,. i~,
2~2018a
- 1 -
Our Ref . : DK-87-X
TITLE OF THE INVENTION
SIZING AGENT AND PAPER SIZED THEREWITH
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
The present invention relates to a sizing agent for
paper, which is useful for sizing paper or paper board
(hereinafter paper and paper board will be generally
referred to simply as "paper") and paper sized with such
a sizing agent.
DISCUSSION OF BACKGROUND
Heretofore, various sizing agents have been used to
improve various strength and printability of .paper or the
appearance of printed matters. Among such sizing agents,
those using a polyvinyl alcohol, a starch or both of
them, are typical.
However, paper sized with a starch has a drawback
such that when it is subjected to printing, paper powder
is likely to form, and such paper powder tends to
deteriorate the appearance of the printed matter, or such
paper powder is likely to accumulate between printing
rollers, thus leading to a trouble of e.g. rupture of the
paper. Further, paper sized with a starch tends to have
inadequate strength, whereby defects such as picking and
blistering are likely to occur at the printed surface,
and such tendency is particularly remarkable when the
printing speed is high.
,,
21~~~8~
~~ i
- 2 -
On the other hand, paper sized with a polyvinyl
alcohol has a drawback such that it shows tackiness in a
state wet with water, although it exhibits excellent
properties with no substantial formation of paper powder
or with no substantial deterioration of the appearance
due to damage of the printed surface given by high speed
printing. This drawback causes, for example, a printing
trouble such that when the paper sized with a polyvinyl
alcohol is subjected to offset printing, if the paper is
wetted upon contact with damping water, tackiness will be
created, whereby a trouble such as adhesion of the paper
to itself or adhesion of the paper to the printing
rollers, is likely to result. If such a trouble occurs
during printing, the printing operation will have to be
stopped, thus leading to a substantial loss in the
productivity and a loss of materials, and further the
machine is likely to be damaged.
Japanese Unexamined Patent Publication No. 41611/1974
discloses a sizing agent having a non-ionic surfactant
incorporated to a polyvinyl alcohol and having a third
component such as urea, a urea derivative, thiourea, a
thiourea derivative or a guanidine derivative
incorporated. However, this sizing agent requires a
third component such as urea, as an essential component.
Besides, the effect for reducing the tackiness of the
sized paper in a wet state, is still inadequate.
Further, Japanese Unexamined Patent Publication No.
222Q~.80
- 3 -
295693/1993 discloses a surface sizing agent for paper
comprising a polyvinyl alcohol resin and polyethylene
glycol as essential components. However, this sizing
agent has a problem with respect to printability.
Reflecting a trend in recent years for multi-color
printing or weight reduction of medium or low quality
paper such as paper for newspapers, which is subjected to
high speed printing in a large quantity, it has become
common to size such medium or low quality paper, and it
has become common to employ an offset printing system as
a printing system for such sized paper. Therefore, it
has been desired to develop a sizing agent for paper
which presents low tackiness even when the sized paper is
in a wet state and which is excellent in printability.
SUMMARY OF THE INVENTION
It is an object of the present invention to solve the
above problems.
The present invention provides a sizing agent for
paper, which comprises 100 parts by weight of a polyvinyl
alcohol (component A) and from 1 to 20 parts by weight of
a compound (component B) provided with the following
requisites (1) to (4):
(1) the backbone chain is a random copolymer of
ethylene oxide and propylene oxide,
(2) in the backbone chain, the proportion of
oxyethylene units is from 20 to 40~ by weight, and the
proportion of oxypropylene units is from 60 to 80~ by
t
21~0~80
v
- 4 -
weight,
(3) of the two terminals, one terminal is a hydroxyl
group, and the other terminal is a Cl_lo alkoxyl group or
a hydroxyl group, and
(4) the weight average molecular weight is from 600
to 1,200.
The present invention also provides paper sized with
such a sizing agent.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
There is no particular restriction as to component A
i.e. the polyvinyl alcohol (hereinafter referred to
simply as PVA) to be used for the sizing agent of the
present invention. It may be a PVA obtained_by
completely or partially hydrolyzing a polymer or
copolymer obtained by polymerizing one or more fatty acid
vinyl esters, or a copolymer of one or more fatty acid
vinyl esters with one or more other monomers
copolymerizable therewith, or a PVA obtained by post-
modifying such a PVA.
