CN100588996C - Supramolecular composite film material and method for fabricating - Google Patents
Supramolecular composite film material and method for fabricating Download PDFInfo
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- CN100588996C CN100588996C CN200510127428A CN200510127428A CN100588996C CN 100588996 C CN100588996 C CN 100588996C CN 200510127428 A CN200510127428 A CN 200510127428A CN 200510127428 A CN200510127428 A CN 200510127428A CN 100588996 C CN100588996 C CN 100588996C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/21—Urea; Derivatives thereof, e.g. biuret
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
Abstract
The provided optical-anisotropic composite film material with improved hydrolytic stability and mechanical strength is prepared as: (1) forming the lyotropic liquid crystal layer with pi-conjugated system and cyclic organic compound with substituted polar group; (2) forcing orientation force to remove solvent and form crystal film; (3) treating the film with inorganic salt solution to form supramolecular insoluble structure; (4) dipping the last product with adhesive to form filled film; (5) drying.
Description
Related application
The application requires the right of priority of No. the 60/578th, 338, the U.S. Patent application submitted on June 8th, 2004, and the content of its disclosure is as a reference incorporated herein with way of reference.
Technical field
The present invention relates in general to crystal composite film material field.Especially, the present invention relates generally to microelectronics, optics, communication, computer technology and other association area.
Background technology
The development need of modern technologies is created material, the especially compound substance that makes new advances, and it is configured for making the basis of optics, electronics and other element with desired performance.
Compound or compound substance are meant by two or more different component in other words by the system of different phase compositions.Wherein a kind of component is continuous, and is called as matrix or base material, and other component is with snotter (inclusions), especially with the form of particle, fiber, layer.Be distributed in the matrix, and be known as filler or disperse phase.Compound substance or compound are heterogeneous dispersant systems, and its performance is not the simple combination of each component property.Performance of composites can by improve interaction between matrix and the filler, by selecting suitable filler and being controlled by the ratio that changes each component.The physical-chemical parameters of filler particles has vital role in obtaining to have the compound substance of desired performance.
A kind of composition that is used to obtain optically transparent material is disclosed in United States Patent (USP) the 4th, 143, in No. 017, said composition comprises multipolymer, water and the organic filler that contains the unsaturated diol class, the mechanical property that final compound substance improves is given in these organic fillers, has kept the higher optical property of component simultaneously.These fillers are the polyfunctional monomers that contain at least one carboxyl, and it is as crosslinking chemical.
The various types of filler molecules that contain polymerizable groups are at European patent EP0, are described in 389, No. 420.
Filler can be the various combination of material, and these materials can be organic and/or inorganic.For example, comprising the polymerizable mesogenic objects system of organic and inorganic filler and water soluble polymer dispersions is described in No. 0040629, PCT patent disclosure WO 0040655 and WO.Employed inorganic constituents is an alkali salt.
Another example of the polymer composition that uses in the LCD backlight system is disclosed in European patent EP 0,847, in No. 424, said composition comprises the polymer film of covering with polymer adhesive, and this polymer adhesive contains organic and inorganic filler.This bonding agent is transparent and keeps its optical property for a long time.
At anisotropic membrane based on iodine modified polyethylene alcohol (PVA), the optical property of having studied the bi-component liquid crystal system is (referring to Bahadur, B., Liquid Crystals:Applications and Uses, ed., Vol.1, World Scientific, Singapore, NewYork, July 1990, p.101).
Yet multiple optical material based on polymkeric substance especially has the film based on PVA of dye additive, has relatively low thermal stability, and this has limited their application.
A kind of polymkeric substance of specific type is a supermolecule polymer, referring to for example Brandveld, and L., Supramolecular Polymers, Chem.Rev., 101,4071-97 (2001).Its structural unit is connected by non-covalent bond such as hydrogen bond, complex bonds and aromatic hydrocarbons-aromatic hydrocarbons key.Monomer is the self assembly dish type molecule that is generally organic dyestuff, and it contains the ionic group of various replacements.In aqueous solution, such dish type molecule presents congregation, and forms lyotropic liquid crystal.
In forming the supermolecule polymer composition, the vital role of the intermolecular bonding of hydrogen bond type is described in No. 1,300,447, European patent EP for example.Such key is results of interaction between the functional group of adjacent polymer chains seemingly.
United States Patent (USP) the 5th, 730 has disclosed the method for the film that obtains to comprise polymeric matrix for No. 900.According to the method for this disclosure, initial soln comprises replace and the polycyclic compund contain polymerizable groups in substituting group of dish type, and liquid crystal material.Matrix is through orientation (orientation) polymer substrate.Form film, the liquid crystal snotter (inclusions) that this film comprises polymeric matrix and is equivalent to the filler of combination in processing with after further cooling off through disclosing.The conversion of this binary mixture causes forming the matrix-polymeric system that has protective seam, and keeps liquid crystal property in telolemma.Yet, with an organic solvent, need be respectively the system component selective solvent, need high temperature and/or ultraviolet radiation, make above-mentioned polymerization process technical sophistication and be unsuitable for environment.
The another kind of compound of optical film material that is used to obtain to have the modification of new capability is that the water-soluble dichroic organic dyestuff by the modification with planar molecule structure provides.The characteristics of the molecule aggregate of heterocycle molecule and such compound are to have strong dichroism in limit of visible spectrum.The shortcoming that does not have prior art based on the method for the manufacturing crystal film of this class material.This manufacture method comprises the following stage (step).In the phase one, water-soluble dye forms the lyotropic liquid crystal phase.This comprises mutually by the molecular column aggregation of the dish type of dichroic dyestuff (referring to for example Yeh, P., et al., Molecular CrystallineThin Film E-Polarizer, Mol.Mater., 14 (2000)).These molecules in addition in dilute solution, also can assemble (referring to Lydon, J., Chromonics, In:Handbook ofLiquid Crystals, 1998, pp.981-1007).In subordinate phase, apply shearing force to lyotropic liquid crystal phase (with the form of printing ink or paste), so that molecular columns orientation on the shearing force direction (align).The high thixotropic of the liquid crystal through applying provides the high molecular assemblyization under the shear-induced state, and is stopping shear action later on its maintenance.In the phase III of this method, the evaporation of solvent (water) causes unidirectional crystallization, and forms organic solid crystals film by the liquid crystal phase through preorientation, as at United States Patent (USP) the 6th, 563, and institute's general description in No. 640.The characteristics of such crystal film (TCF) are the high optical anisotropy of refractive index and absorption index aspect, show as at Bobrov, Yu.A., J.Opt.Technol., 66, the polaroid performance of the excellence that is described in detail in 547 (1999), and be suitable for as at Ignatov, L. wait people's Society for Information Display, Int.Symp.Digest ofTechnical Papers, Long Beach, California, May 16-18, the commerce aspect LCD of institute's general description is used among the Vol.XXXI, 834-838 (2000).
