CA2006427A1 - Light-polarizing films or sheets containing stilbene dyestuffs - Google Patents

Light-polarizing films or sheets containing stilbene dyestuffs

Info

Publication number
CA2006427A1
CA2006427A1 CA002006427A CA2006427A CA2006427A1 CA 2006427 A1 CA2006427 A1 CA 2006427A1 CA 002006427 A CA002006427 A CA 002006427A CA 2006427 A CA2006427 A CA 2006427A CA 2006427 A1 CA2006427 A1 CA 2006427A1
Authority
CA
Canada
Prior art keywords
acid
dyestuffs
dyestuff
light
solution
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.)
Abandoned
Application number
CA002006427A
Other languages
French (fr)
Inventor
Uwe Claussen
Friedrich Wilhelm Krock
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE3921669A external-priority patent/DE3921669A1/en
Application filed by Individual filed Critical Individual
Publication of CA2006427A1 publication Critical patent/CA2006427A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/52Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/60Pleochroic dyes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/36Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41Compounds containing sulfur bound to oxygen
    • C08K5/42Sulfonic acids; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B35/00Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/02Disazo dyes
    • C09B35/039Disazo dyes characterised by the tetrazo component
    • C09B35/205Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of a diaryl- or triaryl- alkane or-alkene
    • C09B35/215Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of a diaryl- or triaryl- alkane or-alkene of diarylethane or diarylethene
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B56/00Azo dyes containing other chromophoric systems
    • C09B56/04Stilbene-azo dyes

Abstract

Light-polarizing films or sheets containing stilbene dyestuffs Abstract Light-polarizing films or sheets, preferably based on vinyl alcohol homopolymers or copolymers contain dyestuffs of the formula in which X and Y have the meanings given in the description.
Le A 26 394 -US

Description

The invention relates to stilbene dyestuffs and light-polarizing films or sheets containing stilbene dyestuffs.

Films based on polyvinyl alcohol (PVA) containing iodine or dichroic dyestuffs as polarizing agents are known.

Until now, it has been very predominantly the iodine-containing polarizers which have found industrial appli-cations, for example in passive liquid crystal displays for the visualization of information. In the absence of moisture, these polarizers are characterized by excellent light fastness and outstanding dichroic properties in the long-wave region of the visible spectrum. The active agent of these films is the iodine/PVA complex (M.M.
Zwick. J. Appl. Polym. Sci. 9, 2393-2424 ~1965)), which admittedly absorbs a wide band of the daylight spectrum, but not all of it. In the short-wave region, a ~hole", i.e. a region of diminished extinction, is present, which is the reason that the sheets have a characteristic blue .. . .. . . . ..
colour.

This has disadvantageous consequences, if it is desired to produce white light. The light transmitted in unpolar-ized form diminishes the dichroism and thus the polariza-tion performance in this region. To increase it again, it is necessary to increase the concentration of iodine complex. However, this correction in the short-wave region results in excessive extinction in the long-wave Le A 26 394 - 1 -~ 7 region. This leads to a significant decrease of the transmitted light in the transmission setting in combina-tion with a decrease in the brightness of the display which is equipped with this sheet. To achieve acceptable degrees of brightness, compromises must be made.

An important critical parameter of a display is its readability under various illumination conditions; it is usually stated as ~perceived contrast ratio" (PCR =
Tl/TIl); this ratio should be as large as possible. From this follows that the transmission on the one hand has to made as small as possible in the blocked setting (T¦¦) (readability in the dark) and, on the other hand as large as possible in the transmission setting (Tl) (readability in the light). This requires a very uniform polarizing performance of the filter over the entire spectral range, which can usually not be achieved by means of the iodine sheet.

There has not been a lack of attempts to replace iodine by dyestuff triples of dichroic dyestuffs to produce a neutral grey colour having a uniform dichroism. However, this requires a range of high-performance dyestuffs. In addition to good light and weather fastness, they must have a high extinction and a high dichroism in the matrix; in addition, they must not have secondary den-sities which have lower dichroism. ~hus, preferablypolyazo dyestuffs have been proposed, for example based on 4 nitro-4' stilbenedisulfonic acid (JA 59/145,255, JA
60/156,759, JA 60/168,743) or of substituted benzidine.

Le A 26 394 - 2 -2~ 2~7 In addition, numerous individual dyestuffs have been mentioned, for example Direct Red 2, 31, 81, Direct Orange 26, 107, Direct Green 85, Direct Blue 1, 106, 107, 109, 190, 202, Direct Black 17, 19, Direct Yellow 12,44 etc. (JA 60/230,606, JA 60~159,705, EP 182, 632). How-ever, although dichroism is a wide-spread property with dyestuffs (cf. W. Hanle, H. Scherer, Zeitschr. Natur-forsch. 6a, 437-439 (1951)), it has sofar not been possible to achieve or surpass the spectral properties of the iodine sheet. This can be attributed, on the one hand, to the lack of good blue shades, and, on the other hand, to the requirement of high dichroism of the system dyestuff/ matrix.

Surprisingly, it has now been found that certain novel stilbene dyestuffs have excellent dichroic properties and are highly suitable for the production of light-polariz-ing films or sheets.

(In what follows, a definition of a radical or index once given is maintained in the further text).
... . . .. . ... . ... ... . .
The invention relates to light-polarizing films or sheets containing dyestuffs which, in the form of their free acid, conform to the formula X ~ H=CH ~ =N-Y
~~ SO~H HO~S

Le A 26 394 - 3 -;7 in which X signifies -CN, -CF3, halogen, -NH2, -NHRl~ -NRlR2~
RlCONH-, -COOH, -CONH2, -CONHRl, -CONR~R2, -COORl, -OH, -OR1, -O-CO-R1, -N=N-Y1, or a substituted or S unsubstituted heterocyclic radical, Rl, R2 signify alkyl, cycloalkyl, aryl or aralkyl, which may be interrupted by O and/or S, and Yr Ylsignify a substituted or unsubstituted aryl or heterocyclic radical, in particular ~ R3 ~6 in which R3 signifies H, -OH, -ORl, -NH2, -NHRl, -NRlR2, -NH-COR1, -O-COR', -N=N=R1l, a heterocyclic radical, R4, R5, R7, R8, R9, RlD s ignify H, halogen, -OH, -ORl, -NH2, -NHRl, -NRlR2, -Rl, -S03H, -NH-CO-Rl, -O-CO-Rl, -SO2-NH2, -SO2-NHRl, -SO2-NRlR2, R6 - ~~ signifies H, -N=N=Rll, heterocyclic radical and Rll signifies a substituted or unsubstituted aryl radical, preferably a substituted or unsubstitut-ed phenyl or naphthyl radical or a substituted or unsubstituted heterocyclic radical containing a maximum of eight azobridges.

Preferred radicals y, yl and Rll of the benzene series are as follows:

Le A 26 394 _ 4 _ . . .... . - :

In particular, suitable radicals are those which are derived from phenol and aniline and its substitution products, if appropriate subsequently alkylated or acylated. Examples are:
H , ~ CH3 ~ ~ C2H5 -CH2-CH2-OH , ~ H , ~ H

H2 ' ~ `CH3 ~ `CH2-CH2-OH

,CH3 ~ ,CH3 `c}l2-cH2-ocH3 `CH2-CH2-CN
.