Among the above PVAs, preferred is a PVA obtained by
hydrolyzing a polymer or copolymer of a fatty acid vinyl
ester. Particularly preferred is a PVA obtained by
completely or partially hydrolyzing a polymer of vinyl
acetate. The fatty acid vinyl ester is preferably vinyl
acetate, but may be others such as vinyl propionate and
vinyl formate.
Said other monomers copolymerizable with fatty acid
. . 2120180
- 5 -
vinyl esters, include, for example, olefins such as
ethylene and propylene; polymerizable monocarboxylic
acids such as acrylic acid, methacrylic acid, crotonic
acid and isocrotonic acid; polymerizable dicarboxylic
acids such as malefic acid, fumaric acid and itaconic
acid; polymerizable dicarboxylic anhydrides such as
malefic anhydride; esters and salts of polymerizable
monocarboxylic acids and polymerizable dicarboxylic
acids; polymerizable acid amides such as acrylamide and
methacrylamide; acrylates such as methyl acrylate, ethyl
acrylate and butyl acrylate; methacrylates such as methyl
methacrylate, ethyl methacrylate and butyl methacrylate;
vinyl halides such as vinyl chloride and vinyl fluoride;
vinylidene halides such as vinylidene chloride and
vinylidene fluoride; monomers having glycidyl groups,
such as allylglycidyl ether and glycidyl methacrylate;
and alkylvinyl ethers.
The average degree of polymerization of PVA is
preferably from 500 to 4,000, more preferably from 1,000
to 3,000, with a view to increasing the strength of
paper. Further, PVA is preferably water-soluble, and its
degree of hydrolysis is usually at least 90 mold,
preferably at least 95 mold, more preferably at least
97.5 mold with a view to low moisture sensitivity and
high strength of paper. In the present invention, a
plurality of PVA differring in the degree of
polymerization, the degree of hydrolysis or the units
' 2.~20.~~0
- 6 -
constituting PVA, may be used in combination.
Component B to be used in the present invention is a
compound wherein the backbone chain is a random copolymer
of ethylene oxide and propylene oxide, which comprises
from 20 to 40~ by weight of oxyethylene units and from 60
to 80~ by weight of oxypropylene units, and one of the
two terminals is a hydroxyl group and the other is a C1_
alkoxyl group or a hydroxyl group, and which has a
weight average molecular weight of from 600 to 1,200.
10 If the proportions of the oxyethylene units and the
oxypropylene units in the backbone chain are outside the
above ranges, if the carbon number of the alkoxyl group
is 11 or more, or if the weight average molecular weight
is outside the range of from 600 to 1,200, the effect for
reducing the tackiness of the sized paper in a wet state,
tends to be inadequate. Further, if the backbone chain
of component B is a block copolymer of ethylene oxide and
propylene oxide, the effect for reducing the tackiness of
the sized paper in a wet state, is small as compared with
the case where the backbone chain is a random copolymer.
Component B includes, for example, compounds
satisfying the above requirements (1) to (4), as
identified in the following items (i) and (ii). Among
them, a compound of type (X) as identified in the
following item (i) is preferred.
(i) A compound wherein the backbone chain is a random
copolymer comprising oxypropylene units and oxyethylene
~z~o~~o
units, and one of the two terminals is an alkoxyl group
and the other is a hydroxyl group, obtained by
conventional addition-polymerization in the presence of a
Cl-to alcohol, propylene oxide and ethylene oxide
(hereinafter referred to as a compound of type (X)).
(ii) A compound which is a random copolymer
comprising oxypropylene units and oxyethylene units,
wherein both terminals are hydroxyl groups, obtained by
conventional addition-polymerization in the presence of
diethylene glycol and/or dipropylene glycol, propylene
oxide and ethylene oxide (hereinafter referred to as a
compound of type (Y)).
In the present invention, such compounds.may be used
alone or in combination as a mixture of two or more of
them, as component B. The amount of component B to be
used is from 1 to 20 parts by weight, preferably from 2
to 10 parts by weight, per 100 parts by weight of PVA.
If the amount of component B is less than 1 part by
weight, the effect for reducing tackiness of the sized
paper in a wet state to itself or to printing rollers,
tends to be low. On the other hand, if it exceeds 20
parts by weight, it impairs the effect of PVA as a sizing
agent.