Optical anisotropic film by this technology manufacturing is restricted in high humidity environment.As at United States Patent (USP) the 6th, 563, disclosed in No. 640, film can be handled with the solution that contains divalence or trivalent metal ion in addition.The final products of this processing have formed insoluble film.Yet water cut can fluctuate with high temperature and high humidity, and it causes the stability decreases of optical characteristics.
Summary of the invention
The invention provides the optical anisotropy composite film material of the operating characteristic with improvement, the operating characteristic of improvement comprises with respect to the hydrolytic stability of environmental factor and physical strength.These and other advantage of the present invention can obtain by forming supramolecular composite film material.This supramolecular composite film material comprises the matrix of the crystal film that is made of the organic supermolecular that contains polar group, and the bonding agent of representing water-soluble fatty compounds of group, and this water-soluble fatty compounds of group contains at least two functional groups.
Preferably, according to supramolecular composite film material of the present invention, wherein each supermolecule is to have pi-conjugated system and the chain of the ring-type organic molecule that connected by pi-pi bond, described supermolecule have general formula M}n (F) d,
Wherein M is an organic molecule; N is the number of molecule in the described chain, and quantity is up to 10000, and F is the polar group that is exposed to space between supermolecule; And d is the number of each molecule Semi-polarity group, changes between 1 to 4.
According to supramolecular composite film material of the present invention, wherein said polar group is ionizable.
According to supramolecular composite film material of the present invention, wherein said ionizable polar group combines with one or more counter ion counterionsl gegenions.
According to supramolecular composite film material of the present invention, wherein said counter ion counterionsl gegenions are alkaline-earth metal ions.
According to supramolecular composite film material of the present invention, wherein said supramolecular matrix account for described composite film material quality up to about 95%.
According to supramolecular composite film material of the present invention, wherein said bonding agent is water miscible.
According to supramolecular composite film material of the present invention, the described functional group of wherein said binder molecule interacts and forms hydrogen bond and/or chemical bond.
According to supramolecular composite film material of the present invention, the functional group of wherein said binder molecule and supramolecular ring-type organic molecule interact and form hydrogen bond and/or ionic link.
According to supramolecular composite film material of the present invention, described supramolecular matrix is not disturbed in the interaction of wherein said bonding agent and described ring-type organic molecule.
According to supramolecular composite film material of the present invention, the described functional group of wherein said binder molecule and the polar group of described ring-type organic molecule interact, and described ring-type organic molecule belongs to different supermolecule or same supramolecular different fragments.
According to supramolecular composite film material of the present invention, wherein said bonding agent contains amino and/or oh group.
According to supramolecular composite film material of the present invention, wherein said bonding agent is selected from methylol ureas and derivant thereof.
According to supramolecular composite film material of the present invention, wherein said bonding agent further comprises dibasic alcohol or polyvalent alcohol adjuvant.
According to supramolecular composite film material of the present invention, the ratio of the amount of wherein said pure adjuvant and described bonding agent is at (0.1-1.0): in 2 the scope.
According to supramolecular composite film material of the present invention, wherein said material is anisotropic and has crystal structure that described crystal structure has along one of optical axis
Interplanar distance.
According to supramolecular composite film material of the present invention, wherein said material is a polarization.
According to supramolecular composite film material of the present invention, wherein said material is a kind of retardation plate or optical filter.
The present invention further provides the method that is used to make supramolecular composite film material with these useful performances.In a specific embodiment, this method may further comprise the steps: (i) form the molecular lyotropic liquid crystal layer of oversubscription by the cyclic organic compounds of the polar group with pi-conjugated system and replacement; (ii) described layer is applied outside dipole-dipole force, and further remove and desolvate, form crystal film; (iii) handle crystal film, the supramolecular insoluble crystal film that formation is made up of described organic molecule with inorganic salt solution; (iv) use can with the described insoluble film of the interactional adhesive-dipping of polar group, then form film through filling; And (v) dry described film through filling makes the formation supramolecular composite film material.
According to the method for manufacturing supramolecular composite film material of the present invention, wherein the content of the described organic molecule in described lyotropic liquid crystal is in about 3% to 50% the scope of mass ratio.
According to the method for manufacturing supramolecular composite film material of the present invention, wherein the content of the described organic molecule in described lyotropic liquid crystal is in about 7% to 30% the scope of mass ratio.
According to the method for manufacturing supramolecular composite film material of the present invention, wherein said lyotropic liquid crystal be based on water or water with can with the potpourri of the miscible organic solvent of water in.
According to the method for manufacturing supramolecular composite film material of the present invention, wherein said lyotropic liquid crystal comprises that further mass ratio is up to 5% surfactant.
According to the method for manufacturing supramolecular composite film material of the present invention, wherein said lyotropic liquid crystal comprises that further mass ratio is up to 5% plastifier.
According to the method for manufacturing supramolecular composite film material of the present invention, wherein said outside dipole-dipole force is the mechanical shearing to described layer.
According to the method for manufacturing supramolecular composite film material of the present invention, wherein said outside dipole-dipole force comprises and is selected from one or more external force that apply electric field and apply magnetic field.
According to the method for manufacturing supramolecular composite film material of the present invention, wherein removing described solvent from described lyotropic liquid crystal is to carry out under the condition of the relative humidity of the temperature between about 20 ℃ to 60 ℃ and 40% to 70%.
