CN104788275A

CN104788275A - Manufacturing method for liquid crystal material

Info

Publication number: CN104788275A
Application number: CN201510106439.7A
Authority: CN
Inventors: 松本隆; 楠本哲生; 齐藤佳孝; 长岛丰; 野濑清香
Original assignee: Dainippon Ink and Chemicals Co Ltd
Current assignee: DIC Corp
Priority date: 2009-11-20
Filing date: 2010-11-17
Publication date: 2015-07-22
Also published as: CN104557360A; CN102070384A; CN104557360B

Abstract

The invention provides a manufacturing method for liquid crystal materials, and specifically relates to a manufacturing method for a compound expressed in a general formula (I), the electrical resistivity value of the compound expressed by the general formula (I) is defined as that when adding 80% by mass of a liquid crystal composition (M-1) which contains compounds expressed by formulas (A-1) and (A2) in mass ratio of 1 to 1 and electrical resistivity value of the compound is higher than 1.0*10<13> [omega]m to a compound in the content of 20% by mass, the coumpond being expressed by the general formula (1), the compound expressed by the general formula (1),through any method of (I)-(V), the compound which is expressed by the general formula (1) and whose electrical resistivity is displayed to be smaller than 8.0*10<11> [omega]m is separated out. For obtained crystal, the crystalline compound expressed by the general formula (1) is filtered from a solution containing any solvent of (VI)-(XI), solvent used in recrystallization contained in the filted crystal is distilled and removed, so that the crystalline compound which is expressed by the general formula (1) and whose electrical resistivity is higher than 8.0*10<11> [omega]m is obtained.

Description

The manufacture method of liquid crystal material

The application is the applying date is on November 17th, 2010, and application number is 201010552287.0, and denomination of invention is the divisional application of the Chinese patent application of " manufacture method of liquid crystal material ".

Technical field

The present invention relates to the manufacture method of the liquid crystal material with high resistivity value.

Background technology

Liquid crystal display device with LCD TV, portable phone or PC etc. for the people's livelihood purposes of representative is widely used in industrial use.These product life is long, for several years to the more than ten years, in order to normally run during this period, requires high stability to the liquid crystal material that it uses.The representational stability indicator of liquid crystal material has resistivity value.In order to make liquid crystal display device normally run, its resistivity value of liquid crystal material used is sufficiently high, and must suppress through time deterioration.

In order to improve the stability of liquid crystal material, much study up to now always.Such as, as the method for the moisture in removing liquid crystal material, metal ion, disclose the method (with reference to patent documentation 1) that liquid crystal material contact with silica gel, the method that liquid crystal material is contacted with activated alumina (reference patent documentation 2), spent ion exchange resin carry out the method (reference patent documentation 3) processed, the method (reference patent documentation 4) making liquid crystal material and zeolitic contact.And disclose by putting into liquid crystalline cpd between relative pair of electrodes, apply electric field, thus the Na that the degree of excursion that causes of removing electric field is larger ⁺, K ⁺deng metal ion or SO ₄ ^2-, NO ₃ ^-, Cl ^-the method of isoiony impurity etc. (with reference to patent documentation 5 ~ 7).These process for purification are the methods for removing the impurity be contained in liquid crystal material.

On the other hand, a lot of aspect such as high-speed responsive, high-contrast is related to the requirement of liquid crystal material.These physical property cannot be reached by independent compound, but by plurality of liquid crystals compound, deal with requirement as liquid-crystal composition.Now, the importantly each liquid crystalline cpd of precise, makes its ratio of mixture accurately correspond to target value.If this is because ratio of mixture produces error, then physical property just change, cannot be modulated into the liquid-crystal composition met the demands.

Here, most liquid crystalline cpd is at room temperature solid.Therefore, if distillation removes nearly all solvent from the liquid crystalline cpd of the solution state be dissolved in solvent, then crystallization carries out at a heat, the overall solid becoming to be integrated.If liquid crystalline cpd not exclusively distillation uses except desolventizing, then can produce the unfavorable conditions such as stability reduction, be therefore unsatisfactory.Therefore, need under reduced pressure to remove the solvent be brought in the crystallization of liquid crystalline cpd.But, if the block of its solid obtained is large, then brings inner solvent into non-volatile, cannot remove.In addition, if obtained as block, then weighing during liquid-crystal composition modulation must be carried out while crushing block, therefore operates and just becomes extremely difficult, also cannot guarantee the exactness weighed.On the other hand, if liquid crystalline cpd is modulated as powder, then solvent distillation removing, weigh time fine setting all can become easy.But method for refining as previously shown processes liquid crystal material under mesomorphic state or solution state, and the liquid crystalline cpd obtained after process can not become powder.In addition, these methods need special device, numerous and diverse operation when implementing, and are therefore disadvantageous in productivity.

In order to obtain liquid crystalline cpd easily as powder, recrystallization is effective, and the example carrying out refining liquid crystalline cpd by recrystallization in practice also has a lot (patent documentation 8).Recrystallization carries out in the following way: by compound dissolution in solvent, utilizes the evaporation of temperature head, solvent, the difference etc. of solubleness that the change etc. of the ratio of mixture of solvent causes, makes crystallization, leaching crystallization.Now by the speed of separating out etc. of adjustment crystallization, the crystallization of uniform and delicate can be obtained.The particle of the liquid crystalline cpd of the powder so obtained is thin, therefore easily can carry out the distillation removing of solvent, in addition, owing to easily picking up, therefore easily weigh, also can regulate addition imperceptibly.

In order to obtain the liquid crystal material with high resistivity value, the each liquid crystalline cpd forming this material also needs to have high resistivity value, when carrying out recrystallization as the final operation before weighing, quality has requirement, and the liquid crystalline cpd therefore after its recrystallization must have high resistivity value.But because the solvent of general rank contains ion component etc., therefore use it to carry out recrystallization, then can there is the impact due to these compositions, the resistivity value of the liquid crystalline cpd after recrystallization does not reach the problem of realistic scale.The refining of solvent is undertaken by distillation usually, but distills the impurity that cannot remove near boiling point, and cannot remove the metal cation component of trace.

As above, although pump up the simple and practical method being obtained the liquid crystalline cpd with high resistivity value by recrystallization, also concrete solution is not reported so far.

Prior art document

Patent documentation 1: Japanese Laid-Open Patent Publication 62-210420 publication

Patent documentation 2: Japanese Laid-Open Patent Publication 58-1774 publication

Patent documentation 3: Japanese Laid-Open Patent Publication 52-59081 publication

Patent documentation 4: Japanese Laid-Open Patent Publication 63-261224 publication

Patent documentation 5: Japanese Laid-Open Patent Publication 50-108186 publication

Patent documentation 6: Japanese Laid-Open Patent Publication 51-11069 publication

Patent documentation 7: Japanese Unexamined Patent Publication 4-86812 publication

Patent documentation 8: Japanese Unexamined Patent Publication 2007-176818 publication

Summary of the invention

The problem that invention will solve

The problem that the present invention will solve is to provide easy manufacture method, the liquid-crystal composition employing the liquid crystalline cpd obtained by this manufacture method and the liquid crystal display device of the liquid crystalline cpd by recrystallization operation with high resistivity value.

Solve the scheme of problem

The subject compound to the present application such as the present inventor conducts in-depth research, and found that can solve above-mentioned problem by specific manufacture method, thus completes the present invention.