~1~ . --~3N5N_Rl 1 ~=N-Rl 1 , Le A 26 394 - 5 -=N-RIl ~ =N-Rll ~ =N-Rl _Ri 1 ~N_Rl 1 , ~
OCH3 HN~ 503H
COCH~
Preferred radicals y, yl and Rll of the naphthalene series are listed below:

~ R9 Rl2 = -OH, -NH2 _ ~ ~4 . . ~ . . .

R8~R9 Rl3 i8 H, if Rl~ = -N=N-Rll or H, and is -N=N-Rl1, if R14 = -OH, -NH2, R14 is -OH, -NH2, -N=N-R , Le A 26 394 - 6 -.... _ . _ .. .. ... . . . . . . .

R 15 R ~ 5 6 ' ~R14 R15)~R16 Rl5, Rl6 are H, -OH, -ORl, -O-CORl, -NH2, -NH-R1, -NR1R2, -NH-CO-Rl, -S03H, Rl7 is H, -SO3H.

In particular, the following radicals y, yl and R11 of the naphthalene series are preferred:

~ 18 ~ R17 Rl8 is H, OH, NH2, -NH-CO-Rl, -NH-Rl, -N=N-Rl1, -S03H, R2 R2 1 R2 o - ~ 3H

R1~ is H, -N=N-R11, R20, R2l are OH, NH2, -O-CO-R1, -NH-CO-Rl, Le A 26 394 ~ 7 ~

D~:27 OH OH R20 OH Rl 7 \~ ' ~ ' ~ 18 Preferably, Y, Y~ and Rll are derived from the (sub-stituted) I acid:
OH

HO ~5 ~R

R is -NH-Rl, -NH-CO-Rl, -N=N-Rll Halogen preferably represents F, Cl, Br, I.
Alkyl (Rl, R2) preferably represents Cl-C6-alkyl (methyl, ethyl).
Cycloalkyl (Rl, R2) preferably represents C3-C7-cvcloalkyl (cyclopentyl, cyclohexyl).

Aryl (Rl, R2) preferably represents phenyl and naphthyl.

Aralkyl (Rl, R2) preferably represents phenyl-C,-C4-alkyl (benzyl, phenethyl).

Suitable substituents for the alkyl and cycloalkyl radicals (Rl, RZ) are, for example, halogen (Cl, Br, F), -OH, -CN, Cl-C4-alkoxy and the like.

Suitable substituents for the aryl and aralkyl radicals (Rl, R2) are, for example, halogen (Cl, Br, F), -OH~ Cl-C4-Le A 26 394 - 8 -.. , _ . .... ..

alkoxy (methoxy), Cl-C4-alkyl (methyl), CF3, NO2, CN.

Preferred radicals X, R3 and R6 of the heterocyclic series have the formula:

; ~ R
-X jz ; in which . 5 X is a C or an N atom, where the free valence of ; carbon has been saturated by a double bound, and Z represents the remaining members of a preferably 5- or 6-membered monocyclic or bicyclic or tricyclic ring 10 which can contain 1 to 3 heteroatoms from the series con-sisting of N, O, S and is substituted or unsubstituted.

In particular, they are derived from the following heterocyclic systems:
triazole, pyrazole, benzotriazole, naphthotriazole, oxazole, imidazole, thiazole, oxadiazole.

Preferred radicals y, yl and Rll of the heterocyclic series have the formula ~'Rl 9 -C z in which Z represents the remaining members of a preferably Le A 26 394 - 9 -..

2~ 27 5- or 6-membered monocyclic or bicyclic or tricyclic ring, which can contain 1 to 3 heteroatoms from the series con-sisting of N, 0, S and is substituted or unsubstituted, S the free valence of carbon being saturated by a double bond.

In particular, Y, Y~ and R11 are derived from the follow-ing heterocyclic systems:
thiophene, triazole, pyrazole, pyridine, benzotriazole, pyridone, naphthotriazole.

In addition, R11 is derived from the following hetero-cyclic systems:
thiadiazole, thiazole, benzothiazole.

Suitable heterocyclic radicals (Y, Y~ and R11) are in particular a substituted 5-amino- or 5-hydroxypyrazole radical, for example R2 2~T=N
~N_R23 in which R12 R22 is H, C~-C4-alkyl (methyl), -COOH, R23 is ~ 503H ~ 503H, ~ =N ~ S03H
Further preferred radicals Y, Y~ and R~1 are those of the Le A 26 394 - 10 -formula:
~ A-N=N ~ L

in which A is a substituted or unsubstituted phenylene or naphthalene radical, L is a substituted or unsubstituted phenyl or naphthyl radical and p is 1, 2, 3.
In particular, A represents and L represents ~R3 . ~R9 Preference is given to the group of symmetrical compounds of the formula - -Y1-N=N ~ H=CH ~ N=N-Y
~ 503H Ho35 in which Y~ is Y.

Le A 26 394 - 11 -2t)~ 7 A further preferred group of compounds conforms to the formula OH
Y-N=N ~ H=CH ~ N= ~

A further preferred group of compounds conforms to the formula Y-N=N ~ H=CH ~ =N ~ ~
sO3H 503H R5 H035 18 A further preferred group of compounds conforms to the formula Rl- ~ N=N ~ H=C ~ N=N-Y

503H sO3H

Dyestuffs I can be prepared in analogy to processes known from the literature.

H2N~CH= C1~3NH2 503H H035 (VI) which can be tetrazotized and coupled onto coupling components serves as starting material. Free amino groups of the coupled products obtained can be diazotized and Le A 26 394 - 12 -coupled again.

The compound 02~ ~ H=C ~ .NH2 S03H H035 (VII) can be used for preparing unsymmetrical dyestuffs. To this end, VII is diazotized and coupled onto suitable coupling components. Free amino groups of the coupled products obtained can be diazotized and coupled again.

The nitro group of the dyestuffs obtained can be reduced, and the amino compound obtained can be diazotized and coupled onto suitable coupling components. This makes the unsymmetrical compounds of the formula I accessible.

The monoamino compound VII can be converted according to Sandmeyer to the corresponding halogen, CN or OH com-pounds etc. (cf. S.Y. Zherdeva et al., J. Org. Chem~ ~SSR
16 (1980) 383) or, for example, to various derivatives (triazoles, pyrazoles etc.). After reduction of the nitro group, the monoamino compounds obtained can be coupled, after diazotization, to give azo dyestuffs.

Compound VII can furthermore be acylated at the amino group in a known manner (acetylated, benzoylated);
subsequent reduction of the nitro group gives amino-containing intermediates, for example Le A 26 394 - 13 -C~3 C,~ ~CH=CH~ ; .2 (VIII) which like VII are suitable for the preparation of unsymmetrical dyestuffs. In particular, they can be diazotized and coupled onto suitable coupling components.
After elimination of the acyl group, the dyestuffs obtained can be diazotized and coupled again. Compound VIII like VII can be converted according to Sandmeyer to derivatives which, after elimination of the acyl group, can be diazotized and coupled to give azo dyestuffs.

In particular, the invention relates to light-polarizing films (sheets) which contain an organic polymer and one or more compounds of the formula I.