According to the method for manufacturing supramolecular composite film material of the present invention, wherein said solvent is removed being less than about 1 hour time under about 20 ℃ temperature.
According to the method for manufacturing supramolecular composite film material of the present invention, wherein said inorganic salt solution is the solution of alkali salt.
According to the method for manufacturing supramolecular composite film material of the present invention, wherein said solution concentration is in mass ratio is about 5% to 30% scope.
According to the method for manufacturing supramolecular composite film material of the present invention, wherein said solution concentration is in mass ratio is about 10% to 20% preferable range.
According to the method for manufacturing supramolecular composite film material of the present invention, wherein said insoluble crystal film washed with water before with described adhesive-dipping, and drying is less than 20 minutes approximately under the temperature between 20 ℃ to 70 ℃ then.
According to the method for manufacturing supramolecular composite film material of the present invention, the aqueous solution of wherein said bonding agent is used for described dipping.
According to the method for manufacturing supramolecular composite film material of the present invention, the working concentration of wherein said bonding agent is in mass ratio is about scope of 0.5% to 20%.
Description of drawings
By reading that the present invention provide hereinafter describes in detail and appended claim and with reference to accompanying drawing, other purpose of the present invention and advantage will become apparent, wherein:
Fig. 1 represents is the relation curve of the relative humidity of thickness for inorganic salts and with methylolurea and glycerine (MCG1) dipping solution processing crystal film (TCF) time of supramolecular composite film.With the TCF (curve 2) of MC (2%)+G1 (1%) processing and the TCF (curve 1) that MC of no use (2%)+G1 (1%) handles.
Fig. 2 represents is before 230 ℃ of baked tests and afterwards, through and the indanthrone handled without methylolurea (MC) dipping solution, naphthalene tetracarboxylic acid Yi Ji the relation curve of the contrast of the insoluble TCF of the sulfonated derivative of perylene tetracarboxylic acid (INP) and transmittance (CR-T curve).Before baked test undressed TCF (1) and behind baked test undressed TCF (2), before baked test through the TCF (3) of 10% MC solution-treated and at baked test after the TCF (4) of 10% MC solution-treated.
Fig. 3 represents is before 230 ℃ of baked tests and afterwards, through and the CR-T curve of the insoluble TCF of the INP that handles without the MCG1 dipping solution.Before baked test undressed TCF (1) and behind baked test undressed TCF (2), before baked test through the TCF (3) of MC (4%)+G1 (2%) solution-treated and at baked test after the TCF (4) of MC (4%)+G1 (2%) solution-treated.
Fig. 4 represents is before environmental test and afterwards, through and the CR-T curve of the insoluble TCF of the INP that handles without the MCG1 dipping solution.Before environmental test undressed TCF (1) and after environmental test undressed TCF (2), before environmental test through the TCF (3) of MC (2.5%)+G1 (1.2%) solution-treated and in environmental test after the TCF (4) of MC (2.5%)+G1 (1.2%) solution-treated.
The insoluble TCF of the aqueous solution of the sulfonated products potpourri that is based on indanthrone that Fig. 5 represents before 230 ℃ of baked tests and afterwards, through and the CR-T curve handled without dipping solution.Before baked test undressed TCF (1) and behind baked test undressed TCF (2), before baked test through the TCF (3) of MC (2.5%)+G1 (1.2%) solution-treated and at baked test after the TCF (4) of MC (2.5%)+G1 (1.2%) solution-treated.
Embodiment
The invention provides the optical anisotropic film of the compound substance that in wide wavelength coverage, has selectivity optics performance, and the method that obtains this class film.This material can be based on the various organic substances that can form the lyotropic liquid crystal phase in solution.This material is applied (coating) on substrate, then lyotropic liquid crystal is applied outside dipole-dipole force mutually and except that desolvating, forms the anisotropic crystal film of the ordering system that comprises organic molecule.
The physical strength that increases and the physical property of improvement have been guaranteed the suitable function of blooming, especially their stability under high temperature and super-humid conditions, it is by providing with handling film with interactional inorganic salts of liquid crystal molecule and water-soluble organic compounds.
The optical anisotropic film of the compound substance of this disclosure is compared with undressed film to have: with respect to the higher stability of environmental factor, the mechanical property and the better optical characteristics of improvement.Another specific embodiment of the present invention provides the method that obtains described film.
The present invention adopts the supermolecule of being made up of organic molecule, and these organic molecules have plane configuration, contain the polar group of replacement, also connect by non-covalent pi-pi bond.With regard to their chemical constitution, these molecules belong to the ring compound (comprising aromatic compounds and heterogeneous ring compound) of the conjugated system with π key.It can be polarity or nonpolar modification group that these molecules comprise what be substituted.Polar group is hydrophilic, and is that described organic compound molecule is provided at the dissolubility in water and other polar solvent.Non-polar group is hydrophobic, and dissolubility and the needed spectral characteristic of decision in non-polar solvent.The such compound of one class is provided by organic dyestuff.
Described supermolecule comprises the chain of the ring-type organic molecule that has pi-conjugated system and connected by π-π (aromatic hydrocarbons-aromatic hydrocarbons) key, and it has following general formula:
{M}n(F)d，
Wherein, M is an organic molecule; N is the number (up to 10000) of molecule in the chain, and F is the polar group that is exposed to space between supermolecule; And d is the number (changing between 1 to 4) of each molecule Semi-polarity group.
Polar group can be ionizable and non-ionizable.Ionizable polar group is the anionic group of strong inorganic acid normally, comprises the carboxylic group that sulfonic group, sulfate radical and phosphate groups and polarity are less.In addition, these groups can be the kation fragments, have the amphiprotic group of pH correlated performance as amino with some.In solution, polar group always is combined with one or more (identical or different) counter ion counterionsl gegenions.The multivalence counter ion counterionsl gegenions can belong to different molecules simultaneously.The ionizable polar group does not comprise hydroxyl, chlorine, bromine or the like.
