U.S. patent number 3,918,976 [Application Number 05/363,702] was granted by the patent office on 1975-11-11 for polyester film with anthroquinone dye for a photographic film support.
This patent grant is currently assigned to Fuji Photo Film Co., Ltd.. Invention is credited to Atsuaki Arai, Noburo Hibino, Masaki Okazaki, Kunihira Seto.
United States Patent |
3,918,976 |
Arai , et al. |
November 11, 1975 |
Polyester film with anthroquinone dye for a photographic film
support
Abstract
A polyethylene terephthalate film for an X-ray photographic film
support colored blue by one or more anthraquinone dyes represented
by the general formula ##SPC1## Wherein X represents a hydrogen
atom; an alkyl group having 1-15 carbon atoms; a cycloalkyl group;
an aryl group; an aryl group substituted by an alkyl group having
1-10 carbon atoms, a carboxyl group, or a halogen atom; an aralkyl
group; or an aralkyl group substituted by an alkyl group having
1-10 carbon atoms, a carboxyl group, or a halogen atom.
Inventors: |
Arai; Atsuaki (Minami ashigara,
JA), Okazaki; Masaki (Minami ashigara, JA),
Hibino; Noburo (Minami ashigara, JA), Seto;
Kunihira (Minami ashigara, JA) |
Assignee: |
Fuji Photo Film Co., Ltd.
(Minami ashigara, JA)
|
Family
ID: |
12888684 |
Appl.
No.: |
05/363,702 |
Filed: |
May 24, 1973 |
Foreign Application Priority Data
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May 24, 1972 [JA] |
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47-51500 |
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Current U.S.
Class: |
430/521;
250/472.1; 8/489; 8/512; 430/533 |
Current CPC
Class: |
G03C
1/7954 (20130101); G03C 1/83 (20130101); C09B
1/325 (20130101); C09B 1/514 (20130101) |
Current International
Class: |
C09B
1/00 (20060101); C09B 1/514 (20060101); C09B
1/32 (20060101); G03C 1/795 (20060101); G03C
1/83 (20060101); G03C 001/84 (); G03C 001/78 () |
Field of
Search: |
;96/84R,87R
;260/378,376,381,4R ;250/472 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1,937,486 |
|
Feb 1970 |
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DT |
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1,137,595 |
|
Dec 1968 |
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UK |
|
4,313,826 |
|
Jun 1968 |
|
JA |
|
Other References
Chemical Abstract, Vol. 74, 1971, No. 76715 k, Stepanov et al.
.
Hagashi et al., Chemical Abstract, Vol. 72, 1970, No.
95291u..
|
Primary Examiner: Bowers, jr.; Charles L.
Assistant Examiner: Brammer; J. P.
Attorney, Agent or Firm: Sughrue, Rothwell, Mion, Zinn &
Macpeak
Claims
What we claim is:
1. A photographic film having a support comprising a polyethylene
terephthalate film containing at least one compound represented by
the formula: ##SPC3##
wherein X represents a hydrogen atom; an alkyl group having 1-15
carbon atoms; a cycloalkyl group; an aryl group substituted by an
alkyl group having 1-10 carbon atoms, a carboxyl group, or a
halogen atom; an aralkyl group; or an aralkyl group substituted by
an alkyl group having 1-10 carbon atoms, a carboxyl group, or a
halogen atom, the size of said compound being less than the wave
length of visible light and said compound having been mixed with
said polyethylene terephthalate under melting condition and a
silver halide light-sensitive emulsion layer coated on said
support.
2. A support as claimed in claim 1 wherein the cycloalkyl group has
5 or 6 carbon atoms, the aryl group is monaryl and the aralkyl
group is monoaryl wherein the alkyl moiety has one or two carbon
atoms.
3. A support as claimed in claim 1 wherein from about 0.01 to about
0.5 g of the at least one compound represented by the general
formula is present per kilogram of the polyethylene terephthalate
film.
4. A support as claimed in claim 3 wherein the polyethylene
terephthalate has an intrinsic viscosity of from about 0.55 to
about 0.70, determined in a 1:1 by weight mixture of phenol and
tetrachloroethane at 25.degree.C.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a polyester film to be used as a
support in a light-sensitive photographic film, and more
particularly, to a polyester film for a photographic film support
colored blue by an anthraquinone dye.
2. Description of the Prior Art
Light-sensitive photographic films having a colored support are
known. It is desirable that in light-sensitive photographic
materials, particularly in X-ray photographic films, the film
support be colored blue to facilitate the discrimination of
photographic images. The photographic image formed on an X-ray
photographic film prepared by coating an X-ray photographic
emulsion on a colorless support film has a soft, poor black tone,
and hence it is not easy to clearly see the images formed thereon.
This means that when the spectral absorption of the developed
silver of the X-ray film is measured, the absorption in the short
wave length region is large.