The invention provides:

1. the manufacture method of compound that represents of general formula (1), is characterized in that,

The resistivity value of the compound represented by general formula (1) is defined as, and is containing compound and resistivity value that formula (A-1) and (A-2) represent for 1.0 × 10 with the mass ratio of 1:1 ¹³the compound that the general formula (1) being added with 20 quality % in liquid-crystal composition (M-1) the 80 quality % of more than Ω m represents and the resistivity value of the liquid-crystal composition obtained time,

By any one method of following (I) ~ (V), described resistivity value is shown as and is less than 8.0 × 10 ¹¹the compound that the general formula (1) of Ω m represents is separated out, for the crystallization obtained, the compound that the general formula (1) of leaching crystalline state represents from the solution of any one solvent containing following (VI) ~ (XI), by solvent used for recrystallization contained in the crystallization of leaching distillation removing, obtaining resistivity value defined above is 8.0 × 10 ¹¹the compound that the general formula (1) of the crystalline state of more than Ω m represents;

Wherein, general formula (1) is:

In formula (1), R ¹represent the alkene oxygen base of the alkyl of carbonatoms 1 ~ 6, the thiazolinyl of carbonatoms 2 ~ 6, the alkoxyl group of carbonatoms 1 ~ 6 or carbonatoms 2 ~ 6,

A represents 1,2 or 3,

A ¹and A ²represent the group selected from the group of following (a) group, (b) group and (c) group composition independently of one another:

(a) anti-form-1,4-cyclohexylidene, 1 methylene radical existed in this group or the methylene radical of non-conterminous more than 2 can be substituted by-O-or-S-,

(b) Isosorbide-5-Nitrae-phenylene, the 1-CH=existed in this group or-CH=of non-conterminous more than 2 can be substituted by nitrogen-atoms,

C () Isosorbide-5-Nitrae-dicyclo (2.2.2) is octylene, naphthalene-2,6-bis-base, perhydronaphthalene-2,6-bis-base and 1,2,3,4-naphthane-2,6-bis-base and chroman-2,6-bis-base,

Hydrogen atom contained in above-mentioned (a) group, (b) group or (c) group can be replaced by fluorine atom, trifluoromethyl, trifluoromethoxy or chlorine atom separately, there is multiple A ¹time, they are same to each other or different to each other,

Z ¹represent singly-bound ,-CH ₂cH ₂-,-CH=CH-,-C ≡ C-,-CH ₂o-,-OCH ₂-,-CF ₂o-,-OCF ₂-,-COO-or-OCO-, there is multiple Z ¹time, multiple Z ¹be same to each other or different to each other,

Y ¹represent the alkene oxygen base of the alkyl of hydrogen atom, fluorine atom, chlorine atom, trifluoromethyl, trifluoromethoxy, carbonatoms 1 ~ 6, the thiazolinyl of carbonatoms 2 ~ 6, the alkoxyl group of carbonatoms 1 ~ 6 or carbonatoms 2 ~ 6;

Formula (A-1) and (A-2) are:

(I) method of ~ (V) is:

(I) be dissolved in after in solvent, crystallization separated out from the solution obtained,

(II) be dissolved in solvent, after adopting the column chromatography (columnchromatography) being filled with sorbent material this solution refining, crystallization separated out from the solution obtained,

(III) be dissolved in solvent, after adopting the column chromatography being filled with sorbent material to refine this solution, after being concentrated by the solvent portions obtained, make crystallization,

(IV) be dissolved in solvent, after adopting the column chromatography being filled with sorbent material to refine this solution, add one kind or two or more non-polar solvent and/or one kind or two or more polar solvent in the solution obtained after, make crystallization,

(V) be dissolved in solvent, after adopting the column chromatography being filled with sorbent material to refine this solution, after being concentrated by the solvent portions obtained, after adding one kind or two or more non-polar solvent and/or one kind or two or more polar solvent further in the solution obtained, make crystallization;

(VI) solvent of ~ (XI) is:

(VI) solvent only formed by a kind of non-polar solvent,

(VII) solvent formed by non-polar solvent of more than two kinds,

(VIII) solvent formed by a kind of non-polar solvent and a kind of polar solvent,

(IX) solvent formed by non-polar solvent of more than two kinds and a kind of polar solvent,

(X) solvent formed by a kind of non-polar solvent and polar solvent of more than two kinds,

(XI) solvent formed by non-polar solvent of more than two kinds and polar solvent of more than two kinds,

The non-polar solvent of described (VI) to (XI) and polar solvent are the solvents of the important document shown in any one meeting following (i) ~ (iii):

I () is filled with in the refining step of the column chromatography of sorbent material in the employing of the compound that general formula (1) represents, non-polar solvent that use during the compound stripping that general formula (1) is represented, that have passed the chromatographic column being filled with sorbent material or polar solvent

(ii) summation of the concentration of lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is the non-polar solvent of below 0.05ppb,

(iii) summation of the concentration of lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is the polar solvent of below 1.0ppb;

2. the recrystallization method now carried out;

3. by liquid crystalline cpd that the manufacture method of the application obtains;

4. the liquid-crystal composition containing the liquid crystalline cpd obtained by the manufacture method of the application;

5. use the liquid crystal display device of the liquid-crystal composition containing the liquid crystalline cpd obtained by the manufacture method of the application.

Invention effect

Manufacturing method according to the invention, just can obtain the liquid crystalline cpd with high resistivity value by easy recrystallization operation.Thus, according to the present invention, can obtain can the liquid-crystal composition this point of liquid crystal display device of life-time service for making, be useful.

Embodiment

In general formula (1), A ¹or A ²in at least one party be preferably selected from group (A):

Or group (B):

Further, in group (B), more preferably following structure:

A ¹or A ²in at least one party when selecting from group (A), preferred the opposing party is selected from anti-form-1,4-cyclohexylidene, Isosorbide-5-Nitrae-phenylene or group (A).

A ¹or A ²in at least one party when selecting from group (A), Y ¹be preferably fluorine atom, R ¹be preferably methyl, ethyl, propyl group, butyl, amyl group, vinyl, methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy, 3-butenyloxy and 4-amylene oxygen base, be more preferably methyl, ethyl, vinyl, propyl group, butyl, vinyl, 3-butenyl or amyl group, Z ¹be preferably singly-bound ,-CH ₂cH ₂-,-CF ₂o-or-OCF ₂.

A ¹or A ²in at least one party when selecting from group (B), R ¹and Y ¹be preferably methyl, ethyl, propyl group, butyl, amyl group, vinyl, methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy, 3-butenyloxy and 4-amylene oxygen base independently of one another, Z ¹be preferably singly-bound ,-CH ₂cH ₂-,-CH ₂o-,-OCH ₂-,-CF ₂o-or OCF ₂-.

Be 1.0 × 10 at resistivity value ¹³the resistivity value of the liquid-crystal composition of the compound that the general formula (1) being added with 20 quality % in the liquid-crystal composition (M-1) of more than Ω m represents is lower than 8.0 × 10 ¹¹during Ω m, it is bad sometimes to there is display in the liquid crystal display device employing the liquid-crystal composition of the compound represented containing general formula (1), on the other hand, the resistivity value of the liquid-crystal composition of the compound that the general formula (1) being added with 20 quality % in (M-1) represents is 8.0 × 10 ¹¹during more than Ω m, can not this thing happens, life-time service also can run no problemly.In order to obtain higher reliability, it is desirable to increase resistivity value, but repeat refining step to improve resistivity value, then cause yield to reduce, become and can not manufacture at an easy rate.Therefore, in practical, be 1.0 × 10 at resistivity value ¹³be added with in the liquid-crystal composition (M-1) of more than Ω m 20 quality % refining after the resistivity value of the liquid-crystal composition of compound that represents of general formula (1) be preferably 8.0 × 10 ¹¹Ω m, is preferably 1.0 × 10 ¹²Ω m, is preferably 5.0 × 10 ¹²Ω m, is preferably 1.0 × 10 ¹³Ω m.This resistivity value is more high better, but liquid crystalline cpd is organism, or limited.