Non-polar group mainly belongs to polytype organic fragment, as methyl, ethyl, ethoxy etc.
The organic compound molecule of being considered has plane configuration, has elliptical shape usually.These molecules can be symmetries or asymmetric, around substituting group is arranged in simultaneously.These molecules are amphiphilics, and can contain the substituted radical of identical or different chemical characteristic simultaneously.
Just as is known, being used to form molecule aggregate or supramolecular expulsive force is that π-π between the planar molecule (for example, the planar molecule of dyestuff) interacts.Solvation, that is, modification causes forming the supramolecular ordering structure of same type with the preferential interaction of polar group and solvent, is known as lyotropic liquid crystal (LLC) system (system) or middle phase.The characteristics of LLC system are: its phasor has the stable region in very wide concentration, temperature and pH value scope.
Forming such LLC middle by the organic substance of being considered in polar solvent is the necessary condition that realizes the object of the invention mutually.Polar solvent can be water or water and can with the potpourri of water with the miscible organic solvent of any ratio.
The water soluble organic substance matter of phase in the middle of utilization of the present invention can form, these organic substances are described in detail in the disclosed patented claim of U.S. US2001/0029638 number, its full content is as a reference incorporated herein with way of reference, and includes but not limited to the compound of following type:
-polymethin dyes (for example, false isocyanine (peudoisocyanine), pinacyanol);
-triarylmethane dyes (for example, alkaline pasture, acid light blue 3);
-diamido xanthene dye (for example, sulfo group rhodamine);
-acridine dye (for example, basic yellow K);
-sulfonation acridine dye (for example, trans-quinacridone);
The soluble derivative of-anthraquinone dye (for example, active light blue KX);
The vat dyestuffs goods of-sulfonation (for example, flavanthrone, flavanthrone, vat yellow 4K, the dark green G of urn, the purple C of urn, indanthrone, perylene purple, RM vat scarlet RM wo 2G);
-azo dyes (for example, benzopurpurine 4B, direct fast yellow O);
-water-soluble diazine colors (for example, cloth fast blue r 3);
-Huangization dioxazine dye preparations (pigment violet dioxazine);
-solubility thiazine dye (for example, methylenum careuleum);
-water soluble metal phthalocyanine derivant (for example, eight carboxyl CuPc salts);
-fluorescer;
-chlorination glycocoll disodium (disodium chrologlycanate);
And some other compounds, the benzimidazole (purple) of Bao Kuo perylene tetracarboxylic acid diimides red (PADR), PADR and the benzimidazole of naphthalene tetracarboxylic acid (yellow, claret), benzimidazole and phenanthro--9,10:2, the sulfonic derivative of 3-quinoxaline etc.
Be to form mutually in the middle of the lyotropic liquid crystal by the ionizable organic molecule that utilizes water-soluble sulfonic derivative (individually or the potpourri of this compounds) form.
Cation counterbalancing ion in disclosed system can be, but be not limited to: H
+, NH
4 +, K
+, Li
+, Na
+, Cs
+, Ca
2+, Sr
2+, Mg
2+, Ba
2+, Co
2+, Mn
2+, Zn
2+, Cu
2+, Pb
2+, Fe
2+, Ni
2+, Al
3+, Ce
3+, La
3+Deng, and these kations and other cationic potpourri.
When being dissolved in the water, the molecule of these sulfonic derivatives or their potpourri forms as the coin of piling up is piled up does not wait (bar-shaped) aggregation.Each aggregation in such solution all is the micella with electrostatic double layer, and whole solution is high degree of dispersion (colloidal state) lyophily system simultaneously.When solution concentration (that is, micellar concentration) increases, do not wait the axle aggregation to present spontaneous ordering, also it is called automatic ordering.This causes the formation of the middle phase of nematic lyophily (nematic lyotropic), and this system becomes liquid crystal thus.The high-sequential of dye molecule makes their centre can be used for mutually obtaining through being orientated the dichroic material of (orientation) in post.The film that is formed by these materials has optical anisotropy highly.By usual way,, can be easy to confirm liquid crystal state for example by polarizing microscope.
In the middle of the LLC mutually described in the content of sulfonic derivative or their potpourri be in mass ratio is 3 to 50% scope, the most normally in mass ratio is 7 to 30% scope.Described LLC system can contain mass ratio in addition up to 5% surfactant and/or plastifier.
By the number (being generally 1 to 4) of sulfo group and the number and the characteristic of other substituting group (as ethyl, methyl, chlorine, bromine) in the change dye molecule, can be controlled at the hydrophilic-hydrophobic balance of the aggregation that forms in the liquid crystal solution and change solution viscosity.This influences supramolecular size and dimension again successively, and influences the degree of these supramolecular molecular assemblyizatioies, and it provides the high stability of needed dissolubility with relevant LLC system.Distance between the supermolecule normally exists
Scope in.
All above-claimed cpds, separately or with the form of potpourri, can in solution, form phase in the middle of the stable LLC, wherein potpourri be each other potpourri or with the potpourri of other dichroic dyestuff and with the potpourri of some organic compounds (it is colourless or weak absorption in limit of visible spectrum).Remove desolvate after, can form mutually in the middle of these and has the anisotropic of higher optical characteristics to the small part crystal film.
Concentrate LLC solution by evaporating solvent (for example being heated to relatively low temperature) or by decompression distillation or by diafiltration.This processing can cause forming cream pasty mass or so-called " printing ink ", and it can keep the sufficiently long time of liquid crystal state.
By on the substrate surface of cleaning, applying (coating) solution or concentrate forms one deck LLC system.Substrate is normally made by glass or polymkeric substance, includes but not limited to: polyethylene terephthalate (PET), polycarbonate, polyarylate etc., and can have any desirable shape.
Then, the LLC layer is orientated.Some known methods that apply outside dipole-dipole force are arranged, and these methods are based on utilizes various factors: mechanical effect, electro ultrafiltration, magnetic action etc.Intensity of force must be enough to that dynamics unit's (supermolecule) of phase provides needed orientation in the middle of the LLC, and intensity of force depends on the performance of liquid crystal solution, as its character, concentration, temperature etc.Formed is the fundamental characteristics of disclosed material and the correlated product made by this material through orientation texture.Further description can be referring to United States Patent (USP) the 5th, 739, and is No. 296, the 6th, 174, No. 394 and the 6th, 563, No. 640, that its full content is as a reference incorporated herein with way of reference.
