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Патент USA US2848302

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United States Patent 0 ”"
‘i
2,848,296
Patented Aug. 19, 1958
2
?bers, a prime example of vinylidene cyanide interpoly~
2,848,296
mer ?bers present an even greater dyeing problem since
they contain no carboxyl groups and hence there is no
PROCESS FOR THE BASIC DYEIL‘IG 0F VINYLI
DENE CYANIDE INTERPOLYMERS
Hansjiirg Heller, Basel, Switzerland, assignor to The B. F.
Goodrich Company, New York, N. Y., a New York
corporation
No Drawing. Application November 17, 1955
Serial No. 547,550
7 Claims. (Cl. 8-55)
'10
This invention relates to methods for enhancing the
dyeability of certain types of synthetic ?bers, and more
particularly relates to a process for dyeing vinylidene
cyanide interpolymer ?bers involving the use of certain
speci?c aromatic acids in basic dye baths as promoters to
improve the pickup of the basic dyes by the ?bers. '
driving force or ionic charge to help the dye enter the
?bers. Weak, easily scoured 01f colo-rings result from
attempts to apply basic dyes to these ?bers.
In considering this problem I have postulated that the ’
carboxyl groups do not have to be tied to the polymer
chains to bring about dye ?xation-and that certain aro
matic acids useful as developers for basic dyes should be
capable, when applied to vinylidene cyanidezvinyl acetate
copolymer ?ber either before dyeing or right in the dye
bath, of ?xing basic dyes in the ?ber. In order that an
acid be suitable for this purpose, it should be able to
penetrate the ?ber to be dyed and simultaneously to form
an insoluble lake with the basic dye. This mechanism is
entirely different from the action of the swelling agents
set out above. A conventional swelling agent opens up
Vinylidene cyanide ?ber-forming interpolymers are de
scribed in U. S. Patents Nos. 2,615,865 through 2,615,880,
2,628,954, 2,650,911, 2,654,724, 2,654,728, 2,657,197,
2,716,104 through 2,716,106, and in copendiug applica
20
tions Serial Nos. 402,823, ?led January 7, 1954, now Pat
ent No. 2,786,046, and 407,595, ?led February 1, 1954, ‘
now abandoned. As described therein, synthetic ?bers
spun from such interpolymers possess unusually high
the ?ber structure and allows a more rapid establishment
of normal distribution equilibrium of the dye between
dye bath and ?ber. A swelling agent acts on the ?ber,
whereas the acid developer should interact with the dye
itself.
This invention represents the successful application of
25 this approach to the problem.
strength and other desirable properties.
To be of value to the trade, however, any synthetic
An object of this invention is to provide an economical
?ber produced must be readily and successfully dyeable, - process for treating vinylidene cyanide interpolymer ?bers
preferably with the dyes and techniques currently in use.
to render them more readily dyeable with basic dyes.
Like many hydrophobic synthetic ?bers and ?laments,
Another object is to provide a process of dyeing vinylidene
30
those made from vinylidene cyanide interpolymers have
cyanide interpolymerr?bers that will not require expen
slick, smooth surfaces and are resistant to penetration by
sive materials, high temperatures, or potentially toxic
ordinary dyestuffs. Further, these polymeric ?bers offer
concentrations of chemicals.
a minimum of points or molecular groups to which dye
Yet another object is to provide vinylidene cyanide in
molecules may become a?‘ixed. Heretofore, the dyeing
terpolymer ?bers, ?laments, yarns and fabrics, which are
35
of vinylidene cyanide interpolymer ?bers with basic dyes
dyeable with standard, commercially available, basic dyes;
alone has produced weakly colored ?bers lacking in at
which possess, when so dyed, light, cleaning and launder
tractiveness and in resistanceto laundering.
ing fastness comparable to dyed woolen ?bers and fabrics.