Accordingly, to correct this fault, the support film is typically
colored using a blue dye having absorption in the long wave length
region. That is to say, the image of an X-ray photographic film
having a support film colored with a blue dye has a sharp or clear
black tone, and can be easily distinguished.
Further, when a support film colored using a dye having absorption
in the short wave length region is used as the support for an X-ray
photographic film of the type where a photographic emulsion such as
a gelatino silver iodobromide emulsion is coated on both surfaces
thereof, a filter desensitization action occurs at X-raying.
For the above purposes, the dyes used for coloring a polyester film
for an X-ray photographic film support are required to satisfy
various requirements, i.e., to have good heat resistance,
sublimation resistance, miscibility with the support film and to
have a proper color hue (less yellow component). Further, they must
be inactive to the gelatino silver halide emulsion to such an
extent that they do not have any harmful influence on the
photographic properties thereof, such as sensitivity, gamma, fog,
etc.
As described in U.S. Pat. Nos. 2,071,250 and 2,905,707, colored
polyester films can be prepared by conducting the polycondensation
of the components forming the polyester after adding a dye to at
least one component prior to the polycondensation, or by mixing a
powdery, chip-like or pellet-like polyester with a dye in any
proper manner, extruding the mixture into a colored molten sheet by
melt extrusion to form a substantially amorphous non-oriented film,
biaxially stretching the sheet to about 2.5 times its original
dimensions, and heat-treating to provide a film having dimensional
stability. Such a method as described above in which the molten
material is colored before it is formed into a sheet or film is
excellent as compared to other methods in the point that a
uniformly colored polyester film is obtained.
Since the industrial production of polyester films is conducted by
a melt extruding method with heating, the coloring dye used is
required to have good heat resistance, i.e., it should be capable
of enduring temperatures of 270.degree.C to 320.degree.C. A
polyester film has a stable physical structure and hence it is not
easy to color the film by dyeing. Therefore, it is preferred, as
mentioned above, to employ the method in which the coloring matter
is dispersed or dissolved in the polyester by adding it during the
synthesis of the polymer or at melting the polymer during heating
for molding or fabrication. Therefore, the coloring dye used is
required to have a high heat stability so as to endure molding
temperatures of 270.degree.C to 320.degree.C and not decompose and
fade. The above-mentioned method of coloring a polyester before it
is formed into a sheet or film also has the advantage that it does
not need an additional coloring step because the coloring is
conducted in the molding step.
Polyester is formed into film through the steps of drying, melting
by heating, extruding, stretching and heat-treating. Among those
steps, the drying step is preferably conducted under reduced
pressure at temperatures of 135.degree.C to 210.degree.C (as
described in the specification of Japanese patent publication No.
618/1953). If a drying step is not employed in the case of forming
a polyester film, hydrolysis occurs upon melting the polyester by
heating, which results in making the formation of a film impossible
or producing a film having poor properties, e.g., low strength.
On the other hand, a polyester film is usually produced using a
tenter system, and hence edge loss is inevitable. For reuse of the
cut-off edges of the polyester film, they are collected,
pulverized, and dried with fresh polyester chips. When the
polyester film has been colored with a dye having poor sublimation
resistance, the dye used for the coloring sublimates from the
cut-off edges during drying. Consequently, not only is dye lost by
sublimation, but the dye thus sublimated stains the dryer, and
further the sublimed dye is deposited on the inside wall of the
dryer and falls down therefrom to cause uneven coloring.
Furthermore, when extruding polyethylene terephthalate from an
extrusion die onto a die casting drum for cooling, the die is apt
to sublimate.
Also, when polyester is colored with a prior art coloring matter or
dye as described above, the coloring matter or dye sublimates at
extruding to stain the casting drum to give an uneven dye density
in the colored film. Therefore, it is necessary to color polyesters
using coloring matter or a dye which has good sublimation
resistance.
When coloring a molten polyester, it is necessary that the coloring
dye be easily and uniformly dispersed or dissolved in the polyester
and, in particular when the colored polyester is used as a support
for a photographic film, the polyester is required to provide a
film having high transparency and a surface free of optical
defects. Therefore, turbidity cannot be formed in the support film
caused by insufficient dispersion of the coloring matter or foreign
matter present in the support film.
As is well known, in order to obtain a polyester film having useful
properties it is necessary that an amorphous, non-oriented
polyester film prepared by melting and extruding be subjected to
stretching and a heat treatment under proper temperature
conditions, and even if coloring matter has been uniformly
dispersed without reducing the transparency of the film in the
amorphous and non-oriented film, it sometimes happens that spaces
are formed between the fine dispersed particles of the dye or
coloring matter which do not undergo plastic deformation when the
polyester itself undergoes plastic deformation in the subsequent
stretching step, which results in increasing light scattering to
causes turbidity or clouding of the film.
