GB2255570A - Polarizing film and dichroic dyestuffs therfor - Google Patents
Polarizing film and dichroic dyestuffs therfor Download PDFInfo
- Publication number
- GB2255570A GB2255570A GB9209764A GB9209764A GB2255570A GB 2255570 A GB2255570 A GB 2255570A GB 9209764 A GB9209764 A GB 9209764A GB 9209764 A GB9209764 A GB 9209764A GB 2255570 A GB2255570 A GB 2255570A
- Authority
- GB
- United Kingdom
- Prior art keywords
- resin
- polarizing film
- formula
- methyl
- polarizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 claims description 46
- 239000011347 resin Substances 0.000 claims description 46
- 230000002209 hydrophobic effect Effects 0.000 claims description 26
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000004898 kneading Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 229920000131 polyvinylidene Polymers 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 229920005668 polycarbonate resin Polymers 0.000 claims 2
- 239000004431 polycarbonate resin Substances 0.000 claims 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 229920005672 polyolefin resin Polymers 0.000 claims 1
- 239000010408 film Substances 0.000 description 65
- 239000000975 dye Substances 0.000 description 46
- -1 polyethylene Polymers 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 229920006214 polyvinylidene halide Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KQIKKETXZQDHGE-FOCLMDBBSA-N 4,4'-diaminoazobenzene Chemical compound C1=CC(N)=CC=C1\N=N\C1=CC=C(N)C=C1 KQIKKETXZQDHGE-FOCLMDBBSA-N 0.000 description 1
- CSBWDHPVCIKAHN-UHFFFAOYSA-N 4-[(4-aminophenyl)diazenyl]aniline;dihydrochloride Chemical compound Cl.Cl.C1=CC(N)=CC=C1N=NC1=CC=C(N)C=C1 CSBWDHPVCIKAHN-UHFFFAOYSA-N 0.000 description 1
- KOGDFDWINXIWHI-OWOJBTEDSA-N 4-[(e)-2-(4-aminophenyl)ethenyl]aniline Chemical compound C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1 KOGDFDWINXIWHI-OWOJBTEDSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920006373 Solef Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000006149 azo coupling reaction Methods 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012789 electroconductive film Substances 0.000 description 1
- 229940035423 ethyl ether Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
- C09B35/02—Disazo dyes
- C09B35/039—Disazo dyes characterised by the tetrazo component
- C09B35/205—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of a diaryl- or triaryl- alkane or-alkene
- C09B35/215—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of a diaryl- or triaryl- alkane or-alkene of diarylethane or diarylethene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
- C09B35/36—Trisazo dyes of the type
- C09B35/362—D is benzene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/60—Pleochroic dyes
- C09K19/601—Azoic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polarising Elements (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Liquid Crystal (AREA)
Description
225550 1 POLARIZING FILM AND DICHROIC DYESTUFFS THEREFOR This invention
relates to a polarizing film with excellent polarizing characteristics and excellent in durability, containing a hydrophobic resin and an oriented specific dichroic dyestuff and a process for preparing the same.
In the prior art, as the polarizing film to be used for liquid crystal display or photographic filter, film substrates of polyvinyl alcohol type resins, etc. in which iodine or a dichroic dye is incorporated to impart polarizing performance thereto have been generally known.
However, such polarizing films are inferior in heat resistance, humidity resistance, and for that reason, normally both surfaces are covered with durable protective films for practical uses. It has, therefore, been desirable to have polarizing films having satisfactory durability.
On the other hand, proposals have also been made to produce a polarizing film by the use of a dichroic dye and a polyester type resin (Japanese Laid-open Patent Publication No. 68008/1983), etc., but even when the dichroic ratio is improved, if a dye with high dichroism is employed, the orientation is still insufficient, whereby only a low polarizing performance could be obtained.
Further, European Patent No. 348964 discloses a film having a dichroic organic compound with liquid crystallinity dispersed in a hydrophobic resin, but since said dichroic organic compound with liquid crystallinity, will change to the isotropic liquid state, liquid crystal state and crystalline state depending on the temperature, and therefore it has been required to control the temperatures of the molding treatments such as kneading, 2 molding, stretching, etc. in order that the dichroic organic compound maintains the predetermined state, and also to set the temperature suitable for processing of the hydrophobic resin forming the matrix, which involves the problem that for the combination of the above dichroic compound and the hydrophobic resin, the processing temperature can only be chosen with difficulty.
