CN1752776A - Preparation method of reflection circularly polarized light polaroid - Google Patents
Preparation method of reflection circularly polarized light polaroid Download PDFInfo
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- CN1752776A CN1752776A CN 200510086722 CN200510086722A CN1752776A CN 1752776 A CN1752776 A CN 1752776A CN 200510086722 CN200510086722 CN 200510086722 CN 200510086722 A CN200510086722 A CN 200510086722A CN 1752776 A CN1752776 A CN 1752776A
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Abstract
The present invention provides a preparation method of reflected circular polarized light Polaroid. Said method includes the following steps: uniformly mixing glass state liquid crystal, photopolymerisable monomer, photoinitiator and antipolymerizer, film-forming or making them into powder which can be applied on the surface of baseplate; utilizing proximity glass state liquid crystal film with different central reflecting wavelength or molecular diffusion between powder to create concentration gradient of mesomorphic element, adopting proper process at a certain temperature to make orietation so as to obtain mesomorphic elementary spiral arrangement structure and pitch gradient distribution, cooling and fixing the mesomorphic elementary spiral arrangement structure and pitch gradient distribution, then irradiating and cross-linking the above-mentioned film so as to obtain the invented liquid crystal reflecting type circular polarized light polaroid.
Description
Technical field
The invention belongs to the polaroid technical field, particularly a kind of preparation method of reflection circularly polarized light polaroid, the reflection circularly polarized light polaroid optical property of preparation is stable.
Background technology
The helical arrangement structure and the pitch gradient distribution that realize mesomorphic unit in the liquid crystal material are the effective means that obtains reflection circularly polarized light polaroid, this material is at full-color demonstration, information demonstration and storage medium, reflecting polarizer, aspect such as ornament materials and reflectance coating has wide development potentiality, and so how the helical arrangement of the mesomorphic unit set up and pitch gradient are distributed effectively and steadily in the long term is fixed up is the key point that obtains to have the liquid crystal circularly polarized light polaroid of good optical property.
Fixedly the helical arrangement structure and the pitch gradient of mesomorphic unit distribute to mainly contain two kinds of methods at present, to obtain reflection circularly polarized light polaroid: one is, making photolytic activity micromolecule rate of propagation difference set up pitch gradient by the intensity of illumination difference distributes: be about to the micromolecule liquid crystal, photopolymerizable monomer, light trigger, light absorber composition blend such as (not having light absorber among the patent U.S.P 5691789) is even, after adopting certain technology film forming, it is carried out illumination at a certain temperature, because illumination intensity difference on the thickness, direction and speed difference that the monomer that optical activity is different spreads along thickness, just the concentration gradient that forms mesomorphic unit on the film thickness direction distributes, suitably under the alignment conditions, liquid crystal molecule is arrangement architecture and pitch gradient distribution in the shape of a spiral, the cross-linked network that the photopolymerizable monomer polymerization forms is fixed up this helical arrangement structure and the pitch gradient distribution of liquid crystal molecule, thereby obtain to have the liquid crystal reflective polarizer material of suitable foveal reflex wavelength and reflection bandwidth, Europe, a large amount of relevant reports are arranged in the patent such as the U.S. and Japan, comprising EP 0,606 940, EP 0 860 716 A2, U.S.P 5691789 etc., this method advantage is a simple and fast, weak point is at first to need to adopt certain technology to be incorporated in the film chamber small-molecule mixture, is not easy extensive film forming; The speed that cross-linked network forms is very fast, and the liquid crystal molecule that photoactive monomer moves, orientation is damaged in the diffusion process is difficult to adequate time and the orderly arrangement of relative ideal is carried out in the space.
