Note: Descriptions are shown in the official language in which they were submitted.
~224598
PAPER SIZING AGENT
FIELD OF THE INVENTION
This invention relates to a paper sizing agent
and, more particularly, it relates to a paper sizing agent
which shows sizing efficiency superior to a rosin type
sizing agent while hardly foaming during use.
BACKGROUND OF THE INVENTION
Hitherto, as an internal sizing agent, a so-called
rosin type sizing agent which employs rosin as raw material
has been generally used. However, rosin is a natural
substance and has some problems such as fluctuation of
price, instability of supply and the like. Therefore, as
synthesized sizing agents which take the place of this,
so-called petroleum resin sizing agents which employ, as
raw material, petroleum resin obtained from a mixture of
C5 and Cog fractions which can be obtained from naphtha
cracked oil and other various synthesized sizing agents have
been proposed.
However, until several years ago, such synthesized
sizing agents, except the petroleum resin sizing agent,
were hardly put to practical use due to problems related
to efficiency an price, and the petroleum resin sizing
agent practically used was also limited in use due to
problems related to efficiency.
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1~:24598
However, recently substantial use has been made
of synthesized sizing agents superior in efficiency and
price to the rosin type sizing agents. Such agents are
water-soluble salts of alkenyl succinic acids which are
made from highly branched olefins and malefic android.
The paper sizing process using water-soluble salts of
alkenyl succinic acids as internal sizing agents has been
well-known as described in Japanese Patent Publication
No. 565/65 (corresponding to US. Patent 3,139,373).
In this Publication, it is described that water soluble
salts of alkenyl succinic acids have an alkenyl group
having 8 to 15 carbon atoms and those having an alkenyl group having
16 or more carbon atoms cannot afford a satisfactory sizing
efficiency. Presently, there is no known sizing agent
which is the water soluble salt of alkenyl succinic acid
which has an alkenyl group having 16 or more carbon atoms
or-a sizing agent containing this salt and which shows a
sizing efficiency superior to the rosin type sizing agent.
Water-soluble salts of alkenyl succinic acids
have been said to have a problem in practical use due to
foaming as described in Japanese Patent Publication
(unexamined) No. 27003/79. The present inventors have found
that the foam is formed only when the sizing agent is
obstructed from fixing on pulp during sizing and the us-
fixed water-soluble salt of alkenyl succinic acid or a
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1224598
reaction product of alkenyl succinic acid with aluminum
sulfate remains in a pulp slurry. Thus, the present
inventors found that when fixing proceeds normally, there
is no problem in practical use since there is almost no
foaming. The undesirable obstruction to fixing of the
sizing agent on pulp is herein referred to as "fixing
obstruction".
However, though the obstruction to fixing of
the sizing agent in the paper making process is a rare
phenomenon, the foaming phenomenon caused by the unfixed
sizing agent consisting of the water-soluble salt of
alkenyl succinic acid causes serious damage to the process
and the quality of the produced paper.
In this way, conventionally, when the water
soluble salt of the reaction product of the monoolefin
with malefic android was used as a sizing agent, the
principal object was only the sizing efficiency.
Accordingly, this resulted in attention only being given
to the relationship of the number of carbon atoms in the
monoolefin used as raw material with the sizing efficiency.
However, the relationship of its structure with the sizing
efficiency andthefoaming nature was not investigated.
Therefore, foaming problems were often caused during actual
use as a sizing agent. Further, there were caused problems
that satisfactory results could not be obtained when a
~224598
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l monoolefin having 16 or more carbon atoms was used as
raw material.