According to the present invention, the outside dipole-dipole force that acts on the lyotropic liquid crystal systems layer of organic molecule produces by mechanical shearing.This is that directed machinery by one or more dissimilar alignment apparatus moves and realizes, this alignment apparatus comprises being parallel to and applies (coating) laminar surface or surperficial therewith angled blade, cylindrical scraper plate or flat board, also comprises channel mould (slot die) or any other alignment apparatus.The distance of setting from this surface to orientation utensil edge is so that obtain the film of required thickness.
Remove the process of desolvating and be in the relative humidity of room temperature, 40-70% and under temperate condition, carried out about 1 hour thereafter, or by in about 20 to 60 ℃ temperature range, heating so that save time.This processing make substrate cover the last layer organic supermolecular through the orientation thin layer, be called crystal film (TCF).
Select to remove the mode of desolvating,, provide relaxation for the stress that in applying the process of outside dipole-dipole force, produces simultaneously so that exclude the possibility of the orientation effect of the previous LLC structure that forms of infringement.Should carefully avoid over-drying LLC layer before forming TCF on the substrate surface.Solvent removal step is carried out in suggestion under super-humid conditions.The key factor of guaranteeing the high-crystallinity of material layer is to remove the speed and the directivity characteristics of dissolving agent process from system.Resulting layer is rendered as the enough thin continuous film with ordering molecular structure, and wherein organic molecule is converged into a plurality of integral body (ensembles) of ordered orientation.The formation of this structure is that the particular fluid crystalline state by molecule in the solution is determined that they enter the quasicrystal aggregation of one dimension and/or bidimensional mutual orientation in this solution, have had local order.When applying (coating) on substrate surface, when applying outside dipole-dipole force simultaneously, such system obtains macroscopic orientation.This orientation not only obtains keeping in dry run, and because crystallization even can strengthen.
The method according to this invention, essential step thereafter are to handle the supramolecular TCF that obtains with the aqueous solution of mineral salt, so that this film is changed into insoluble form.For this purpose, can use, for example barium chloride (BaCl
2) solution, concentration is in 5 to 30% scope, and optimum range is 10-20%.During handling, Ba
2+Ion is by NH
4 +Ion (counter ion counterionsl gegenions of supramolecular polar group) replaces, and forms insoluble organic barium sulphate.Thereafter by washing in water to remove the hole that can partly infiltrate film and the unreacted barium chloride in the fault of construction.Then, carry out the film drying in room temperature or under 20 to 70 ℃ high temperature in air, depend on temperature, the time was about 20 minutes.
The next step of technological process of the present invention is with the insoluble TCF of the solution impregnation of water-soluble organic bond, this bonding agent can be at first and sulfonate radical and other polar group of being exposed to the organic molecule in space between supermolecule interact rapidly, form crosslinked then.
Bonding agent is selected from fatty compound, comprises methylol ureas (MC), for example, and monomethylol urea (H
2N (CO) NHCH
2OH) and dimethylolurea (HOH
2CHN (CO) NHCH
2OH), it is by urea (urea, NH
2CONH
2) obtain with the interaction of formaldehyde (HCHO).The MC molecule can be by their amino and the interaction of hydroxy functional group and polymerization each other.This causes forming the big molecule of all lengths, the compound from dimer and tripolymer to oligomer and high molecule mass, and its degree of polymerization is approximately or surpasses 100, and chain length surpasses macromolecular heap spacing.
When monomer solution being put on the TCF surface, the MC molecular diffusion is in film, and diffusion between heap.Depend on privileged site and concentration in film, binder molecule presents different transformations.These molecules each other or and the polar group of organic dye molecule between form ionic link or hydrogen bond.
The polycondensation of MC is to carry out under the condition of pH＜5, and by various acid catalysis in addition.Can quicken this process by heating.This reacts with following The Representation Equation:
-NHCH
2OH+HOCH
2NH→-NHCH
2OCH
2NH-+H
2O
-NHCH
2OH+HOCH
2NH→-NHCH
2NH-+H
2O+CH
2O
According to their length and conformation, the MC molecule of polymerization is in conjunction with the separated structures fragment of TCF (organic supermolecular by crystallization forms), itself or belong to same supermolecule or belong to different supermolecules.This MC molecule can be in the volume of TCF and is carried out polymerization by crosslinked from the teeth outwards, forms solid-state laminated film.Final film thickness depend on originally the TCF layer thickness and the concentration of MC solution.The TCF that obtains by dipping has sufficiently high intensity and elasticity.Cross-linked network piles up with dye molecule and combines, thereby has increased the TCF structure.
If dipping solution only contains the MC molecule, the polymer film that forms on the TCF surface is rigidity, fragility so, and can pass devitrification in time.In order to obtain stable and resilient film, the alcohols that suggestion will have two or more OH groups is incorporated in the dipping solution.Optimum adjuvant is glycerine (G1) or other dibasic alcohol and polyvalent alcohol, its can and the MC copolymerization be incorporated between the amino group and form crosslinkedly, produce plasticization in addition.Moreover the MC solution that glycerine is introduced dipping significantly (15-20%) improves the optical characteristics of TCF.Can significantly improve the environmental stability of TCF with MC+G1 solution impregnation and the thin surface aggregate thing film of formation.The best ratio of MC and G1 is 2 in dipping solution: (0.1-1.0) (w/w).This process is pressed, and for example following method is carried out: sample is immersed in the potpourri of the low concentration aqueous solution of MC or MC and alcohol (binary or trihydroxy alcohol), the time is 10 seconds to tens seconds.At last, drying is through the film of modification in room temperature or under the temperature of 20 to 70 ℃ of risings, and the time is 1-20 minute (or by changing these modes).This dry run also is accompanied by from TCF surface and removes the process of excess binder from the supermolecule organic structure.