Use in the present invention refining before the resistivity value of compound that represents of general formula (1) enough high time, need not carry out of the present invention refining.In addition, if too low, just need repeatedly to repeat the present invention.Therefore, lower value is preferably 9.9 × 10 ¹¹Ω m, is preferably 8.0 × 10 ¹¹Ω m, is preferably 5.0 × 10 ¹¹Ω m, is preferably 1.0 × 10 ¹¹Ω m, is preferably 1.0 × 10 ¹⁰Ω m, is preferably 1.0 × 10 ⁹Ω m, is preferably 1.0 × 10 ⁸Ω m, higher limit is preferably 9.9 × 10 ¹¹Ω m, is preferably 8.0 × 10 ¹¹Ω m, is preferably 5.0 × 10 ¹¹Ω m, is preferably 1.0 × 10 ¹¹Ω m, is preferably 1.0 × 10 ¹⁰Ω m, is preferably 1.0 × 10 ⁹Ω m, is preferably 1.0 × 10 ⁸Ω m.

Before carrying out of the present invention refining, as long as have the purity of the degree standing use, then need not carry out other process for purification or recrystallization, but in order to obtain the liquid crystalline cpd of abundant purity, preferably carry out other process for purification or recrystallization in advance.In addition, use in the present invention refining before the chemical purity of compound that represents of general formula (1) be not particularly limited, but owing to not carrying out other refining just uses after of the present invention refining, therefore wish that chemical purity is high, preferred use counts the material of more than 95% with the area ratio of gas-chromatography (chromatographic column: DB-1, carrier gas: helium), is preferably more than 97%, is preferably more than 99%, be preferably more than 99.5%, be more preferably more than 99.8%.Now, in chemical purity decision, the compound of resistivity value can not be reduced or confirmed its characteristic, confirmed its impact, that compound that defines admissible concentration can be contained in compound that general formula (1) represents.

The kind of used non-polar solvent is refined as the application, preferred hexane or its constitutional isomer, heptane or its constitutional isomer, octane or its constitutional isomer, sherwood oil, benzene,toluene,xylene or isopropyl benzene, more preferably hexane or its constitutional isomer, heptane or its constitutional isomer or toluene.These can be used alone or use two or more.

In addition, the kind of used polar solvent is refined as the application, particular methanol, ethanol, 1-propyl alcohol, 2-propyl alcohol, acetone, 2-butanone, vinyl acetic monomer, ether, tetrahydrofuran (THF), methyl t-butyl ether, acetonitrile or propionitrile, more preferably methyl alcohol, ethanol, acetone or 2-butanone.These can be used alone and also can use two or more.

In addition, preferably before carrying out recrystallization, carry out column chromatography process, removing becomes the ionic impurity of the reason that resistivity value reduces.As the finishing agent that column chromatography uses, preferably use silica gel, aluminum oxide or their both sides.When using both sides, they mixing can be filled, also can layeredly fill.Finishing agent also prior pure water or organic solvent etc. can clean rear use.In addition, aluminum oxide can use acidity, alkalescence or neutral aluminum oxide.As developing solvent, the single or mixed solvent preferably selected from hexane and constitutional isomer, heptane and constitutional isomer thereof and toluene.Owing to eliminating ionic impurity by column chromatography process, therefore the ionic concn contained by developing solvent is not limited, commercially available first grade can be used.The solution obtained after column chromatography process becomes the ionic impurity of the reason that resistivity reduces owing to eliminating, even if therefore also can not affect resistivity value when recrystallization containing the solvent used to some extent.Therefore, the solvent removing part or all can be distilled from the solution after column chromatography process, also can not distill removing.

For recrystallization, as long as use the single or mixed solvent selected from the hydrocarbon system solvent that the concentration summation of lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is below 0.05ppb, its modulator approach does not limit.When the summation of the above-mentioned ionic concn of the solvent used is more than 0.05ppb, such as, processes by being used alone or in combination the finishing agents such as ion exchange resin, silica gel, aluminum oxide, can below 0.05ppb be.In addition, recrystallization advance row by column chromatography process refining when, when the distillation a part of solvent of removing or the solution that do not distill removing and obtain are suitable for recrystallization from solution after this is refining, no longer add recrystallization solvent and be also fine.

With regard to the usage quantity of solvent during crystallization with regard to recrystallization, as a whole, relative to the compound that the general formula (1) of 1g represents, 0.5mL ~ 100mL can be used.But if the usage quantity of solvent is few, then the compound that general formula (1) represents does not dissolve and residual quantitative change is many, the improvement effect of resistivity reduces.On the other hand, if the usage quantity of solvent is many, then the amount of the crystallization of separating out reduces, and the rate of recovery can reduce.Therefore, with regard to the usage quantity lower value of solvent, relative to the compound that the general formula (1) of 1g represents, be preferably 0.8mL, be preferably 1mL, be preferably 2mL, be preferably 3mL, be preferably 4mL, as higher limit, similarly be preferably 50mL, be preferably 30mL, be preferably 20mL, be preferably 10mL, be preferably 8mL, be preferably 5mL.

With regard to recrystallization, can pass through at the compound dissolution making general formula (1) represent after solvent, be cooled to the temperature lower than temperature when dissolving and carry out.With regard to compound, preferably make it dissolve completely, but do not reduce in the improvement effect of resistivity, in the scope of the partial crystallization after not hindering, the operation of filtration, also can remain undissolved part.Do not dissolve and residual compound is preferably below the 10 quality % of total amount, be preferably below 5 quality %, be preferably below 3 quality %, be preferably below 1 quality %, be preferably below 0.5 quality %.

Also can cool during crystallization, can chilling also can Xu Leng.After cooling, temperature can be remained necessarily, also slowly can cool limit and make crystallization in limit.In addition, when making crystallization, can carry out stirring also can leaving standstill.When in the same size, the crystal size of crystallization can not become excessive, preferably stir.In addition, as the method for other recrystallization, also after the compound dissolution making general formula (1) represent is in the solvent that solvability is high, the low solvent of solvability can be added and makes crystallization to carry out recrystallization.Now, can cool, also can not cool especially.

In addition, when adding solvent after making crystallization, if addition is many, then the crystallization of separating out can be dissolved again, and this is not preferred; If the temperature of the solvent added is high, then the crystallization of separating out can be dissolved again, and this is not preferred.Therefore, the quantity of solvent after interpolation preferably controls less than 1.5 times into quantity of solvent during precipitation operation, and preferably controlling is less than 1.2 times, and preferably controlling is less than 1.1 times.The temperature of solvent of adding is preferably less than 30 DEG C, is preferably less than 20 DEG C, is preferably less than 10 DEG C, be more preferably the temperature of added solution ± 5 DEG C.

In addition, in order to take out the crystallization of precipitation, leaching crystallization, can adopt the method for natural filtration, filtration under diminished pressure, pressure filtration or centrifuging.In addition, when filtering, the impact of the oxidation caused to prevent the oxygen in air or prevent moisture to be brought in crystallization, preferably carries out in rare gas or nitrogen atmosphere.In addition, as filtering medium, can use comprise paper Mierocrystalline cellulose, glass fibre, membrane filter, diatomite etc. in usual filter progress by the material used.In addition, during filtration, at room temperature can carry out, can cool, or also can heat.

The present invention is the method combining the compound having the manufacture general formula (1) of following operation to represent:

(A) operation of compound dissolution in organic solvent general formula (1) represented;

(B) solution obtained in (A) is injected the column chromatography being filled with finishing agent, what represented by general formula (1) is compound loaded in the operation of finishing agent;

(C) developing solvent is flowed in column chromatography, the operation of the compound stripping that general formula (1) is represented;

(D) operation separated out in the solution making crystallization obtain from (A);

(E) operation separated out in the solution making crystallization obtain from (C);

(F), after distillation removes completely in the solution obtained from (C) by solvent, be dissolved in new organic solvent, make the operation of crystallization;

(G), in the solution obtained from (C) by a part of solvent after distillation removing, the operation of crystallization is made;

(H), in the solution obtained from (C) by a part of solvent after distillation removing or after not distilling and adding organic solvent adjustment quantity of solvent except desolventizing, the operation of crystallization is made;

(I) operation that the crystallization of separating out the arbitrary operation by (D) ~ (H) is filtered;

(J) operation of the solvent used during distillation removing recrystallization from the crystallization obtained by (I).Wherein, the operation of (B) and (C) can be omitted.