Therefore, in the case of producing a film support for photographic
films, care must be taken so that the coloring matter is dispersed
in the polyester as very fine particles or is dissolved in the
polyester as a molecular dispersion to prevent the formation of
spaces which increase the scattering of light in the film in the
stretching step.
Typical of the processes use to produce polyester films in
accordance with the present invention are those described in U.S.
Pat. No. 3,488,195 Hunter and the references described therein.
This reference discloses various extrusion, biaxial orientation and
like procedural steps, especially at column 2, which can be used
with the film of the present invention. See especially U.S. Pat.
No. 2,779,684 Alles and U.S. Pat. No. 2,823,421 Scarlett, cited in
this patent.
SUMMARY OF THE INVENTION
One object of this invention is thus to provide a coloring matter
or a dye for coloring a polyester for use as the support of a
photographic material satisfying the heretofore described severe
conditions regarding photographic properties, heat resistance,
sublimation resistance and color hue.
That is to say, according to this invention there is provided a
polyester film for use as a support of a photographic film
comprising a substantially homogeneous mixture of a polyester and a
1,4-diarylaminoanthraquinone dye.
In greater detail, the inventors discovered that the coloring
matter or dye represented by general formula I satisfies the
above-described requirements necessary for photographic films, in
particular, X-ray photographic films: ##SPC2##
wherein X represents a hydrogen atom; an alkyl group having 1-15
carbons atoms, a cycloalkyl group; an aryl group; an aryl group
substituted by an alkyl group having 1-10 carbon atoms, a carboxyl
group, or a halogen atom; an aralkyl group or an aralkyl group
substituted by an alkyl group having 1-10 carbon atoms, a carboxyl
group, or a halogen atom.
Most highly preferred of the cycloalkyl groups are those having 5
or 6 carbon atoms, and of the aryl or aralkyl groups most highly
preferred are those which are monoaryl and, for aralkyl, where the
alkyl moiety has 1 or 2 carbon atoms. Within the classes
cycloalkyl, aryl or monoaryl, this narrow class offers superior
results.
The dye used in this invention is stable even if it is heated for
several hours at temperatures above 270.degree.C and further is not
decomposed even if the dye is heated while dispersed in a molten
polyester for more than 3 hours in the absence of air.
Also, it has been confirmed that the dye in this invention has a
particularly high sublimation resistance and that the uneven dyeing
occurring in the case of using ordinary dyes does not occur under
polymerization reaction condition (see U.S. Pat. No. 2,823,421 to
Scarlett) in which the polycondensation is conducted under high
vacuum after dispersing the dye in the components forming the
polyester or during the step of dispersing the dye in a molten
polyester at a high temperature under a high vacuum.
Still further, the dye of this invention is readily-soluble in
ordinary organic solvents such as petroleum saturated hydrocarbons,
aromatic hydrocarbons, aliphatic or aromatic halogenated
hydrocarbons, ethers, ketones and esters, and hence the dye is
suitable for producing an excellent colored support for
photographic films by using an ordinary colored subbing layer as
described in Japanese Pat. No. 13826/1968 on a transparent
synthetic high molecular weight film.
Specific examples of such solvents are benzene, toluene,
chloroform, methylene chloride, ethyl ether, tetrahydrofuran,
acetone, methyl ethyl ketone, ethyl acetate and butyl acetate.
DETAILED DESCRIPTION OF THE INVENTION
The polyester used in this invention includes not only those
consisting of only repeating units of ethylene terephthalate but
also those containing up to about 2% of another component or
components in addition to the repeating units of ethylene
terephthalate. As such other components there can be illustrated
isophthalic acid, phthalic acid, adipic acid, diethylene glycol,
triethylene glycol, propylene glycol, cyclohexane dimethanol, and
HO--CH.sub.2 --OH, where n is 3 or 8.
Specific examples of the dyes used in this invention are given
below, but the invention is not to be limited thereto.
Compound 1:
1,4-bis(2',6'-dimethyl-4'-hydroxyanilino)-anthraquinone,
Compound 2:
1,4-bis(2',6'-dimethyl-4'-methoxyanilino)-anthraquinone,
Compound 3:
1,4-bis(2',6'-dimethyl-4'-n-decyloxyanilino)-anthraquinone,
Compound 4:
1,4-bis(2',6'-dimethyl-4'-bezyloxyanilino)-anthraquinone,
Compound 5:
1,4-bis[2',6'-dimethyl-4'-(p-methyl)benzyloxyanilino]anthraquinone,
Compound 6:
1,4-bis[2',6'-dimethyl-4'-(o-methyl)benzyloxyanilino]anthraquinone,
Compound 7:
1,4-bis[2',6'-dimethyl-4'-(o-chloro)benzyloxyanilino]anthraquinone,
Compound 8:
1,4-bis(2',6'-dimethyl-4'-phenethyloxyanilino)-anthraquinone,
Compound 9:
1,4-bis(2',6'-dimethyl-4'-phenoxyanilino)-anthraquinone,
Compound 10: 1,4-bis[2'
,6'-dimethyl-4'-(p-tert-octyl)-phenoxyanilino]anthraquinone,
Compound 11: 1,4-bis[2'
,6'-dimethyl-4'-(p-carboxy)-phenoxyanilino]anthraquinone,
Compound 12: 1,4-bis(2'
,6'-dimethyl-4'-cyclohexyloxyanilino)-anthraquinone.