It has now been found that a polarizing film having excellent polarizing performance and high durability can be provided by incorporating a dichroic dye with a specific structure in a hydrophobic resin and to transform the dichroic dyestuff to a specific state.
More specifically, the polarizing film of the present invention is a resin film containing 0.001 to 15 parts by weight of a dichroic dye represented by the formula 1 R2 N N=N Q N=N N / -Q7 \ R2 R3 [I] wherein Q is -N=N- or -CH=CH-, IR,, R2 are straight or branched alkyl groups having 1 to 10 carbon atoms and R. is hydrogen or methyl on 100 parts by weight of a hydrophobic resin, characterized in that said dichroic dye is oriented in the hydrophobic resin.
Films with a dyestuff of formula 1, wherein both R, are Cl-loalky], especially methyl; both R. are C5-10alky], especially n-pentyl or n-hexyl; both R3are hydrogen or methyl and Q is -N=W, are preferred The process for preparing the polarizing film comprises adding 0.001 to 15 parts by weight of a dichroic dye of formula 1 (above) to 100 parts-, by weight of a hydrophobic 3 resin, melting and kneading the mixture, then forming the kneaded product into a film and subjecting the film obtained to monoaxial stretching to a 2 to 12-fold.
Detailed description of the invention: 1 Polarizing film (1) Constituent components (a) Hydrophobic resin The hydrophobic resin to be used as the component constituting the polarizing film of the present invention is not limited to a particular resin, provided that it is a hydrophobic, thermoplastic resin which can be molded into a transparent film, and also can be stretched, as exemplified by homopolymers or copolymers including polyolefins such as polyethylene, polypropylene and the like; polyvinylidene halides such as polyvinylidene fluoride, polyvinylidene chloride and the like; polyesters such as polyethylene terephthalate, polybutylene phthalate and the like; polycarbonates; poly(meth)acrylates; polyethers; polystyrenes; polysulfones; polyamides, or resins comprising mixtures of these resins and so on.
Preferred are polyolefinic resins such as polyethylene, polypropylene and the like, polyvinylidene cyanide, polyvinylidene halide type resins such as polyvinylidene fluoride, polyvinylidene chloride and the like; or polycarbonate type resins and so on.
These hydrophobic resins may have a molecular weight which is not particularly limited, provided the resin can be molded into a film by known film fabrication and subjected to normal stretching methods.
4 (b) Dichroic dye The dichroic dye to be used as the active component in the polarizing film of the present invention preferably is an azo type dye represented by formula 1 (above).
Such azo type dye can be synthesized according to a known method. For example, the azo dye can be prepared by azo coupling a diamine compound such as 4,4'diaminostilbene or 4,4'-diaminoazobenzene with two molecules of diaikylaminobenzene.
The dyes of formula 1 (above) wherein both R, and both R2 are Cl,Oalkyl, both R3 are methyl and Q is a group of formula -N=N- or -CH=CH- are new and therefore per se also object of the instant invention. Among these new dyes again those wherein both R, are Cl-1.alkyl, both R2are C5- 10alkyl, both R3are methyl and 0 is a group of formula -N=N-, are preferred.
Specific dichroic dyes for polarizing films according to the instant invention include the following compounds:
H5C2 \ M -Q7 IZ=M N=N --& N / C2H5 1 CH3 E5C2 C2H5 113C (Dichroic dye A.) H3C \ N N=N -&N=W-& N=N N / CH3 /-Q- -Q-- \ C5Ell H11C5 (Dichroic dye B) H13C6\ 1"r -& N=N -1N /C61113 N -Q7 \ c 6H13 HIC 1113C6 C113 (Dichroic dye C) H3C \ N N=N -& N = N -&N=N - JIN / C313 -Q \ c 5H11 E11C5 C11, H3C (Dichroic dye D) 115C2 -N lq / m =CII 0 = - 1 \ C2H5 / C2115 H5C2 CE3 I-13C (Dichroic dye E) (c) Other components formulated In addition to the dichroic dye and the hydrophobic resin which are essential components, as optional components, additives such as W-ray absorber, antioxidant, other dyes, etc.
can be incorporated.
6 (2) Quantitative ratio The dichroic dye may be contained in the polarizing film of the present invention at a quantitative ratio of 0.001 to 15 parts by weight, preferably 0.001 to 5 parts by weight, more preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the abovementioned hydrophobic resin.
(3) Orientation In the polarizing film of the present invention, it is important that the dichroic dye should be oriented in the hydrophobic resin.