It should be noted that, described in claim " be about to ... being meant to before ", above-mentioned operation each other, does not insert other operations betwixt.

In the present invention, carry out in the operation of above-mentioned (B) and (C) utilizing the refining of column chromatography.Carry out this operation then can remove its use organic solvent in ionic impurity.Therefore, for the polar solvent and the non-polar solvent that pass through column chromatography, the summation of above-mentioned ionic concn does not limit, and uses commercially available first grade to be also fine.

In the present invention, when meeting more than any one of following (a) ~ (f), after recrystallization, during leaching crystallization, can polar solvent be there is, the electrostatic produced in filter progress can be relaxed rapidly.Therefore, be very useful reducing in the disasters danger that electrostatic causes.

A (), as the composition of the organic solvent used in (A), uses polar solvent.

Polar solvent is used during the operation of (b) (B).

Polar solvent is added in the developing solvent of (c) (C).

Before the operation of (d) (D) ~ (H), in operation or after operation, at once add polar solvent.

(e) (I) operation be about to start before or add polar solvent in operation.

(f) polar solvent as impurity be contained in refining before the compound that represents of general formula (1) in.

It should be noted that no matter add polar solvent by above-mentioned any mode, if introduced distillation except the operation of desolventizing and polar solvent is distilled removing completely by this operation before leaching crystallization, would not show and relax the effect of electrostatic.In this case, in order to relax electrostatic during leaching crystallization, after distillation removes desolventizing, before leaching crystallization, need to add polar solvent again.

In the mode of the electrostatic produced when can relax rapidly leaching crystallization, representational mode is as follows, but the invention is not restricted to these examples.

1. (A) → (B) → (C) → interpolation polar solvent → (E) → (I) → (J)

2. (A) → (B) → (C) → (E) → interpolation polar solvent → (I) → (J)

3. (A) → (B) → (C) → interpolation polar solvent → (G) → (I) → (J)

4. (A) → (B) → (C) → (G) → interpolation polar solvent → (I) → (J)

5. in the operation of (A) → (B) → (C) → (F), before crystallization, add polar solvent → (I) → (J)

6. (A) → (B) → (C) → (F) → interpolation polar solvent → (I) → (J)

7. in the operation of (A) → (B) → (C) → (H), before crystallization, add polar solvent → (I) → (J)

8. (A) → (B) → (C) → (H) → interpolation polar solvent → (I) → (J)

9. (A) → interpolation polar solvent → (D) → (I) → (J)

10. (A) → (D) → interpolation polar solvent → (I) → (J)

Polar solvent → (B) → (C) → (E) → (I) → (J) is added in 11. solution obtained in (A)

12. (A) → (B) → add polar solvent → (E) → (I) → (J) in the developing solution of (C)

With regard to polar solvent, as long as use the single or mixed solvent selected from alcoholic solvent, ketones solvent, esters solvent, ether solvent or nitrile solvents that the concentration summation of lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is below 1.0ppb, its modulator approach does not limit.When the summation of the above-mentioned ionic concn of the solvent used is more than 1.0ppb, such as, processes by being used alone or in combination the finishing agents such as ion exchange resin, silica gel, aluminum oxide, can below 1.0ppb be.

In solvent of operation (B) and (C) middle use, if the ratio of non-polar solvent is little, namely the ratio of polar solvent is large, then the polarity of solution entirety increases, and the effect of column chromatography can reduce.Therefore, in the solvent used in these operations, the ratio of non-polar solvent is preferably 80 more than volume %, is preferably 90 more than volume %, is more preferably 95 more than volume %.In addition, by solvent contained before leaching crystallization, the ratio of non-polar solvent is preferably 50 more than volume %, is preferably 60 more than volume %, is preferably 70 more than volume %, is preferably 80 more than volume %, is preferably 90 more than volume %.But according to the ratio of polar solvent and non-polar solvent, the solubleness of the compound that general formula (1) represents can increase, and the yield of recrystallization may reduce, and therefore needs to pay attention to.Here, the ratio of non-polar solvent is being meant to of 80 volume %, the such as mixed solvent of non-polar solvent 80mL and polar solvent 20mL.

Meet in the mode of aforementioned (a) ~ (f), representational mode is as follows, but the invention is not restricted to these examples.

13.(A)→(B)→(C)→(E)→(I)→(J)

14.(A)→(B)→(C)→(F)→(I)→(J)

15.(A)→(B)→(C)→(G)→(I)→(J)

16.(A)→(B)→(C)→(H)→(I)→(J)

17.(A)→(D)→(I)→(J)

Before in illustrative mode, in 11 ~ 13, because used solvent all utilizes sorbent material to process when column chromatography process, therefore the solvent of the quality of commercially available first grade degree can be used, and owing to there is no concentration operation in operation, can easy operating aspect be particularly therefore very useful.

In recrystallization operation, with regard to the distillation removing of solvent used during recrystallization after leaching crystallization, can under reduced pressure carry out in room temperature or carry out while heating.Now, heat protocol is not particularly limited, as long as can carry out the method controlled in the scope in design temperature upper and lower several years, just can use any method.From the viewpoint of the easiness implemented, can enumerate the container that liquid crystalline cpd is housed immersed possess temperature adjustment function and the method filled in the container of solution or with the heating such as mantle heater the method for the container of liquid crystalline cpd is housed, the stream of the liquid further after heating is flow through in the shelf setting being placed with liquid crystalline cpd carries out the method that heats thus.In addition, when distillation is except desolventizing, because liquid crystalline cpd is cooled due to heat of gasification, so for the object reducing temperature reduction, the solution do not heated also can be utilized to carry out aforementioned schemes.In addition, do not use these methods, not control temperature and distilling except desolventizing is also possible.In order to shorten the activity duration, lower limit temperature is preferably set to 20 DEG C, is preferably set to 30 DEG C, is preferably set to 35 DEG C, is preferably set to 40 DEG C further.As ceiling temperature, because the distillation removing speed improving temperature then solvent is accelerated, therefore preferably higher ceiling temperature, if but temperature is too high, then and can cause the decomposition of liquid crystalline cpd, oxidation etc., this is not preferred.In addition, if be heated to more than melting point, then the solid that can all become to be integrated when being cooled to room temperature after drying, can not obtain as powder, be therefore not preferred.Therefore, preferably lower than melting point, be preferably 60 DEG C, preferably 55 DEG C, be preferably 50 DEG C, be preferably 45 DEG C, be preferably 40 DEG C.Container or the shelf that can make to be equipped with liquid crystalline cpd during solvent distillation removing are static, and them also can be made to move.But, from the viewpoint of efficiency, preferably make them rotate or vibration.

The crystallization obtained by manufacture method of the present invention and crystallization of the present invention, other refiningly just mix with other liquid crystalline cpds not carrying out afterwards further, modulating liquid crystal composite.After making liquid-crystal composition, also can carry out the process utilizing filtration or finishing agent as required.

Not containing the solvent used during recrystallization in preferred liquid crystalline cpd, as long as but below dysgenic concentration can not be caused when making liquid-crystal composition.Its concentration is preferably below 200ppm, is preferably below 100ppm, is preferably below 50ppm, more preferably below 20ppm.

Embodiment

Below, enumerate embodiment to further describe the present invention, but the invention is not restricted to these embodiments.In addition, " % " in following embodiment and the composition of comparative example is meant to " quality % ".In the analysis of ionic concn in a solvent, use ion chromatograph (chromatographic column: IC NI-424, developing solvent: two (2-hydroxyethyl) imino-three (hydroxymethyl) methane+2mM phenyl-boron dihydroxide+5 μMs of anti-form-1s of 8mM4-Para Hydroxy Benzoic Acid+2.8mM, 2-cyclohexane diamine-N, N, N', N'-tetraacethyl), the concentration of lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is calculated by absolute standard curve method.The resistivity value of liquid-crystal composition is by liquid-crystal composition is loaded mensuration cell, and the resistance value when 25 DEG C of mensuration impressed voltage (DC) 1V obtains.Purity is calculated by the area ratio of gas-chromatography (chromatographic column: DB-1, carrier gas: helium).