One expedient to encourage dye penetration is to open
Still another object is to provide materials which when
the ?ber structure by the action of a swelling agent.
added to a basic dye bath enter the synthetic ?bers to be
Swelling agents are often applied to the ?bers before the 40 dyed and in turn react with the dye to form an insoluble
?bers are immersed in the dye bath, or they may be added
lake or color which is fast to scouring.
directly to the dye bath. Phenylphenol, benzoic acid and
These and other objects are attained according to this
mono-chlorobenzene have been used in pre-dye treat
invention by treating vinylidene cyanide interpolymer
ments. Swelling agents useful for incorporation into the
?bers with an aromatic acid selected from the group con
dye bath include: aromatic amines such as aniline, p 45 sisting of 2-hydroxy-3-naphthoic acid (also known as
chloroaniline, alpha-napththylamine and m-toluidine,
nitroaromatic compounds such as p-nitrotoluene, o-nitro
toluene, nitrobenzene, m-dinitrobenzene and p-nitrodi
phenyl as well as methyl salicylate, salicylic acid, chloro
salicyclic acid, quinoline, isoquinoline, acetophenone,
chloroacetophenone, N,N-diphenyl formamide, N,N-di
phenyl acetamide and benzaldehyde. The use of these
and similar materials, however, can result in increased
cost and may require extra care in handling to avoid the
effects of odious and toxic vapors.
beta-hydroxynaphthoic acid) and N-beta-naphthyl-beta
alanine and dyeing the ?bers with a basic dye. The
?bers may be treated with the acid developer immediately
after the ?bers are formed, as by spinning a solution of
the polymer through a spinnerette and then passing the
?laments so formed through a developer bath and then
to the dye bath, or, alternatively, and more simply, the
developer may be added directly to the dye bath and the
55 dye applied to the ?bers, or yarns, or fabrics made there
from, at any other desired time. It is desirable, but not
Basic dyes are salts of colored organic cations with
essential, that a conventional swelling agent also be
simple anions, which are usually inorganic in nature. In
present in the dye bath.
a basic dye this positive charge is found to be directly
When a number of other aromatic acid developers are
connected with the color of the dye, and destruction of
used
in place of 2-hydroxy-3-naphthoic acid and N-beta~
the charge always results in loss of color. The charge 60 naphthyl-beta-alanine it is sometimes possible to achieve
has been found to be distributed over a large area of the
better dyeing results than when either the basic dye or
cation of a basic dye, which results in an unusually small
basic dye plus swelling agent is used alone, but the depth electrostatic potential of this dye cation. On hydrophilic
of shade and brilliance of hue in the color of the dyed
?bers such as wool and silk, basic dyes are largely ?xed
?bers is discovered to be outstandingly superior when
65
by an ion exchange mechanism:
either 2-hydroxy-3-naphthoic acid or N-beta-naphthyl
beta-alanine
is used. Other aromatic acids tested as
Fiber —COOH + DyeG3 ,2‘ Fibet~0009 DyeeB + 119’
The ionic mechanism is always complemented by adsorp
tion of the dye within the ?ber structure. In the case of
promoters of basic dyeing of vinylidene cyanide inter
polymer ?bers include: benzoic acid, phthalic acid, p
hydroxy benzoic acid, salicylic acid, p-arnino benzoic acid,
many synthetic ?bers adsorption becomes very important 70 anthranilic acid, and Z-naphthoic acid, among others.
since only a few incidental carboxyl groups are found in
Acetic acid has also been found to give results comparable
these ?bers. Vinylidene cyanidezvinyl acetate copolymer
to these aromatic acids.
2,848,296
Beta-hydroxynaphthoic acid or N-beta-naphthyl-beta
alanine gives good results in the practiceof this invention
4
when added to a standard wool dye bath at a concen
of fabric in the test beakers. The proper amount of
dispersion was added to each beaker and the beakers
were covered with watch glasses to reduce loss of mate
tration of 2% to 20% on weight of fabric (0. w. f.)
rial by steam distillation as the contents were heated to
with a preferred range of 8%. to 12% o. w. f. being. used
in most cases. The use of a swelling agent along with
boiling and held at that temperature for one-half hour.
Then 0.2 gram of a basic dye, dissolved in 30'grams of
the acid developer is preferred, for as shown ‘later,
water was added to each beaker and the bath was held
at boilfor one more hour. The dyeconcentration was
5' percent 0. w. f.
the two provide a synergistic action; better dyeing results
being obtained when both are used than when either‘
developer or swelling agent is-used alone with a basic
dye.