Optical characteristics and thermal stability through the TCF of MC+G1 solution-treated are significantly improved, and this mainly is combined into unified system by MC and G1 molecule with the dyestuff fragment and explains.This may be relevant with two aspects: (i) between the carbonyl of the hydroxyl of MC and G1 and dyestuff and sulfo group, form hydrogen bond, and the (ii) interaction between the sulfo group of the amino of MC and dyestuff.In addition, the MC molecule can show polymerization when pH＜5-6, form their spatial network.The G1 molecule can participate in the polycondensation reaction with MC.As a result, the TCF based on compound substance that MC and G1 play the bonding agent effect has appearred.This compound substance presents the intensity of increase, and it can be confirmed by the thickness unchangeability of the TCF that handles through (MC+G1) under the condition that increases humidity.Data just as illustrated in fig. 1 can see that the thickness of contrast (untreated) TCF sample depends on the relative humidity (RH) of air, present especially significantly to change in the scope of RH 〉=60-70%.In general, in the RH of this research scope, the thickness of undressed TCF increased～and 32%.With after the 2%MC-1%G1 solution impregnation, it is about 13% that the thickness of sample has increased, but it becomes littler to the dependence of relative humidity.In a test, the thickness of the TCF through flooding is 520nm when RH=37%, has only increased 30nm (having increased by 5.7%) when RH=72%.
The step of said sequence provides solid-state composite membrane, and its characteristics are to have high strength and thermal stability.In this compound substance, the chemical conversion product of these organic compounds plays filler, and with the TCF film of the supermolecule organic compound of inorganic salts dippings as matrix.The quality that contains the TCF film of polar group account for total quality of materials up to 95%.This material is high stability with respect to environmental factor such as high temperature, can stand the short time heating up to 230 ℃ of (in 30 minutes).Long-term work still can keep the optical characteristics of film under humidity (RH=95%) that increases and high temperature (up to 80 ℃) condition.
Under all above-mentioned situations, formed film all is a crystalline state, and interplanar distance is approximately
These films are birefringent and present dichroic, polarization and phase shift (delay) performance, the latter with relevant with respect to the difference of the refractive index on the mutually perpendicular direction of optical axis.This film can also have the performance of optical filter.In addition, these films can combine the mechanical property of above-mentioned performance and improvement, and can carry out corresponding operating function.
Experimental section
Test according to method and system of the present invention.These embodiment only are used for illustrative purposes, rather than are used for limiting the scope of the invention by any way.
Being prepared as follows of supramolecular composite film material.Utilize rotary evaporator will comprise that sulfonated derivative, the total concentration of indanthrone, naphthalene tetracarboxylic acid He perylene tetracarboxylic acid (INP) are that aqueous solution evaporate to the dye strength of 5% organic compound potpourri is 10-16%, to guarantee to form the lyotropic liquid crystal phase.Then, surfactant Triton X-100 is added in the solution, so that improve the wetting state of substrate surface.The working concentration of resulting " black " printing ink is 13%.
Printing ink is put on the surface of glass substrate, utilize mayer (Mayer) rod to be orientated as the orientation utensil.Applying of film is to carry out under the condition of 20 ℃ and RH=65-70%.Under the same conditions after the drying, by being immersed in 10% barium chloride (BaCl
2) 1-2 makes TCF change into the insoluble form of water (Ba-form) second in the aqueous solution.Then, mention sample, also use the air knife drying with deionization (DI) water washing in the upright position.
This composite film material presents anisotropic optical property.The polarization parameter of TCF (control sample) and chromaticity coordinate (color coordination) are shown in Fig. 1 and the table 1.Measurement is to carry out in the air of room temperature and relative humidity RH=45%.
Polarization parameter and chromaticity coordinate (control sample) that table 1 is measured before baking based on the TCF of " black " printing ink
Here and hereinafter, T is the transmissivity of individual sample in nonpolarized light; H0 and H90 are two parallel and two cross polarization sheets transmissivities in nonpolarized light respectively; EP is a polarization efficiency; CR is a contrast; And Kd is the dichroic ratio.
For the thermal stability that improves TCF with improve its optical property, flooded sample in 30 seconds by immersing down in 10% the MC solution, then flushing and use the air knife drying in DI water at 20 ℃.The optical characteristics of TCF after dipping and the drying is shown in the table 2.
Table 2 before baking, measure based on the polarization parameter of the TCF of " black " printing ink and chromaticity coordinate (sample is immersed in 10% the MC solution, washs in DI water, uses compressed air drying then)
Then, heat 20 minutes (baked test) with control sample with the TCF sample that MC floods down at 230 ℃.The optical characteristics of TCF after the baking is shown in the table 3.
Polarization parameter and chromaticity coordinate that table 3 is measured after baking based on the TCF of " black " printing ink
Undressed (contrast) TCF and shown in Figure 2 at the relation curve of contrast of toasting front and back and transmissivity with the sample of MC dipping.
Utilize mayer (Mayer) rod as the orientation utensil, the printing ink with 11.5% prepares the TCF sample on glass substrate.Under the condition of 20 ℃ and RH=65-70%, apply printing ink.Under the same conditions after the drying, by being immersed in 10% barium chloride (BaCl
2) 1-2 changes into the insoluble form of water (Ba-form) with TCF second in the aqueous solution.Then, mention sample, also use the air knife drying with the DI water washing in vertical position.
The optical characteristics of these TCF (control sample) that record in the air of room temperature and relative humidity RH=45% is shown in the table 4.
Polarization parameter and the chromaticity coordinate of the TCF that table 4 is measured before baking (control sample) based on 11.5% printing ink
For the thermal stability that improves TCF with improve its optical property, by coming sample is handled in 30 seconds in the solution that under 20 ℃, is immersed in various MC+G1 (2: 1), then flushing and use the air knife drying in DI water.This processing has significantly improved the hardness of TCF.The optical characteristics of TCF after dipping and the drying is shown in the table 5.