There is no particular restriction as to the form of
the sizing agent of the present invention. For example,
it may be a mixture of component B and powdery PVA, a
mixture of component B and an aqueous PVA solution, or
the one having an additional component incorporated
thereto, as the case requires. At the time of mixing,
component B may be used alone or as previously dissolved
or dispersed in an organic solvent or water.
The sizing agent of the present invention may contain
or may be used in combination with other components, as
the case requires, to such an extent not to impair the
effects of the present invention. As such other
components, starches such as corn starch and oxidized
starch, water-soluble cellulose compounds such as
carboxymethyl cellulose (CMC), methyl cellulose and
hydroxyalkyl cellulose, synthetic rubber latexes such as
a styrene-butadiene copolymer latex and a styrene-
butadiene-methacrylate copolymer latex, a water-resisting
agent for PVA, inorganic pigments such as titanium oxide,
clay and calcium carbonate, synthetic resin pigments such
as fine powdery thermosetting resins (such as a urea
resin or a melamine resin) and fine powdery thermoplastic
resins (such as a vinylidene chloride resin, a vinyl
chloride resin or a styrene-butadiene copolymer resin)
and a defoaming agent, may, for example, be mentioned.
In a case where the sizing agent of the present
invention is used in combination with a pigment, the
concentration of a non-volatile content in the sizing
solution is usually limited to a level of from 1 to 20~
by weight, and the amount of pigment is usually less than
400 parts by weight per 100 parts by weight of PVA
2120180
_ 9
contained in the solution in order to avoid a substantial
increase in the weight of paper by sizing.
The sizing agent of the present invention may be
coated on paper or impregnated in paper in the form of an
aqueous solution or an aqueous dispersion. To obtain an
aqueous solution or aqueous dispersion of the sizing
agent, a mixture of PVA (component A) and component B,
may, for example, be dissolved or dispersed in water, or
an aqueous solution or dispersion of PVA and an aqueous
solution or dispersion of component B may be mixed.
Otherwise, one of PVA and component B is dissolved or
dispersed in water, and the other component is then mixed
thereto. To incorporate other components or.a sizing
agent other than PVA, such material may be mixed to the
sizing agent of the present invention in a liquid or
solid form by a method suitable for such material.
The sized paper of the present invention can be
obtained by using, as a sizing solution, an aqueous
solution or aqueous dispersion containing the sizing
agent of the present invention and by coating or
impregnating this solution on one side or both sides of
paper by means of a conventional apparatus such as a gate
roll coater, a size press or a bar coater, followed by
drying the paper.
The amount of the sizing agent of the present
invention contained in the above sizing solution, is
optionally selected depending upon the desired coated
. 2120180
. ..
- 10 -
amount (an increase in the dry weight of paper caused by
coating), the apparatus to be used for coating or the
conditions for the coating operation. It is usually at a
level of from 0.5 to 8 parts by weight per 100 parts by
weight of the total amount of the sizing agent and water
in the sizing solution.
The coated amount of the sizing agent of the present
invention on the paper to be sized, may optionally be
selected depending upon e.g. the desired properties of
sized paper. It is usually at a level of from 0.05 to
0.5 g/m2 per one side of paper.
The paper sized with the sizing agent of the present
invention has excellent properties such that.the
tackiness in a wet state is low, smooth printing can be
conducted even by high speed offset printing, and printed
matters with excellent finish can be obtained.
Now, the present invention will be described in
further detail with reference to Examples and Comparative
Examples. However, it should be understood that the
present invention is by no means restricted to such
specific Examples.
In the following Examples and Comparative Examples,
the structure, composition, etc. of a compound wherein
the backbone chain is a random copolymer of ethylene
oxide and propylene oxide, were analyzed by NMR, etc.
Further, the weight average molecular weight was
calculated from a hydroxyl value which was obtained by
v . ~~~o~so
t
- 11 -
esterifying hydroxyl groups of the compound with phthalic
anhydride in pyridine, followed by titration with
potassium hydroxide.