After a thorough cold water rinse, the dyed pieces
were scoured by boiling for 15 minutes in a water solution
'
As a class, basic dyes have higher a?inity for hydro
phobic ?bers than do other water-soluble dyes. The basic
dyes found on the market today (Astrazones, Genacryls
and Sevrons) have been formulated to give good‘ light 15
fastness on hydrophobic ?bers. They do not, however,
impart enough color to vinylidene cyanide interpolymer
containing 2 percent sodium N-methyl-oleoyl taurate and
2 percent sodium pyrophosphate, and 15 minutes in a
water solution containing 2 percent sodium N-methyl
oleoyl taurate and 2 percent sodium hydroxide.
Each of the fabric pieces was uniformly dyed to a deep
shade of the color produced by the dyeor mixture of
dyes used.
?bers to give acceptable fabrics when used without dye
bath additives.
B-naphthoic
Basic dyes are applied to textile materials by dissolving 20 weak shade
from them
the dye in water in dye bath vats to form a dye liquor,
In a run where only dye with no Z-hydroxy
acid was used, the test pieces dyed to a very
of the dye used and all color was removed‘
by the scourings. Dyes tested included:
usually at a ratio of one part of textile to 10 to 80
Sevron Brilliant Red 4G
parts of dye liquor, and usually at a concentration of 0.2v
Sevron Blue 2G
percent for light colors (e. g. yellows) to 10 percent for
Sevron Green B
extremely dark colors (e. g. blues, or blacks) of dye on 25 Genacryl Yellow 3G
weight of fabric (0. w. f.) to be dyed. The fabric to
Genacryl Orange G
be dyed is usually placed in the dye bath liquor at room
Genacryl Red GB
temperature and the bath is quickly heated to a boil.
Genacryl Blue 6G
Pressure systems are sometimes used to obtain higher
Genacryl Blue 6G 1/3 Blue-Green
30
bath temperatures. From the dye ‘ bath, the colored
Genacryl Yellow 36 1/3 Blue-Green
textiles are transferred to rinsing and scouring baths
Sevron Green B 1/3 Blue-Green
which remove all residual traces of the dye liquor, and
Genacryl Red 6B 1/3 Purple
then to driers which remove all moisture.
Genacryl Orange G 16 Purple
Any vinylidene cyanide interpolymer may be used.
35 Sevron Green B 1/3 Purple
Such interpolymers contain
Genacryl Yellow 3G 1/2 Orange
H ON
Sevron Brilliant Red 4G 1/2 Orange
it as
synthetic ?bers using basic dyes and beta-hydroxynaph
Colors fast to alkaline scour were produced on the
40 thoic acid.
groups in their structure, and the preferred interpolymers
are bicomponent interpolymers in which the vinylidene
cyanide residue shown alternates in 1 to 1 molar ratio
with the residue of the comonomers. Speci?c vinylidene
cyanide interpolymers which may be used are disclosed
in the patents and patent applications set forth in the
second paragraph hereof, the disclosures of which are
incorporated herein by'referenee. The most preferred
interpolyrner is the l to 1 molar interpolymer of vinyli
dene cyanide with vinyl acetate.
Advantages which may be cited for the synthetic mate
rials dyed by the process of this invention include com
plete penetration of the dye into the ?ber, and no change
in hand or feel of the fabric.
‘
The examples given below are intended only to illus
trate the striking advantages of this invention and are
not to be construed as a limitation upon the scope there
of, for there are, of course, numerous possible variations
and modi?cations that will be apparent to those skilled‘
in the art. In the examples all parts are by weight.’ “
Example 1
A supply of 100 percent vinylidene cyanidezvinyl ace
tate copolymer yarn was prepared following the teach
ings of U. S. Patent 2,615,866. The yarn was woven into
a fabric, bleached in a mixture of sodium chloride and
oxalic acid to remove dirt and any residual color cast, ‘
then cut into inch square pieces for dyeingrtests. Each. 7
inch square piece of fabric 'weighed approximately 4.0 "
grams.
Su?icient dispersion of 2-hydroxy-3-naphthoic acid was
made by mixing acid, wetting agent, and water at the
ratio of 0.8 gram of acid, 0.1 gram of sodium N-methyl
oleoyl taurate and 130 grams of water in a laboratory
blender to provide 40 grams of dispersion for each grant 75
Example 2
Inch square pieces of vinylidene cyanidezvinyl acetate
fabric weighing about 4 grams were placed in beakers,
separately covered with 160 grams of dispersions of
various additives at an additive concentration of 10 per?
cent 0. w. f. and heated at boil for one hour.