SUMMARY OF THE INVENTION
The present inventors carried out studies
related to the relationship between the molecular
structure of manliness used as raw materials and the
sizing efficiency and foaming nature. These studies
were carried out in order to develop a synthesized
sizing agent which shows a sizing efficiency superior
to the rosin type sizing agent and hardly foams even
if it receives a fixing obstruction during use. As
a result the present inventors have found that the
sizing efficiency and foaming nature of the water
soluble salt of alkenyl succinic acid remarkably
depend on the macular structure of the olefin used
as raw material, particularly, the condition of
branching which is represented by a value of an
average ratio of the number of ethylene groups to that
of methyl groups
According to the present invention there is
provided a paper composition including a sizing agent
comprising a water soluble salt obtained by a process
comprising the steps of carrying out a thermal addition
reaction of malefic android with a monoolefin having
16 to 24 carbon atoms and a ratio of the number of
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1;~24598
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1 ethylene groups (-SHEA-) to methyl groups (-SHEA of
0.9 or more or a mixture of monoolefins having 16 to
24 carbon atoms and an average ratio of the number
of ethylene groups to methyl groups of O r or more;
and subjecting the reaction product to alkali
saponification to obtain the water soluble salt.
More surprisingly the present inventors have
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1224598
found that even a monoolefin containing 16 or more carbon
atoms (which was conventionally considered to be unsuitable
as raw material for a sizing agent as it could not afford
a satisfactory sizing efficiency) could be used as raw
material for a sizing agent when the average ratio of the
number of ethylene groups to that of methyl groups is OWE
or more. The present inventors found that such a monoolefin
can afford a homogeneous transparent sizing agent by alkali
saponification of a reaction product which is obtained by
the thermal addition reaction with malefic android. Such
a sizing agent causes substantially no foaming even when
receiving a fixing obstruction and has a sizing efficiency
superior to the rosin type sizing agent over a wide range
of addition amounts.
In addition to this, as a result of further-
studies based on the knowledge obtained from these results,
the present inventors have found that a water soluble salt
(A) which is obtained by alkali saponification of a reaction
product obtained by reacting a monoolefin (having 16 to 24
carbon atoms in which the average ratio of the number of
ethylene groups to that of methyl groups is 0.9 or more)
or a mixture thereof with malefic android reduces foaming
without reducing the sizing efficiency when it is mixed
with a conventional paper sizing agent which readily
causes foaming when it receives a fixing obstruction.
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1~:24598
The sizing agent containing the water soluble
salt (A) related to this invention was developed as a
result of clarifying the relationship of the foaming nature
and sizing efficiency in using a sizing agent with the
molecular structure of the olefin used as raw material.
This relationship was not previously known. The present
invention is a paper sizing agent containing the water
soluble salt (A) which is obtained by alkali saponification
of a reaction product obtained by thermal addition reaction
of a monoolefin having 16 to 24 carbon atoms in which the
average ratio of the number of ethylene groups to that of
methyl groups is 0.9 or more, or the mixture thereof.
The monoolefins having 16 or more carbon atoms were previously
considered to be unsuitable as raw material for a paper
sizing agent consisting of a water soluble salt of alkenyl
succinic acid. The sizing agent of the present invention
not only shows a sizing efficiency superior to the rosin
type sizing agent over a wide range of addition amounts
but also causes substantially no foaming when receiving
a fixing obstruction.
DETAILED DESCRIPTION OF THE INVENTION
The oligomer having 16 or more carbon atoms
(which is obtained by polymerization of a monoolefin such as
propylene, battalion and the like or a mixture thereof in
the presence of an acid catalyst such as phosphoric acid,
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i2~4598
and the like or a Friedel-Crafts catalyst such as aluminum
chloride and the Lucas generally known to have a highly
branched structure, and the average ratio of the number of
ethylene groups to that of methyl groups is generally
less than 0.9 The sizing agent obtained from a malefic
android adduce of such a highly branched oligomer having
16 or more carbon atoms is not preferable for purposes of this
invention because the sizing efficiency is insufficient.
Contrary to this, the oligomer having 16 or more
carbon atoms which is obtained by polymerization of a
monoolefin such as propylene, battalion, Helene, octane and
the like or a mixture thereof in the presence of, for
example, an organic aluminum type catalyst has a structure
less branched than that of the oligomers obtained by the
acid catalyst mentioned above, and the average ratio of
the number of ethylene groups to that of methyl groups
is 0.9 or more.