It two is: set up pitch gradient by the hot pressing diffusion of mesomorphic unit between the glassy state liquid crystal film and distribute, the quenching fixedly helical arrangement structure and the pitch gradient of mesomorphic unit distributes, to obtain the reflection circularly polarized light polaroid material, this method is in the laboratory study stage at present, wherein Fa Guo people such as PeterPalffy-Muhoray have carried out comparatively detailed research and report to this technology: the mesomorphic unit concentration gradient is set up in the hot pressing diffusion by mesomorphic unit between the glassy state cholesteric liquid crystal film with different foveal reflex wavelength, the orientation back obtains the molecular spiral arrangement architecture and pitch gradient distributes, cooling is fixed, this technology distributes the helical arrangement structure of the mesomorphic unit that obtained and pitch gradient at an easy rate by quenching and is fixed up, weak point is: glassy state liquid crystal material fragility is bigger, in the use at mechanical external force, be easy to be damaged under the extraneous factor effects such as thermal stress, use limited; Use for a long time under higher temperature, segment " thaws " and destroys the orderly arrangement of mesomorphic unit, optical property instability.
Summary of the invention
The object of the invention is to provide a kind of preparation method of reflection circularly polarized light polaroid, and it is bigger to have solved glassy state liquid crystal material fragility, the optical property problem of unstable.The manufacture method of the reflection circularly polarized light polaroid that proposition is can obtained performance stable,
Concrete technology of the present invention is: with glassy state liquid crystal, photopolymerizable monomer, light trigger, polymerization inhibitor by proportion of composing: the glassy state liquid crystal is 96～50% (weight ratios), and light trigger is 0.22～5% (weight ratio), and polymerization inhibitor is 30～200 * 10
-4% (weight ratio), surplus is that photopolymerizable monomer is mixed, with potpourri be dissolved in mix in the solvent after, make powder after film forming or the drying and be overlying on substrate surface; Molecular diffusion is set up the concentration gradient of mesomorphic unit between glassy state liquid crystal film by having different foveal reflex wavelength (reflected wavelength range is 200-2500nm) or powder, in the glassy state liquid crystal presents the temperature range of liquid crystal phase (0-350 ℃), adopt roll-in, hot pressing, surface technologies such as " nail anchors " to carry out the orientation process of mesomorphic unit, set up the helical arrangement and the pitch gradient distribution (Fig. 1) of mesomorphic unit, the at first motion of cooling " freezing " glassy state liquid crystal segment, the helical arrangement structure of the fixing mesomorphic unit that is obtained and pitch gradient distribute; (irradiation dose is: 0.001-100mW/cm then above-mentioned film to be carried out cross-linking radiation
2), include the motion (Fig. 2) that the formed cross-linked network of photopolymerizable monomer polymerization further limits glassy state liquid crystal segment, and brittle glass attitude liquid crystal played effective toughening effect, thereby obtain the reflection circularly polarized light polarized material with suitable reflection bandwidth (curve F among Fig. 3) that optical property is stable and mechanical property is suitable.
The backbone structure of glassy state liquid crystal of the present invention can be macromolecular materials such as ring-like polysiloxane, linear polysiloxanes, polyacrylic acid, polyamide, and mesomorphic unit can be chirality or achirality mesomorphic units such as cholesterol and derivant, cellulose and derivant thereof, parazon phenolic ester.
Cross-linked network structure of the present invention can form by the photopolymerizable monomer of introducing material system or the glassy state liquid crystal material of photopolymerization own.
The active function groups of photopolymerizable monomer of the present invention can be acryloyl group, methacryl, vinyl, styryl, diacetyl etc., and the quantity of active function groups can for one, two or three, its content is 0-30%.
The constituent of glassy state liquid crystal film of the present invention or powder is removed glassy state liquid crystal, photopolymerizable monomer, initiating agent, polymerization inhibitor, can also comprise that other chirality or achirality micromolecule liquid crystal are to adjust pitch.
The film build method of glassy state liquid crystal film of the present invention can adopt solution to apply thermoplastics film build methods such as (roller coat or spin coating), hot-rolling roll extrusion.
The mesomorphic unit of formation helical arrangement structure of the present invention can be chirality and achirality mesomorphic unit or chirality of sneaking in addition and the achirality mesomorphic unit that the glassy state liquid crystal is connected.