EXAMPLE 1
To a 1.4 wt~ aqueous solution of PVA K-17
(manufactured by Denki Kagaku Kogyo K.K., average degree
of polymerization: 1,700, degree of hydrolysis: 99.0
mold), a compound of type (X) wherein the backbone chain
is a random copolymer of ethylene oxide and propylene
oxide, one of the terminals is a C$ alkoxyl group and the
other terminal is a hydroxyl group, and in the backbone
chain, the proportion of oxyethylene units is 30~ by
weight and the proportion of oxypropylene units is 70~ by
weight, and which has a weight average molecular weight
of 850, was added and mixed as component B in an amount
of 5 parts by weight per 100 parts by weight of PVA in
the aqueous solution, to obtain a sizing solution.
Using this sizing solution, coated paper was prepared
in accordance with the method as described in the
following item (1), and tests for evaluating this coated
paper were conducted in accordance with the methods as
described in the following item (2). The test results
are shown in Table 3.
(1) Preparation of coated paper
The sizing solution was coated on one side of raw
paper (basis weight: 46 g/m2) for newspapers by a coating
rod so that the coated amount of the sizing agent would
2120.~~~
.y
- 12 -
be 0.4 g/m2. The coated paper was dried in air, followed
by one pass treatment by an iron press (70°C). Then, it
was adjusted at 20°C for 24 hours under a relative
humidity of 65~ to obtain coated paper for evaluation
tests.
(2) Tests For evaluating physical properties of the
coated paper
Sticking strength of coated paper/coated paper
A sheet of the coated paper having a width of 30 mm
and a length of 100 mm was dipped in water at a
temperature of 20°C for 5 seconds. Then, it was folded
to a length of 50 mm so that the coated surface was in
contact, and non-coated paper was placed on each exterior
side, followed by pressing under a pressure of 50 kg/cm2
for 5 seconds to obtain a test specimen. Immediately
after the pressing, this test specimen was subjected to T
type peeling by pulling at a speed of 30 mm/min by means
of a tensile tester (UTM-4-100), whereby the load
required for peeling the sticked coated surface, was
measured. This load value was taken as the sticking
strength (g/30 mm) of coated paper/coated paper.
Sticking strength of rubber sheet/coated paper
The coated paper having a width of 100 mm was dipped
in water at 20°C for 5 seconds. Then, this paper was
placed on a rubber sheet (150 x 150 mm, manufactured by
NBR) so that the coated surface contacted the rubber
sheet, and on the non-coated side of the coated sheet,
~~~o~so
_ 13 _
two sheets of non-coated paper were placed, followed by
pressing under a pressure of 10 kg/cm2 for 5 seconds to
obtain a test specimen. Immediately after the pressing,
this test specimen was subjected to T type peeling by
pulling at a speed of 1,000 mm/min by a tensile tester,
whereby the load required for peeling the coated surface
from the rubber sheet, was measured. This load value was
taken as the sticking strength (g/100 mm) of rubber
sheet/coated paper.
RI printabilitY
Using a RI tester, printing was conducted in a wet
state under a printing pressure of 8 mm using ink IPI#6,
and the printed surface was visually evaluated in
accordance with the following evaluation standards of
four grades.
Evaluation standard
0: No change
1: Slight blistering observed
2: Slight picking observed, and blistering observed
3: Rupture of paper observed
EXAMPLES 2 TO 18 AND COMPARATIVE EXAMPLES 2 TO 5 AND 11
TO 13
A sizing solution was prepared in the same manner as
in Example 1 except that component A or B used was
changed as identified in Table 1 or 2. Using this sizing
solution, the tests were conducted in the same manner as
in Example 1, and the results are shown in Table 3 or 4.
2120180
- 14 -
COMPARATIVE EXAMPLE 1
A 1.4 wt~ aqueous solution of PVA K-17 was used as a
sizing solution. Using this sizing solution, the tests
were conducted in the same manner as in Example l, and
the results are shown in Table 4.
COMPARATIVE EXAMPLE 6
To a 1.4 wt~ aqueous solution of PVA K-17, a compound
wherein the backbone chain is a block copolymer of
ethylene oxide and propylene oxide, one of the terminals
is a C8 alkoxy group and the other terminal is a hydroxyl
group, and in the backbone chain, the proportion of
oxyethylene units is 30~ by weight and the proportion of
oxypropylene units is 70~ by weight, and which has a
weight average molecular weight of 850, was added and
mixed as component B in an amount of 5 parts by weight
per 100 parts by weight of PVA in the aqueous solution,
to obtain a sizing solution. Using this sizing solution,
the preparation of coated paper and the tests were
conducted in the same manner as in Example 1. The test
results are shown in Table 4.
