CN101221321A - Production method of laminated sheet used for optical elements - Google Patents
Production method of laminated sheet used for optical elements Download PDFInfo
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- CN101221321A CN101221321A CNA2007100017040A CN200710001704A CN101221321A CN 101221321 A CN101221321 A CN 101221321A CN A2007100017040 A CNA2007100017040 A CN A2007100017040A CN 200710001704 A CN200710001704 A CN 200710001704A CN 101221321 A CN101221321 A CN 101221321A
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Abstract
The invention provides a method for making a laminated sheet for use in an optic element, having a working procedure for performing friction treatment on the surface of a substrate thin film made to be moving in a direction by contacting the substrate thin film with a friction roll which is provided with a rotating roller and friction materials winded on the rotating roller. The rotating roller is arranged in a way that a rotating shaft is inclined relative to the direction vertical to the moving direction of the substrate thin film. The friction materials are provided with lots of fluff which is arranged a required direction and is winded on the rotating roller, with the direction in which the fluff is arranged inclined relative to the rotation direction of the rotating roller.
Description
Technical field
The present invention relates to a kind of laminated sheet used for optical elements.More particularly, the present invention relates to the laminated sheet used for optical elements that uses for the manufacturing of optical elements such as used for liquid crystal display element colorimetric compensation plate, used for liquid crystal display element viewing angle compensation plate, optical phase difference plate, 1/2 wavelength plate, 1/4 wavelength plate and optical activity optical element.
Background technology
In the liquid crystal polymer films that optical element had such as optical phase difference plate, the orientation of liquid crystal polymer need be fixed as the direction of regulation.Method as the orientation of immobile liquid polycrystalline macromolecule, following method is arranged, promptly, on substrate, form the layer of liquid crystal polymer with the surface that has formed a plurality of small groove that has been orientated along the direction of regulation, the glass transition temperature that is heated to liquid crystal polymer is above and make the liquid crystal polymer orientation, cools off thereafter.
But the situation in the past method is easy to generate inequality in the orientation of liquid crystal polymer, is requiring further to improve aspect the homogeneity of the orientation of liquid crystal polymer.
Summary of the invention
So, the objective of the invention is to, in the manufacturing of the laminated sheet used for optical elements that possesses liquid crystal polymer film, the improvement of the homogeneity of the orientation of the liquid crystal polymer of realization gained lamination sheet.
The present invention relates to have liquid crystal polymer film and be laminated in the manufacture method of the laminated sheet used for optical elements of the light-transmitting substrate on its face.Manufacture method of the present invention possesses: with substrate film when a direction moves, by with have the rotation roller and be wound on the friction material on it friction roller contact the operation of its surface being carried out friction treatment; On the substrate film after the friction treatment, form the operation of the liquid crystal polymer film that contains the liquid crystal polymer of having fixed orientation; The operation of stacked light-transmitting substrate on a face of liquid crystal polymer film; The operation that substrate film is peeled off from liquid crystal polymer film.Roller will be rotated so that its turning axle direction disposes with respect to the mode that the direction vertical with the moving direction of substrate film tilts.Friction material has a plurality of fine hair of arranging along the direction of regulation, so that the mode that the orientation of this fine hair is tilted with respect to the sense of rotation of rotating roller is wound on the rotation roller.
According to described manufacture method of the present invention, can improve the homogeneity of orientation of liquid crystal polymer of the lamination sheet of gained.More particularly, can reduce the inequality of the orientation of liquid crystal polymer fully.
Description of drawings
Fig. 1 utilizes sectional view to represent the process chart of an embodiment of the manufacture method of laminated sheet used for optical elements.
Fig. 2 is the vertical view of an embodiment of expression friction treatment.
Fig. 3 is the stereographic map of an embodiment of expression friction roller.
Embodiment
Below will be as required, in the reference accompanying drawing, preferred embodiment be elaborated to of the present invention.But the present invention is not limited to following embodiment.And, in the accompanying drawing, use same-sign for identical element, the repetitive description thereof will be omitted.In addition, wait short of the particularly pointing out of position relation up and down, all be based on position shown in the drawings relation.