In addition, the solvent not recording ionic concn in the solvent of use is commercially available first grade.

The recrystallization (1) of the compound that (embodiment 1) formula (1-1) represents

Contain with the mass ratio of 1:1 formula (A-1) and (A-2), resistivity value is for 1.0 × 10 ¹³the resistivity value of the liquid-crystal composition of the compound (purity 99.90%) that the formula (1-1) being added with 20% in the liquid-crystal composition (M-1) of Ω m represents is 1.0 × 10 ¹¹Ω m.

The compound 25g that this formula (1-1) represents is dissolved in hexane 100mL, injects the column chromatography (diameter 3cm) being filled with 10g silica gel and 10g aluminum oxide in two-layer mode, make it flow until solution surface is consistent with filling oxidant layer.Add the hexane 100mL as developing solvent further, make the compound stripping be adsorbed on weighting agent.Be about in 220mL to the solution obtained the ethanol 4mL that the concentration summation adding lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is 0.20ppb, after making its partial crystallization, in the refrigeration chamber of-18 DEG C, leave standstill 16 hours 5 DEG C of stirrings 10 minutes.In order to leaching crystallised component, inject exerting of strainer of band and adopt funnel (Nutsche).Measure the hot-line electrical potential of the crystallization obtained on the filter, result is 0.0kV, does not find static electrification.The crystallization obtained is transferred in eggplant type flask, with vacuum pump pressure (266Pa), eggplant type flask rotation is distilled except desolventizing.Now, flask is immersed in the hot water bath of 45 DEG C, control temperature.After 20 hours, obtain the compound 22.5g represented as the formula (1-1) of Powdered crystallization.Residual solvent amount in crystallization is 60ppm, and purity is 99.98%.Be 1.0 × 10 at resistivity value ¹³the compound that the formula (1-1) obtained being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 2.0 × 10 ¹²Ω m.

In addition, made the liquid crystal display device using the liquid-crystal composition of the compound represented containing formula (1-1), result shows and does not occur to show bad superperformance.

The recrystallization (2) of the compound that (embodiment 2) formula (1-1) represents

In embodiment 1, use the acetone 4mL that the concentration summation of lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is 0.13ppb to replace ethanol, similarly operate.The hot-line electrical potential of the crystallization obtained on the filter is 0.0kV, does not find static electrification.The compound that the formula (1-1) obtained after drying represents is 22.4g.Residual solvent amount in crystallization is 58ppm, and purity is 99.98%.Be 1.0 × 10 at resistivity value ¹³the compound that the formula (1-1) obtained being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 2.4 × 10 ¹²Ω m.

The recrystallization (3) of the compound that (embodiment 3) formula (1-1) represents

In embodiment 1, under reduced pressure to be about 220mL distillation except desolventizing after being formed as about 150mL from the solution obtained after column chromatography process, the concentration summation adding lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is the ethanol 4mL of 0.20ppb, similarly operates.The hot-line electrical potential of the crystallization obtained on the filter is 0.0kV, does not find static electrification.The compound that the formula (1-1) obtained after drying represents is 23.4g, finds that yield improves.Residual solvent amount in crystallization is 58ppm, and purity is 99.97%.Be 1.0 × 10 at resistivity value ¹³the compound that the formula (1-1) obtained being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 1.8 × 10 ¹²Ω m.

The recrystallization (4) of the compound that (embodiment 4) formula (1-1) represents

In embodiment 1, the solution obtained after column chromatography process is about and does not add ethanol in 220mL and carry out partial crystallization operation, the concentration summation adding lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion before by leaching crystallization is the ethanol 4mL of 0.20ppb, after stirring about 1 point, inject exerting of strainer of band and adopt funnel, carry out same drying operation afterwards.The hot-line electrical potential of the crystallization obtained on the filter is 0.0kV, does not find static electrification.The compound that the formula (1-1) obtained after drying represents is 22.4g.Residual solvent amount in crystallization is 62ppm, and purity is 99.98%.Be 1.0 × 10 at resistivity value ¹³the compound that the formula (1-1) obtained being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 2.0 × 10 ¹²Ω m.

The recrystallization (5) of the compound that (embodiment 5) formula (1-1) represents

In embodiment 1, under reduced pressure to be about 220mL distillation except desolventizing from the solution obtained after column chromatography process, the concentration summation being dissolved in lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion of being heated by the solid 24.9g obtained is in the hexane 50mL of 0.03ppb, the concentration summation adding lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is the ethanol 1mL of 0.20ppb, similarly carries out partial crystallization and operates later operation.The hot-line electrical potential of the crystallization obtained on the filter is 0.0kV, does not find static electrification.The compound that the formula (1-1) obtained after drying represents is 24.0g, has found yield raising.Residual solvent amount in crystallization is 50ppm, and purity is 99.98%.Be 1.0 × 10 at resistivity value ¹³the compound that the formula (1-1) obtained being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 2.2 × 10 ¹²Ω m.

The recrystallization (6) of the compound that (embodiment 6) formula (1-1) represents

In embodiment 5, in the dissolving of the compound that the formula (1-1) when column chromatography process represents, use hexane/toluene mixed solvent (volume ratio 4/1) 50mL, developing solvent uses hexane/toluene mixed solvent (volume ratio 4/1) 75mL, carries out same operation later.The hot-line electrical potential of the crystallization obtained on the filter is 0.0kV, does not find static electrification.The compound that the formula (1-1) obtained after drying represents is 23.8g.Residual solvent amount in crystallization is 65ppm, and purity is 99.98%.Be 1.0 × 10 at resistivity value ¹³the compound that the formula (1-1) obtained being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 1.8 × 10 ¹²Ω m.

The recrystallization (7) of the compound that (comparative example 1) formula (1-1) represents

Analyze the ionic concn of the hexane of commercially available first grade, result is: the concentration summation of lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is 0.20ppb.In embodiment 5, being heated by the solid 24.9g that distillation the solution under reduced pressure obtained after column chromatography process obtains except desolventizing is dissolved in this hexane 50mL, the concentration summation adding lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is the ethanol 1mL of 0.20ppb, similarly carries out partial crystallization and operates later operation.The compound that the formula (1-1) obtained being added with 20% in liquid-crystal composition (M-1) represents and the resistivity value of the liquid-crystal composition obtained is 5.6 × 10 ¹¹Ω m.Compare with before refining step, the raising of resistivity value is insufficient, can not use as liquid-crystal composition material used for liquid crystal display element.

The recrystallization (8) of the compound that (comparative example 2) formula (1-1) represents

Analyze the ionic concn of the acetone of commercially available first grade, result is: the concentration summation of lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is 1.35ppb.In embodiment 5, the concentration summation being dissolved in lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion of being heated by the solid 24.9g that distillation the solution under reduced pressure obtained after column chromatography process obtains except desolventizing is in the hexane 50mL of 0.03ppb, add the acetone 1mL of first grade, similarly carry out partial crystallization and operate later operation.The compound that the formula (1-1) obtained being added with 20% in liquid-crystal composition (M-1) represents and the resistivity value of the liquid-crystal composition obtained is 3.2 × 10 ¹¹Ω m.Compare with before refining step, the raising of resistivity value is insufficient, can not use as liquid-crystal composition material used for liquid crystal display element.

The recrystallization (9) of the compound that (embodiment 7) formula (1-1) represents

In embodiment 1, under reduced pressure to be about 220mL distillation except desolventizing from the solution obtained after column chromatography process, the concentration summation being dissolved in lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion of being heated by the solid 24.9g obtained is in the hexane 50mL of 0.03ppb, carries out same partial crystallization operation.The concentration summation adding lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion before by leaching crystallization is the ethanol 1mL of 0.20ppb, stir and to be injected into exerting of strainer of band after about 1 minute and to adopt in funnel, carry out same drying operation afterwards.The hot-line electrical potential of the crystallization obtained on the filter is 0.0kV, does not find static electrification.The compound that the formula (1-1) obtained after drying represents is 23.9g.Residual solvent amount in crystallization is 60ppm, and purity is 99.98%.Be 1.0 × 10 at resistivity value ¹³the compound that the formula (1-1) obtained being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 2.0 × 10 ¹²Ω m.