The organic polymer is preferably an oriented polymer which forms transparent films and is compatible with dyestuffs which contain acidic groups. Examples of such a polymer are: polyamides, cellulose (acetate), vinyl alcohol homopolymers and copolymers and vinyl acetate homopolymers and copolymers, where the comonomers present can be, for example, ethylene, propylene, crotonic acid, (meth)acrylic acid, maleic acid. Polyvinyl alcohols which have been prepared by complete or partial hydrolysis of polyvinyl acetate, in particular those types which have a viscosity of > 4 mPa.sec2, preferably 20 to 70 mPa.sec2, at 20C in 4% strength agueous solution and a hydrolysis degree of > 80 mole %, preferably 85 to 100 mole %, are preferably used.

Le A 26 394 - 14 -The films preferably have a thickness of 10 to 150 ~.

The films preferably contain 0.01 to 10 % by weight, particularly preferably 0.5 to 6 % by weight, relative to the weight of the film, of the dyestuff.

The films are coloured in the usual manner, for example by colouring the polymer which is dissolved (in water).

The film is prepared from the solution in a manner known per se.

It is recommended to free the dyestuffs or dyestuff salts before use of foreign salts, for example by recrystal-lization, extraction and/or dialysis.

Preferably, these sheets are used which have been stretched at elevated temperature, preferably at 80-160C, by 200 to 1000%

If desired, the dyestuff-containing films can also be subjected to an aftertreatment, for example with aqueous boric acid solution, in order to improve the light permeability or the polarization coefficient. The condi-tions under which this aftertreatment is carried out can vary, depending on the film material and dyestuff.
Preferably, a 1-15 % strength by weight, particularly preferably a 5-10 % strength by weight, boric acid solution is used at 30-80C, particularly preferably at 50-80C. Preferably, surfactants and, if desired, in-Le A 26 394 - 15 -t~ .7 organic salts are added to the boric acid solution. The surfactants can be nonionic, cationic or anionic; prefer-ably, they are nonionic.

Examples of nonionic surfactan~s are: addition products of ethylene oxide with higher alcohols or addition products of ethylene oxide with nonylphenol. Preferably, 0.005-0.5 % by weight, particularly preferably 0.02-0.2 % by weight, of surfactant is used, relative to the water.

Suitable inorganic salts are preferably sodium sulphate and furthermore potassium sulphate, sodium chloride, potassium chloride, sodium nitrate, potassium nitrate.
Relative to the water, preferably 0.1-5 % by weight, particularly preferably 0.3-3 % by weight, of inorganic salts are used. If desired, this can be followed by a fixation treatment with an aqueous solution of a high-molecular-weight cationic compound.

The light-polarizing films or sheets can be compounded or laminated with other materials in a manner known p~r se.
Examples of suitable protective coatings are sheets made of a tetrafluoroethylene/hexafluoroethylene copolymer or another fluorohydrocarbon resin, a polyester, polyolefine or polyamide resin,a polycarbonate or cellulose ester, preferably cellulose (tri)acetate, cellulose (tri)propionate, cellulose (tri)butyrate.

The dichroism of the system can be considerably enhanced Le A 26 394 - 16 -~2~
by addition of lower mono- or polyhydric alcohols, such as methanol, ethanol or glycol, glycerol, trimethol-ethane, trimethylolpropane, pentaerythritol, sorbitol, their ethers, such as glycol monomethyl ether, glycol monoethyl ether, glycol dimethyl ether, diglycol diethyl ether, lower amines such as propylamine, hydroxy amines, such as propanolamine or amides, such as DMF, N-methyl-pyrrolidone, pyrrolidone, ~-caprolactam, to the casting solution. The additives can be used alone or, more advantageously, in mixtures, in which lower monohydric alcohols, for example methanol, ethanol, i-propanol, can also be present as components of the mixture. The addi-tives are preferably added to the casting solution in amounts of 5-50 % by weight, relative to the casting solution.

Besides being used in light-polarizing films, the dye-stuffs of the formula I can be used alone or in mixtures for rendering ordered structures visible in the analysis of polymers and in biological materials.

Example 1 a) Svnthesis of the dvestuff:

R-N ~ H=CH ~ ~N-~
~y ~ 503H

R = ~ 0-~H ~ 03H

Le A 26 394 - 17 -~i5''~7 37 g (0.1 M) of 4,4~-diaminostilbene-2,2~-disulphonic acid are suspended in 1 1 of water. 83 ml of concentrated hydrochloric acid are added and 51 ml (0.22 M) of sodium nitrite solution (as an approximately 30 ~ strength solution) are added dropwise slowly at room temperature.
The suspension is stirred overnight. After this time, it should be possible to detect a nitrite excess which is destroyed by the addition of sulphamic acid solution.
This tetrazonium salt solution is slowly added dropwise at room temperature, while controlling the pH, to a solution of 69 g (0.2 M) of l-hydroxy-6-benzoylamino-naphthalene-3-sulphonic acid in 0.5 1 of water, the pH
being maintained between 6.5 and 7 by dropwise addition of 10 per cent strength sodium hydroxide solution. After stirring overnight, the precipitated dyestuff is filtered off with suction and washed several times with small portions of water. The dyestuff is then dissolved in water and subjected to dialysis, to separate off salts;
the dyestuff solution obtained is then evaporated, and the residue is dried. Yield: 98.7 g.
b) Manufacture of the sheet 9.9 g of ~MOWIOL 28-99 (hydrolyzed polyvinyl acetate;
degree of hydrolysis 99.4 + 0.4 mole %; viscosity of the 4 % strength agueous solution at 20C:28 i 2.0 mPa.sec2;
from Hoechst AG) and 0.1 g of the dye of Example la are dissolved in 190 ml of water by heating the mixture at Le A 26 394 - 18 -90C for 2 hours with stirring. 5 g of methanol and 2.5 g of glycerol are added to 92.5 g of the 1 %
strength, relative to the polymer, dyestuff solution obtained. By means of a knife, 500 ~ thick layers are applied from this solution to a clean glassplate, and the layers thus obtained are dried in air at room temperature on a support in an exactly horizontal position. The resulting dry sheets are peeled off from the glassplate;
they have a violet colour and are about 40-50 ~ thick.

c) Stretching of the sheets To produce dichroic properties, the sheets are stretched.
To this end, they are heated in a drying cabinet at a constant temperature of 130C for 15 minutes and then stretched at a speed of about 10 cm/min to about 700 % of their original length. The stretched sheets have a dichroic ratio of about 28 at the absorption maximum (557 nm), measured with polarized light; losses due to reflection were not taken into account in the measure-ment.

d) Sheet manufacture on the castin~ machine 0.2 g of the dyestuff of Example la is dissolved in 100 g of hot water. 10 g of glycerol are added, and 19.8 g of ~OWIOL 28-99 are stirred into the cooled solution. After stirring at room temperature for 1 hour, the mixture is heated to 90C, and stirring is continued at this temperature until, after about 3 hours, a homoge-Le A 26 394 - 19 -~ 7'~7 nous solution has been formed. At 50C, 5 g of methanol are then stirred in. The warm solution is filtered through a filter press, while injecting air, and is then degassed by evacuation. The casting solution is pourable and stable at 30C.