Fig. 1 utilizes sectional view to represent the process chart of an embodiment of the manufacture method of laminated sheet used for optical elements.The manufacture method of present embodiment possesses: utilize the operation of substrate film 10 being carried out friction treatment that contacts with friction roller; On the substrate film after the friction treatment 10, form the operation of the liquid crystal polymer film 20 that contains the liquid crystal polymer of having fixed orientation; The operation of stacked light-transmitting substrate 30 on a face of liquid crystal polymer film 20; The operation that substrate film 10 is peeled off from liquid crystal polymer film 20.Through these operations, just can obtain the stacked laminated sheet used for optical elements 1 with lamination formation of light-transmitting substrate 30 on a face of liquid crystal polymer film 20.
In the present embodiment, at first, prepared substrate film 10 carries out its surperficial friction treatment (Fig. 1 (a)).Fig. 2 is the vertical view of an embodiment of expression friction treatment.In the embodiment shown in Figure 2, by with the substrate film 10 of the strip (direction of representing with D1 among the figure in a certain direction.Below be called " MD " direction.) when moving, on stand 60,3 pairs of substrate film of friction roller 10 are carried out obliterating, friction treatment is carried out on the surface of substrate film 10 continuously.
As the concrete example of macromolecular material used in the substrate film 10, can enumerate polyimide, polyamide, polyamidoimide, polyetherimide, polyetherketone, polyetheretherketone, polyketone, polyethersulfone, polyphenylene sulfide, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polycarbonate, polyacrylate, polymethacrylate and tri acetyl cellulose, polyvinyl alcohol (PVA), epoxy resin and phenolics.The macromolecule membrane that uses as substrate 10 no matter be uniaxial extension film or double shaft extensioning film can, no matter be that individual layer can or have a plurality of layers laminated body.In addition, both the material of stacked metal forming on macromolecule membrane can be used as substrate film 10, also metal forming can be used as substrate film 10.As metal forming, can enumerate metal formings such as copper, stainless steel, steel.
Particularly preferred substrate film 10 is strip and the macromolecule membrane with independence.As strip and macromolecule membrane, preferably use the film of polyethylene terephthalate, polyphenylene sulfide, polyetheretherketone (PEEK), polyvinyl alcohol (PVA) or polyimide with independence.
The thickness of substrate film 10 is not particularly limited, and can select according to application target, usually the scope of preferred 10 μ m~10mm.The width of substrate film 10 also is not particularly limited, the scope of usually preferred 1cm~500cm.
Fig. 3 is the stereographic map of the friction roller 3 in the presentation graphs 2.Friction roller 3 has rotation roller 4 and is wound on friction material 5 on its outer peripheral face.Represented state that friction material 5 is partly rolled out among Fig. 3.
As preferred friction material 5, weave cotton cloth, felt, rubber, bristle.As weaving cotton cloth the preferred material that constitutes by nylon fiber, cotton fiber etc. that uses.The friction cloth that especially preferably will have the fine hair of arranging along ordinate uses as friction material 5.In addition, fine hair 7 preferably tilts towards head end ground from its root.When fine hair 7 was made of a plurality of fibers, preferably fine hair integral body tilted towards head end from its root.Have the friction cloth of the fine hair that has tilted like this by use, just can obtain the effect that the homogeneity of the orientation of liquid crystal polymer improves more significantly.
Preferred 2 °~40 ° of angle beta.When angle beta during, then have the tendency that effect that the homogeneity of the orientation of liquid crystal polymer improves diminishes less than 2 °.Even angle beta is made as more than 40 °, with angle beta is that 2 °~40 ° situation is compared, also be difficult to obtain the bigger increase of effect of the present invention, yet as the effective use of the friction material of the raw material supplying difficulty that will become, thereby the tendency that causes production cost to increase is arranged.Based on identical reason, more preferably 3 °~15 ° of angle betas.