The recrystallization (10) of the compound that (embodiment 8) formula (1-1) represents

Contain with the mass ratio of 1:1 formula (A-1) and (A-2), resistivity value is for 1.0 × 10 ¹³the compound (purity 99.90%) that the formula (1-1) being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 1.0 × 10 ¹¹Ω m.

The concentration summation being dissolved in lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion of being heated by the compound 25g that this formula (1-1) represents is in the hexane 50mL of 0.03ppb, the concentration summation adding lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is the ethanol 1mL of 0.20ppb, after making its partial crystallization, in the refrigeration chamber of-18 DEG C, 16 hours are left standstill 5 DEG C of stirrings 10 minutes.In order to leaching crystallised component, be injected into exerting of strainer of band and adopt in funnel.Measure the hot-line electrical potential of the crystallization obtained on the filter, it is 0.0kV, does not find static electrification.The crystallization obtained is transferred in eggplant type flask, with vacuum pump pressure (266Pa), eggplant type flask is rotated and distills except desolventizing.Now, flask is immersed in the hot water bath of 45 DEG C, control temperature.After 20 hours, obtain the compound 23.8g represented as the formula (1-1) of Powdered crystallization.Residual solvent amount in crystallization is 60ppm, and purity is 99.97%.Be 1.0 × 10 at resistivity value ¹³the compound that the formula (1-1) obtained being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 1.6 × 10 ¹²Ω m.

The recrystallization (11) of the compound that (embodiment 9) formula (1-1) represents

In embodiment 8, the concentration summation being dissolved in lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion of being heated by the compound 25g that formula (1-1) represents is in the hexane 50mL of 0.03ppb, does not add ethanol and carries out same partial crystallization operation.The concentration summation adding lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion before by leaching crystallization is the ethanol 1mL of 0.20ppb, stir and to be injected into exerting of strainer of band after about 1 minute and to adopt in funnel, carry out same drying operation afterwards.The hot-line electrical potential of the crystallization obtained on the filter is 0.0kV, does not find static electrification.The compound that the formula (1-1) obtained after drying represents is 24.0g.Residual solvent amount in crystallization is 65ppm, and purity is 99.98%.Be 1.0 × 10 at resistivity value ¹³the compound that the formula (1-1) obtained being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 1.8 × 10 ¹²Ω m.

The recrystallization (12) of the compound that (embodiment 10) formula (1-1) represents

In embodiment 1, in the compound dissolution that formula (1-1) when column chromatography process represents, use hexane/alcohol mixed solvent (volume ratio 50/1) 100mL, developing solvent uses hexane/alcohol mixed solvent (volume ratio 50/1) 100mL, does not add ethanol and similarly carry out the later operation of partial crystallization in the solution obtained.The hot-line electrical potential of the crystallization obtained on the filter is 0.0kV, does not find static electrification.The compound that the formula (1-1) obtained after drying represents is 22.3g.Residual solvent amount in crystallization is 58ppm, and purity is 99.98%.Be 1.0 × 10 at resistivity value ¹³the compound that the formula (1-1) obtained being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 1.4 × 10 ¹²Ω m.

The recrystallization (13) of the compound that (embodiment 11) formula (1-1) represents

In embodiment 1, in the leaching operation of crystallization, use the centrifugal filter being provided with PTFE filter cloth, other carry out same operation.The absolute value of the hot-line electrical potential of the crystallization that filter cloth obtains is 0.2kV, does not almost find static electrification.The compound that the formula (1-1) obtained after drying represents is 22.5g.Residual solvent amount in crystallization is 55ppm, and purity is 99.98%.Be 1.0 × 10 at resistivity value ¹³the compound that the formula (1-1) obtained being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 1.4 × 10 ¹²Ω m.

The recrystallization (14) of the compound that (embodiment 12) formula (1-1) represents

Contain with the mass ratio of 1:1 formula (A-1) and (A-2), resistivity value is for 1.0 × 10 ¹³the compound (purity 99.90%) that the formula (1-1) being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 1.0 × 10 ¹¹Ω m.The compound 100g that this formula (1-1) represents is dissolved in hexane 400mL, refines by column chromatography (weighting agent: silica gel and aluminum oxide, developing solvent: hexane 400mL).Be about 900mL at 5 DEG C to the solution obtained to stir 10 minutes and after making its partial crystallization, in the refrigeration chamber of-18 DEG C, leave standstill 16 hours.In order to leaching crystallised component, inject exerting of strainer of band and adopt funnel.The crystallization obtained is transferred in eggplant type flask, with vacuum pump pressure (266Pa), eggplant type flask rotation is distilled except desolventizing.Now, flask is immersed in the hot water bath of 45 DEG C, control temperature.After 20 hours, obtain the compound 90.0g represented as the formula (1-1) of Powdered crystallization.Residual solvent amount in crystallization is 56ppm.Be 1.0 × 10 at resistivity value ¹³the compound that the formula (1-1) obtained being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 3.0 × 10 ¹²Ω m.

The recrystallization (15) of the compound that (comparative example 3) formula (1-1) represents

In embodiment 12, after the solution under reduced pressure obtained after coupled columns chromatography carries out distilling and obtains the compound represented as the formula (1-1) of crystallization, add the hexane 800mL of commercially available first grade, dissolve, for the solution obtained, carry out recrystallization similarly to Example 1 and drying operation.The compound that the formula (1-1) obtained being added with 20% in liquid-crystal composition (M-1) represents and the resistivity value of the liquid-crystal composition obtained is 6.0 × 10 ¹¹Ω m.Compare with before refining step, the raising of resistivity value is insufficient, can not use as liquid-crystal composition material used for liquid crystal display element.

The recrystallization (16) of the compound that (embodiment 13) formula (1-1) represents

In embodiment 12, the solution obtained after column chromatography process is about the distillation a part of solvent of removing 900mL and after forming about 300mL, carries out same recrystallization and drying operation.The receipts amount of the compound that the formula (1-1) obtained represents is 93.3g, and yield improves.Add this compound of 20% in the liquid-crystal composition (M-1) and the resistivity value of liquid-crystal composition that obtains is 3.0 × 10 ¹²Ω m.

The recrystallization (17) of the compound that (embodiment 14) formula (1-1) represents

In embodiment 12, in the dissolving of the compound that the formula (1-1) when column chromatography process represents, use hexane/toluene mixed solvent (volume ratio 4/1) 200mL, developing solvent uses hexane/toluene mixed solvent (volume ratio 4/1) 300mL, carries out same operation.The receipts amount of the compound that the formula (1-1) obtained represents is 89.5g.Add this compound of 20% in the liquid-crystal composition (M-1) and the resistivity value of liquid-crystal composition that obtains is 2.8 × 10 ¹²Ω m.

The recrystallization (18) of the compound that (embodiment 15) formula (1-1) represents

Contain with the mass ratio of 1:1 formula (A-1) and (A-2), resistivity value is for 1.0 × 10 ¹³the compound (purity 99.90%) that the formula (1-1) being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 1.0 × 10 ¹¹Ω m.The compound 25g that this formula (1-1) represents is dissolved in hexane 100mL, be injected into and be filled with in the column chromatography (diameter 3cm) of 10g silica gel and 10g aluminum oxide in two-layer mode, make it flow until solution surface is consistent with filling oxidant layer.Add the hexane 100mL as developing solvent further, make the compound stripping be adsorbed on weighting agent.Under reduced pressure from the solution obtained, distillation removes desolventizing.The concentration summation being dissolved in lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion of being heated by the runic 24.9g obtained is in the hexane 50mL of 0.03ppb, after making its partial crystallization, in the refrigeration chamber of-18 DEG C, 16 hours are left standstill 5 DEG C of stirrings 10 minutes.In order to leaching crystallised component, be injected into exerting of strainer of band and adopt in funnel.The crystallization obtained is transferred in eggplant type flask, with vacuum pump pressure (266Pa), eggplant type flask rotation is distilled except desolventizing.Now, flask is immersed in the hot water bath of 45 DEG C, control temperature.After 20 hours, obtain the compound 23.4g represented as the formula (1-1) of Powdered crystallization.Residual solvent amount in crystallization is 60ppm, and purity is 99.98%.Be 1.0 × 10 at resistivity value ¹³the compound that the formula (1-1) obtained being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 2.8 × 10 ¹²Ω m.