As already mentioned above, the monoolefin or
monoolefin mixture in which the average ratio of the number
of ethylene groups to that of methyl groups is 0.9 or
more and the number of carbon atoms is 16 to I preferably
16 to 20, can be suitably used for the purposes of this
invention as paper sizing agent for all types of paper.
A monoolefin having 25 or more carbon atoms or the
mixture thereof is not preferable because the reaction
1224598
1 product obtained from reacting it with malefic android
does not easily afford a homogeneous aqueous solution
by alkali saponification and the obtained sizing agent
cannot afford a satisfactory sizing effect though it
shows a low foaming nature.
Examples of the monoolefin or monoolefin
mixture used in this invention in which the number of
carbon atoms is 16 to 24 and the average ratio of the
number of ethylene groups to methyl groups is 0.9 or
more include oligomers obtained by polymerization of
a monoolefin having 3 to 8 carbon atoms such as
propylene, battalion, Helene, octane and the Lowe or
a plurality thereof, straight chain inner olef.ins
obtained by dehydrogenation of n-paraffin and the like
- and straight chain ~-olefins obtained by polymerization
of ethylene and the like/ and mixtures thereof ~11
of the sizing agents obtained from these monoo:Lefin$
or monoolefin mixtures causes little foaming when
receiving a fixing obstruction. The oligomers of
n-butylene or straight chain inner olefins are preferably
used due to the particularly excellent sizing efficiency.
It is also possible to use a monoolefin mixtures
prepared by mixing the monoolefins having 16 to 24 carbon
atoms which has the average ratio of the number of ethylene
groups to that of methyl groups of 0.9 or more with those
having the average ratio of 0.9 or less. In this case, the
thus prepared monoolefin mixture must be adjusted so that
1~245g8
the average ratio of the number of ethylene groups to that
of methyl groups is 0.9 or more.
On the other hand, a monoolefin or monoolefin mix-
lure in which the average ratio of the number of ethylene
groups to that of methyl groups is 22 or more is not suit-
able for the purposes of this invention because they are
composed of a monoolefins having 25 or more carbon atoms.
Therefore, the average ratio of number of ethylene groups
to that of methyl groups is preferably 0.9 or more and less
than 22.
The reaction product of a monoolefin or mixture
thereof with malefic android used in this invention can be
obtained by thermal addition reaction of the monoolefin
with malefic android in the absence of catalyst. The no-
action is preferably carried out in an inert atmosphere swishes nitrogen under atmospheric or some increased pressure,
at 180 to 250C, more preferably at 200 to 230C, followed
by reacting at the same temperature for 1 to 30 hours,
preferably for 3 to 20 hours. The mow ratio of the moo-
olefin to the malefic android is not necessarily limited but is preferably used in an amount of 0.5 to 3 mow per
mow of monoolefin. After the reaction is over, the us-
reacted monoolefin and the malefic android are removed by
distillation to afford a liquid reaction product having
rather low viscosity. The saponification value (JIG K 5902)
of the reaction product is about 250 to 350. Depending on
the reaction conditions, a small amount of by-products may
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i224598
be formed. The by-products can be removed as distillation
residue by distillation under reduced pressure, but the
amount of by-product is small and its removal is not
alleges required, The reaction product thus obtained is
saponified by alkali and made a transparent solution to
afford the sizing agent of this invention,
Examples of the alkali used for saponification in
this invention include alkali metal hydroxides such as
sodium hydroxide, potassium hydroxide and the like, ammonia,
or water soluble amine such as trimethylamine, diethylamine
and the lice, but the use of sodium hydroxide or potassium
hydroxide is desirable. The amount of alkali used for
saponification is 0.8 to 1.2 times, preferably 0.9 to 1.1
times, the amount corresponding to the saponification value
of the reaction product of the monoolefin with malefic ashy-
drive. The foaming nature of the obtained sizing agent in-
creases with the decrease of the amount of alkali, and when
the amount is Less than 0.8 times the amount corresponding
to the saponification value, the foaming increases rather
substantially though the sizing effect is little influenced,
The sizing agent related to this invention can be
obtained by reacting a monoolefin or monoolefin mixture
having 16 to 24 carbon atoms in which the average ratio of
the number of ethylene groups to that of methyl groups is
0.9 or more with malefic android and saponifying the
resulting reaction product independently or saponifying
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1~2~sg~
after mixing it with the other substance such as rosin or
a reaction product of a monoolefin or monoolefin mixture
having 15 or less carbon atoms with malefic android.