The concentration gradient of mesomorphic unit of the present invention can be set up by molecular diffusion having between different foveal reflex wavelength glassy state liquid crystal material layers and the layer or have between the glassy state liquid crystal powder of different foveal reflex wavelength.
The orientation of mesomorphic unit of the present invention can be in film forming procedure or technologies such as the after-applied roll-in of film forming, hot pressing realize that orientation temperature carries out in the liquid crystal phase temperature range of glassy state liquid crystal.
Process for cooling of the present invention can be quenching or progressively cooling.
The present invention prepares the preparation methods with liquid crystal reflective polaroid that mesomorphic unit molecular spiral arrangement architecture and pitch gradient distribute and compares with external above-mentioned two kinds, has the following advantages:
1, the selected material system of the present invention, processing characteristics with thermoplastics, can adopt solution to apply thermoplastics film build method system films such as (roller coat or spin coating), hot-rolling roll-in, to its PROCESS FOR TREATMENT of carrying out next step, overcome small-molecule mixture complex forming technology and the drawback that is not easy to obtain the large tracts of land film then.Film-forming process of the present invention is simple, ripe, realizes large-scale production easily;
Helical arrangement structure of glassy state liquid crystal sub-chain motion " freezing " fixing mesomorphic unit that is obtained and pitch gradient distributed when 2, the present invention was at first by quenching, then the material that is obtained is carried out cross-linking radiation, include the motion that the formed cross-linked network of photopolymerizable monomer polymerization further limits glassy state liquid crystal segment; The polarizer material that obtains higher in serviceability temperature, even when surpassing the liquid crystal phase transition temperature of glassy state liquid crystal, optical property is still relatively stable, the limited disadvantage of serviceability temperature when overcoming simple use glassy state liquid crystal.The present invention can obtain the reflection circularly polarized light polaroid that serviceability temperature is higher, optical property is stable.
3, the present invention introduces the photopolymerization network, and effective toughness reinforcing glassy state liquid crystal material overcomes the bigger disadvantage of glassy state liquid crystal fragility, enlarges the application of polarized material.The present invention can obtain the liquid crystal reflective circularly polarized light polaroid with molecular spiral arrangement architecture and pitch gradient distribution that mechanical property is suitable, optical property is stable.
Description of drawings
Fig. 1 is molecular spiral arrangement architecture of the present invention and pitch gradient distribution plan.
Fig. 2 is cross-linked network figure of the present invention.
Fig. 3 is the transmission collection of illustrative plates of broadband reflection formula circularly polarized light polarized material of the present invention.Wherein, the B-glass substrate, roll-in orientation rear center reflection wavelength is the reflection circularly polarized light polarized material about 560nm under C-100 ℃ of condition, roll-in orientation rear center reflection wavelength is the reflection circularly polarized light polarized material about 660nm under D-100 ℃ of condition, roll-in orientation rear center reflection wavelength is the reflection circularly polarized light polarized material about 730nm under E-100 ℃ of condition, roll-in orientation rear center reflection wavelength is about 680nm under the F-100 ℃ of condition, and reflection wave is wide to be broadband reflection formula circularly polarized light polarized material about 200nm.
Embodiment
Embodiment 1
The preparation of mesomorphic unit density gradient distribution composite membrane
With the foveal reflex wavelength is that the glassy state cyclosiloxane liquid crystal (this foveal reflex wavelength is meant at different glassy state liquid crystal and is obtained under the same process condition) of 550nm, 660nm, 750nm mixes with methylene chloride, light trigger, photopolymerizable monomer, solvent etc. respectively, at first applying the foveal reflex wavelength on glass substrate is the mixed solution of 550nm, under the lucifuge condition, the normal temperature solvent flashing; After 24 hours, applying the foveal reflex wavelength on the basis of this film is the mixed solution of 660nm, under the lucifuge condition, and the normal temperature solvent flashing; After 24 hours, applying the foveal reflex wavelength on the basis of this film is the mixed solution of 750nm, and under the lucifuge condition, the normal temperature solvent flashing obtains composite membrane.