The recrystallization (19) of the compound that (comparative example 4) formula (1-1) represents

In embodiment 15, the runic 24.9g that distillation the solution under reduced pressure obtained after column chromatography process obtains except desolventizing is heated and is dissolved in the hexane 50mL of commercially available first grade, carry out same recrystallization and drying operation.The compound that the formula (1-1) obtained being added with 20% in liquid-crystal composition (M-1) represents and the resistivity value of the liquid-crystal composition obtained is 6.0 × 10 ¹¹Ω m.Compare with before refining step, the raising of resistivity value is insufficient, can not use as liquid-crystal composition material used for liquid crystal display element.

The recrystallization (20) of the compound that (embodiment 16) formula (1-1) represents

Contain with the mass ratio of 1:1 formula (A-1) and (A-2), resistivity value is for 1.0 × 10 ¹³the compound (purity 99.90%) that the formula (1-1) being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 1.0 × 10 ¹¹Ω m.The concentration summation being dissolved in lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion of being heated by the compound 50g that this formula (1-1) represents is in the hexane 50mL of 0.03ppb, carries out recrystallization similarly to Example 1 and drying operation.The receipts amount of the compound that the formula (1-1) obtained represents is 23.4g, and purity is 99.97%.Add this compound of 20% in the liquid-crystal composition (M-1) and the resistivity value of liquid-crystal composition that obtains is 2.0 × 10 ¹²Ω m.

The recrystallization (21) of the compound that (comparative example 5) formula (1-1) represents

In embodiment 16, recrystallization solvent uses the hexane 50mL of commercially available first grade, carries out same recrystallization and drying operation.The compound that the formula (1-1) obtained being added with 20% in liquid-crystal composition (M-1) represents and the resistivity value of the liquid-crystal composition obtained is 5.0 × 10 ¹¹Ω m.Compare with before refining step, the raising of resistivity value is insufficient, can not use as liquid-crystal composition material used for liquid crystal display element.

The recrystallization (22) of the compound that (embodiment 17) formula (1-1) represents

In embodiment 15, in the dissolving of the compound that the formula (1-1) when column chromatography process represents, use hexane/toluene mixed solvent (volume ratio 4/1) 50mL, developing solvent uses hexane/toluene mixed solvent (volume ratio 4/1) 75mL, carries out same operation.The receipts amount of the compound that the formula (1-1) obtained represents is 23.0g, and purity is 99.97%.Add this compound of 20% in the liquid-crystal composition (M-1) and the resistivity value of liquid-crystal composition that obtains is 2.6 × 10 ¹²Ω m.

The process of the recrystallization solvent that (embodiment 18) utilizes ion exchange resin to carry out

Analyze the ionic concn of the ethanol of commercially available first grade, result is: the concentration summation of lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is 1.84ppb.The mixture 5g of filling male ion-exchange resin and anionite-exchange resin in glass chromatotube, passes into the ethanol 50mL of first grade to clean ion exchange resin.Afterwards, pass into the ethanol 100mL of first grade, be collected in clean glass flask.Analyze the ethanol obtained, result is: the concentration summation of lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is 0.15ppb.Use the ethanol that this obtains, operate in the same manner as the method described in embodiment 1, the hot-line electrical potential of the crystallization that result obtains on the filter is 0.0kV, does not find static electrification.The compound that the formula (1-1) obtained after drying represents is 22.5g.Residual solvent amount in crystallization is 56ppm, and purity is 99.98%.Be 1.0 × 10 at resistivity value ¹³the compound that the formula (1-1) obtained being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 2.4 × 10 ¹²Ω m.

The process of the solvent that (embodiment 19) utilizes silica gel and aluminum oxide to carry out

Analyze the ionic concn of the hexane of commercially available first grade, result is: the concentration summation of lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is 0.20ppb.Filling gel and each 5g of aluminum oxide in glass chromatotube, the hexane 50mL passing into first grade cleans.Afterwards, pass into the hexane 150mL of first grade, be collected in clean glass flask.Analyze the hexane obtained, result is: the concentration summation of lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is 0.03ppb.Use the hexane that this obtains, operate in the same manner as the method described in embodiment 1, the hot-line electrical potential of the crystallization that result obtains on the filter is 0.0kV, does not find static electrification.The compound that the formula (1-1) obtained after drying represents is 22.4g.Residual solvent amount in crystallization is 60ppm, and purity is 99.98%.Be 1.0 × 10 at resistivity value ¹³the compound that the formula (1-1) obtained being added with 20% in the liquid-crystal composition (M-1) of Ω m represents and the resistivity value of the liquid-crystal composition obtained is 2.2 × 10 ¹²Ω m.

(embodiment 20)

In embodiment 1, the compound using replacement formula of the compound shown in following table (1-1) to represent, carries out same operation.The hot-line electrical potential of the crystallization that the strainer of arbitrary compound when filter operation obtains is 0.0kV, does not find static electrification.Here, the resistivity value in table be add in the liquid-crystal composition (M-1) 20% each compound and the resistivity value of liquid-crystal composition that obtains.

Table 1

In addition, make the liquid crystal display device of the liquid-crystal composition containing each compound after using operation, result shows and does not occur to show bad superperformance.

Claims

Wherein, general formula (1) is:

A represents 1,2 or 3,

Formula (A-1) and (A-2) are:

(I) method of ~ (V) is:

(II) be dissolved in solvent, after adopting the column chromatography being filled with sorbent material to refine this solution, crystallization separated out from the solution obtained,

(V) be dissolved in solvent, after adopting the column chromatography being filled with sorbent material to refine this solution, after being concentrated by the solvent portions obtained, after adding one kind or two or more non-polar solvent and/or one kind or two or more polar solvent further, make crystallization;

(VI) solvent of ~ (XI) is:

(VI) solvent only formed by a kind of non-polar solvent,

(VII) solvent formed by non-polar solvent of more than two kinds,

Non-polar solvent and the polar solvent of described (VI) to (XI) are the solvents meeting the important document shown in following (i):

I () is filled with in the refining step of the column chromatography of sorbent material in the employing of the compound that general formula (1) represents, non-polar solvent that use during the compound stripping that general formula (1) is represented, that have passed the chromatographic column being filled with sorbent material or polar solvent.

2. manufacture method according to claim 1, is characterized in that, is shown as by described resistivity value and is less than 8.0 × 10 ¹¹the compound dissolution that the general formula (1) of Ω m represents in solvent after, the column chromatography being filled with sorbent material is adopted to refine, from the solution obtained after a part of solvent of distillation removing, do not add solvent and the crystallization of the compound that general formula (1) is represented, or do not distill and do not add solvent further except desolventizing and the crystallization of the compound that directly makes general formula (1) represent from the solution obtained yet, when filtering the crystallization of separating out, solvent in the solution together existed with this crystallization is the solvent only do not formed by one kind or two or more non-polar solvent containing polar solvent.

3. manufacture method according to claim 1, it is characterized in that, when filtering the crystallization of the compound that the general formula (1) of separating out represents, solvent in the solution together existed with this crystallization is the mixed solvent that the one kind or two or more solvent only formed by non-polar solvent is formed, before crystallization, the summation of adding the concentration of lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is further the one kind or two or more non-polar solvent of below 0.05ppb.

