Note: Descriptions are shown in the official language in which they were submitted.
20~~18~
SPECIFICATION
DEINKING AGENT
[Field of Industrial Application]
This invention relates to a deinking agent to be
used for the reclamation of waste papers including
newspapers and magazines. More particularly, it .
relates to a deinking agent whereby a deinked,pulp
having a high b value and showing good defoaming
properties of a flotation reject can be obtained by
deinking, for example, newspapers or magazines
according to a compromise between the flotation and
washing methods.
[Prior Arts]
It has long been a practice to reclaim waste
papers including newspapers and magazines. Recently
the effective utilization of waste papers has become
more and more important in conjunction with the
problems of the shortage of pulp resources and an
increase in the cost thereof. Further, it has been
attempted to use deinked pulp in the production of
higher quality products. On the other hand, recent
improvements in printing techniques, printing systems
and printing ink compositions as well as the
reclamation of such waste papers that were never
- 1 -
204~~8~
recovered before have made it difficult to deink waste
papers. In order to facilitate deinking, therefore,
attempts have been made to improve deinking devices.
In order to remove inks and other impurities from
waste paper, there have been used alkaline agents such
as caustic soda, sodium silicate, sodium carbonate and
sodium phosphate, bleaching agents such as hydrogen
peroxide, hydrosulfites and hypochlorites and,
sequestering agents such as EDTA and DTPA together
with deinking agents including anionic surfactants
such as alkylbenzenesulfonates, higher alcohol
sulfates, a-olef.insulfonates and dialkyl
sulfosuccinates, ethylene oxide adducts of higher
alcohols, alkylphenols. and fatty acids, and nonionic
surfactants such as alkanolamides, either alone or-in
the form of a mixture thereof. Although these
deinking agents show excellent foaming properties in
the flotation treatment, their abilities to collect
ink are limited. In the washing method, on the other
hand, they are poor in detergency and, furthermore,
the good foaming properties thereof cause troubles in
draining. As a result, only a deinked pulp of a low
grade can be obtained thereby. Furthermore, even when
a pulp of a high whiteness is obtained, a dull color
remains to restrict the utilization of the deinked
- 2 -
204~18~
pulp (for example, employed in a decreased amount
under the surface of cardboard or added in a decreased
amount to newspapers), or it is unavoidable to
increase the amount of a bleaching agent so as to do
away with the dullness. In order to obtain a deinked
pulp which is free from dullness and has a light color
tone, it ~s necessary to elevate the b value.
Although the b value can be elevated by using a large
amount of alkalis, other problems including increases
in sticky matters, the draining load and the
brittleness of the obtained pulp might occur in this
case. Thus no effective means had been known for
solving these problems.
The present inventors proposed the use of a
reaction product obtained by aiding an alkylene oxide
to a mixture of a natural fat and a trihydric or
higher alcohol as a deinking agent (cf. Japanese
Patent Laid-Open No. 239585/1985).
As the result of investigations on the behaviors
of such a reaction product in a deinking process in
detail, however, it was found out that it had some
disadvantages. That is, a compound obtained by using
a natural fat and a trihydric or higher alcohol at a
molar ratio of from 1 . 0.5 to 1 . 3 frequently causes
foaming troubles in the flotation, dehydration,
- 3 -
204182
draining and papermaking stages. Further, the deinked
pulp thus obtained was not completely free from a dull
color, though it had a high whiteness.
[Disclosure of the Invention]
The present inventors have conducted extensive
studies in order to develop a dein~ing agent which
shows a good deinking performance (a high b value)
when used in deinking according to a compromise
between the flotation and washing methods and has good
defoaming properties of a reject in the flotation
stage, thus causing no foaming troubles. As a result,
they have surprisingly found out that a deinking agent
comprising a specific nonionic surfactant as an
essential component satisfies the above requirements,
thus completing the present invention.
Accordingly, the present invention provides a
deinking agent comprising an ester mixture as the
active ingredient, wherein the ester mixture is
obtained by adding ethylene oxide and propylene oxide
at a molar ethylene oxide/propylene oxide ratio of
from 0.5 to 4 (preferably from 1.8 to 2.2) to an ester
mixture which is obtained by reacting a natural fat or
a reaction product, preliminarily obtained by reacting
a natural fat with glycerol, with a monohydric or
dihydric alcohol at a molar ratio of the alcohol to
- 4 -
204~18~
the glycerol in the natural fat of from 0.02/1 to 1/1
(preferably from 0.05/1 to 0.48/1) and which has a
hydroxyl value of from 3 to 50, preferably from 3 to
28 (in the case of a monohydric alcohol), or from 10
to 150, preferably from 10 to 78 (in the case of a
dihydric alcohol) in such a manner as to give an
addition mol number of the ethylene oxide of from 5 to
200, preferably from 10 to 100 (in the case of a
monohydric alcohol) or from l0 to 400, preferably from
20 to 200 (in the case of a dihydric alcohol).