COMPARATIVE EXAMPLE 7
A 1.4 wt~ aqueous solution of oxidized starch (MS-
3800, manufactured by Nippon Shokuhin Kako K.K.) was used
as a sizing solution. Using this sizing solution, the
tests were conducted in the same manner as in Example l,
and the results are shown in Table 4.
COMPARATIVE EXAMPLE 8
.. 212180
- 15 -
To a 1.4 wt~ aqueous solution of PVA K-17, a
commercially available paraffin emulsion was incorporated
in a weight ratio of PVA/paraffin emulsion (non-volatile
content) - 3/1, to obtain a sizing solution. Using this
sizing solution, the tests were conducted in the same
manner as in Example l, and the results are shown in
Table 4.
COMPARATIVE EXAMPLE 9
To a 1.4 wt~ aqueous solution of PVA K-17,
polyoxyethylene nonylphenyl ether as a non-ionic
surfactant and urea were incorporated in a weight ratio
of PVA/polyoxyethylene nonylphenyl ether/urea = 100/5/10,
to obtain a sizing solution. Using this sizing solution,
the tests were conducted in the same manner as in Example
l, and the results are shown in Table 4.
COMPARATIVE EXAMPLE 10
With respect to the non-coated paper (raw paper for
newspapers, basis weight: 46 g/m2), the tests for
evaluating the physical properties were conducted in the
same manner as in Example l, and the results are shown in
Table 4.
COMPARATIVE EXAMPLE 14
To a 1.4 wt~ aqueous solution of PVA K-17, a
commercially available polyethylene glycol (PEG 6000,
manufactured by Daiichi Kogyo Seiyaku) was incorporated
in a weight ratio of PVA/polyethylene glycol = 100/20, to
obtain a sizing solution. Using this sizing solution,
_2~2Q180
- 16 -
the tests were conducted in the same manner as in Example
l, and the tests results are shown in Table 4.
10
20
212a~.80
i _ ,~ _
U
3 U
~"'I O O O O O I~ N O O O .1J
I a -l.1 ~ t~ I~ t~ I~ I~ l0 I~ I~ I~
~ O ~ U O
;~
r-I
O ~ ~ s..i
U .-I
a)
U
f~
O
U o 0 0 0 o M ~ 0 0 0
I ~ ~ M M M M M N M M M M
,~y ..f.;
r-i
O U ~ '"~
O
x
0 0
x v
U o ~ u..,
~-i
p~ 0 0 0 0 0 0 o t~ o o O
~
~.,
.G ~1 tn u7 tn tn d~ tD o M in
rti
U
.~
r a~ c0 c0 m N c0 0o ra ~ m
N
tn
r-I -f.
~ ,~
r-1
'-1
U '~
D ~,
O
U
3
~s
I~
3
p
s~ ~ a~
~ 3
U
O ~ O
~ ~ o
~-i
~
~
..c~
.
~
O
~
r..1 ~ ~ x
c~f
~
U
.-
I
z O O
U ~
.-i 1~
.u l
cIf 1
tT
p b -
r~
W ~v
~
c~ O
~
~
.-..-..-.
H ~, x x x x x x x x x x ~ a~
~ ~
~.
U
H W
U
~ ~
O
~ ~r
~
Lf7N ~ r1 N L17l.nLf,LC7t1,
~
O .t1
O
U
O
~ O
W ~ I~
r1
O
tJ1
m, i.a
W
~
U
dP Q1 01 01 01 01 a1 01 01 01 CO 4-1
1-i Q1 ~1 01 Q1 01 01 p
1-1 ~
l 4-I
r 01 01 01 01 ~ ~
O
~
O
f~
C
~
.
'-I
'-1
4-I
iJ~
O I~
I O ,1
p ~ U ~
p
U -r,
3
O O o 0 0 0 0 0 0 0 0 0
rt
t~, a~ 0 0 0 0 0 0 0 0 0 0 ~
~, ' ~
~'
O~ t~ t~ t~ t~ t~ t~ t~ t~ t~ t~ ~ .n
O a~ ' '
a~
c~
U
~
U 1r r-ir-tr-IrI r-I r-Ir-Ir-Ir-1r-1 ~ p
sr c~
,7, r!1
~
U .-1
LT L2
r-~
O
~C '~
'zf ..~
~1, ca
.u
~ H
:~'
O
.