Orientation process
Place on 65 ℃ of hot platforms at composite membrane that is obtained and the mylar through rubbing, after half a minute mylar is covered the composite membrane surface, roll-in is orientated.
It is fixing that molecular spiral structure and pitch gradient distribute
Composite membrane after the roll-in orientation on the hot platform is cooled off rapidly; Then under the normal temperature condition, the rapid composite membrane that obtains of previous step is carried out ultraviolet light irradiation cross-linking, obtain having the distribution of firm molecular spiral arrangement architecture and pitch gradient (the foveal reflex wavelength is about 650nm, and reflection bandwidth is about 200nm) and the good reflection circularly polarized light polaroid material of pliability.
Embodiment 2
The preparation of mesomorphic unit density gradient distribution composite membrane
With the foveal reflex wavelength is that the glassy state cyclosiloxane high molecule liquid crystal of 550nm, 660nm, 750nm mixes with light trigger, polymerization inhibitor, methylene chloride etc. respectively, after the vacuum drying, makes powder respectively; Three kinds of powder being obtained ratio in 1: 1: 1 is mixed.
Orientation process
The mixed-powder that will have different foveal reflex wavelength places through the alcohol swab glass baseplate surface that orientation process crosses of polishing, the mylar substrate that then surface is placed with the glass substrate of mixed-powder and crosses through the polishing orientation process places on 90 ℃ of hot platforms, after half a minute mylar is covered the composite membrane surface, roll-in is orientated.
It is fixing that molecular spiral structure and pitch gradient distribute
With the composite membrane after the roll-in orientation on the hot platform, cooling rapidly; The normal temperature ultraviolet light irradiation cross-linking must have the reflection circularly polarized light polaroid material of firm molecular spiral arrangement architecture and pitch gradient distribution (the foveal reflex wavelength is about 650nm, and reflection bandwidth is about 200nm).
Claims (8)
1, a kind of preparation method of reflection circularly polarized light polaroid, it is characterized in that: concrete technology is: with glassy state liquid crystal, photopolymerizable monomer, light trigger, polymerization inhibitor by proportion of composing: the glassy state liquid crystal is 96～50 weight %, light trigger is 0.22～5 weight %, and polymerization inhibitor is 30～200 * 10
-4Weight %, surplus is that photopolymerizable monomer is mixed, with potpourri be dissolved in mix in the solvent after, make powder after film forming or the drying and be overlying on substrate surface; Molecular diffusion is set up the concentration gradient of mesomorphic unit between glassy state liquid crystal film by having different foveal reflex wavelength or powder, in the glassy state liquid crystal presents 0～350 ℃ of scope of temperature of liquid crystal phase, adopt roll-in, hot pressing, surface " nail anchor " technology to carry out the orientation process of mesomorphic unit, helical arrangement and the pitch gradient of setting up mesomorphic unit distribute, the at first motion of cooling " freezing " glassy state liquid crystal molecule segment, the helical arrangement structure of the fixing mesomorphic unit that is obtained and pitch gradient distribute; Then above-mentioned film is carried out cross-linking radiation, irradiation dose is: 0.001～100mW/cm
2Include the motion that the formed cross-linked network of photopolymerizable monomer polymerization further limits glassy state liquid crystal segment, obtain the liquid crystal reflective circularly polarized light polaroid material that optical property is stable and mechanical property is suitable with molecular spiral arrangement architecture and pitch gradient distribution; Described reflected wavelength range is 200-2500nm.
2, in accordance with the method for claim 1, it is characterized in that: the backbone structure of described glassy state liquid crystal is macromolecular materials such as ring-like polysiloxane, linear polysiloxanes, polyacrylic acid, polyamide, and mesomorphic unit is cholesterol and derivant or cellulose and derivant, parazon phenolic ester chirality or achirality mesomorphic unit; Described cross-linked network structure forms by the photopolymerizable monomer of introducing material system or the glassy state liquid crystal material of photopolymerization own; The active function groups of described photopolymerizable monomer can be acryloyl group, methacryl, vinyl, styryl, diacetyl etc., and the quantity of active function groups is 1～3, and its content is 0-30%.