The dye, or a combination of the dyes of this invention, gives an
excellent color to a support for photographic films when it (or
they) is used in an amount of about 0.01 to about 0.5 g per
kilogram of the polyester chips. As one strays further and further
outside this preferred range, the excellent results obtainable
begin to decrease in effect. Accordingly, it is best to be within
the range 0.01 to 0.5 g per kilogram recited.
Most preferred polyester materials as are used in the present
invention have an intrinsic viscosity of about 0.55 to about 0.70,
determined in a mixture of phenol and tetrachloroethane (1:1 by
weight) at 25.degree.C. While it will be obvious to one skilled in
the art that this is not a limitative range, polyester materials
meeting this criterion are very suitable for use in forming
photographic film supports.
When the aminoanthraquinone dyes of the present invention are used
in dispersed form in the polyester, best results in forming a
photographic film support are obtained when the size thereof is
less than the wave length of visible light, most preferably, when
the diameter of any vacant spaces formed between the polyester
matrix and the particles of the dyes or coloring material is less
than one tenth the wave length of visible light (less than about
125 angstroms). Such a product illustrates amazingly low haze, and
while this parameter is not limitative, since final product
qualities will vary depending on the user, such a product is highly
preferred.
Many aminoanthraquinone dyes capable of giving a blue tone when
used for coloring molten polyester are known as described in, e.g.,
British Pat. Nos. 1,137,595 and 1,196,707, but dyes satisfying the
three factors of heat stability, sublimation resistance and color
hue in the case of coloring molten polyesters and in the steps of
stretching and heat treatment of the polyester film are scarcely
found among such known dyes. In particular, a preferred blue dye
used for coloring the support of an X-ray photographic film is one
having low absorption in the yellow region in the spectral
absorption spectra of the colored film. A dye having high
absorption in the yellow region is undesirable since the film
support colored by such a dye shows a yellowish blue-green hue and
loses its purity. From such view points, there are significant
restrictions on the selection of prior art dyes giving a desired
color.
As 1,4-diaminoanthraquinone dyes among the aminoanthraquinone dyes
useful for a support for a photographic film, the following dyes
are described in, e.g., U.S. Pat. No. 3,488,195, Japanese patent
publication No. 15187/1970, British Pat. No. 1,137,595 and Belgian
Pat. No. 700,302;
Compound A: 1,4-bis(2',6' -diethylanilino)anthraquinone
Compound B: 1,4-bis(2',6' -trimethylanilino)anthraquinone and the
following dyes are described in British Pat. No. 1,196,707 and
Belgian Pat. No. 715,614.
Compound C: 1,4-(2',6' -triethylanilino)anthraquinone,
Compound D: 1,4-bis(2',3' ,5' ,6'
-tetramethylanilino)anthraquinone,
Compound E: 1,4-bis(2',3' ,4' ,5' ,6'
-pentamethylanilino)anthraquinone.
As is clear from the results of sublimation resistance comparison
tests made using typical examples of the dyes of this invention and
the aforesaid known dyes, the 1,4-diarylaminoanthraquinone dyes
used in this invention are superior to known
1,4-bis(alkyl-substituted anilino)anthraquinone dyes as shown
above, and hence the dyes of this invention do not cause uneven
coloring in the coloring of molten polyesters.
The sublimation resistance of the dyes was tested in the following
manner: 2 mg of the dye was placed in the bottom of a hard glass
test tube having an inside diameter of 18 mm and a length of 200
mm, and then 10 g of polyethylene terephthalate chips (4 mm .times.
4 mm .times. 2.5 mm) was placed on the dye. Several of such test
tubes, each containing a different dye, were prepared, connected to
vacuum pipe lines and evacuated for 5 minutes under a pressure of
0.1 mm.
Then, while connected to the vaccum pipe lines, the test tubes were
immersed in an oil bath heated to 180.degree.C .+-. 2.degree.C to
2/3 the whole length of the tubes, and after continuing the
evacuation and heating for 4 hours, the test tubes were
withdrawn.