Polarization parameter and chromaticity coordinate that table 5 is measured before baking based on the TCF of 11.5% printing ink
Then, heat 20 minutes (baked test) with control sample with through the TCF sample that (MC+G1) floods down at 230 ℃.The optical characteristics of TCF is shown in the table 6 after the baking.
Polarization parameter and chromaticity coordinate that table 6 is measured after baking based on the TCF of 11.5% printing ink
Control sample and those samples with the 4%MC+2%G1 solution impregnation are shown in Figure 3 in the data before and after the baked test.
Utilize mayer (Mayer) rod as the orientation utensil, the printing ink with 12% prepares the TCF sample on glass substrate.Under the condition of 20 ℃ and RH=65-70%, apply printing ink.Under the same conditions after the drying, by being immersed in 10% barium chloride (BaCl
2) 1-2 changes into the insoluble form of water (Ba-form) with TCF second in the aqueous solution.Then, mention sample, also use the air knife drying with the DI water washing in the upright position.
The optical characteristics of these TCF (control sample) that record in the air of room temperature and relative humidity RH=45% is shown in the table 7.
Polarization parameter and chromaticity coordinate that table 7 is measured before environmental test based on the TCF (control sample) of 12% printing ink
In order to improve the environmental stability of TCF, by coming sample is handled in 30 seconds in the solution that under 20 ℃, is immersed in 2.5%MC+1.25%G1, then flushing and use the air knife drying in DI water.This dipping has significantly improved the hardness of TCF.The optical characteristics of TCF after dipping and the drying is shown in the table 8.
Polarization parameter and chromaticity coordinate that table 8 is measured before environmental test: sample is immersed in the solution of 2.5%MC+1.25%G1 through the TCF of dipping based on 12% printing ink
Then, heat 24 hours (environmental test) with control sample with under the condition of TCF sample at 80 ℃ and relative humidity=90% of (MC+G1) dipping.TCF optical characteristics after this test is shown in the table 9.
Table 9 after environmental test, the polarization parameter of the TCF of printing ink and chromaticity coordinate based on 12%
Untreated (contrast) TCF and shown in Figure 4 with the sample of (MC+G1) dipping contrast and the relation curve of transmissivity before and after the environmental test.
Being prepared as follows of supramolecular composite film material.Utilize rotary evaporator to comprise indanthrone with the sulfonated derivative of perylene tetracarboxylic acid, total concentration are aqueous solution evaporate to the dye strength of 5% organic compound potpourri is 10%.After adding surfactant Triton X-100, the working concentration of resulting " royal purple " printing ink is 7-8%.
Printing ink is put on the surface of glass substrate, utilize mayer (Mayer) rod to be orientated simultaneously as the orientation utensil.Coated film under the condition of 20 ℃ and RH=65-70%.Under the same conditions after the drying, by being immersed in 10% barium chloride (BaCl
2) 1-2 changes into the insoluble form of water (Ba-form) with TCF second in the aqueous solution.Then, mention sample, also use the air knife drying with the DI water washing in vertical position.
The theoretical characteristics of these TCF (control sample) that record under the condition of room temperature and relative humidity RH=45% is shown in Figure 10.
The polarization parameter (control sample) that table 10 is measured before baking based on the TCF of " royal purple " printing ink
In order to improve based on the thermal stability of the TCF of royal purple printing ink and to improve its optical property, by coming sample is handled in 30 seconds in the solution that under 20 ℃, is immersed in 2.5%MC+1.25%G1, then flushing and use the air knife drying in DI water.This processing has significantly improved the hardness of TCF.The optical characteristics of TCF after dipping and the drying is shown in the table 11.
The polarization parameter (sample being immersed in the solution of 2.5%MC+1.25%G1) that table 11 is measured before baking based on the TCF of " royal purple " printing ink
Then, the TCF sample of control sample and warp (MC+G1) dipping heats 20 minutes (baked test) down at 230 ℃.The optical characteristics of TCF is shown in the table 12 after the baking.
The polarization parameter of TCF that table 12 is measured after baking through dipping based on " royal purple " printing ink
Undressed (contrast) TCF and shown in Figure 5 through the sample of (MC+G1) dipping contrast and the relation curve of transmissivity before and after the environmental test.
More than be for the purpose of illustration and description to the description of specific embodiment of the present invention and embodiment, though describe the present invention, should not regard limitation of the present invention as by some previous embodiment.They are not exhaustive or the present invention are limited to disclosed definite form really, and clearly, according to multiple improvement, the embodiment of above-mentioned instruction and to change all be possible.Therefore protection scope of the present invention is included in general range disclosed herein, and is contained by appended claim and equivalence replacement institute thereof.
Claims (32)
1. supramolecular composite film material comprises:
Contain polar group and the supramolecular matrix of crystallization in crystal film, and
The aliphatics bonding agent that contains at least two functional groups;
Wherein each described supermolecule is to have pi-conjugated system and the chain of the ring-type organic molecule that connected by pi-pi bond, and described supermolecule has general formula:
{M}n(F)d，
Wherein M is an organic molecule; N is the number of molecule in the described chain, and quantity is up to 10000, and F is the polar group that is exposed to space between supermolecule; And d is the number of each molecule Semi-polarity group, changes between 1 to 4;
The described functional group of described binder molecule and described supramolecular ring-type organic molecule interact and form hydrogen bond and/or ionic link.
2. supramolecular composite film material according to claim 1, wherein said polar group is ionizable.
3. supramolecular composite film material according to claim 2, wherein said ionizable polar group combines with one or more counter ion counterionsl gegenions.
4. supramolecular composite film material according to claim 3, wherein said counter ion counterionsl gegenions are alkaline-earth metal ions.
5. supramolecular composite film material according to claim 1, wherein said supramolecular matrix account for described composite film material quality up to 95%.
6. supramolecular composite film material according to claim 1, wherein said bonding agent is water miscible.
7. supramolecular composite film material according to claim 1, the described functional group of wherein said binder molecule interacts and forms hydrogen bond and/or chemical bond.
8. supramolecular composite film material according to claim 1, described supramolecular matrix is not disturbed in the interaction of wherein said bonding agent and described ring-type organic molecule.