Next
Sevron Brilliant Red 4G basic dye was added, and the
bath boiled under watch glasses for one hour, Follow~
ing the dyeing step were a cold water rinse and one 15
minute alkaline scour also at a bath ratio of 40 to l.
The proportions used for each beaker and step were:
Step:
Proportions
Dyeing ______ __ 3 percent Sevron Brilliant Red 4G.
10 percent additive.
Scouring _____ ... 2 percent sodium N-methyl-oleoyl
'
'
taurate.
2 percent sodium hydroxide.
Percents are on weight of fabric (0. w. f.)_. Listed
below are the additives used and visual evaluation of
the color produced:
Additive:
Color produced
‘ Control—no additive ______ __ Very pale pink.
Beta-hydroxynaphthoic acid--. Brilliant red.
N-naphthyl-beta-alanine ____ __ Red.
Acetic acid _______________ ... Lighter than control.
o-Nitrotoluene ____________ _. Slightly darker than
control.
Acetophenone ____________ __ Same as control.
Beta-naphthol ____________ -2 Very slightly darker
than control.
Beta-naphthoic acid ________ _. Slightly darker than
control.
Anthranilic acid_>._‘__‘_______,._. Same as control.
2,848,296
5
6
Example 3
The depth of shade of each sample obtained with each
dye was rated visually from 1 to 5, 1 being lightest; 5 be
The procedure of Example 2 was followed using Gen
acryl Blue GG dye in place of Sevron Brilliant Red 4G.
ing deepest.
A summing of the ranks assigned to each dye for each
Instead of one scour as in Example 2, two scours as de- 5 additive gave the ?nal ranking of the additives, those
scribed in Example 1 were given to each dyed piece of
having highest count being most effective:
10%
10%
Control, beta- N-beta10%
10%
No eddi- hydroxy- uephthyl- o-nitro- o-phenyl
Dye (type)
tive
naphthoie
betaalanine
toluene
phenol
acid
Celanthrene Pure Blue BRS (ace
............................. .-
l
2
3
4
5
Celanthrene Red 3BN (acetate).._..
tat
1
8
3
3
5
Oelanthrene Fast Yellow GL (ace
tate) _____________________________ __
1
3
2
4
5
Latyl Red B (acetate) _____________ _-
1
3
2
4. 5
4. 5
Sum of ranks (acetate dyes) ........ __
4
11
10
15. 6
19. 5
Genacryl Yellow 3G (basic) ________ __
- 1
5
4
2.5
1
5
2
3. 5
3. 5
Sevron Brilliant
1
5
4
2. 5
2. 5
ed 4G (basic)
Genaeryl Red GB (basic) _____ __
fabric.
4.5
4. 5
2.5
2. 5
1
5
3
3
3
1
5
3
3
-3
Sevron Blue 2G (basic) ____________ __
1
5
2
4
3
Sum of ranks (basic dyes) __________ -_
7
34. 5
22. 5
21
20
Listed below are the additives used and visual
All of the additives used in Examples 2 and 3 except
30
the two materials of this invention, beta-hydroxynaph
thoic acid and N-beta-naphthyl-beta-alanine, have been
Color produced
previously known as swelling agents for use with acetate
Control (no additive) ______ __ Light blue.
dyes. Examples 2 and 3 illustrate that the previously
Beta-hydroxynaphthoic acid-_. Deep blue.
known swelling agents have some bene?cial effect when
'used with basic dyes on vinylidene cyanide:vinyl acetate
N-naphthyl-beta-alanine ____ _. Deep blue.
Acetic acid _______________ _- Slightly darker than
fabric, but do not give the deep colors that are produced
control.
when the materials of this invention are used. Example 4
o-Nitrotoluene ____________ __ Light blue.
o-Phenylphenol ___________ __ Light blue.
Salicylic acid _____________ ._
p-Hydroxy benzoic acid ____ ...
Benzoic acid ____________ ___,
Beta-naphthoic acid ________ _.
1
Genaeryl Orange G (basic)-
Genadryl Blue 6G (basic).___
evaluation of the color produced:
Swelling agent:
2. 5
Sevron Green B basic) .......... ._
Light blue.