In such polarizing film, it can be judged whether the dichroic dye is oriented in the hydrophobic resin or noby measuring the dye orientation coefficient FD value.
FD value is determined by measuring the absorbance from the change in light intensity of the maximum absorption wavelength of the polarized light passed through a sample film which vibrated in parallel and vertical to the stretching axis of the film, and calculating according to the following formula:
X D = --------A+ wherein X represents the absorbance of the polarized light in parallel to the stretching axis, and A+ represents the absorbance of the polarized light vertical to the stretching axis.
7 The dichroic dye in the hydrophobic resin is oriented to an orientation degree generally of 0.45 to 0.95, preferably 0.75 to 0.95.
(4) Physical properties The polarizing film of the present invention generally obtains a polarization degree of 80% or higher by orientation of the above dichroic dye.
Also, heat resistance and humidity resistance are improved so that the change ration of the polarization degree after 1,000 hours may be within 5%, particularly within 2%.
11 Process for preparing polarizing film (1) Formulation First, the above dichroic dye and the hydrophobic resin are mixed at a predetermined ratio, melted and kneaded at a temperature not lower than the melting point of the dichroic dye, for example, between the melting point and the melting point + 20OoC, preferably the melting point + 50C to the melting point + 150oC.
Kneading can be performed by means of a mixer such an extruder, Brabender Plastograph, etc. Of these mixers, kneading may be preferably performed by use of Brabender Plastograph, etc.
(2) Preparation of film (a) Film molding The kneaded resin composition as described above is fabricated into a film at above 8 z kneading temperature by employment of the T-die method or the inflation method.
The thickness of the film at this time may be 100 to 750 pm.
(b) Stretching It is important that the polarizing film of the present invention should have the dichroic dye oriented to a high degree within the thus molded film.
For orienting the dichroic dye to a high degree, the film obtained is monaxially stretched. In the method for practicing said monoaxial stretching, it is generally performed by use of a roll stretching machine, calendering rolls, etc.
The temperature at stretching, when the melting point of the hydrophobic resin is defined as Trn and the glass transition point as Tg, may be preferably Trn - 1 0OoC to Trn - 50C orTg-50oCtoTg+10OoC. Under such temperature, stretching is effected monoaxially to 2 to 12-fold, more preferably to 3 to 1 0-fold.
The film thickness of the polarizing film of the present invention thus obtained is generally 10 to 150 pm, preferably 30 to 100 pm.
(111) Uses The polarizing film thus prepared, other than uses of films or sheets as such, can also be used in various molded products by application of various methods. For example, depending on the use, lamination may be effected with other polymers, or on the polarizing film surface of the present invention, a transparent electroconductive film or indiumtin oxide can be formed by vapor deposition, sputtering or the coating method and provided for practical applications.
9 EXAMPLES
In the following, the present invention is described in more detail by referring to Examples, but the present invention is not limited at all to the following Examples.
The polarizing performance of the polarizing film was measured by use of the following measuring method, and evaluation standards.
(1) Polarizing performance In a spectrophotometer (MPS-2000, produced by Shimazu Seisakusho K.K', two sheets of polarizing films are superposed so that the stretching directions are in parallel, and placed in the optical path of the spectrophoto meter to determine the light transmittance (T1) at the maximum absorption wavelength in the visible region. Then the two sheets of the polarizing films are placed so that the stretching directions cross at right angles in the optical path and light transmittance is determined at the same wavelength. The polarization degree (V) is calculated according to the following formula:
VN= FT 11 --T 2 T +T, TI+T I +T2 Example 1
An amount of 120 g of a polypropylene resin (IFY-4, produced by Mitsubishi Petrochemical Company) and 0.9 g of the dichroic dye A (formula hereinabove) are blended uniformly on a Brabender Plastograph at 240oC to prepare a masterbatch.
The masterbatch obtained (110 g) and 780 g of a polypropylene resin were formed into film using of a 15 mm extruder equipped with T-dice (dice width 120 mm).
Next, after the film is passed through a roll stretching machine as shown in Fig. 1, first through the low speed rolls 6 (0.085 m/min.), and then stretched to 6.5-fold in the longitudinal direction by the high speed cooling rolls 5 (5.5 m/min.) to obtain a polarizing film with a thickness of about 75 pm.
The polarizing characteristics of the polarizing film obtained were 36.0% of transmittance (light transmittance at the maximum absorption wavelength of one sheet polarizing film; TO), 98.5% of polarizing degree (V), with no variance in the width direction being recognized.