To produce a sheet, the casting solution is applied continuously by means of 250 ~ knife to the casting wheel (wheel diameter 25 cm, rotating speed about 7.5 min per revolution) which has been preheated to about 50C. The layer is dried by passing heated air over it, and the solidified sheet is continuously peeled off the wheel and additionally dried. The sheet obtained is about 40 ~
- thick. It is stretched as described above in c), leading to similar results.

e) Exactly analogously as in Example la, analogous dyestuffs are obtained by using the coupling components mentioned, which are incorporated into sheets according to lb. Stretching according to lc gives dichroic sheets.
~ I H . . ..
.~ ~~, .
c~ ~.,~-C'3-G'l OH

OH
!
c3s~5~3H
!~H 2 OH
~.' 5~3H
Le A 26 394 - 20 -- Z~ 27 Further dyestuffs are prepared analogously to Example la from the following coupling components:
OH H;C-CO-NH OH
~35 503.~ ~ ~

H~ <~3-Co-HH OH

CH3-CO-h'H ~ 503H H2N ~
. 503H

NH ~ H035 CO-NH ~ NC-CH2-CH2-N ~ 3 OH OH OH
CH3-CO-N ~
303H ~ 03H ~ 303H

NH-CO

Le A 26 394 - 21 .
.

2~64Z7 OH ~2N O.Y
~CO-N~ ~
503H ~503H

~C ~503 H C O - N~503H

~0 NH R

OH
~N~503H C~3 503H

,~ NH2 OH
CH3 - O~N~So3H

;' C~, ~503H
OH

Le A 26 394 - 22 -~3C-CO~ OH COCH

H35~o3H OH 503 O~O_NH OH

HO~} H03S~

<~ H035 The products obtained from the coupling onto phenols can be ''sealedll by subsequent alkylation (methylation, ethylation, benzylation).

Exam~le 2 a) 17.3 q (0.1 mol) of 4-aminobenzenesulphonic acid are dissolved in 200 ml of water together with about 7 ml of sodium hydroxide solution (45 ~ strength), : and 28 ml of concentrated hydrochloric acid are then added all at once. The freshly precipitated suspen-sion is diazotized at 5-10C with 7 g of sodium nitrite in 15 ml of water. After 15 minutes, the product is filtered off with suction and washed on the filter with icewater. The moist product is Le A 26 394 - 23 -~ 7 immediately stirred into 100 ml of water (caution:
the dry product is explosive). To the suspension of the diazonium salt thus obtained is added dropwise, with vigorous stirring, a cold solution of 34.1 g (0.1 mol) of 8-amino-1-hydroxy-naphthalene-3,6-disulphonic acid monosodium salt and 5.5 g of sodium carbonate in 100 ml of water over a period of 45 minutes. The mixture is stirred for 12 hours while warming to room temperature, the product is filtered off with suction and washed neutral. This gives a dyestuff paste of the formula:

H03S ~ = ~

b) The dyestuff paste from a) is dissolved together with 40 g of sodium carbonate in about 500 ml of water, if necessary with heating, and then cooled to below 10CC. The tetrazonium salt solution from 18.5 g (0.05 mol) of 4,4~-diaminostilbene-2,2'-disulphonic acid prepared according to Example la is added dropwise to the suspension obtained over a period of 30 minutes, while maintaining the pH at 6.5 to 7 by metering in 10% strength sodium hydroxide solution. The mixture is stirred over-night, the dyestuff is filtered off with suction, washed neutral with water and then dissolved in water and dialyzed, to separate off salts. The Le A 26 394 - 24 -dyestuff solution is evaporated and the residue is dried. The dyestuff obtained has the structure:
HO 3S~
R-N'N~H=C~l~N=N-R
503~

13035~3H .
c) The following coupling components which can be prepared analogously to 2a) can also be used:

H035 ~ N= ~

: NH2 OH
H035 ~ N=N ~ N= ~ S

H35~N.~o3H

.; S03~

H035 ~ Ns ~ S03H

OH

Le A 26 394 - 25 -Zl[)0~427 OH
H03S ~ N=N ~ 503H
H035 ~ '~`
0}~

H03S ~ ' ~ 503H

d) Exactly analogously, the dyestuff of the structure:

R-N=N ~ H=CH ~ =N-R

R = H035 ~ H03 ~ 03H

is obtained by coupling the tetrazonium salt solu-tion of Example la first at a pH of 4.5-5.5 onto 1-hydroxy-8-aminonaphthalene-3,6-disulphonic acid and then coupling the diazonium compound from 4-amino-benzenesulphonic acid prepared according to Example 2a twice onto the product at a pH of 7-7.5.

The other components mentioned in c) can also be reacted in reverse order to give analogous dye-Le A 26 394 - 26 -20~42~7 stuffs.
Example 3 a) At a maximum temperature of 10C, a solution of 30.6 g (0.2 mol) of 2,5-dimethoxyaniline in 500 ml of water (to which concentrated hydrochloric acid is added until a clear solution is formed) is added dropwise to the tetrazonium salt solution prepared according to Example la, with stirring, while maintaining a pH of 3 to 4.5 by simultaneous meter-ing in of sodium hydroxide solution. After stirring overnight and warming to room temperature, the coupling reaction is completed. The product is filtered off with suction and carefully washed neutral with water. The dyestuff obtained after drying weighs 52.4 g and has the formula:

R-N=N ~ H=CH ~ N=N-R

R - H2N ~

. .
Instead of 2,5-dimethoxyaniline, it is also possible to use 2-methoxy-5-methylaniline, 2,5-dimethyl-aniline, 3-methylaniline, 3-acetylaminoaniline, Le A 26 394 - 27 -2~ i427 1-naphthylamine, 1-amino-2-ethoxy-naphthalene-6-sulphonic acid or anilinomethanesulphonic acid etc.

b) The intermediate product obtained in a) is tetrazot-ized in aqueous hydrochloric acid with sodium nitrite while letting it stand overnight at room temperature, and the tetrazonium salt solution obtained, after destruction of the nitrite excess, is coupled onto l-hydroxy-6-benzoylamino-naph-thalene-3-sulphonic acid at a pH of 6.5 to 8. The dyestuff obtained has the formula:

R-N=N ~ H=CH ~ =N-R

R CH3-CO-NHJ~03H OCH !

c) The other compounds mentioned in Example le and 2c can also be used as components of the final coupling reaction, preferably benzoyl I acid, acetyl gamma-acid or acetyl K acid; phenolic coupling components can subsequently be ~sealed~ by alkylation. The dyestuffs obtained are incorporated according to Example lb into a sheet, which is subsequently stretched.

Le A 26 394 - 28 -Example 4 a) 9.6 g (0.01 mol) of the dyestuff from Example le formed by coupling of the tetrazonium salt from la onto l-hydroxy-6-acetylaminonaphthalene-3-sulphonic acid are stirred in 200 ml of 2N sodium hydroxide solution at 80CC until the acetyl groups have been completely cleaved off (monitoring of the reaction by thin-layer chromatography). The reaction mixture is neutralized, cooled, and is filtered off with suction and the residue washed neutral.

b) The dyestuff formed according to a) is dissolved in 100 ml of IN sodium hydroxide solution, 1.8 g of sodium nitrite are added to the solution, and the solution is then run into excess hydrochloric acid.
After standing overnight at room temperature, the tetrazonium salt solution has been formed; excess nitrite is destroyed by means of sulphamic acid, 2 g of phenol dissolved in sodium hydroxide solution are then added dropwise, and the pH is brought to about 9 with sodium hydroxide solution. After stirring for 3 hours, the coupling reaction is completed. The product i5 filtered off with suction and washed neutral.

c) The dyestuff formed according to b) is dissolved in 100 ml of lN sodium hydroxide solution, and 4 g of dimethyl sulphate are added to the solution with Le A 26 394 - 29 -stirring. Afer about 1 hour, the methylation is completed. The producted is filtered off with suction, washed neutral and dried. The dyestuff obtained has the formula:

R-N=N ~ H=C ~ N=N-R

OH

CH3{~N=N~C03H

Instead of dimethyl sulphate, it is also possible to convert the phenolic groups with diethyl sulphate or benzyl bromide to the ethers.