As the monohydric alcohol to be used in the
present invention, alkanols-1 and alkanols-2,
unsaturated alcohols and cyclic alcohols having 1 to
24 carbon atoms may be used. Examples thereof include
aliphatic alcohols such as octanol, nonano~, decanol,
undecanol, lauryl alcohol, myristyl alcohol, cetyl
alcohol, stearyl alcohol, eicosanol, oleyl alcohol,
elaidyl alcohol and linoleyl alcohol and synthetic
alcohols such as methyl alcohol, ethyl alcohol, propyl
alcohol, isopropyl alcohol, 2-ethylhexanol,
hexan-2-ol, 2-hexenol, cyclononanol and cyclodecanol.
As the dihydric alcohol to be used in the present
invention, a,(~-glycols, 1,2-diols, symmetric a-glycols
and cyclic 1.2-diols having 2 to 23 carbon atoms may
be used. Examples thereof include hexadecane-1,2-
- 5 -
204'182
diol, octadecane-1,2-diol, eicosane-1,2-diol, ethylene
glycol, propylene glycol, butanediol, hexanediol,
cyclononane-1,2-diol, butanoyi-oc-glycol and hexanoyl-
Ot-glycol .
As the fat to be used in the present invention,
vegetable oils such as coconut oil, palm oil, olive
oil, soybean' oil, rapeseed oil, linseed oil, castor
oil and sunflower oil, terrestrial animal fats such as
lard, beef tallow and bone oil, aquatic animal oils
such as sardine oil and herring oil, hardened or semi-
hardened oils obtained therefrom and recovered oils
collected during the refining procedureythereof may be
cited. Further, monoesters or diesters obtained by
preliminarily reacting these natural fats with
glycerol may be used therefor.
It is important in the present invention that the
molar ratio of the monohydric or dihydric alcohol to
the glycerol in the natural fat range from 0.02/1 to
1/1. It is also important that the hydroxyl value
(OHV) of the ester mixture range from 3 to 50 (in the
case of a monohydric alcohol) or from 10 to 150 (in
the case of a dihydric alcohol).
In the calculation of the molar ratio of the
monohydric or dihydric alcohol to the glycerol, the
term "glycerol in the natural fat" means the sum of
- 6 -
204182
the glycerol binding to tatty acids so as to
constitute the natural fat and the glycerol which is
further added in order to modify the fat.
A compound where the molar ratio and hydroxyl
value fall within these ranges is effective in
removing fine ink spots and thus can give a deinked
pulp having a light color and a high b value. When
these values are outside these ranges, the dull color
of the obtained deinked pulp remains unremoved.
In the present invention, ethylene oxide and
propylene oxide may be added either at random (random
addition) or successively (block addition). The
former is preferable from the viewpoint of reducing
foaming troubles.
It is required that the molar ethylene
oxide/propylene oxide ratio range from 0.5 to 4.0 and,
that the addition molar number of ethylene oxide range
from 5 to 200 (in the case of a monohydric alcohol) or
from 10 to 400 (in the case of a dihydric alcohol).
When these values do not fall within the ranges as
specified above, the ability to liberate ink from
waste papers is deteriorated. In the case of the
flotation treatment, furthermore, the defoaming
properties of a reject in the flotation pit are
deteriorated. It is therefore essential to use a
204~18Z
compound satisfying the aforesaid requirements in
order to give a deinking agent which gives a deinked
pulp having a high b value and showing good defoaming
properties of a flotation reject.
In the present invention, the method of adding
ethylene oxide and propylene oxide is not particularly
restricted. Thus it may be performed under conditions
commonly employed for adding alkylene oxides to a
compound having active hydrogen. Namely, a catalytic
amount of an alkaline material is added to the mixture
of a natural fat =triglyceride) or the reaction
product, obtained by reacting a natural fat With
glycerol, with a monohydric or dihydric alcohol
optionally together with a glycerol ester originating
in said fat. Next, the resulting mixture is reacted
with ethylene oxide and propylene oxide at
approximately 100 to 200°C under 1 to 3 kg/cm2~ (gauge)
for several hours.