In all cases, it was observed that the dye had migrated up the
stack of polythylene terepthalate chips placed on the dye, with a
dye density distribution from the bottom of the polyethylene
terephthalate in contact with the dye to the top of the
polyethylene terepthalate chips. This was due to the sublimation of
the dye and absorption of the dye by the polythlene terepthalate
The more the dye had moved up the layer of polyethylene
terepthalate chip the greater the degree of sublimation. The
results are shown in the following table, which shows the dyes of
this invention are excellent in sublimation resistance.
Comparison of Sublimation Resistances of Dyes
______________________________________ Tested dyes Sublimation
resistance (distance the sublimated dye moved)
______________________________________ Dye of this invention
Compound 1 4 mm Compound 3 5 mm Compound 4 6 mm Compound 6 5 mm
Compound 8 4 mm Comparison dye Compound A 50 mm Compound B 48 mm
Compound C 40 mm Compound D 43 mm
______________________________________
Synthesis examples of typical dyes used in this invention are
described below:
SYNTHESIS EXAMPLE 1
Synthesis of 1,4-bis(2',6'
-dimethyl-4'-hydroxyanilino)anthraquinone (Compound 1):
A mixture of 9.0 g of 1,4,9,10-tetrahydroxyanthracene, 4.2 g of
2,6-dimethyl-4-hydroxyaniline, 4.2 g of boric acid, and 40 ml of
n-butanol was refuxed at normal pressure for 25 hours in an oil
bath at 100.degree.-115.degree.C. The reaction product was cooled
to room temperature and after adding thereto 3 ml of 6 N
hydrochloric acid followed by stirring, the solid product was
collected by filtration, washed with water and dried. The crude
product was purified by means of column chromatography using silica
gel (Merck Kieselgel-60) and recrystallized from
chloroform-methanol (1:1 volume) to provide compound 1 as
blue-violet crystals. The amount of the crystals was 6.8 g and
their melting point was above 320.degree.C.
Visible absorption spectrum: .lambda..sub.max.sup.acetone : 375 nm,
543 nm (sh), 586 nm, and 631 nm.
Elementary analysis: Found: C; 75.15%, H; 5.56%, N; 5.85%.
Calculated as C.sub.30 H.sub.26 O.sub.4 N.sub.2 : C; 75.29%, H;
5.48%, N; 5.85%.
From the results of the above analyses and the results of
measurements of the nuclear magnetic resonance absorption spectra
and mass spectra, it was confirmed that the compound prepared in
this synthesis example was 1,4-bis(3',6'
-dimethyl-4'-hydroxyanilino)anthraquinone.
SYNTHESIS EXAMPLE 2
Synthesis of 1,4-bis(2',6'
-dimethyl-4'-n-decyloxyanilino)anthraquinone (Compound 3):
1. Synthesis of 2,6-dimethyl-4-n-decyloxyaniline:
After dissolving 6 g of metallic sodium in 300 ml of absolute
ethanol, 40 g of 2,6-dimethyl-4-hydroxyaniline was added to the
solution. Then, while refluxing the solution at normal pressure
while heating, 55 g of decyl bromide was added dropwise to the
solution over a period of 30 minutes and the mixture was heated at
the boiling point of the solvent at normal pressure for 2 hours.
After removing ethanol by distillation at normal pressure, the
residue was dissolved in ethyl ether. The solution was washed with
a 0.1 N aqueous sodium hydroxide solution and then water and dried
over Glauber's salt. After distilling away ether, the residue was
distilled at 162.degree.-163.degree.C at 0.5 mm Hg and a liquid
having a boiling point of 162.degree.-163.degree.C/0.5 mm Hg was
obtained.
(2) Synthesis of 1,4-bis(2',6'
-dimethyl-4'-n-decyloxyanilino)anthraquinone:
A mixture of 4.8 g of 1,4,9,10-tetrahydroxyanthracene, 9.5 g of
2,6-dimethyl-4-n-decyloxyaniline and 4.0 g of boric acid was
refluxed for 48 hours at normal pressure in an oil bath at
140.degree.-160.degree.C under a nitrogen gas blanket. The reaction
product was cooled and dissolved in 100 ml of chloroform. The
solution was washed with 6 N hydrochloric acid and then the
chloroform layer thus formed was washed with water until it became
neutral, dried over Glauber's salt, and concentrated by reduced
pressure disillation. By recrystallizing the residue from ethanol,
6.5 of the compound was obtained as blue-violet crystals. The
melting point was 100.degree.-101.degree.C.
Visible absorption spectrum: .lambda..sub.max.sup.acetone : 544
nm(sh), 584 nm and 628 nm.
Elementary analysis: Found: C; 79.21%, H; 8.85%, N; 3.77%.
Calculated as C.sub.50 H.sub.66 O.sub.4 N.sub.2 : C; 79.11%, H;
8.76%, N; 3.69%.