They can be mixed after saponification. The sizing agent
can also be obtained by reacting the monoolefin or moo-
olefin mixture used in this invention with malefic android
after mixing with a monoolefin or monoolefin mixture having
15 or less carbon atoms and saponifying the obtained
reaction product.
The water soluble salt (A of the malefic android
adduce of the monoolefin or monoolefin mixture having 16 to
24 carbon atoms in this invention is desirably present in
an amount of 10% by weight or more in the effective component
of the sizing agent. The more the proportion occupied in
the effective component of the sizing agent increases, the
larger the restraining effect on foaming when it receives
a fixing obstruction during use. However, even if the
amount is less than 10% by weight, the restraining effect
on foaming can be exhibited.
The sizing agent related to this invention can
be added to a paper stock in the same manner as that of
the conventional rosin type sizing agent. For example,
it can be fixed on a pulp by adjusting the pi to about 4.0
to 5.5, preferably 4.2 to 5.0, by adding aluminum sulfate
after adding the sizing agent related to this invention to
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1~24598
a pulp slurry which is in or after the beating process.
The agent of this invention can be used together with
other sizing agents such as a conventional rosin type
sizing agent, a petroleum resin sizing agent and the
like in any ratio, and may also be used for surface sizing.
In case of internal sizing, the amount (addition
amount) of the sizing agent used in this invention is in
the range of 0.01 to 5.0% by weight, preferably 0.05 to
3.0% by weight, based on the weight of the dry pulp. When
surface sizing is carried out the sizing agent is coated
in an amount of 0.005 to 0.5 g/m2 on a dry weigh basis.
As explained in the above, even a monoolefin or
monoolefin mixture having 16 or more carbon atoms which was
conventionally said not to afford a satisfactory sizing
agent in the case of reacting it independently with malefic
android can afford a paper sizing agent showing an excellent
sizing efficiency and a low foaming nature. This good
results are made possible by selecting a monoolefin or
monoolefin mixture in which the average ratio of the number
of ethylene groups to that of methyl groups is 0.9 or more.
The sizing agent of this invention is not only
superior to the rosin type sizing agent over a wide range
of addition amounts but it also remarkably restrains the
foaming in receiving a fixing obstruction.
The characteristics of the sizing agent related
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1~4598
to this invention are explained above, and this invention
is further specifically illustrated by the following
Comparative Examples and Examples. However, the scope of
the invention is not limited to these examples. The average
ratio of the number of ethylene groups to that of methyl
groups in the Comparative Examples and Examples are measured
by the nuclear magnetic resonance spectral method.
COMPARATIVE EXAMPLE
A mixture of 250 parts by weight of propylene
oligomers having 8 to 10 carbon atoms in which the average
ratio of the number of ethylene groups to that of methyl
groups was 0.80 and 200 parts by weight of malefic android
were heated to 215C in an autoclave under nitrogen atmosphere
and reacted for 3 hours in the absence of catalyst. After
the reaction was over, the reaction mixture was taken out
and the unrequited oligomers and malefic android were
removed by distillation under reduced pressure to afford 294
parts by weight of a yellowish brown oily reaction product.
The saponification value of this reaction product was 502.
The potassium hycLroxide corresponding to the specification
value of the reaction product and water were added to the
obtained reaction product, and the mixture was stirred at
90C for 2 hours and saponified to give a transparent sizing
agent containing 40~ by weight of the solid component
(Sizing agent A). The pi of this sizing agent was 10.1.