Instead of phenol in 4b), it is also possible to use the other coupling components listed in ~ables le and 2c as end groups.

Example S

a) The tetrazonium salt solution from Example la is added dropwise at about lO~C to the solution of 68.4 g (0.2 mol) of 1-hydroxy-8-acetylaminonaph-thalene-3,6-disulphonic acid (monosodium salt) in 0.8 1 of water, during which the pH is maintained at 6.5-7.5 by dropwise addition of 2N sodium hydroxide Le A 26 394 - 30 -:

'' 4~7 solution. The coupling reaction is then allowed to go to completion overni.ght, while heating to room temperature. The product is filtered off with suction, washed neutral with water and dried. Yield:
62.5 g of a blue-violet soluble dyestuff.
b) 20 g of the dyestuff from 5a) are heated in 200 ml of 2N sodium hydroxide solution at about 80C, until the acetyl groups have been cleaved off. The mixture is then acidified with hydrochloric acid, the pro-duct is filtered off with suction, washed neutral and dried. This gives 15.3 g of a dyestuff which, in the form of the free acid, has the following formula: HO3S
R-N=N ~ H=CH ~ =N-R

R = HO35 ~ O3H

An analogous dyestuff is also obtained from l-hydroxy-8-acetylaminonaphthalene-3,5-disulphonic acid, followed by cleavage.

The dyestuffs can be incorporated according to Example lb into a sheet and stretched according to lc.

"Unsvmmetrical" dyestuffs A suitable intermediate for the preparation of "un-symmetrical'- compounds is 4-amino-4'-nitrostilbene-2,2'-Le A 26 394 - 31 -2C~ 27 disulphonic acid.

Example 6 21.2 g(0.05 mol) of 4-amino-4'-nitrostilbene-2,2'-disul-phonic acid are suspended in 400 ml of water, and 40 ml of concentrated hydrochloric acid are added. Diazotiza-tion is carried out by dropwise addition of 12.8 ml of 30% strength sodium nitrite solution (0.05 mol + 10 %) at a maximum temperature of 10C, and stirring is then continued at about 20C overnight. The nitrite excess is then destroyed by addition of sulphamic acid.

The diazonium salt solution obtained is added dropwise to a solution of 17.2 g (0.05 mol) of 1-hydroxy-6-benzoyl-aminonaphthalene-3-sulphonic acid in 160 ml of water at about 20C, during which the pH is kept in the range from 7 to 8 by dropwise addition of sodium hydroxide solution.
After stirring overnight, the precipitated dyestuff is filtered off with suction, washed neutral with a small amount of water and dried. Yield: 28.5 g (75 %). This gives a dyestuff of the structure:

02N~H=CH~N=~
-S03H HO3S ~ NH-C ~

Exactly analogously as described above, an analogous Le A 26 394 - 32 -2~ i42~

dyestuff is obtained by replacing 1-hydroxy-6-benzoyl-aminonaphthalene-3-sulphonic acid by 1-hydroxy-6-anilino-naphthalene-3-sulphonic acid.

b) Further suitable coupling components are the ones mentioned in the Table of Examples le and 2c, preferably acetyl I acid, acetyl gamma-acid, R acid, acetyl R acid, benzoyl R acid, acetyl H acid, benzoyl H acid, Chicago SS acid, benzoyloxy C acid or phenol. The dyestuffs obtained according to a) or b) can be incorporated in accordance with Example lb in a sheet which is stretched in accordance with Example lc.

In addition, they can be reduced as described in 9a) to the amino compounds, which are diazotized and then coupled onto suitable coupling components, for example those the Tables of Examples le and 2c. -Example 7 a) 4-Benzoylamino-4'-nitrostilbene-2,2'-disulphonic acid:

200 g (0.5 mol) of 4-amino-4~-nitrostilbene-2,2'-disul-phonic acid are suspended in l l of water, and the mixture is brought to a pH of 9 with 40% strength sodium hydroxide solution. At about 10C, 77 g (0.5 mol + 10%) of benzoyl chloride are added dropwise with vigorous stir-Le A 26 394 - 33 -42~

ring, during which the pH is maintained at 9 by dropwise addition of sodium hydroxide solution. As soon as the pH
remains stable, stirring at room temperature is continued for 1 hour, the product is filtered off with suction, washed neutral and dried. This gives 233 g.

b) 4-Amino-4'-benzoylaminostilbene-2,2~-disulphonic acid:

151 g (0.3 mol) of the product from a) are suspended in 2.5 1 of water, 100 g of 45~ strength sodium hydroxide solution and 200 g of sodium sulphide trihydrate are added, and the mixture is slowly heated to 80C until the starting material has disappeared (TLC). 200 g of sodium chloride are added to the hot solution. After cooling, the product is filtered off with suction and washed carefully neutral with water. The dry product weighs 113 g.

c) Diazotization of 4-amino-4'-benzoylaminostilbene-2,2'-disulphonic acid in accordance with the pro-cedure of Example 6a, destruction of the nitrite excess with sulphamic acid, and coupling of the product onto 1-hydroxy-6-benzoylaminonaphthalene-3-sulphonic acid, while maintaining a pH of 7-8, gives a dyestuff of the structure:
. .

Le A 26 394 - 34 -~(.) H OH
~3 C O - NH~ H = C 1~ ~ - C o~3 The corresponding dyestuff which has an acetylamino group on the stilbene radical is obtained analogously.

Further suitable coupling components are the ones men-tioned in Examples le and 2c, preferably phenyl I acid, acetyl R acid, benzoyl K acid, acetyl gamma-acid, acetyl H acid, benzoyl H acid, Chicago SS acid and phenol (followed by methylation). The dyestuffs obtained can be incorporated in accordance with Example lb in a sheet which is stretched in accordance with Example lc.

ExamPle 8 a) At a maximum temperature of 1ODC, a solution of 7.8 g (0.05 mol) of 2,5-dimethoxyaniline in 125 ml of water (dissolved with the concentrated hydro-chloric acid addition until a clear solution is formed) is added dropwise to the diazonium salt solution prepared according to Example 6a, with stirring, while maintaining a p~ of 3 to 4.5 by metering in sodium hydroxide solution. After stirring overnight, during which the temperature is allowed to rise to room temperature, the coupling reaction is completed. The product is filtered off with suction and carefully washed neutral with water.