From the above results, it was confirmed that the compound prepared
in this synthesis example was 1,4-bis(2',6'
-dimethyl-4'-n-decyloxyanilino)anthraquinone.
SYNTHESIS EXAMPLE 3
1,4-bis(2',6' -dimethyl-4'-benzyloxyanilino)anthraquinone (Compound
4):
(1) Synthesis of 2,6-dimethyl-4-benzyloxyaniline:
40 g of 2,6-dimethyl-4-hydroxyaniline was added to a solution of 6
g of metallic sodium in 250 ml of anhydrous ethanol and after
dropwise adding 32 g of benzyl chloride to the solution during 1
hour at refluxing temperature, the mixture was further heated under
reflux for 2 hours. The reaction mixture above obtained was worked
up similar to this method described in Example 2 - (1), and the
residue was distilled to give a fraction having a boiling point of
145.degree.C/0.5 mm Hg. The product was allowed to stand and
solidified. The melting point thereof was 71.degree. -
72.degree.C.
2,6-Dimethyl-4-benzyloxyaniline was also produced by the following
method.
A mixture of 51 g of the 2,6-dimethyl-4-hydroxy-4'-sulfoazobenzene
(Compound 2) prepared according to the method described in Example
1, 13.3 g of sodium hydroxide, 250 ml of ethanol, and 250 ml of
water was heated to 45.degree. - 50.degree.C, and, while stirring
the homogeneous solution thus prepared, 32 g of benzyl chloride was
added to the solution. The resulting mixture was reluxed for 1.5
hours, whereby a solid precipitated. After distilling away ethanol
under reduced pressure, the precipitate was collected by
filtration, washed with water and dried to give 54.5 g of the
sodium salt of 2,6-dimethyl-4-benzyloxy-4'-sulfoazobenzene.
The product was added to 2000 ml of water containing 60 g of sodium
hydroxide and after heating the mixture to 40.degree.-50.degree.C,
200 g of sodium hydrosulfite was added. After heating at 80.degree.
- 90.degree.C for a further 2 hours, the reaction mixture was
cooled and extracted twice with 300 ml of ethyl ether. The ether
layer separated was washed with water, dried over anhydrous sodium
sulfate, and ether was evaporated.
By recrystallizing the residue from benzene-petroleum ether (1:2 by
weight), 25 g of the desired product was obtained as acicular
crystals having a melting point of 73.degree.-74.degree.C.
Elementary analysis: C; 79.19, H; 7.55, N; 5.99% (calculated for
C.sub.15 H.sub.17 NO: C; 79.26, H; 7.54, N; 6.16%).
(2) Synthesis of 1,4-bis(2',6' -dimethyl-4'-benzyloxy-anilino)
anthraquinone:
A mixture of 2.4 g of 1,4,9,10-tetrahydroxyanthracene, 9.0 g of
2,6-dimethyl-4-benxyloxyaniline and 2.0 g of boric acid was heated
at 160.degree.C for 16 hours and the reaction mixture thus obtained
was treated in the same manner as described in Example 2. Then, by
purifying the crude dye obtained by column chromatography using
SiO.sub.2 and recrystallizing it from ethanol, 3.7 g of Compound 4
was obtained as blue-violet acicular crystals. The melting point of
the dye was 193.degree.-194.degree.C.
Visible absorption spectra: .lambda..sub.max.sup.acetone : 544 nm
(sh), 582 nm, and 626 nm.
Elementary analysis: C; 80.45%, H; 5.71%, N; 4.11% (calculated for
C.sub.44 H.sub.38 O.sub.4 N.sub.2 : C; 80.22%, H; 5.81%, N;
4.25%).
Infrared absorption spectra: .nu. : 1580 cm.sup..sup.- 1,
1491cm.sup.-.sup.1, 1256 cm.sup.-.sup.1, 1158 cm.sup.-.sup.1.
Nuclear magnetic resonance spectra (in deutero-chloroform)
(.delta.,ppm):
2.17 (singlet) Ar--CH.sub.3 5.02 (singlet) --OCH.sub.2 Ar 6.55
(singlet) anthraquinone nucleus H 6.73 (singlet) aniline nucleus
Ar--H 7.38 (singlet) benzyl nucleus Ar--H 7.71 (multiplet)
anthraquinone nucleus H 8.41 (multiplet) anthraquinone nucleus H
11.69 (broad singlet) NH
From the above results, the compound obtained in this example was
confirmed to be 1,4-bis(2',6'
-dimethyl-4'-benzyloxyanilino)anthraquinone.
SYNTHESIS EXAMPLE 4
1,4-bis(2',6' -dimethyl-4'-phenethyloxyanilino)anthraquinone
(Compound 8):
(1) Synthesis of 2,6-dimethyl-4-phenethloxyaniline:
The same procedure as in Example 3-(1) was conducted using 46 g of
phenethyl bromide in place of benzyl chloride and the reaction
mixture was then treated by an ordinary method as in Example 2. By
recrystallizing the crude product thus obtained from benzene,
2,6-dimethyl-4-phenethyloxyaniline having a melting point of
60.degree.-61.degree.C was obtained.