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I
COMPARATIVE EXAMPLE 2
A mixture of 332 parts by weight of propylene
oligomers having 16 to 21 carbon atoms in which the average
ratio of the number of ethylene groups to that of methyl
groups was 0.87 and 166 parts by weight of malefic android
were reacted in the same manner as described in Comparative
Example 1 and the unrequited reactants were removed to afford
194 parts by weight of a yellowish brown oily reaction product.
The saponification value of this reaction product was 320.
This product was saponified in the same manner as described
in Comparative Example 1 and adjusted so as to have 40 % by weight
of the solid component. However, the product was in an
emulsion state and could not afford a homogeneous trays-
parent sizing agent. The pi of this emulsified sizing
agent (Sizing agent B) was 10.1.
EXAMPLE
A mixture of 230 parts by weight of n-butylene
oligomers having 16 to 20 carbon atoms in which the average
ratio of the number of ethylene groups to that of methyl
groups was 0.93 and 100 parts by weight of malefic android
were reacted in the same manner as described in Comparative
Example 1. Unrequited reactants were removed to afford 159
parts by weigh-t of a reaction product. The saponification
value of this reaction product was 350. This product was
saponified in the same manner as described in Comparative
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1~2459~
Example 1 to give a transparent sizing agent related to
this invention containing OWE by weight of the solid
component (Sizing agent C). The pi of this sizing agent
was 10.1.
EXAMPLE 2
225 parts by weight of a straight chain inner olefin
having 16 carbon atoms with the average ratio of the number
of ethylene groups to that of methyl groups being 6.1 and
100 parts by weight of malefic android were reacted in
the same manner as described in Comparative Example 1.
Unrequited reactants were removed to afford 156 parts by
weight of a yellowish brown oily reaction product.
The saponification value of this reaction product was 352.
This product was saponified in the same manner as described
in Comparative Example 1 to give a transparent sizing agent
related to this invention containing 20% by weight of the
solid component sizing agent D). The pi of this sizing
agent was 10Ø
EXAMPLE 3
20 parts by weight of the reaction product obtained
in Example 1 and 80 parts by weight of the reaction product
obtained in Comparative Example 1 were mixed.
The saponification value of this mixture was 472. This was
saponified in the same manner as described in Comparative
Example 1 to afford a transparent sizing agent related to
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1~24598
this invention containing 40% by weight of the solid
component (Sizing agent E). The pi of this sizing agent was
10.1.
EXAMPLE 4
50 parts by weight of Sizing agent C obtained in
Example 1 and 50 parts by weight of Sizing agent A obtained
in Comparative Example 1 were mixed to give a transparent
sizing agent related to this invention containing 40% by
weight of the solid component (Sizing agent F). The pi of
this sizing agent was 10.1.
EXAMPLE 5
40 parts by weight of Sizing agent D obtained in
Example 2 and 80 parts by weight of Sizing agent A obtained
in Comparative Example 1 were mixed and water was added
thereto to afford a transparent sizing agent related to
this invention containing 30% by weight of the solid
component (Sizing agent G). The pi of this sizing agent
was 10.1.
EXPEL 6
With respect to the sizing agents A and B obtained
in the above-mentioned Comparative Examples 1 to 2 and the
sizing agents C, D, E, F and G obtained in Examples 1 to 5,
the sizing test was carried out. As a sizing agent for
comparison, a commercial reinforced rosin sizing agent
(RF Size 880 L-50 manufactured by Hymen Industry Co.) was
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1~:24598
used. The testing method is as follows.
A 3% slurry of hardwood bleached raft pulp
which was adjusted to the beating degree C.F.=400 cc was
prepared and to this slurry was added Sizing agent A,
Sizing agent s, Sizing agent C, Sizing agent D, Sizing
agent E, Sizing agent F, Sizing agent G or the reinforced
rosin sizing agent in an amount of 0.2% by weight, 0.5%
by weight or 1% by weight as solid component based on
the weight of dry pulp and aluminum sulfate was added
with stirring to make the pi of the slurry 4.5. The pulp
slurry was diluted with water adjusted to pH-S.0 by aluminum
sulfate to make the pulp concentration about 0.2~ by weight.