40
Light blue.
Light blue.
Darker than control.
Phthalic acid _____________ __ Light blue.
has illustrated that the effect of beta-hydroxynaphthoic
acid and N-beta-naphthyl-beta-alanine is speci?c for basic
dyes; they are only moderately e?ective as swelling agents
for acetate dyes and cannot be classed as general swelling
agents. It is believed that these naphthoic acids react
with basic dyes forming new dyes, which in turn show
improved attraction to vinylidene cyanide:vinyl acetate
synthetic ?bers and fabrics.
These examples show that vinylidene cyanide:vinyl
acetate copolymer fabric can be dyed to pale shades,
Example 5
which are not scour fast, by basic dyes alone, or with ad
ditives which are merely swelling agents, but deep shades
Dispersions of beta-hydroxynaphthoic acid were pre
of color which are scour fast are obtained when beta
pared as in Example 1. Sevron Green B was selected as
hydroxynaphthoic acid or N-beta-naphthyl-beta-alanine
a representative basic dye and inch square, 4 gram pieces
of vinylidene cyanide:vinyl acetate fabric were dyed as in
Example 3 using a series of concentrations of additive
Example 4
in percent 0. w. f. for each of two concentrations of dye
Five dyeings were made of inch square, 4 gram pieces
in percent 0. w. f. The color shades of the dyed pieces
of vinylidene cyanide:vinyl acetate fabric for each of 55 were rated visually as follows:
eleven dyes, four of which were acetate dyes and seven of
which were basic dyes. Various additives were made up
is used as the additive.
into dispersions by dissolving 2.5 grams of the agent in
25 grams of ethyl alcohol and pouring this solution into
a solution of 0.025 gram of sodium N-methyl-oleoyl 60
taurate in 100 grams of water. Next 0.5 gram of octyl
alcohol was added and the dispersion was diluted to 250
ml. 40 ml. of this ?nal dispersion per gram of fabric
gave a ratio of 10 percent 0. w. f. of the swelling agent.
Concentration
Relative depth of shade
Sevron
Green B,
additive concentration in
percent 0. w. 1'.
percent 0. w. t‘.
6%
3%
Dye solutions or dispersions were prepared by shaking
2.0 grams of dye in 200 grams of water. 12 ml. of this
solution, equal to 3 percent dye o. w. if. were used per
acid 0. w. 15. is a preferred concentration for this basic
gram of fabric. Dyeing and scouring procedures were
dye promoter through a wide range of dye concentration,
the same as those followed in Example 3.
The ?ve dyeings run with each dye included:
Approximately 10 percent of beta-hydroxynaphthoic
although as little as 2 percent and as high as 18 percent
70 of promoter also gives satisfactory dyeing results.
(1) No additive (control)
(2)
(3)
(4)
(5)
10 percent 0. w. f. beta-hydroxynaphthoic acid
10 percent 0. w. f. N-naphthyl-beta-alanine
10 percent 0. w. f. o-nitrotoluene
10 percent 0. w. f. o~phenylphenol
Example 6
A series of four parallel dyeings was run using six
basic dyes.
Make-up of dispersions and dyeing were
75 carried out as in Example 3. The dyed pieces were inch
2,848,296
7
it is intended that this inyention'shall be limited and de
?ned only in accordance with the appended claims.
square, four gram pieceswof vinylidene cyanidezvinyl ace
tate fabric. The dyeing. series included:
I claim:
(1) 4 percentv dye o. w. f.
1. The process-of dyeing vinylidene cyanide interpoly—
(2) 4 percent dye o. w. f. plus 15% beta-hydroxy
mer textiles which comprises treating said textiles with a
basic dye in the presence of an‘additive selected from the
naphthoic acid 0. w. f.
(3) 4 percent dye o. w. t. plus 40 percent methyl salicyl
class consisting of 2-hydroxy-3-naphthoic acid and N
ate (a swelling agent) 0. w. f.
beta-naphthyl-beta-alanine.
(4) 4 percent dye o. w. f. plus 15 percent beta-hydroxy
2. The process of dyeing vinylidene cyanidezvinyl ace
naphthoic acid plus-'20 percent 0; w. f.- methyl salicyl 10 tate copolymer textiles which comprises treating said tex
ate
tiles with a basic dye in the presence of an additive
selected from the group consisting of 2-hydroxy-3-naph
thoic acid and N-beta-naphthyl-beta-alanine.
