
| KR100960580B1 (en) | 2010-06-03 |
| CN1497036A (en) | 2004-05-19 |
| TW200404884A (en) | 2004-04-01 |
| TWI327592B (en) | 2010-07-21 |
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