In the friction treatment, the hardness on consideration substrate film 10 surfaces is set the conditions such as revolution of friction pressure, friction roller.Specifically, the translational speed with substrate film 10 is set at 0.5~100m/ minute (preferred 1~30m/ minute) usually, the revolution of friction roller is represented to be set at the scope of 1~1000 (preferred 5~200) with all speed ratios.Friction pressure so long as friction material 5 get final product with the degree that substrate film 10 slightly contacts.Specifically, when the fine hair of friction material 5 by napping fiber when making, set friction pressure as follows, that is, the amount of pushing of high-quality green tea preferably reaches 100 μ m~5000 μ m, more preferably reaches 100 μ m~2000 μ m.
After the friction treatment, on substrate film 10, form the liquid crystal polymer film 20 (Fig. 1 (b)) that contains the liquid crystal polymer of having fixed orientation.Liquid crystal polymer film 20 for example is to utilize the method comprise following operation to form, and the solution that will contain liquid crystal polymer is coated on the operation on the substrate film 10, with the operation of the solution drying that is coated with, utilize heating to make the operation of liquid crystal polymer orientation.
Used liquid crystal polymer is thermic (thermotropic) liquid crystal polymer that shows liquid crystal liquid crystal property when fusion in the present embodiment.Thermotropic liquid crystalline polymer is the nematic phase orientation to take place under mesomorphic state, twisted-nematic is orientated mutually or changes the orientation that mixes of (tilt) angle that tilts on thickness direction, becomes the liquid crystal polymer of vitreousness in the temperature province below the liquid-crystalization transition temperature.Liquid crystal polymer film 20 preferably shows nematic liquid crystal phase, twisted nematic liquid crystal phase or the dirty solution crystalline phase of homogeneous.The preferred backbone chain type liquid crystal macromolecule of liquid crystal polymer, side chain type liquid crystal macromolecule or their potpourri.
As the backbone chain type liquid crystal macromolecule, for example can enumerate polyesters, polyamide-based, polycarbonate-based, polyimide, polyurethanes, polybenzimidazoles class, polybenzoxazole class, polybenzothiozole class, polyazomethine (Port リ ァ ゾ メ チ Application), polyesteramide class, polyestercarbonate class and the liquid crystal polymer of polyester-imide class or their potpourri.
As the side chain type liquid crystal macromolecule, for example can enumerate the polymkeric substance of the main chain with straight chain shape or ring-shaped structure of polyacrylate, polymethacrylate, polyethylene kind, polysiloxane-based, polyethers, poly-malonate class or polyesters, combine the liquid crystal polymer of mesogen base or their potpourri as side chain.
In the middle of them, consider preferred backbone chain type liquid crystal macromolecule, wherein special preferred polyester class liquid crystal polymer from the synthetic viewpoint that reaches the easness of orientation.The polyesters liquid crystal polymer is the liquid crystal polymer that aromatic series or aliphatic diol unit, aromatic series or aliphatic dicarboxylic acid unit, aromatic series or aliphatic hydroxyl carboxylic acid are contained as constituting the unit.
The solvent of lysate polycrystalline macromolecule can be from can suitably selecting the solvent of lysate polycrystalline macromolecule.As the concrete example of preferred solvent, can enumerate ketone such as acetone, methyl ethyl ketone and cyclohexanone; Tetrahydrofuran is Ji ethers such as dioxs; Halogenated hydrocarbons such as chloroform, ethylene dichloride, tetrachloroethane, triclene, zellon and o-dichlorobenzene; Amide solvent such as dimethyl formamide and dimethyl acetamide; Dimethyl sulfoxide (DMSO) and N-Methyl pyrrolidone.They can use separately, or use as a plurality of mixed solvent of combination.Though the concentration of solution is according to the viscosity of liquid crystal polymer and difference, yet be generally 5~50 quality %, preferred 10~30 quality %.
The method of solution coat on substrate film 10 of liquid crystal polymer is not particularly limited, for example can adopts slit die cladding process, sliding mould cladding process, curtain cladding process, rolling method, print process, dip-coating method.Preferred 10~the 2000mm of brushing width, more preferably 100~1000mm.Utilizing heating to remove from the solution that is coated with desolvates.Perhaps, also can not use the solution of liquid crystal polymer, the method that liquid crystal polymer melt extrudes be coated liquid crystal polymer on the substrate film 10 and utilize with T pattern etc.