U
r1 N M V~ In l0 t~ 00 Q1 O ~ N
'
~ v U
x ., ~ .,~
o
w o 0
z
z z
~
~, 212a~.8~
0 0 0 0 0 0 0 o W
~ ~ t~ t~ t~ t~ t~ t~ t~ rti
~ o
.~ U o
,t
D., O
.,-~
cU
O W ~
U .,~
O
_ >~
O Q' P4
O
0 0 0 0 0 0 0 0 ~
x ~ ~ M M M M M M M M
.~ .i ~ al
'~ p
O a~ ~
x
0 0
1-a ~ U
pq U ~ 0 0 0 0 0 0 0 0
-7-~ Lf7In u~ tn 00 lO lD tn ,~ O
O~
~
.1.)
o ~ ~ ~ ~ ~ ~ ~ ~
W
r-I
W
--i
r-I
3 ~
~
3
p
a~
p
3
O
U
4a ~ '.~
~
O c~ -~-~
r-I O
c0 c0 r-Io x x ~ s~ W
~ ~
p ~ ~ ~-~IO O ~ t5~
a~ y,~
,
o ~
~
x
a~
~ a
z U o o
~ ~
.r,
c~
cr
,
0
U '
4~ ~ N
~
O ~
-
_
x x x x x ~ ~ x .~ v
~~
N
~ U U
E ~W
W
W
H O ~
I y ar m nr m un o m
N 'r1
-s",
O ,-O
O
~ ~
O
N
4-I
r-I
O m y n s-a
~ r-'~i W ~
~ U
O O
O
~ O t~ a~ o~ o~ o~ o~ o~ ~D W
dp
1..~ a1 O1 Q1 O1 Q1 O1 of O1 (Jj
t-~ ~ O
r-1
O
U
f~ ~ ~
.~ .~
'-I
'a
W ~
O ~
O
-t
I w
c~ U ~
W 3
W N
~~
O O~-I 0 0 0 0 0 0 0 0 ~
a ~ ~..i O O O O O O O O '
~
i~ C~ O d' t~ I~ t~ I~ t~ ~ O
U ..Q
<v
O fLf ~ ~ w w w . w
U a~ r1 ri N ri r1 r1 r1 ~""I~
E
?-~
S.-~
,7y
~,
. ~-1
~ CT ..Q
r1 .J~
O
a'
'L~
Q
.~-~
. O ~
r H
r~
r-1N M 'd'1~ l0 t~ 00 ~ N
'
r~ r-Ir-1 r1 r-ir-Iri r-I~
x - N
o
w z
z
2~20.~80
- 19 -
s~
U U tn
~
r-i o o N o0 0 0 0 0
1 1 1
I per., ~ r~ co m t~ I I ~ t~ t~ 1 O
~
O .~
O
~
W 0
U ~ ~
r
-II
v O U r~
.~ s~
p U I O O 00 N O 1 I I I O C7 O L~
p
x I .~'t M M r1 d~ M M M M 1 Pa
-1.~
U ~, .~
.-t
p ~
U O
U
3~
sa ~
~
s.., N
0 0 0 0 0 0 0 0 0
t!7LIBM t0 tf7
I I I I I ~
-1..~ ~ CO N ~ CO Lf1tf1O r"i
~ ""~
~ ty.~
.7-~
.~'. r-Il0
c~ !~ ~
U
.~
~
U
~
r-I ~ -J-)
~
ri
r-I
p 3 b,
~
~
3
x ~
U
-I
r
O ~n ~ .~
~' 3
U
O
O
U
'~
W rt3
.J~ ~
L7~
O I 00 00 00 00 00 1 I I I M 00 00
f~ I i
r-1 J
cW--I
,~ .
.
U
O
~'.r
-n-!