When used together with known dein~irig agents
such as higher alcohol sulfates, alkylbenzene-
sulfonates, higher alcohols or alkylphenol/ethylene
oxide adducts, the deinking agent of the present
invention exerts an excellent performance. The
deinking agent of the present invention may be added
at any one of the waste paper breaking, high-
- 8 -
204'7182 '
concentration bleaching and pre-flotation stages.
Alternately, it may be added in portions at each of
these stages. It may be added preferably in an amount
of from 0.03 to 1..0~ by weight based on the starting
waste papers.
[Examples
To further illustrate the present invention, and
not by way of limitation, the following Production
Examples and Examples will be given.
Production Example 1
154.2 g of beef tallow, 9.7 g of stearyl alcohol
and 1.5 g of 100 KOH were fed into a 1.5-Q autoclave
and heated to 130°C under stirring at approximately
600 rpm.
Next, the above mixture was reacted with 833.9 g
of an ethylene oxide/propylene oxide mixture (molar
ratio: 2-2/1) at 130 to 140°C under 1 to 3 kg/cm2
( gauge ) .
After the completion of the reaction, the mixture
was cooled to 80°C and the pH value thereof was
adjusted to approximately 6 with acetic acid. The
yield of the reaction product (invention product No. 1
given in Table 1) was 98~.
Production Example 2
200.7 g of beef tallow, 4.6 g of 2-ethylhexanol
_ g -
2~4"7.8
and 2.0 g of 100 KOH were fed into a 1.5-Q autoclave
and heated to 150°C under stirring at approximately
600 rpm.
Next, the above mixture was reacted with 494.2 g
of ethylene oxide in portions at 150 to 160°C under 1
to 3 kg/cm2 (gauge).
After the completion of the addition of ethylene
oxide, the mixture was cooled to 120 to 130°C. and then
reacted with 298.6 g of propylene oxide under 1 to 3
kg/cm2 (gauge).
Then the mixture was cooled to 80°C and the pH
value thereof was adjusted to approximately 6 with
acetic acid. The y~.eld of the reaction product
(invention product No. 11 given in Table 2) was 99~.
Production Example 3
138.0 g of beef tallow, 2.0 g of ethylene glycol
and 1.3 g of 100$ KOH were fed into a 1.5-Q autoclave
and heated to 13'0°C under stirring at approximately
600 rpm.
Next, the above mixture was reacted with 858.4 g
of an ethylene oxide/propylene oxide mixture (molar
ratio: 1.8/1) at 135 to 140°C under 1 to 3 kg/cm2
(gauge) .
After the completion cf the reaction, the mixture
was cooled to 80°C and the pH value thereof was
- 10 -
2~4'~~,8~
adjusted to approximately 6 with acetic acid. The
yield of the reaction product (invention product No.
31 given in Table 5) was 98~.
Production Example 4
100.0 g of beef tallow, 2.4 g of ethylene glycol
and 1.3 g of 100 KOH were fed into a 1.5-Q autoclave
and heated to 150°C under stirring at approximately
600 rpm.
Next, the above mixture was reacted with 540.2 g
of ethylene oxide in portions at 155 to 165°C under 1
to 3 kg/cm2 (gauge).
After the completion of the addition of ethylene
oxide, the mixture was cooled to 120 to 130°C and then
reacted with 356.1 g of propylene oxide under 1 to 3
kg/cmz (gauge).
Then the mixture was cooled to 80°C and the pH
value thereof was adjusted to approximately 6 with
acetic acid. The yield of the reaction product
(invention product No. 41 given in Table 6) was 99~.
Example 1
A recovered waste newspaper/magazine mixture
(50/50 by weight) was cut into pieces (2 x 5 cm) and a
given amount thereof was fed into a bench
disintegrator. Then water, 0.8~ (based on the
starting waste papers) of caustic soda, 2.5$ (based on
- 11 -
2~14'~9.82
the starting waste papers) of sodium silicate No. 3,
2.8~ (based on the starting waste papers) of 30$
hydrogen peroxide and 0.2~ (based on the starting
waste papers) of each of the deinking agents listed in
Table 1 were added thereto. After disintegrating at a
pulp concentration of 5~ at 45°C for 20 minutes, the
mixture was aged at 45°C for 60 minutes. Next, it was
diluted with water to a pulp concentration of,l.0~ and
subjected to flotation at 30°C for 10 minutes. After
the completion of the flotation, the obtained pulp
slurry was concentrated until the pulp concentration
reached 6~ and then diluted with water so as to give a
concentration of 1$. Then it was treated with a TAPPI
sheet machine to thereby give a pulp sheet.