After the drying, to be heated to the glass transition temperature of liquid crystal polymer above and make the liquid crystal polymer orientation with being formed at liquid crystal polymer film 20 (Fig. 1 (b)) on the substrate 10, liquid crystal polymer film 20 is cooled to the glass transition temperature less than liquid crystal polymer under the state that has been orientated.Utilize cooling to show glassy phase, the orientation of liquid crystal polymer is fixed.The heating-up temperature in described when heating is made as more than the glass transition temperature of liquid crystal polymer, and in the temperature below the inversion temperature of isotropic phase of liquid crystal polymer.More particularly, heating-up temperature generally is made as 50~300 ℃, preferably is made as 100~250 ℃.Preferred 10 seconds~60 minutes of heat time heating time, more preferably 30 seconds~30 minutes.Heating means are not particularly limited, and for example can use infrared ray heating, warm braw heating, hot-rolling heating, dielectric to heat, utilize the heating of electric heater.During cooling after the heating, for the purpose of enhancing productivity, also can the application of air cooling, used the refrigerant cools of water etc.
The thickness of having fixed the liquid crystal polymer film 20 after the orientation of liquid crystal polymer can be according to suitably decisions such as the light wavelengths that sees through optical element.For example when being used for the very important purposes of visible light such as display applications, more than the preferred 0.05 μ m of the thickness of liquid crystal polymer film 20, more preferably more than the 1 μ m, further more than the preferred 2 μ m.If thickness then has the tendency that is difficult to control accurately thickness less than 0.05 μ m.Though the upper limit of thickness is not particularly limited, when becoming blocked up, then have the tendency that the restraint as optical element dies down.Based on this viewpoint, below the preferred 100 μ m of the thickness of liquid crystal polymer film 20, more preferably below the 30 μ m.
In liquid crystal polymer film 20 and opposite side substrate film 10, adhesive phase 41 is located in stacked light-transmitting substrate 30 (Fig. 1 (c)) therebetween.
Light-transmitting substrate 30 is the laminar transparency carriers that can support the strip of liquid crystal polymer film 20.Light-transmitting substrate 30 preferably has the isotropy of optics.Material as constituting light-transmitting substrate 30 can use glass or plastics.When light-transmitting substrate 30 was plastic sheeting, light-transmitting substrate 30 preferably contained more than one plastics that are selected from the group that is made of polymethylmethacrylate, polystyrene, polycarbonate, polyethersulfone, polyphenylene sulfide, polyarylate, amorphous polyolefin and tri acetyl cellulose.Preferred 0.5~200 μ m of the thickness of light-transmitting substrate 30, more preferably 1~200 μ m.
Preferred 0.5~200 μ m of the thickness of adhesive phase 41, more preferably 1~100 μ m.When the thickness of adhesive phase 41 surpasses 200 μ m,, therefore the tendency that is difficult to solidify fully will be arranged because the curing rate of bonding agent reduces.
Light-transmitting substrate 30 for example is to form adhesive phase 41 on liquid crystal polymer film 20, utilizes laminating to be laminated on this adhesive phase 41.At this moment, preferably get rid of sneaking into of bubble as far as possible.Perhaps, prepare also can make laminar adhesive phase 41 in advance, utilize its method that is clipped between liquid crystal polymer film 20 and the light-transmitting substrate 30 is come stacked light-transmitting substrate 30.For the situation of the bonding agent that uses light-cured type or electron ray curing type, after stacked, utilize the irradiation of light or electron ray that adhesive phase 41 is solidified.The curing of adhesive phase 41 can after no matter still peeling off before substrate film 10 is peeled off.
After light-transmitting substrate 30 stacked, substrate film 10 is peeled off, just can obtain having the lamination sheet 1 (Fig. 1 (d)) that the lamination that stacked gradually liquid crystal polymer film 20, adhesive phase 41 and light-transmitting substrate 30 constitutes.