(2) Synthesis of 1,4-bis(2',6'
-dimethyl-4'-phenethyloxyanilino)anthraquinone:
The same procedure as described in Example 3-(2) was followed using
9.6 g of 2,6-dimethyl-4-phenethyloxyaniline in place of
2,6-dimethyl-4-benzyloxyaniline, and the reaction mixture obtained
was subjected to a similar treatment to the method as in Example
2-(2). The crude product obtained was purified by column
chromatography using SiO.sub.2 and recrystallized from ethanol to
give 4.9 g of anthraquinone dye as blue-violet crystals. The
melting point of the compound was 136.0.degree.-137.0.degree.C.
Visible absorption spectra: .lambda..sub.max.sup.acetone : 544 nm
(sh), 582 nm, 626 nm.
Elementary analysis of the compound: C, 80.73%, H, 6.15%, N, 4.13%
(calculated for C.sub.46 H.sub.42 O.sub.4 N.sub.2 : C, 80.44%, H,
6.16%, N, 4.08%).
Infrared absorption spectra: .lambda. : 1580 cm.sup.-.sup.1, 1495
cm.sup.-.sup.1, 1264 cm.sup.-.sup.1, 1160 cm.sup.-.sup.1.
Nuclear magnetic responance spectra (in deutero-chloroform
solution) (.delta., ppm): ##EQU1##
From the above results, the compound obtained in this example was
confirmed to be 1,4-bis(2'
,6'-dimethyl-4'-phenethyloxyanilino)anthraquinone.
The following examples are intended to illustrate the present
invention but not to limit it in any way. In all examples, unless
otherwise indicated, polyethylene terephalate having an intrinic
viscosity of [.eta.] = 0.67 was employed.
EXAMPLE 1
The dye (Compound 4 ) prepared in Synthesis example 3-(2) was mixed
with polyethylene terephthalate chips (the chips had a size of 4 mm
.times. 4 mm .times. 2.5 mm; chips of this size were used in all
examples where chips were used, unless otherwise indicated) and the
mixture was kneaded and formed into a film by melt extrusion at
290.degree.C so that the film prepared contained 0.025 weight %
dye. The film was then stretched to give a blue film having a
thickness of 0.180 mm. The stretching conditions were: first step,
3.5 times at 85.degree.C; second step, 3.5 times at 100.degree.C.
No reduction in transparency and no formation of clouds or
turbidity due to nondispersed particles was observed in the film.
The casting drum was also not stained by the dye during the
formation of the film.
Both surfaces of the film were irradiated with ultraviolet rays for
1 minute at 80.degree.C in air by means of a 1 KW quartz mercury
lamp as described in Japanese patent publication No. 2603/1968, and
then a gelatin dispersion having the following composition was
coated on the surfaces and dried for 2 minutes at 120.degree.C to
give a gelatin dispersion layer about 6 microns thick.
______________________________________ Gelatin 1 part by weight
Acetic acid 1 " Methanol 20 " Acetone 60 " Methylene chloride 10 "
Trichloroethane 5 " Phenol 5 "
______________________________________
A gelatino silver iodobromide emulsion for X-ray photographic film
containing 100 g of silver iodobromide, 30 g of gelatin and 1 mol%
of silver bromide was coated on the subbing layers to give a
medical X-ray photographic film. The emulsion layer thickness was 6
microns. The image obtained by X-raying through a human body using
the medical X-ray film and developing it could be easily
distinguished as a clear image, and the photographic properties
such as sensitivity, gamma and fog were not affected.
When the X-ray photographic film was stored under severe
temperature and humidity conditions, no change was observed in the
color of the support of the photographic film before and after the
development.
EXAMPLE 2
Both surfaces of a polyethylene terephthalate film having a
thickness of 180 microns were irradiated with ultraviolet rays for
1 minute at 80.degree.C. in air using a 1 KW quartz mercury lamp as
described in Japanese patent publication No. 2603/1968, and
thereafter a gelatin dispersion having the following composition
was immediately applied to the surfaces and dried for 2 minutes at
120.degree.C.
______________________________________ Gelatin 1 part by weight
Water 1 " Salicylic acid 0.3 " Methanol 20 " Acetone 60 " Benzyl
alcohol 3 " Methylene chloride 14 " o-Chlorophenyl 3 "
1,4-Bis(2',6'-dimethyl-4'- phenethyloxyanilino)- anthraquinone
(compound 8) 0.2 " ______________________________________
a gelatino silver iodobromide X-ray photographic emulsion
containing 100 g of silver iodide, 60 g of gelatin and 3 mol% of
bromine was coated on the surfaces of the colored subbing layers
which had been applied to both surfaces of the polyethylene
terephthalate film to yield a medical X-ray film. The thickness of
the emulsion layer was 7 microns. No harmful influence was observed
on the photographic characteristics of the X-ray photograph
obtained by X-raying through a human body using the X-ray film.