Le A 26 394 ~ 35 ~

Instead of 2,5-dimethoxyaniline, it is also possible touse2-methoxy-5-methylaniline, 2,5-dimethylanili-ne, 3-methylaniline, 3-acetylaminoaniline, l-naph-thylamine, 1-amino-2-ethoxynaphthalene-6-sulphonic acid etc.

b) The intermediate obtained in a) is diazotized in the form of a paste in aqueous hydrochloric acid with sodium nitrite, the diazotization being allowed to go to completion by standing overnight and warming to room temperature. Excess nitrite is destroyed by means of sulphamic acid.

The diazonium salt solution is coupled onto 1-hydroxy-6-anilinonaphthalene-3-sulphonic acid at pH
6.5 to 7.5. The dyestuff obtained has the formula:
S ~ OC~3 R-CH-C ~ N=N ~ N=N-R

It is also possible to USQ the other compounds mentioned in Examples le and 2c as components of the end coupling.

c) Exactly analogously as described in 8a and b, the Le A 26 394 - 36 -4~;D7 dyestuff of the formula R-CH=CH ~ = ~ =N-R~

R = ~ ONH ~

H03S ~ NH ~
is obtained by using the diazonium salt from Example 7c.

It is also possible to use the other compounds mentioned in Examples le and 2c as components of the S end coupling.

If benzoyl chloride in Example 7a is replaced by other active acid derivatives, for example acetic anhydride, propionic anhydride, 4-methylbenzoyl chloride etc., and the procedure according to 7b and then according to 7c and 8c is repeated, analogous dyestuffs in which the benzoyl group is replaced correspondingly are obtained.
. . .
Example 9 a) The dyestuff of Example 6a which still contains a Le A 26 394 - 37 -Z~ 27 nitro group is reduced in an ethanol/water mixture with sodium sulphide or analogously to the procedure in DOS ~German Patent Specification) 3,805,513, Exzmple 3, to the amino compound. Another possible reduction is that using iron powder in weakly acidic aqueous medium according to Bechamp.

Exactly analogously, the corresponding nitro-con-taining dyestuffs of Example 6b can be reduced to the amino compounds.

b) 18.1 g (0.025 mol) of the dyestuff obtained in a) are suspended in 300 ml of water, 20 ml of con-centrated hydrochloric acid are added, and the mixture is diazotized by dropwise addition of 6.4 ml of 30% strength sodium nitrite solution (0.025 M
+ 10%) at a maximum temperature of 10C, and stir-ring is allowed to continue overnight at room temperature. The nitrite excess is then destroyed by addition of sulphamic acid.

The diazonium salt solution obtained is added - 20 dropwise to a solution of 8 g ~0.025 mol) of 1-amino-8-hydroxynaphthalene-2,4-disulphonic acid in 80 ml of water at about 20C, while maintaining the pH at about 7. After stirrinq overnight, the precip-itated dyestuff is filtered off with suction, washed with a small amount of water and dried. The dyestuff obtained has the structure:

Le A 26 394 - 38 -SO H
'"'''2 OH ~-CH~N=N-R' ? ~ ;S~ S03H

OH
SO~H

H O 3 S~NI~ - C C~3 It is also possible to use the other compounds mentioned in Examples le and 2c as coupling components.

The same reaction sequence 9a, b can also be carried out with the dyestuff from Example 8b and its analogues. This dyestuff is also obtained by deacylating the dyestuff from Example 8c with 2N hydrochloric acid or 2N sodium hydroxide solution at about 80C and diazotizing and coupling the intermediate thus obtained as described in 9b.

Example 10 a) 5 g (about 0.05 mol) of phenol are dissolved in 100 ml of water with the addition of sodium hydroxide solution, until a clear solution has been obtained, and the diazonium salt solution obtained in Example 6a is then added dropwise at about 10C, during which a pH of about 9 is maintained by addition of sodium hydroxide solution. After stirring overnight, the mixture is neutralized, the precipitate filtered off with suction and washed.

Le A 26 394 - 39 _ ~r~;~7 The moist paste is reacted analogously to the procedure in Example 4c in a~leous alkaline solution with dimethyl sulphate, until complete methylation has taken place. This gives a dyestuff of the structure:

N02{~CH=CH~N=N{~_CH3 Likewise, other (substituted) phenols can also be used instead of phenol.
If dimethyl sulphate is replaced by benzyl bromide, the corresponding benzylated compound is obtained;
other alkylating agents, for example diethyl sul-phate, are also suitable.

b) The dyestuff obtained in a) is reduced with sodium sulphide in ethanol and water or with iron powder in weakly acidic medium to the amine. This amine is diazotized analogously to Example 6a with sodium nitrite, and excess nitrite is then destroyed by means of sulphamic acid.
The diazonium salt solution obtained is coupled in accordance with the further procedure in Example 6a onto 1-hydroxy-6-henzoylaminonaphthalene-3-sulphonic acid at a pH between 7 and 8, which gi~es a dyestuff of the formula below:

Le A 26 394 _ 40 -R-l~'=N~H=CH~N=N-R ' 0~

R = }~ 3C ~3 H0 3 5~NH - C G~) It is also possible to use the other compounds mentioned in Examples le and 2c as components of the end coupling, preferably acetyl I acid, N-phenyl I acid and acetyl H
acid.

The dyestuffs obtained are incorporated according to Example lb into a sheet, which is subsequently stretched.

The dyestuffs obtained according to a) or b) can be incorporated in accordance with Example lb in a sheet which is stretched in accordance with Example lc.

Exam~le 11 (Condensation dyestuffs) The condensation reaction for the preparation of azo dyestuffs is described in Houben-Weyl, Methoden der Organischen Chemie (Methods of organic chemistry), Vol.
10/3, Part 3, p. 339-346.
5 a) The preparation of the following dyestuff is de-scribed there on page 343:

Le A 26 394 - 41 -2~4Z7 2-N=N ~ N=N ~ H=CH ~ N=N ~ N=N-R

R = H035 ~
b) The following dyestuffs are prepared by suitable modification of the procedure given there:

H3C- ~ N:N ~ H=CH ~

N
H3C- ~ s ~ H=CH

N - N ~ HrCH ~ =N ~
H035 ~ NS03H S03H CH
CH
Nl Nl ~
H03S ~ N S03H
~ .' Exam~ 2 a) The compound 2~-C~l Le A 26 394 - 42 -is prepared by the procedure in J. Org. Chem. USSR 16 ~1980) 388.

Exactly analogously, it is also possible to prepare the corresponding bromine compound or the cyanide instead of the chlorine compound.
b) The compound of Example 12a is reduced analogously to the procedure in Example 7b, 10b or in J. Org.
Chem., USSR 16 (1980) 386, 389 to the amino com-pound. This compound is converted into the corres-ponding diazonium salt, for example as described in 6a, and then as also described in 6a, coupled onto 1-hydroxy-6-benzoylaminonaphthalene-3-sulphonic acid, while maintaining a pH of about 7-8. This gives the dyestuff of the structure:

Cl ~ H=CH ~ N=
503H HO35 ~ NH-C ~

Further suitable coupling components are those mentioned in Tables le and 2c.

c) If the procedure of Example 8 is repeated and the diazonium salt solution prepared in 12b is used instead of that used in 8a, and the product is first coupled onto 3-methylaniline and then onto 1-hydroxy-6-anilinonaphthalene-3-sulphonic acid, a Le A 26 394 _ 43 _ dyestuff of the structure:

R-HC=CH ~ =N ~ =N-R

R Cl { ~ R~ . ~`NH~

is obtained.