Example 2
By use of the dichroic dye of formula B (above) in place of the dichroic dye A, a polarizing film was prepared in the same manner as described in Example 1 except for preparing a masterbatch by blending on a Brabender Plastograph at a temperature of 210 o C.
The characteristics of the polarizing film obtained were TO = 36.8%, V=97. 0%, with no variance in the width direction being recognized.
Example 3
With a polyvinylidene fluoride (Solef 1008, produced by Solvay) as the binder resin, a polarizing film was prepared according to the same method as in Example 2 using the dichroic dye of formula B (above). The characteristics of the polarizing film obtained were To = 38.0%, V = 96. 3%, with no variance in the width direction being recognized.
11 Example 4
Using a vinylidene cyanide-vinyl acetate copolymer (synthesized product of Mitsubishi Petrochemical Company) and the dichroic dye of formula D (above) a film was fabricated in the same manner as in Example 2, at 210oC.
The film is stretched in the roll stretching machine shown in Fig. 1 at 180oC, a velocity of 20 mm/min. to 6.0-fold in the longitudinal direction to obtain a polarizing film of about 80 pm.
The characteristics of the polarizing film obtained are TO = 39.0%, V = 96.5%, with no variance in the width direction being recognized.
Example 5
An amount of 120g of a polycarbonate (L-1250, produced by Teijin) and 0.9 g of a dichroic dye of formula D (above) are blended uniformly on a Brabender Plastograph at 2500C to prepare a masterbatch.
The masterbatch obtained (110 g) and 780 g of a polycarbonate are formed into a film with use of a 15 mm extruder equipped with a T-dice (dice width 120 mm) at 250oC.
The film is stretched in the roll stretching machine shown in Fig. 1 at 1750C, a velocity of 20 mmImin. to 5.0-fold in the longitudinal direction to obtain a polarizing film of about 80 pm.
The characteristics of the polarizing film obtained are TO = 35.0%, V=96. 0%, with no variance in the width direction being recognized.
12 Effect of the invention:
The polarizing films of the present invention contain a dichroic dye readily orientable in a hydrophobic resin to a high degree, and therefore have excellent polarizing performance, and also excellent heat resistance and humidity resistance, thus having high durability.
Therefore, there is substantially no change caused by heat or moisture, and polarizing characteristics can be maintained for a long term.
Brief description of the drawing
The Figure is a roll stretching machine used in preparing the polarizing film of the present invention.
Explanation of symbols 1. Extruder 2. T-die 3. Chill roils 4. Nip rolls 4'. Nip rolls 5. High speed (cooling) rolls 6. Low speed (pre-heating) rolls 13 Example 6
14.3 g (0.05 mols) 4,4'-diamino-1,1'-azo-benzene-dihydrochloride are dissolved in a mixture of 200 mI of water and 18 mi of 30% hydrochloric acid with stirring at -5oC. 25 mi 4N-sodium nitrite solution are added dropwise. Stirring is continued for several hours at a temperature below + 50C. The excess of sodium nitrite is then destroyed by the addition of a little amidosulfonic acid.
19.7g 3-methyl-N-methy]-N-pentylaniline are dissolved in 150mi methanol. The diazonium-salt solution (above) is added slowly, while stirring, at a temperature below 50C. Then about 75mi of an aqueous sodium carbonate solution 20% is added to raise the pH to 5.0 to 5.5. The mixture is stirred at room temperature for 10 hours. Finally the dyestuff is filtered off, washed with hot water, dried and purified in a chromatographic column (on silica gel, liquid = hexane/ethylether 3:1) Xmax (in chloroform) of the dyestuff is 534nm.
This dyestuff, as well as all the other dyestuffs mentioned in this application, has (DSCmeasurements) a low melting range, enabling good solubility in the resin, and good heat stability,which prevent the dyestuff from being thermally destroyed during melting, mixing with the resin and film drawing.
The melting range of this dyestuff is 110 to 1300C. Thermal decomposition begins at 2800C.
HW/CU 14
Claims (11)
- CLAIMS:A polarizing resin film containing 0.001 to 15 parts by weight of a dichroic dye of formula 1 R' \ - / R' N -Q N=IN -l Q -l 1 R2 R3 R3 _\ R 2 (1) wherein Q is -N=N- or -CH=CH-, R, and R2 independently are straight or branched alkyl groups having 1 to 10 carbon atoms and R3 is hydrogen or a methyl group, based on 100 parts by weight of a hydrophobic resin, and whereby the said dichroic dye is oriented in the hydrophobic resin.