After this, on lamination sheet 1 and faces light-transmitting substrate 30 opposite sides, stack gradually protection (over coat) layer 42 and protective film 50 (Fig. 1 (e)).Protective seam 42 is to use the bonding agent identical with adhesive phase 41 to form.As protective film 50, use film with release property.For example, pet film is used as protective film.
Embodiment
Below will enumerate embodiment is specifically described the present invention.But the present invention is not limited to following embodiment.
Use has the device of the formation identical with device shown in Figure 2, will as the PEEK film (wide, the thick 80 μ m of 20cm) of substrate film with 20m/ minute speed conveyance in, make it to contact friction roller, friction treatment has been carried out on the surface of PEEK film with the 1500rpm rotation.As friction roller, having used has reeled in rotation roller (diameter 150mm) utilize napping fiber formed the friction roller of the nylon cloth (friction material) of fine hair.Nylon cloth by so that in-line direction (being the orientation of fine hair) be wound on the rotation roller in the mode of the angle tilt of the regulation shown in the table 1 with respect to the sense of rotation of rotation roller.Friction roller by so that its turning axle direction with respect to the direction vertical with the MD direction tilt 45 ° towards setting.In addition, so that the mode that the high-quality green tea of nylon cloth (fine hair) reaches 500 μ m to the amount of pushing of PEEK film with friction roller to the backup of PEEK film.With the PEEK winding film after the friction treatment on roller.
PEEK film after the friction treatment is rolled out, utilize rolling method on it, to be coated on to have dissolved in the N-Methyl pyrrolidone solution of polyesters liquid crystal polymer,, formed the liquid crystal polymer film that contains liquid crystal polymer the solution drying that is coated with.Thereafter, by cooling off the orientation of having fixed the liquid crystal polymer in the liquid crystal polymer film after 20 minutes in heating under 200 ℃.
Next, on liquid crystal polymer film, be sandwiched in stacked therebetween the acrylic tackifier of thickness 100 μ m as the tri acetyl cellulose film (TAC film) of isotropy transparent membrane.After this, from liquid crystal polymer film, the PEEK film is peeled off, on the face of the liquid crystal polymer film that has exposed, utilized the solution of slit die cladding process coating acrylic compounds oligomer.By solution irradiation ultraviolet radiation to being coated with, make the polymerization of acrylic compounds oligomer, formed the protective seam (the about 5 μ m of thickness) that the solidfied material by acrylic resin constitutes.
Obtained having the strip lamination sheet of the lamination formation that has stacked gradually protective seam, liquid crystal polymer film, acrylic tackifier layer (adhesive phase) and TAC film (light-transmitting substrate) as described above.The lamination sheet of gained is the twisted-nematic phase oriented film of whole homogeneous.Measured its parameter, the result is, distortion angle is-240 °, and the time-delay of λ=550nm is 760nm.
The lamination sheet of gained that utilized observation by light microscope, in order to following benchmark evaluation the homogeneity of orientation of its liquid crystal polymer.
A: in orientation, do not have inequality, be very neatly arranged.
B: in orientation, see slightly uneven.
C: in orientation, see a lot of inequalities.
In addition, use the lamination sheet of gained to make infiltration type stn liquid crystal panel.Electrode on the face of the inboard that possesses a pair of transparency carrier faced mutually, is located at them, utilize printing to be formed on them and implemented in the liquid crystal panel of alignment films of orientation process, to by alignment films be formed at and enclose liquid crystal material in the space of the sealant defined around the transparency carrier and formed the liquid crystal material layer.Use ZLI-2293 (メ Le Network corporate system) as liquid crystal material,, make the direction orientation of liquid crystal material layer, be torqued into twist angle=+ 240 ° along regulation by regulating the orientation process direction of alignment films.In addition, the time-delay of the λ=550nm of liquid crystal panel is 800nm.At the display surface side configuration polaroid (Sumitomo Chemical (strain) system SR1862AP) of liquid crystal panel, the lamination sheet of configuration gained has obtained infiltration type stn liquid crystal panel between polaroid and liquid crystal cell.After this, apply driving voltage (1/160 dutycycle (duty) drives with optimal bias (bias)) by driving circuit, the configuration light source has been measured contrast (contrast) with normal black pattern (nomarlly black mode).