Further suitable coupling components are those mentioned in Tables le and 2c.

Instead of 3-methylaniline, it is also possible to use2,5-dimethoxyaniline,2-methoxy-5-methylaniline, 2,5-dimethylaniline, 3-acetylaminoaniline, 1-naph-thylamine, l-amino-2-ethoxynaphthalene-6-sulphonic acid or anilinomethanesulphonic acid etc.

d) If the corresponding bromine or cyano compound is used in 12b and c) instead of the chlorine compound from 12a, analogous dyestuffs are obtained.

Example 1~

The known compound of the following formula obtained by Le A 26 394 _ 44 _ 2~)~64'~;7 coupling of diazotized 4-amino-4'-nitrostilbene-2,2'-disulphonic acid onto l-aminonaphthalene-4-sulphonic acid analogously to the procedures in Houben-Weyl, Methoden der Organischen Chemie (Nethods of Organic Chemistry), Vol. 10/3, Part 3, p. 428, 429:

02N{~CH = CI~N~>~
S03H 503H ~

is reduced analogously to the procedure of Examples 7b, lOb or 12b to the amino compound.

The compound which is an isomer with respect to the position of the sulpho group is obtained analogously by coupling onto 2-aminonaphthalene-6-sulphonic acid, followed by reduction to the amino compound.

b) The amino compound prepared in a) is diazotized according to the procedure in Example 6a, and the product is coupled as described there onto l-hydroxy-6-anilinonaphthalene-3-sulphonic acid. This gives a dyestuff of the structure:

Le A 26 394 _ 45 _ zf )~ 7 R-N~N ~ H=C ~ ' OH
R = ~ R' = -N

Analogously, the use of 2-aminonaphthalene-6-sulphonic acid in 12a, reduction, diazotization and coupling onto phenyl I acid gi~es the isomeric dyestuff:

R-N=N ~ H=CH ~ ' OH
R =H ~ R~ = _ ~ S03H

. .

~e A 26 394 - 46 -

Claims (6)

1. Light-polarizing films or sheets containing dye-stuffs which, in the form of the free acid, conform to the formula in which X signifies -CN, -CF3, halogen, -NH2, -NHR1, -NR1R2, R1CONH-, -COOH, -CONH2, -CONHR1, -CONR1R2, -COOR1, -OH, -OR1, -O-CO-R1, -N=N-Y1, or a substituted or unsubstituted heterocyclic radical, R1, R2 signify alkyl, cycloalkyl, aryl or aralkyl, which may be interrupted by O and/or S, and Y, Y1 signify a substituted or unsubstituted aryl or heterocyclic radical.
2. Light-polarizing films or sheets containing dye-stuffs of Claim 1 in which y, y1 are in which A is a substituted or unsubstituted phenylene or naphthalene radical, L is a substituted or unsubstituted phenyl or naphthyl radical and p is 1, 2, 3.

Le A 26 394
3. Light-polarizing films or sheets containing dye-stuffs of Claim 1 where y, y1 are , in which R3 signifies H, -OH, -OR1, -NH2, -NHR1, -NR1R2, -NH-COR1, -O-COR1, -N=N=R11, a heterocyclic radical, R4, R5, R7, R8, R9, R10 signify H, halogen, -OH, -OR1, -NH2, -NHR1, -NR1R2, -R1, -SO3H, -NH-CO-R1, -O-CO-R1, -SO2-NH2, -SO2-NHR1, -SO2-NR1R2, R6 signifies H, -N=N=R11, a heterocyclic radical and R11 signifies a substituted or unsubstituted aryl radical, preferably a substituted or unsubstitut-ed phenyl or naphthyl radical or a substituted or unsubstituted heterocyclic radical containing a maximum of 8 azobridges.
4. Light-polarizing films or sheets containing dye-stuffs of Claims 1 and 3 in which y, y1 and R11 are radicals from the benzene series of the formula , Le A 26 394 or radicals from the naphthalene series of the formulae in which R12 = -OH, -NH2 , R13 is H, if R14 = -N=N-R11 or H, and is -N=N-R11, if R14 = -OH, -NH2, R14 is -OH, -NH2, -N=N-R11, , R15, R16 are H, -OH, -OR1, -O-COR1, -NH2, -NH-R1, -NHR1R2, -NH-CO-R1, -SO3H, R17 is H, -SO3H.
in particular of the formulae Le A 26 394 - 49 - , , in which R18 denotes H, OH, NH2, -NH-CO-R1, -NH-R1, -N=N-R11, -SO3H, , in which R19 denotes H, -N=N-R11, R20, R21 denote OH, NH2, -O-CO-R1, -NH-CO-R1, , , and in which R is NH-R1, -NH-CO-R1, -N=N-R11.
5. Light-polarizing films or sheets according to Claims 1 and 4 containing dyestuffs of the formula (II) where y1 is Y.

Le A 26 394 - 50-
6. Films and sheets according to Claims 1-5 containing dyestuffs of the formula or Le A 26 394 - 51 -
CA002006427A 1988-12-23 1989-12-21 Light-polarizing films or sheets containing stilbene dyestuffs Abandoned CA2006427A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3843411 1988-12-23
DEP3843417.2 1988-12-23
DEP3821669.1 1989-07-01
DE3921669A DE3921669A1 (en) 1988-12-23 1989-07-01 LIGHT-POLARIZING FILMS OR FILMS CONTAINING STYLE DYES

Publications (1)

Publication Number Publication Date
CA2006427A1 true CA2006427A1 (en) 1990-06-23

Family

ID=25875521

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002006427A Abandoned CA2006427A1 (en) 1988-12-23 1989-12-21 Light-polarizing films or sheets containing stilbene dyestuffs

Country Status (4)

Country Link
US (1) US5007942A (en)
EP (1) EP0374655B1 (en)
JP (1) JPH02269136A (en)
CA (1) CA2006427A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5785718A (en) * 1996-05-31 1998-07-28 Bayer Aktiengesellschaft Substantive stilbene-azo dyestuffs