3. The process of dyeing vinylidene cyanidezvinyl ace
15 tate. copolymer textiles which comprises treating said tex
The following dyes were used:
Acridene Red
Methylene Blue
Methyl Violet
Genacryl Blue 6G
tiles with a basic dye in the presence of from 4 percent
to 18, percent on weight of fabric of an additive selected
from the group consisting of 2-hydroxy-3-naphthoic acid
Genacryl Yellow 36
Genacryl Red 63
and ' N-beta-na-phthyl-beta-alanine.
20
When visually rated for depth‘of shade'produced in
the dyed fabric the ranking for each dye was 4>2>~3>1.
The results of this experiment show the synergistic action
of the basic dye promoter of this invention and methyl
4‘. The process of dyeing vinylidene cyanidezvinyl ace
tate copolymer textiles which comprises treating said tex
tiles with a basic dye in the presence of from 4 percent
to 18 percent on weight of fabric of 2-hydroxy-3-naph
thoic acid.
salicylate, which is a conventional swelling agent. 25
5. The process of dyeing vinylidene cyanide:vinyl ace
Neither promoter nor swelling agent alone with the dye
tate copolymer textiles which comprises treating said tex
produces as ?ne a shade as the two together with the dye.
tiles with a basic dye in the presence of from 4 percent to
18 percent on weight of fabric of N-beta-naphthyl-beta
Example‘ 7
alanine.
30
6. The process of dyeing-vinylidene cyanide:vinyl ace
When a series of dyeings similar to that in Example 6
tate copolymer textiles which comprises treating said tex
was run under pressure at 250° F., the e?ect of the pro
moter was even more pronounced.
tiles with a basic dye in the presence of from 4 percent
to 18 percent on Weight of fabric of an additive selected
The series included:
(1) 4 percent dye o. w. f.
from the group consisting of 2-hydroxy-3-naphthoic acid
(2) 4 percent dye o. w. t. plus 7.5 percent 0. w. f. beta 35 and N-beta-naphthyl-beta-alanine plus from 5 percent to
hydroxynaphthoic acid
40 percent on. Weight of fabric of a second additive se
(3) 4 percent dye o. w. f. plus 15 percent 0. w. f. beta
lected from the group consisting of methyl salicylate, o
hydroxynaphthoic acid
(4) 4 percent dye o. w. f. plus 20 percent 0. w.- f.'n1ethyl
phenylphenol, acetophenone, N,N-diphenylformamide
and o-nitrotoluene.
7. The process of dyeingvinylidene cyanidewinyl ace
tate copolymer textiles which comprises treating said tex
Sevron Brilliant Red 4G and Sevron Green B were the
tiles with a basic dye at a dye bath ratio of 18 to 80
dyes selected. Visual comparison of the dyed samples
parts dye liquor to 1 part textile, and a dye concentra
gave the same ranking for both dyes: 3>2>4>1.
tion of from 0.2 to 10 percent of dye per 1 part of tex
The above examples have shown the unique action of 45 tile in the presence of from 4 percent to 18 percent on
beta-hydroxynaphthoic acid and N-beta-naphthyl-beta
weight of fabric of an additive selected from the class
alanine. They are not true swelling agents that open up
consisting of ‘ 2-hydroxy-3-naphthoic acid and N-beta
salicylate
a ?ber structure, but promoters that are believed to react
with basic dyes to form new dyes which in turn react
40
naphthyl-beta-alanine, the dyeing being accomplished by
holding the dye bathv at the equivalent of boiling tem
with the ?ber to give a dyed article of pleasing appear 50 perature for at least one hour.
ance which is color fast to scouring.
It is not intended that this invention be limited to the
References Cited in the ?le of this patent
speci?c examples disclosed herein, for various modi?ca
tions and variations may be employed in the practice of
this invention without deviating from its scope. Other
UNITED STATES PATENTS
2,270,706
Heymann ____________ __ Jan. 20, 1942
1,093,276
France ______________ __ May 3, 1955
vinylidene cyanide copolymers and interpolymers as dis
FOREIGN PATENTS
closed in ,the patents listed in paragraph two herein can
be dyed with basic dyes by this technique. Therefore,
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