The pulp was made into paper by a TAIPEI standard sheet
machine according to the general method and after pressing
for dehydration (4 kg/cm2 x 1 mix), the wet paper was dried
by a rotary dryer at 105~C for 3 minutes. The basis weight
of this hand-made paper was 60 g/m2.
The obtained paper was allowed to stand in a
room at 20~C and 65% humidity for 24 hours, and then the
sizing degree was measured by JIS-P-8112 Stockigt sizing
degree testing method. The results are summarized in
Table 1.
Next, in order to examine the foaming under the
conditions in which the pulp slurry concentration was low
and the sizing agent could easily receive the fixing
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12~459B
obstruction, a 0. owe by weight of slurry of hardwood
bleached raft pulp which was adjusted to a beating
degree C.F.=400 cc was added with Sizing agent A,
Sizing agent B, Sizing agent C, Sizing agent D, Sizing
agent E, Sizing agent F, Sizing agent G or the reinforced
rosin sizing agent in an amount of 0.5~ by weight (as
solid component) based on the weight of dry pulp, and
aluminum sulfate was added to make the pi of the pulp
slurry 4.5. Then 500 ml of this pulp slurry was put in
lo a l of Erlenmeyer flask and sealed. It was attached
to a horizontal reciprocating shaker (Shaking frequency
156 shaking/min, Amplitude 70 mm) and shook for l minute.
The volume of foam in the pulp slurry was then measured
by the Broadway bubble measuring scale (Pulp and Paper
Engineering, Vol. 2, No. 11, p. 22). The results are
summarized in Table 1.
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1~:24598
Table
Stockigt Sizing Foam Content
Sizing Agent Degree (sea) (I by volume)
o _ 0.5* 1.0* 0.5
A (Coup. Example 1) 15.3 28.5 32.8 0.52
B ( " 2) 0 2.0 6.2 0.05
C (Example 1) 19.0 29.8 33.7 0.02
D ( " 2) 15.8 28.5 32.5 0.02
E ( " I 16.0 28.6 33.0 0.25
F ( " 4) 17.5 30.0 33.5 0.12
G ( " 5) 15.5 28.5 33.0 0.24
Reinforced Rosin 9.1 23.1 31.6 0.31
Sizing Agent
Note: "*": Addition amount of sizing agent (% by weight)
Sizing agent A in the examples obtained from the
propylene oligomer mixture having 8 to 10 carbon atoms in
which the average ratio of the number of ethylene groups
to that of methyl groups is 0.80 shows a sizing effect
superior to the reinforced rosin sizing agent. However, the
foaming amount in receiving a fixing obstruction is larger
than that of the reinforced rosin sizing agent. In the emulsi-
fled sizing agent B in this example obtained from the
mixture of propylene oligomers having 16 to 21 carbon atoms in
which the average ratio of the number of ethylene groups to that
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~459~3
of methyl groups is 0.87, the amount of the foaming is
less than that of the reinforced rosin sizing agent.
However, the sizing effect is apparently substantially
inferior to the reinforced rosin sizing agent.
On the contrary, Sizing agent C obtained from
the oligomer mixture of n-butylene in which the average
ratio of the number of ethylene groups to that of methyl
groups is 0.93 and Sizing agent D obtained from the straight
chain inner olefin having of 16 carbon atoms in which the
average ratio of the number of ethylene groups to that
of methyl groups is 6.1 which are related to this invention
show not only a sizing effect superior to the reinforced
rosin sizing agent over a wide range of addition amount
but also substantially less foaming than that of the
reinforced rosin sizing agent.
Sizing agent E of this invention obtained by
mixing the reaction product obtained in Comparative Example
1 with the reaction product obtained in Example 1 followed
by saponification, and Sizing agents F and G obtained by
saponification followed by mixing show an excellent efficiency
superior to the reinforced sizing agent over a wide range of
addition amounts and at the same time the foaming when
receiving a fixing obstruction is suppressed.
While the invention has been described in detail
and with reference to specific embodiments thereof, it will
be apparent to one skilled ion the art that various changes
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and modifications can be made therein without departing
from the spirit and scope thereof.
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