The b value of the obtained pulp sheet was
measured with a color difference meter. The
percentage defoaming of the flotation reject was
determined in accordance with the following equation:
percentage reject volume after 30 seconds
defoaming of flota- _ (1 - ) x 100
tion reject !~) reject volume
A larger value means: better defoaming
properties while a smaller value means worse defoaming
properties.
The term "b value" as used herein means the value
of b of the Lab color space in accordance with
- 12 -
2~4'~1.8~
Hunter's color difference formula. The relation
thereof with the tristimulus values (X, Y and Z) is as
follows:
b = 7.0 (Y - 0.847 Z) /~
As the above equation shows, the value is a
function of Y and Z. A positive b value means the
intenseness of yellowness, while a negative one means
that of blueness.
Table 1 shows the molar monohydric alcohol/
glycerol ratio and deinking performance of each
deinking agent.
- 13 -
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Example 2
Recovered waste magazines were cut into pieces (2
x 5 cm) and a given amount thereof was fed into a
high-concentration pulper. Then water, 0.5~ (based on
the starting waste papers) of caustic soda, 1.5~
(based on the starting waste papers) of sodium
silicate No. 3, 1.0~ (based on the starting waste
papers) of 30~ hydrogen peroxide and 0.05 (based on
the starting waste papers) of each of the deinking
agents listed in Table 2 were added thereto to conduct
disintegration at a pulp concentration of 15~ at 45°C
for 20 minutes. Next, it was diluted with water to a
pulp concentration of 4.0~ and then further diluted
with water to a pulp concentration of 1.0~. Then it
was subjected to flotation at 30°C for 10 minutes. -
After the completion of the flotation, the obtained
pulp slurry was concentrated until the pulp
concentration reached 6~ and then diluted with water
so as to give a concentration .of 1~. Then it was
treated with a TAPPI sheet machine to thereby give a
pulp sheet.
The b value of the obtained pulp sheet was
measured with a color difference meter and the
percentage defoaming of the flotation reject was
determined.
- 15 -
204'18
Table 2 shows the molar ethylene oxide/propylene
oxide ratio and deinking performance of each deinking
agent.
- 16 -
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Example 3
Recovered waste magazines were cut into pieces (2
x 5 cm) and a given amount thereof was fed into a '
low--concentration pulper. Then water, 0.5~ (based on
the starting waste papers) of caustic soda, 1.0~
(based on the starting waste papers) of sodium
silicate No. 3, 0.8~ (based on the starting waste
papers) of 30~ hydrogen peroxide, 0.05 (based on the
starting waste papers) of a chelating agent (DTPA) and
0.065 (based on the starting waste papers) of each of
the deinking agehts listed in Table 3 were added
thereto to conduct disintegration at a pulp
concentration of 4~ at 40°C for 15 minutes. Next, it
was diluted with Water to a pulp concentration of 1.0~
and subjected to flotation at 30°C for 10 minutes.
After the completion of the flotation, the obtained
pulp slurry was concentrated until the pulp
concentration reached 6~ and then diluted with water
so as to give a concentration of 1~. Then it was
treated with a TAPPI sheet machine to thereby give a
pulp sheet.
The b value of the obtained pulp sheet was
measured with a color difference meter and the
percentage defoaming of the flotation reject was
determined.
- 18 -
204"7182
Table 3 shours the ethylene oxide addition mol
number and deinking performance of each deinking
agent.
- 19 -
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204"~18~
Example 4
A recovered waste newspare/magazine mixture
(50/50 by weight) was cut into pieces (2 x 5 cm) and a
given amount thereof was fed into a bench
disintegrator. Then water, 0.8~ (based on the
starting waste papers) of caustic soda, 2.0~ (based on
the starting waste papers) of sodium silicate No. 3,
1.5~ (based on the starting waste papers) of 30$
hydrogen peroxide and 0.5~ (based on the starting
waste papers) of each of the deinking agents listed in
Table 4 were added thereto to conduct disintegration
at a pulp concentration of 5~ at 50°C for 15 minutes
and then aging at 50°C for 2 hours. Next, it was
diluted with water to a pulp concentration of 1.0~ and
subjected to flotation at 30°C for 10 minutes. After
the completion of the flotation, the obtained pulp
slurry was concentrated until the pulp concentration
reached 6~ and then diluted with water so as to give a
concentration of 1~. Then it was treated with a TAPPI
sheet machine to.thereby give a pulp sheet.
The b value of the obtained pulp sheet was
measured with a color difference meter and the
percentage defoaming of the flotation reject Was
determined.
Table 4 shows the order of the addition od the
- 21 -
~4"7182
alkylene oxides to the glycerol ester and deinking
performance of each deinking agent.