9. supramolecular composite film material according to claim 1, the described functional group of wherein said binder molecule and the polar group of described ring-type organic molecule interact, and described ring-type organic molecule belongs to different supermolecule or same supramolecular different fragments.
10. supramolecular composite film material according to claim 1, wherein said bonding agent contains amino and/or oh group.
11. supramolecular composite film material according to claim 10, wherein said bonding agent is selected from the methylol ureas.
12. supramolecular composite film material according to claim 1, wherein said bonding agent further comprise dibasic alcohol or polyvalent alcohol adjuvant.
13. supramolecular composite film material according to claim 12, the ratio of the amount of wherein said pure adjuvant and described bonding agent are at (0.1-1.0): in 2 the scope.
14. supramolecular composite film material according to claim 1, wherein said material are anisotropic and have crystal structure that described crystal structure has 3.4 ± 0.3 along one of optical axis
Interplanar distance.
15. supramolecular composite film material according to claim 1, wherein said material is a polarization.
16. supramolecular composite film material according to claim 1, wherein said material are a kind of retardation plate or optical filter.
17. a method of making supramolecular composite film material may further comprise the steps:
Form supermolecule lyotropic liquid crystal layer, described supermolecule is made up of the ring-type organic molecule of the polar group with pi-conjugated system and replacement;
Described layer is applied outside dipole-dipole force, and remove thereafter and to desolvate, form crystal film;
Handle described crystal film with inorganic salt solution, form the supramolecular insoluble crystal film of forming by described organic molecule;
With with the described insoluble crystal film of the interactional adhesive-dipping of described polar group, form film through filling; And
Dry described film through filling forms supramolecular composite film material.
18. the method for manufacturing supramolecular composite film material according to claim 17, wherein the content of the described organic molecule in described lyotropic liquid crystal is in the scope of mass ratio 3% to 50%.
19. the method for manufacturing supramolecular composite film material according to claim 18, wherein the content of the described organic molecule in described lyotropic liquid crystal is in the scope of mass ratio 7% to 30%.
20. the method for manufacturing supramolecular composite film material according to claim 17, wherein said lyotropic liquid crystal be based on lyotropic liquid crystal water or described be water with can with the potpourri of the miscible organic solvent of water in.
21. the method for manufacturing supramolecular composite film material according to claim 17, wherein said lyotropic liquid crystal comprise that further mass ratio is up to 5% surfactant.
22. the method for manufacturing supramolecular composite film material according to claim 17, wherein said lyotropic liquid crystal comprise that further mass ratio is up to 5% plastifier.
23. the method for manufacturing supramolecular composite film material according to claim 17, wherein said outside dipole-dipole force are the mechanical shearings to described layer.
24. comprising, the method for manufacturing supramolecular composite film material according to claim 17, wherein said outside dipole-dipole force be selected from one or more external force that apply electric field and apply magnetic field.
25. the method for manufacturing supramolecular composite film material according to claim 17, wherein removing described solvent from described lyotropic liquid crystal is to carry out under the condition of the relative humidity of the temperature between 20 ℃ to 60 ℃ and 40% to 70%.
26. the method for manufacturing supramolecular composite film material according to claim 25, wherein said solvent is removed in the time that is less than 1 hour under 20 ℃ temperature.
27. the method for manufacturing supramolecular composite film material according to claim 17, wherein said inorganic salt solution are the solution of alkali salt.
28. the method for manufacturing supramolecular composite film material according to claim 27, wherein said solution concentration are in mass ratio is 5% to 30% scope.
29. the method for manufacturing supramolecular composite film material according to claim 28, wherein said solution concentration are in mass ratio is 10% to 20% preferable range.
30. the method for manufacturing supramolecular composite film material according to claim 17, wherein said insoluble crystal film washed with water before with described adhesive-dipping, and drying is less than 20 minutes under the temperature between 20 ℃ to 70 ℃ then.
31. the method for manufacturing supramolecular composite film material according to claim 17, the aqueous solution of wherein said bonding agent is used for described dipping.
32. the method for manufacturing supramolecular composite film material according to claim 17, the working concentration of wherein said bonding agent are in mass ratio is 0.5% to 20% scope.
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| US11/132,746 US7651738B2 (en) | 2004-06-08 | 2005-05-18 | Supramolecular composite film material and method for fabricating |
| US11/132,746 | 2005-05-18 |
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| US2553961A (en) | 1947-11-14 | 1951-05-22 | John F Dreyer | Laminated polarizer |
| RU2047643C1 (en) * | 1993-05-21 | 1995-11-10 | Хан Ир Гвон | Material for polarizing coating |
| DE19623147B4 (en) | 1995-06-08 | 2007-05-03 | Fuji Photo Film Co., Ltd., Minami-Ashigara | Film, process for making the same and its use in a liquid crystal display |
| US7204938B2 (en) * | 2003-04-22 | 2007-04-17 | Nitto Denko Corporation | Two-phase polymeric materials and methods for making |
| US20050104037A1 (en) * | 2003-09-23 | 2005-05-19 | Lazarev Pavel I. | Two-phase film materials and method for making |
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Non-Patent Citations (4)
| Title |
|---|
| 用"表面离子"法制备组分可控的LB膜超分子体系. 何平笙，邹纲，方堃.物理化学学报，第20卷第10期. 2004 |
| 用"表面离子"法制备组分可控的LB膜超分子体系. 何平笙，邹纲，方堃.物理化学学报，第20卷第10期. 2004 * |
| 界面具有超分子结构的复合膜形成过程. 丁健，王小平，白纯芳.天津大学学报，第34卷第6期. 2001 |
| 界面具有超分子结构的复合膜形成过程. 丁健，王小平，白纯芳.天津大学学报，第34卷第6期. 2001 * |
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| KR100723128B1 (en) | 2007-05-30 |
| TWI311104B (en) | 2009-06-21 |
| KR20070006651A (en) | 2007-01-11 |
| JP2006323342A (en) | 2006-11-30 |
| KR20060119689A (en) | 2006-11-24 |
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