Table 1
The angle of inclination of the orientation of fine hair | The homogeneity of optics | The contrast of | |
Embodiment | |||
1 | 2° | B | 48 |
|
5° | |
50 |
|
10° | A | 52 |
Embodiment 4 | 15° | |
50 |
|
40° | A | 51 |
Comparative example 1 | 0° | |
42 |
As shown in table 1,, compare with respect to the embodiment 1~5 that the sense of rotation of rotation roller has tilted according to the direction of orientation that makes fine hair with the comparative example 1 that the direction of orientation that does not make fine hair tilts, can see tangible improvement aspect the optics homogeneity of the lamination sheet of gained.In addition, used the liquid crystal panel of the lamination sheet that the method for utilizing embodiment 1~5 obtains to demonstrate good contrast.
Claims (3)
1. manufacture method that has liquid crystal polymer film and be laminated in the laminated sheet used for optical elements of the light-transmitting substrate on its face, it possesses:
With substrate film when a direction moves, utilize the operation of its surface being carried out friction treatment that contacts with friction roller with rotation roller and friction material wound thereon;
On the described substrate film after the friction treatment, form the operation of the liquid crystal polymer film that contains the liquid crystal polymer of having fixed orientation;
The operation of stacked light-transmitting substrate on a face of described liquid crystal polymer film;
The operation that described substrate film is peeled off from described liquid crystal polymer film,
With described rotation roller so that its turning axle direction dispose with respect to the mode that the direction vertical with the moving direction of described substrate film tilts,
Described friction material has a plurality of fine hair of arranging along the direction of regulation, so that the orientation of this fine hair is wound on the described rotation roller with respect to the mode that the sense of rotation of described rotation roller tilts.
2. the manufacture method of laminated sheet used for optical elements according to claim 1, wherein, with described friction material so that the orientation of this fine hair be wound on the described rotation roller with respect to the sense of rotation of described rotation roller mode with 2 °~40 ° angle tilt.
3. the manufacture method of laminated sheet used for optical elements according to claim 1 and 2, wherein, described friction material is the friction cloth with a plurality of fine hair of arranging along in-line direction.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101707228B (en) * | 2009-11-20 | 2011-08-24 | 无锡尚德太阳能电力有限公司 | Stacking method and stacking device for manufacturing thin-film photovoltaic component |
CN102347393A (en) * | 2010-08-02 | 2012-02-08 | 无锡尚德太阳能电力有限公司 | Alignment method and system for manufacturing film photovoltaic assembly |
CN105093695A (en) * | 2015-08-18 | 2015-11-25 | 京东方科技集团股份有限公司 | Rubbing roll and manufacturing method thereof |
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2007
- 2007-01-12 CN CNA2007100017040A patent/CN101221321A/en active Pending
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101707228B (en) * | 2009-11-20 | 2011-08-24 | 无锡尚德太阳能电力有限公司 | Stacking method and stacking device for manufacturing thin-film photovoltaic component |
CN102347393A (en) * | 2010-08-02 | 2012-02-08 | 无锡尚德太阳能电力有限公司 | Alignment method and system for manufacturing film photovoltaic assembly |
CN102347393B (en) * | 2010-08-02 | 2013-03-27 | 无锡尚德太阳能电力有限公司 | Alignment method and system for manufacturing film photovoltaic assembly |
CN105093695A (en) * | 2015-08-18 | 2015-11-25 | 京东方科技集团股份有限公司 | Rubbing roll and manufacturing method thereof |
WO2017028414A1 (en) * | 2015-08-18 | 2017-02-23 | 京东方科技集团股份有限公司 | Rubbing roller and manufacturing method therefor |
US20170176783A1 (en) * | 2015-08-18 | 2017-06-22 | Boe Technology Group Co., Ltd. | Rubbing roller and manufacturing method thereof |
US10274759B2 (en) | 2015-08-18 | 2019-04-30 | Boe Technology Group Co., Ltd. | Method for manufacturing a rubbing roller |
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