5C
.~
.J-~
~
x I~
~ ~ ,~y
t~"
N
r~
2
U
.-i
~
c
i W ~ ~
~ O
O tT
x W
O U
~
_ _ _ U
O I x >C DC ~C O I 1 I I DC DG >C W ~ N
U N
f~
~
H U
U
a-i
O
O ~-i
O ,
O
I ~' ~
~n
b
I O t!~t!1Ln tI7 O O O O In tt~ll~N H fail
~ ""i
O N '"~
W
W W O
.-1 U
O U ~
V7 U
(U 01 a1 01 01 01 01 O~ O~ o1 O1 01 0\ ~
r-I C>a
~'. p
1 I ~ p
O ~ o~ ~ O1 01 Q1 Q1 01 01 01 01 01 .
dP .,
1-~ r-1
i-~ .J~
r-I p
~ ~
U O
O U
~
~
C-1 ~ W
.~ U O
O W
I ~ ~
~ O
U
W O ~
N .i.~
~ U
O O o 0 0 0 0 0 0 o O o 0 0 ~ .C
ri
, p 0 0 0 0 0 0 0 0 0 0 0 0
~,
~ I~ I~ I~ I~ I~ t~ I L~ t~ I I~ t~ I~ t~
O ~ x
~
U 1-y..~ i--1r-i~-ir-Ir-~r-I .--Ir-I r-I r-Ir1 r-iU ~
,~y
~",
,
N
~
~-i
O
U
O
-~
~ ~
~ H ~
!~
~
U
I ~ N
I
I ,--iN M d' tt1l0 I~ CO 01 O r1 N M d~
!C3
QJ
~
r-ir-i r~ r~ f-iU U
~
U
o
~s
-~
x
.-i
o
U
a,
-N
w
c?,
z
z z
_ 2120~.8~
- 20 -
x
U
o O o o r-iO o O O O r1 ,-IO o 0 o r-~r-~
H
~,
O
,.Q
O
1a \
L7~
W ~..
O
Y~
tD 00 I~ O 01 01 O 01 00 C~ O~ I~ CO GO CO 00 O O
O O O r-1 O O r1 O O O O O O O O O --~
,
W
N W
~ O
~ U
x ~
U U
ri U
a..)
~,
M
U
r~
(U
H
U
0
O M
U \
W ...
s.., O
U
CO N ri l0 tn d~ LC1ltd~ O M O r1 N M 'c1'CO lfl
r1 N N N N N N N N N N N N N N N N N
W W N
N -1-~
~
U
4..~ ~ \
o x ~
U a~
~n ~ ~
.'., w Ca.,
a~
0
r1 N M 'd~ In l0 t~ 00 Ql O r-1N M d~ Lc7l0 I~ 00
r1 rd rd rd r-I r-Ir~ r~ r1
'~
41 U U U U U N U N U U U U U U U U
r~ir~ r~ r-i r-Ir-Ir1 r-~r1 r1 r1 r-1r~ r-i r~ -I -1 ~
U ~ t~ ~.r~ f~ ~r ~ ~L ~ R~ i~ ~ far~ ~ r r r
C~ f~ t~
ttf!~1a5 ni r6 cU c~ c~ of c~ c~ ct3c~ ~ ~ ctfcd c~
x x x x x x x x x x x x x x x x x x
w w w w w w w w w w w w w w w w w w
212018
,_ -
- 21 -
x
O O O N O O O N r1 N M O O O N
H
O
,.p
O
,~
O
Cn
lE..~
v
01 N N V~ Lf1N r1 h l~ '-IIn h 00 O
~1 N N r1 r-Ir-1r-~ N N N O r1 r1 ,--~N
(~j
O
1~
N
bi
O
~ U
r1
\
x .+~
U U
r~
H O M
U\
W
O
d' M r1 t0 N M N d~ O N h r1 N c!'