- 2. A polarizing film according to claim 1 wherein R, is C,_1.alkyl, R. is Q5-10alkyl, R3 'S hydrogen or methyl and 0 is an azo group.
- 3. A polarizing film according to claim 2, wherein R, is methyl, n-pentyl or hexyl, R2 is n-pentyl or hexyi, and R3 is hydrogen or methyl.
- 4. A polarizing film according to claim 1, wherein the hydrophobic resin is a polyolefinic resin, a polyvinylidene cyanide type resin, a polyvinylidene fluoride type resin or a polycarbonate resin.
- 5. A polarizing film substantially as herein described with reference to any one of the Examples 1 to 6.
- 6. A process for preparing a polarizing film, which comprises adding 0. 001 to 15 parts by weight of a dichroic dye of formula 1, according to anyone of claims 1 to 5 parts by weight of a hydrophobic resin, melting and kneading the mixture, then forming the kneaded product into a film and subjecting the film obtained to monoaxial stretching to 2 to 12-fold.
- 7. A process for preparing a polarizing film according to claim 6, wherein the hydrophobic resin is a polyolefin resin, a polyvinylidene cyanide type resin, a polyvinylidene fluoride type resin or a polycarbonate resin.
- 8. A process for preparing a polarizing film according to claim 6, wherein when the melting point of said hydrophobic resin is defined as Trn and the glass transition point as Tg, stretching is performed to a ratio of 3 to 10-fold at temperature range of:Tm - 1 OOOC to Tm - 50C or Tg - 50oC to Tg + 1000C.
- 9. A dye of formula 1 according to claim 1, wherein both R, and both R2are Cl1.alkyl, both R. are methyl and Q is a group of formula -N=W or CH=CH-.
- 10. A dye of formula 1 according to claim 9, wherein both R, are Clloalky], both R2 are C5-10alkyl, both R3 are methyl and 0 is a group of formula -N=W
- 11. A diazo or tiazo dye substantially as herein described with reference to any one of Examples 1 to 6.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3102871A JPH04333002A (en) | 1991-05-08 | 1991-05-08 | Polarization film and manufacture thereof |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9209764D0 GB9209764D0 (en) | 1992-06-17 |
| GB2255570A true GB2255570A (en) | 1992-11-11 |
| GB2255570B GB2255570B (en) | 1994-12-14 |
Family
ID=14338964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9209764A Expired - Fee Related GB2255570B (en) | 1991-05-08 | 1992-05-06 | Polarizing film and dichroic dyestuffs therefor |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPH04333002A (en) |
| CH (1) | CH683644A5 (en) |
| DE (1) | DE4214025A1 (en) |
| FR (1) | FR2676285B1 (en) |
| GB (1) | GB2255570B (en) |
| IT (1) | IT1254356B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5609796A (en) * | 1993-10-14 | 1997-03-11 | Sumitomo Chemical Company, Limited | Dye containing polarizing film |
| EP2730954A1 (en) * | 2012-11-07 | 2014-05-14 | Samsung Electronics Co., Ltd | Composition, polarizing film and display device including the polarizing film |
| US9207359B2 (en) | 2012-11-07 | 2015-12-08 | Samsung Electronics Co., Ltd. | Polarizing film and display device including the polarizing film |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2047643C1 (en) | 1993-05-21 | 1995-11-10 | Хан Ир Гвон | Material for polarizing coating |
| JP2009217012A (en) * | 2008-03-11 | 2009-09-24 | Osaka Prefecture Univ | Polypropylene polarizing plate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4116861A (en) * | 1977-08-18 | 1978-09-26 | General Electric Company | Dichroic liquid crystal compositions |
| US4128497A (en) * | 1976-09-09 | 1978-12-05 | General Electric Company | Dichroic liquid crystal compositions |
| DE3007259A1 (en) * | 1979-02-28 | 1980-09-11 | Gen Electric | LIQUID CRYSTAL COMPOSITION |
| EP0098522A2 (en) * | 1982-06-30 | 1984-01-18 | Hitachi, Ltd. | Liquid crystal composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4179395A (en) * | 1976-09-09 | 1979-12-18 | General Electric Company | Dichroic dyes having a plurality of azo bonding groups |
| US4842781A (en) * | 1984-02-29 | 1989-06-27 | Mitsui Toatsu Chemicals, Inc. | Colored polarizing film and method of making same |