3, in accordance with the method for claim 1, it is characterized in that: the constituent of described glassy state liquid crystal film or powder can be introduced other chirality or achirality micromolecule liquid crystal to adjust pitch.
4, in accordance with the method for claim 1, it is characterized in that: the film build method employing solution coating roller coat of described glassy state liquid crystal film or spin coating, hot-rolling roll extrusion, thermoplastics film forming.
5, in accordance with the method for claim 1, it is characterized in that: the mesomorphic unit of described formation helical arrangement structure can be chirality and achirality mesomorphic unit or chirality of sneaking in addition and the achirality mesomorphic unit that the glassy state liquid crystal is connected.
6, in accordance with the method for claim 1, it is characterized in that: the concentration gradient of described mesomorphic unit is set up by molecular diffusion having between different foveal reflex wavelength glassy state liquid crystal material layers and the layer or have between the glassy state liquid crystal powder of different foveal reflex wavelength.
7, in accordance with the method for claim 1, it is characterized in that: described mesomorphic unit be oriented in the film forming procedure or the after-applied roll-in of film forming, heat pressing process realize that orientation temperature carries out in the liquid crystal phase temperature range of glassy state liquid crystal.
8, in accordance with the method for claim 1, it is characterized in that: described process for cooling is quenching or progressively cooling.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100867224A CN100426018C (en) | 2005-10-26 | 2005-10-26 | Preparation method of reflection circularly polarized light polaroid |
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| CNB2005100867224A CN100426018C (en) | 2005-10-26 | 2005-10-26 | Preparation method of reflection circularly polarized light polaroid |
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| CN1752776A true CN1752776A (en) | 2006-03-29 |
| CN100426018C CN100426018C (en) | 2008-10-15 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532567A (en) * | 2010-12-23 | 2012-07-04 | 成功大学 | Method for manufacturing polymeric membrane with photonic crystal structure |
| CN102565912A (en) * | 2010-12-14 | 2012-07-11 | 住友化学株式会社 | Method for producing polarizer film |
| CN113534509A (en) * | 2021-06-28 | 2021-10-22 | 华南师范大学 | Light reflection coating, preparation method thereof and optical device |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5691789A (en) * | 1995-10-30 | 1997-11-25 | Li; Le | Single-layer reflective super broadband circular polarizer and method of fabrication therefor |
| TW289095B (en) * | 1993-01-11 | 1996-10-21 | ||
| US5707544A (en) * | 1995-06-07 | 1998-01-13 | Rolic Ag | Chromophore-containing photo cross-linkable liquid crystals |
| US6061108A (en) * | 1997-01-24 | 2000-05-09 | Sharp Kabushiki Kaisha | Broadband cholesteric polarizer and an optical device employing the same |
| TWI273277B (en) * | 2002-09-12 | 2007-02-11 | Fujifilm Corp | Phase difference plate and circular polarizing plate |
-
2005
- 2005-10-26 CN CNB2005100867224A patent/CN100426018C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102565912A (en) * | 2010-12-14 | 2012-07-11 | 住友化学株式会社 | Method for producing polarizer film |
| CN102565912B (en) * | 2010-12-14 | 2016-04-27 | 住友化学株式会社 | The manufacture method of light polarizing film |
| CN102532567A (en) * | 2010-12-23 | 2012-07-04 | 成功大学 | Method for manufacturing polymeric membrane with photonic crystal structure |
| CN102532567B (en) * | 2010-12-23 | 2014-09-03 | 成功大学 | Method for manufacturing polymeric membrane with photonic crystal structure |
| CN113534509A (en) * | 2021-06-28 | 2021-10-22 | 华南师范大学 | Light reflection coating, preparation method thereof and optical device |
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| CN100426018C (en) | 2008-10-15 |
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