4. the manufacture method according to claim 1 or 3, is characterized in that, adopts the column chromatography being filled with sorbent material to be shown as described resistivity value and is less than 8.0 × 10 ¹¹the compound that the general formula according to claim 1 (1) of Ω m represents carry out refining after, after part or all distillation of solvent in the solution obtained is removed, or do not distill except desolventizing, the summation of the concentration of further interpolation lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is the one kind or two or more non-polar solvent of below 0.05ppb, after recrystallization, distillation removing the crystallization of the compound that the solvent used in recrystallization is represented from general formula (1).

5. manufacture method according to claim 1, it is characterized in that, when filtering the crystallization of the compound that the general formula (1) of separating out represents, the solvent in the solution together existed with this crystallization is the non-polar solvent of at least one and the polar solvent of at least one.

6. manufacture method according to claim 1 or 5, it is characterized in that, add one kind or two or more non-polar solvent and/or one kind or two or more polar solvent, the usage quantity of solvent during make to utilize recrystallization to separate out compound crystal that general formula (1) represents is 0.5mL ~ 100mL relative to the compound that 1g general formula (1) represents.

7. manufacture method according to claim 1 or 5, is characterized in that, before the leaching after the crystallization of the compound represented at general formula (1) and in this crystallization, adds one kind or two or more polar solvent according to claim 1.

8. manufacture method according to claim 1 or 5, it is characterized in that, refining rear and before the crystallization of the compound making general formula (1) represent, adding one kind or two or more polar solvent according to claim 1 at the compound adopting the general formula (1) being filled with the column chromatography of sorbent material to represent.

9. manufacture method according to claim 1 or 5, it is characterized in that, in the developing solvent used when the employing of the compound that general formula (1) represents is filled with the column chromatography of sorbent material refining, add one kind or two or more polar solvent according to claim 1.

10. manufacture method according to claim 1 or 5, is characterized in that, the compound adopting the general formula (1) being filled with the column chromatography of sorbent material to represent refining before, add one kind or two or more polar solvent according to claim 1.

11. manufacture method according to claim 1 or 5, it is characterized in that, do not carry out adopt the compound that represents of general formula (1) that is filled with the column chromatography of sorbent material refining after from the solution obtained distillation except desolventizing and the operation adding solvent, directly make crystallization.

12. manufacture method according to claim 1 or 5, it is characterized in that, adopt the compound that represents of general formula (1) that is filled with the column chromatography of sorbent material refining after from the solution obtained, after a part of solvent of distillation removing, carry out the precipitation operation of crystallization.

13. manufacture method according to claim 1 or 5, it is characterized in that, after after employing is filled with refining of the column chromatography of sorbent material, from the solution obtained, distillation removes desolventizing, add lithium ion, sodium ion, ammonium ion, potassium ion, the concentration summation of magnesium ion and calcium ion is the one kind or two or more non-polar solvent of below 0.05ppb, and/or lithium ion, sodium ion, ammonium ion, potassium ion, the concentration summation of magnesium ion and calcium ion is the one kind or two or more polar solvent of below 1.0ppb, after the compound that dissolving general formula (1) represents, carry out the precipitation operation of the crystallization of the compound that general formula (1) represents.

14. manufacture method according to claim 1 or 5, it is characterized in that, before being about to carry out the precipitation operation of crystallization, the concentration summation of adding lithium ion, sodium ion, ammonium ion, potassium ion, magnesium ion and calcium ion is the one kind or two or more non-polar solvent of below 0.05ppb, regulates quantity of solvent.

15. manufacture method according to claim 1 or 5, it is characterized in that, the polar solvent used is the one kind or two or more solvent selected from alcoholic solvent, ketones solvent, esters solvent, ether solvent or nitrile solvents.

16. manufacture method according to claim 15, it is characterized in that, alcoholic solvent is methyl alcohol, ethanol, 1-propyl alcohol or 2-propyl alcohol, ketones solvent is acetone or 2-butanone, esters solvent is vinyl acetic monomer, ether solvent is ether, tetrahydrofuran (THF) or methyl t-butyl ether, and nitrile solvents is acetonitrile or propionitrile.

17. manufacture method according to claim 16, is characterized in that, the polar solvent used is the one kind or two or more solvent selected from methyl alcohol, ethanol, acetone or 2-butanone.

18. manufacture method according to claim 1 or 5, is characterized in that, in the solvent in the solution existed together with this crystallization when filtering the crystallization of the compound that the general formula (1) of separating out represents, the ratio of hydrocarbon system solvent is 50 more than volume %.

19. manufacture method according to claim 1 or 5, is characterized in that, in the solvent in the solution existed together with this crystallization when filtering the crystallization of the compound that the general formula (1) of separating out represents, the ratio of hydrocarbon system solvent is 90 more than volume %.

20. manufacture method according to any one of claims 1 to 3, is characterized in that, in general formula (1), and A ¹and A ²middle at least one party represents following group:

21. manufacture method according to any one of claims 1 to 3, is characterized in that, in general formula (1), and Y ¹represent fluorine atom.

22. manufacture method according to any one of claims 1 to 3, is characterized in that, in general formula (1), and R ¹methyl, ethyl, propyl group, butyl or amyl group, Z ¹represent singly-bound ,-CH ₂cH ₂-,-CF ₂o-or-OCF ₂-.

23. manufacture method according to any one of claims 1 to 3, is characterized in that, in general formula (1), and A ¹and A ²middle at least one party represents following group:

24. manufacture method according to any one of claims 1 to 3, is characterized in that, in general formula (1), and R ¹and Y ¹represent methyl, ethyl, propyl group, butyl, amyl group, vinyl, methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy, 3-butenyloxy or 4-amylene oxygen base independently of one another, Z ¹represent singly-bound ,-CH ₂cH ₂-,-CH ₂o-,-OCH ₂-,-CF ₂o-or-OCF ₂-.

25. manufacture method according to any one of claims 1 to 3, is characterized in that, in general formula (1), and A ¹and A ²middle at least one party represents following group:

26. manufacture method according to any one of claims 1 to 3, it is characterized in that, the non-polar solvent used is hydrocarbon system solvent.

27. manufacture method according to claim 26, it is characterized in that, the hydrocarbon system solvent used is the one kind or two or more solvent selected from the group that hexane and constitutional isomer, heptane and constitutional isomer thereof, octane and constitutional isomer, sherwood oil, benzene,toluene,xylene and isopropyl benzene form.

28. manufacture method according to claim 26, is characterized in that, the hydrocarbon system solvent used is the one kind or two or more solvent selected from hexane and constitutional isomer, heptane and constitutional isomer thereof and toluene.

29. manufacture method according to any one of claims 1 to 3, it is characterized in that, at least one in the solvent in the solution existed together with this crystallization when filtering the crystallization of the compound that the general formula (1) of separating out represents is with the refined non-polar solvent of sorbent material.

30. manufacture method according to any one of claims 1 to 3, it is characterized in that, at least one in the solvent in the solution existed together with this crystallization when filtering the crystallization of the compound that the general formula (1) of separating out represents is the solvent of spent ion exchange resin process.

31. manufacture method according to any one of claims 1 to 3, it is characterized in that, at least one in the solvent in the solution existed together with this crystallization when filtering the crystallization of the compound that the general formula (1) of separating out represents is the solvent with the column chromatography process being filled with sorbent material.

32. manufacture method according to any one of claims 1 to 3, is characterized in that, use silica gel, aluminum oxide or their mixture as sorbent material.

33. manufacture method according to any one of claims 1 to 3, it is characterized in that, when adopting column chromatography to carry out refining, use the one kind or two or more solvent selected from hexane and constitutional isomer, heptane and constitutional isomer thereof and toluene as developing solvent.

34. manufacture method according to any one of claims 1 to 3, it is characterized in that, the described resistivity value of the compound that the general formula (1) obtained with crystalline state represents is shown as 1.0 × 10 ¹²more than Ω m.