| JP2710630B2 (en) * | 1988-06-30 | 1998-02-10 | 三菱化学株式会社 | Polarizing film and method for producing the same |
-
1991
- 1991-05-08 JP JP3102871A patent/JPH04333002A/en active Pending
-
1992
- 1992-04-29 DE DE4214025A patent/DE4214025A1/en not_active Withdrawn
- 1992-05-04 CH CH1427/92A patent/CH683644A5/en not_active IP Right Cessation
- 1992-05-06 GB GB9209764A patent/GB2255570B/en not_active Expired - Fee Related
- 1992-05-07 FR FR9205657A patent/FR2676285B1/en not_active Expired - Fee Related
- 1992-05-08 IT ITRM920346A patent/IT1254356B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4128497A (en) * | 1976-09-09 | 1978-12-05 | General Electric Company | Dichroic liquid crystal compositions |
| US4116861A (en) * | 1977-08-18 | 1978-09-26 | General Electric Company | Dichroic liquid crystal compositions |
| DE3007259A1 (en) * | 1979-02-28 | 1980-09-11 | Gen Electric | LIQUID CRYSTAL COMPOSITION |
| EP0098522A2 (en) * | 1982-06-30 | 1984-01-18 | Hitachi, Ltd. | Liquid crystal composition |
Non-Patent Citations (2)
| Title |
|---|
| CA 114 (18): 166332g * |
| CA 95 (16): 14195n * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5609796A (en) * | 1993-10-14 | 1997-03-11 | Sumitomo Chemical Company, Limited | Dye containing polarizing film |
| EP2730954A1 (en) * | 2012-11-07 | 2014-05-14 | Samsung Electronics Co., Ltd | Composition, polarizing film and display device including the polarizing film |
| US9194980B2 (en) | 2012-11-07 | 2015-11-24 | Samsung Electronics Co., Ltd. | Polarizing film and display device including the polarizing film |
| US9207359B2 (en) | 2012-11-07 | 2015-12-08 | Samsung Electronics Co., Ltd. | Polarizing film and display device including the polarizing film |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2676285A1 (en) | 1992-11-13 |
| IT1254356B (en) | 1995-09-14 |
| ITRM920346A1 (en) | 1993-11-08 |
| ITRM920346A0 (en) | 1992-05-08 |
| JPH04333002A (en) | 1992-11-20 |
| CH683644A5 (en) | 1994-04-15 |
| GB9209764D0 (en) | 1992-06-17 |
| DE4214025A1 (en) | 1992-11-12 |
| FR2676285B1 (en) | 1993-11-05 |
| GB2255570B (en) | 1994-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW555836B (en) | Liquid crystal materials and alignment structures and optical devices containing same | |
| JPH0430986B2 (en) | ||
| EP0348964B1 (en) | Polarizing film | |
| KR960002307B1 (en) | Polarizing film | |
| EP0275077B1 (en) | Anthraquinone compounds and polarizing film containing the same | |
| JPH0470603B2 (en) | ||
| JPH07104448B2 (en) | Polarizing film using perylene dye | |
| GB2255570A (en) | Polarizing film and dichroic dyestuffs therfor | |
| JPH07207169A (en) | Azo dye for polarization film and polarization film using the same | |
| US4514559A (en) | Water soluble disazo compound, copper salt thereof, and sheet or film colored therewith | |
| JPS61285259A (en) | Dichroic dye and polarizing film containing same | |
| JPH01103667A (en) | Anthraquinone pigment and polarizing film prepared therefrom | |
| US5382465A (en) | Anthraquinonic colorant and polarizing film containing the colorant | |
| EP0300770B1 (en) | Polarizing film containing an anthraquinonic colorant | |
| JP2954306B2 (en) | Dye for anthraquinone-based polarizing film and polarizing film using the dye | |
| US8009267B2 (en) | Method of producing optical laminate and image displaying apparatus | |
| JPS60125804A (en) | Polarizing film | |
| JPH03132701A (en) | Polarizing film | |
| JP2955329B2 (en) | Anthraquinone yellow dye and polarizing film using the dye | |
| JP5060853B2 (en) | Method for purifying polycyclic compound, method for producing polycyclic compound, and use of polycyclic compound | |
| JP2966973B2 (en) | Anthraquinone dye and polarizing film using the dye | |
| JPH0762110B2 (en) | Anthraquinone compound and polarizing film using the same | |
| JPH086043B2 (en) | Anthraquinone compound and polarizing film using the same | |
| JP2537233B2 (en) | Polarizing film | |
| JPH0735480B2 (en) | Anthraquinone compound and polarizing film using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19960506 |