Also, no stains were observed on the developing machine or in the
developer used.
On the other hand an X-ray film was prepared in the same way using
a comparison dye, 1,4-bis(2' ,4'
,6'-trimethylanilino)-anthraquinone (Compound B) in place of the
dye of the invention in the composition of the subbing layer, and
the film developed in an automatic developing machine. In this case
the developer was colored blue.
EXAMPLE 3
A mixture of 7 parts by weight of the dye (Compound 8) prepared in
Synthesis Example 4 and 3 parts of 1,4-bis[2' ,4'
,6'-trimethyl-3'-(cyelohexylamido)sulfoanilino]anthraquinone was
mixed [The chips and dye were blended in the dry state and melt
extruded 290.degree.C.] with polyethylene terephthalate chips so
that the film prepared from the mixture contained 0.025% dyes and
then an oriented polyethylene terephthalate film colored
blue-violet and having a thickness of 0.180 mm was prepared as in
Example 1.
The film thus obtained had high transparency and a slightly reddish
blue-violet color as compared with the film obtained in Example 1.
No stains on the casting drum were observed at the formation of the
film.
Both surfaces of the film thus prepared were irradiated with
ultraviolet rays in the manner described in Example 1 and coated
with a subbing layer coating composition having the same
composition as in Example 1, followed by drying. Then, a gelatino
silver iodobromide emulsion for an X-ray photographic film
containing 100 g of silver iodobromide, 60 g of gelatin, and 3 mol%
of silver iodide was coated thereon to give a medical X-ray film.
The silver image obtained by X-raying a human body using the X-ray
film could easily be distinguished as a clear image, and the
photographic characteristics such as sensitivity, gamma and fog did
not change as compared with those of a control film.
EXAMPLE 4
A mixture of 9.5 parts of the dye (Compound 3) prepared in
Synthesis Example 2 and 0.5 part of 4,8-dihydroxy-1,5-bis(2' ,4'
,6'-trimethylanilino)anthraquinone was mixed with polyethylene
terephthalate chips so that the film prepared from the mixture
contained 0.020% dyes, and an oriented film colored blue-violet of
a thickness of 0.180 mm was prepared by the same casting method as
in Example 1.
The film thus obtained had uniformly dispersed dyes therein and
high transparency. Then, a medical X-ray film was prepared by
forming subbing layers on both surfaces of the film and then
applying to the subbing layers the gelatino silver iodobromide
emulsion for X-ray film used in Example 1 in the same manner as in
Example 1.
By ordinary exposure and development, the medical X-ray film gave
an image which could quite easily be distinguished as a clear
image, and the photographic characteristics were almost the same as
those of a control film.
Also, the color of the support film did not change when the
photographic film was stored for a long period of time or when the
photographic film was developed.
EXAMPLE 5
A mixture of 8.7 parts of [1,4-bis(2'
,6'-dimethyl-4'-benzyloxyanilino)anthraquinone] (Compound 4) and
1.3 parts of 1-p-phenethloxyanilino-4-hydroxyanthraquinone was
mixed with polyethylene terephthalate chips as in Example 1 so that
the film prepared from the mixture contained 0.020% dyes, and an
oriented film, which was colored blue and had a thickness of 0.180
mm was prepared from the mixture as in Example 1.
The colored film thus obtained had the same properties as those of
the film obtained in Example 4.
EXAMPLE 6
A colored polyethylene terephthalate film was prepared using a
mixture of 8.8 parts of [1,4-bis(2'
,6'-dimethyl-4'-benzyloxyanilino)anthraquinone] (Compound 4) and
1.2 parts of 1-p-benzyloxyanilino-4-hydroxyanthraquinone according
to the procedure of Example 5. The colored film thus obtained had
the same properties as those of the film prepared in Example 4.
EXAMPLE 7
A colored film was prepared using a mixture of 5.5 parts of
1,4-bis(2' ,6'-dimethyl-4'-phenethyloxyanilino)anthraquinone
(Compound 8) and 4.5 parts of 1,4-bis[2'
,6'-dimethyl-4'-(o-methyl)benzyloxyanilino]anthraquinone (Compound
6) according to the procedure of Example 5. The colored film thus
obtained had properties the same as those of the film prepared in
Example 4.
While the invention has been described in detail and with reference
to specific embodiments thereof, it will be apparent to one skilled
in the art that various changes and modifications can be made
therein without departing from the spirit and scope thereof.
* * * * *