M 'd~M M M M 00 N M r1 M d~ d' 00
r-~ r-~rd
O
U N -7~
to ~ O
x
U U U
.i.~ .,-~
pa
t~ .i-~
O tli
U
r1 N M d~ Lf1l0 h CO Q1 O ri N M d'
O r! r1 r1 r1 r1
U U O N N U U U N U U U ~ N
- r~ r~ r~ r~ r-~r~ r-~r-~r-~r-~r-~ r-~r-~r~
~f ct3(ISt~ t~ t~ t~ cd (L5ILS(U cU lCf
x x x x x ~ x x x x x x se x
w w w w w w w w w w w w w w
v a~ a~ a~ a~ a~ a~ a~ a~ a~ a~ a~ a~ a~
a' .r.,-~ .r-,.r.,.r.,-r.,.r.,.r.,
0
cu ~ ~ ~a ~ ~ ~ ~s ~ ~s
-
w a~ as a~ a~ a~ a~ a~ a~ w ~ a~ a~ as
0 0 0 0 0 0 0 0 0 0 0 0 0 0
U U U U U U U U U U U U U U
. _ 2120180
- 22 -
EXAMPLES 19 TO 20 AND COMPARATIVE EXAMPLES 15 TO 18
In each Example, using a sizing solution as
identified in the following item (1), a coated paper was
prepared by a method as identified in the following item
(2). The tests for evaluating the physical .properties of
the coated paper were conducted in the same manner as in
Example l, and the results are shown in Table 5. In
Comparative Example 18, the non-coated paper (raw paper)
was used. The IGT printability was measured in
accordance with the following item (3).
(1) Sizing solution used
Example 19: same as in Example 1
Example 20: same as in Example 16
Comparative Example 15: same as Comparative Example 1
Comparative Example 16: same as Comparative Example 6
Comparative Example 17: same as Comparative Example 7
(2) Preparation of coated paper
A sizing solution was coated on one side of raw paper
for newspapers having a width of 450 mm (basis weight: 48
g/m2) bY a gate roll coater for test at a coating speed
of 100 m/min so that a dried coated amount would be 0.2
g/m2, to obtain coated paper. This coated paper was
adjusted at 20°C for 24 hours under a relative humidity
of 65~ and used as a test specimen for evaluation.
(3) Test for evaluating IGT printability
Using a IGT printability tester, the IGT strength
(cm/sec) was measured in accordance with TAPPI T-499
<IMG>
2~2Q1~0
,~
- 24 -
a
s~
_
t0 'd~r-I 'ct' l0 ~ t~ QJ
U7 In LC1lI1 I1~ M N
U
~
'b N ~ ..~
U
U ~ 3
H
7 U ~ ~,
W .t
~
C
H ~ O ~r
V1 ,.~
O Q,
U
~ O
W r~
x
O .~ O O
w
V O O W
U ,~ o O O O N M U O
,-i ~ .J..~
W ~ x N
s-.r f..~ b'~ U -i.~
U ~y .-I O t~
fuel 4J rd
Q7
p 3 .c~
w ~ o
O .J~M
b~ O W n M m m n ~''~~
..>~
~ U
U ~ U .
-~-~
_ r1 'v\ N M Itl 'c1' l!7 ~"I
Ul
~ ~ r1
..SG N ~-tS-i M N
t~
U
..~ (~Sitf~
s ~
'z3 O .i
~--
V1 Cta
U
Lf1
U 'Ly ~ .x N U O
-r,
'-I4-t U '~ '~ U U1 U
~ ~
..c~o ~ x ~ I o 1 I a~ w
~ a~
O O O W
N W L~
O
~ s~
O O
O ~ a~
rn H ~
U rn
,-i _ O
m w ~,
r-t
w tz1 t..~
a O ~
.-. O O O
U7
w U
~'
a3 ~ ~ a~ o~ o~
r- 1
i
p., ~ ~ o~ o~ ~ o~ ~ O
O ~
. ~
o~ O O ~ r1
Zs a~
~
O
-,
-a
.t~ O U ~
~ O
U
S~
u-t 1 4-1
u1
O O 0 o o o O .t~
'1 W p
~C
~ O
a~ a~~ c~ c~ t~ ~ I 1 -t~ ~ O
c~
O ~ -1
cd ~ O ~ ..C~
U
U ~' ~ W -I rt ~-i rl ~ x
~"~ '
.
N
C~ ~ U ~
r-i U1
O
r,
U -
~r r-I
U
N ~ U N
o~ o ~ ~ ~O ~ t~ ~ 00
try
r-1N .-~ r~ r1e-ir-ir-~
r-1 r-I
U U (LS t~3 t~fU (L1U
~ U
_
r1 r1 S-~ 1.-yl 1.-~r1 ~-tr1 ~
ri
N
Q1 ~ ~ f~ ~ ~ f~
~ ~
N U
O O
5S >C >C k O >C O k
W W U U W U W U W
f~