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0296102A (en) * 1987-11-02 1990-04-06 Sumitomo Chem Co Ltd Polarizing film consisting of dye system
ATE118621T1 (en) * 1988-03-08 1995-03-15 Toray Industries POLARIZATION FILTER.
US5272259A (en) * 1988-12-23 1993-12-21 Bayer Aktiengesellschaft Stilbene dyestuffs and light-polarizing films or sheets containing stilbene
DE4019309A1 (en) * 1990-06-16 1991-12-19 Bayer Ag NEW LIGHT-POLARIZING FILMS OR FILMS AND DYES FOR THEIR PRODUCTION
US5286420A (en) * 1990-08-25 1994-02-15 Bayer Aktiengesellschaft Production of light polarizing films
DE4227591A1 (en) * 1992-08-20 1994-02-24 Basf Ag Use of liquid dye preparations containing a disazo dye in the ink-jet process and disazo dye
US5423100A (en) * 1992-08-26 1995-06-13 Mitsui Toatsu Chemicals, Inc. Water-soluble azo compounds and polarizing films using the compounds
RU2047643C1 (en) * 1993-05-21 1995-11-10 Хан Ир Гвон Material for polarizing coating
JP3680323B2 (en) * 1993-10-14 2005-08-10 住友化学株式会社 Dye-type polarizing film
EP1150142B1 (en) * 1998-12-18 2005-06-01 Nippon Kayaku Kabushiki Kaisha Color polarizer with support for liquid crystal projector and color liquid crystal projector
US6522468B2 (en) 1999-03-18 2003-02-18 Sumitomo Chemical Company, Limited Light-polarizing film
RU2178900C2 (en) 2000-02-25 2002-01-27 ОПТИВА, Инк. Dichroic polarizer and material for its manufacture
US7015990B2 (en) * 2000-04-24 2006-03-21 Nitto Denko Corporation Liquid crystal display including O-type and E-type polarizer
ES2269490T3 (en) * 2000-12-28 2007-04-01 Ciba Specialty Chemicals Holding Inc. DISCOUNT COLORS AND COPPER COMPLEX, FOR PAPER STAINING.
RU2207603C2 (en) * 2001-06-04 2003-06-27 Хан Ир Гвон Optical device for production and/or transformation of polarized electromagnetic radiation and optical device in the form of liquid crystalline display
US7113337B2 (en) 2001-07-10 2006-09-26 Nitto Denko Corporation Multilayer optical coating
US7053970B2 (en) * 2001-07-26 2006-05-30 Nitto Denko Corporation Liquid crystal display and the method of its fabrication
RU2226708C2 (en) * 2001-09-21 2004-04-10 ОПТИВА, Инк. Liquid-crystal display with reflection polarizer
US7931702B2 (en) * 2006-06-01 2011-04-26 Nippon Kayaku Kabushiki Kaisha Azo compound and salt thereof, and dye-containing polarizing film comprising the compound or salt
US8389122B2 (en) * 2006-06-13 2013-03-05 Nippon Kayaku Kabushiki Kaisha Azo compound and dye polarizing film containing the same
CN101479347B (en) 2006-06-22 2013-08-07 日本化药株式会社 Azo compound and dye polarizing film containing the same
KR20100028525A (en) * 2007-07-09 2010-03-12 미쓰비시 가가꾸 가부시키가이샤 Compound for anisotropic film
TWI406907B (en) * 2007-11-02 2013-09-01 Nippon Kayaku Kk Azo compounds and dye-containing polarizing films containing the same
KR101672555B1 (en) * 2008-05-20 2016-11-03 니폰 가야꾸 가부시끼가이샤 Azo compounds, and dye-based polarizing films and polarizing plates comprising the same
TWI444438B (en) * 2008-06-17 2014-07-11 Nippon Kayaku Kk Azo compound and salt thereof, and dye containing polarizing film and polarizing plate containing the same
CN110945083B (en) * 2017-07-28 2022-07-01 日本化药株式会社 Styrene compound or salt thereof, polarizing film, polarizing plate and display device

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3981558A (en) * 1973-11-12 1976-09-21 Timex Corporation Liquid crystal electro-optical display
US4007077A (en) * 1973-12-27 1977-02-08 Dai Nippon Toryo Kabushiki Kaisha Liquid crystal cells
JPS566430A (en) * 1979-06-27 1981-01-23 Fujitsu Ltd Manufacture of semiconductor device
US4396646A (en) * 1981-07-20 1983-08-02 Polaroid Corporation Method of making patterned polarizers
JPS59145255A (en) * 1983-02-07 1984-08-20 Nippon Kayaku Co Ltd Water-soluble disazo compound
GB2144760B (en) * 1983-08-04 1987-07-22 Photophysics Research Limited Light-polarsing material
JPS60156759A (en) * 1984-01-25 1985-08-16 Nippon Kayaku Co Ltd Water-soluble disazo compound
JPS60159705A (en) * 1984-01-30 1985-08-21 Sekisui Chem Co Ltd Polarizing plate
JPS60168743A (en) * 1984-02-14 1985-09-02 Nippon Kayaku Co Ltd Colored polyvinyl alcohol film
US4514559A (en) * 1984-04-27 1985-04-30 Nippon Kayaku Kabushiki Kaisha Water soluble disazo compound, copper salt thereof, and sheet or film colored therewith
JPS60230606A (en) * 1984-04-30 1985-11-16 Kuraray Co Ltd Polarizing film
CA1269555A (en) * 1984-11-16 1990-05-29 Sumitomo Chemical Company, Limited Light-polarizing film
JPS6289907A (en) * 1985-06-19 1987-04-24 Sumitomo Bakelite Co Ltd Transparent conductive film united with polarizing film
JPH0653012B2 (en) * 1985-06-27 1994-07-20 功 皆川 Fertilizer spraying equipment
JP2668784B2 (en) * 1987-09-11 1997-10-27 日本化薬株式会社 Manufacturing method of polarizing film
JP2510873B2 (en) * 1988-01-18 1996-06-26 日本化薬株式会社 Polarizer

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5785718A (en) * 1996-05-31 1998-07-28 Bayer Aktiengesellschaft Substantive stilbene-azo dyestuffs

Also Published As

Publication number Publication date
EP0374655B1 (en) 1993-09-15
JPH02269136A (en) 1990-11-02
EP0374655A1 (en) 1990-06-27
US5007942A (en) 1991-04-16

Similar Documents

Publication Publication Date Title
CA2006427A1 (en) Light-polarizing films or sheets containing stilbene dyestuffs
US5272259A (en) Stilbene dyestuffs and light-polarizing films or sheets containing stilbene
US7108897B2 (en) Dye type polarizing plate
JP3205096B2 (en) Water-soluble azo dye and polarizing film using the dye
KR20070117557A (en) Coloring matter for anisotropic coloring matter film, composition comprising said coloring matter, anisotropic coloring matter film, and polarizing element
US5340504A (en) Light-polarizing films containing dichroic dyes
WO1989004501A1 (en) Dye-containing polarizing film
JP2001240762A (en) Azo compound or salt thereof and dyestuff polarizing membrane containing the same
US5700296A (en) Azo compound and a polarizing film containing the same
DE3921669A1 (en) LIGHT-POLARIZING FILMS OR FILMS CONTAINING STYLE DYES
US20030098447A1 (en) Polyazo compound or salt thereof and dye-based polarization film containing the same
KR100724317B1 (en) Azo-compounds and dye polarizing films containing them
JP4815721B2 (en) Polyazo compound or salt thereof and dye-based polarizing film containing them
KR100824343B1 (en) Polyazo compound or salt thereof and dye-based polarization film containing the same
JPH0813932B2 (en) Water-soluble azo dye and polarizing film containing the same
JPH09230142A (en) Polarizing element or polarizing plate
JP3680323B2 (en) Dye-type polarizing film
JP3270536B2 (en) Water-soluble azo dye and polarizing film using the dye
JPH09302250A (en) Azo compound and dye-based polarizing film comprising the same
JP3617540B2 (en) Azo compound and polarizing film using the compound
JPH05295282A (en) Water-soluble azo dye and polarizing film produced by using the dye
US5213582A (en) Light-polarizing films or foils containing triphendioxazine or triphendithiazine dyes with good dichrditic properties
JPH02222459A (en) Stilbene dye
JP3803394B2 (en) Azo compound and polarizing film using the compound
US5618868A (en) Polarizing film of a hydrophilic polymer film containing a novel azo compound

Legal Events

Date Code Title Description
EEER Examination request
FZDE Discontinued