- 22 -
204'~18~
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Example 5
A recovered waste newspaper/magazine mixture
(50/50 by weight) was cut into pieces (2 x 5 cm) and a
given amount thereof was fed into a bench
disintegrator. Then water, 0.8~ (based on the
starting waste papers) of caustic soda, 2.5~ (based on
the starting waste papers) of sodium silicate No. 3,
2.8~ (based on the starting waste papers) of 30~
hydrogen peroxide and 0.2$ (based on the starting
waste papers) of each of the deinking agents listed in
Table 5 were added thereto to conduct disintegration
at a pulp concentration of 5~ at 45°C for 20 minutes
and then aging at 45°C fox 60 minutes. Next, it was
diluted with water to a pulp concentration of 1.0~ and
subjected to flotation at 30°C for 10 minutes. After.
the completion of the flotation, the obtained pulp
slurry was concentrated until the pulp concentration
reached 6~ and then diluted with water so as to give a
concentration of 1~. Then it was treated with a TAPPz
sheet machine to thereby give a pulp sheet.
The b value of the obtained pulp sheet was
measured with a color difference meter and the
percentage defoaming of the flotation reject was
determined.
Table 5 shows the molar dihydric alcohol/glycerol
- 24 -
ratio and deinking performance of each deinking agent.
- 25 -
~04'~18~
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214"7182
Example 6
Recovered waste magazines were cut into pieces (2
x 5 cm) and a given amount thereof was fed into a
high-concentration pulper. Then water, 0.5~ (based on
the starting waste papers) of caustic soda, 1.5~
(based on the starting waste papers) of sodium
silicate No. 3, 1.0~ (based on the starting waste
papers) of 30~ hydrogen peroxide and 0.05 (based on
the starting waste papers) of each of the deinking
agents listed in Table 6 were added thereto to conduct
disintegration at a pulp concentration of 15~ at 45°C
for 20 minutes. Next, it was diluted with water to a
pulp concentration of 4.0~ and then further diluted
With water to a pulp concentration of 1.0$. Then it
was subjected to flotation at 30°C for 10 minutes. -
After the completion of the flotation, the obtained
pulp slurry was concentrated until the pulp
concentration reached 6~ and then diluted with water
so as to give a concentration of 1~. Then it was
treated with a TAPPI sheet machine to thereby give a
pulp sheet.
The b value of the obtained pulp sheet was
measured with a color difference meter and the
percentage defoaming of the flotation reject was
determined.
- 2~ - ,
204'718
Table 6 shows the molar ethylene oxide/propylene
oxide ratio and deinking performance of each deinking
agent
- 28 -
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204'71.82
Example 7
Recovered waste magazines were cut into pieces (2
x 5 cm) and a given amount thereof was fed into a
low-concentration pulper. Then watex, 0.5~a (based on
the starting waste papers) of caustic soda, 1.0~
(based on the starting waste papers) of sodium
silicate No. 3, 0.8~ (based on the starting waste
papers) of 30~ hydrogen peroxide, 0.05 (based on the
starting waste papers) of a chelatiiig agent (DTPA) and
0.06 (based on the starting waste papers) of each of
the deinking agents listed in Table 7 were added
thereto to conduct disintegration at a pulp
concentration of 4~ at 40°C for 15 minutes. Next, it
was diluted with water to a pulp concentration of 1.0~
and subjected to flotation at 30°C for 10 minutes. -
After the completion of the flotation, the obtained
pulp slurry was concentrated until the pulp
concentration reached 6~ and then diluted with water
so as to give a concentration of 1~. Then it was
treated with a TAPPI sheet machine to thereby give a
pulp sheet.
The b value of the obtained pulp sheet was
measured with a color difference meter and the
percentage defoaming of the flotation reject was
determined.
- 30 -
~~4"718
Table 7 shows the ethylene oxide addition mol
number and deinking performance of each deinking
agent.
- 31 -
~~~~~8~
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Example 8
A recovered waste newspaper/magazine mixture
(50/50 by weight) was cut into pieces (2 x 5 cm) and a
given amount thereof was fed into a bench
disintegrator. Then water, 0.8~ (based on the
starting waste papers) of caustic soda, 2.0~ (based on
the starting waste papers) of sodium silicate No. 3,
1.5~ (based on the starting waste papers) of ~0$
hydrogen peroxide and 0.5~ (based on the starting
waste papers) of each of the deinking agents listed in
Table 8 were added thereto to conduct disintegration
at a pulp concentration of 5~ at 50°C for 15 minutes
and then aging at 50°C for 2 hours. Next, it was
diluted with water to a pulp concentration of 1.O~S and
subjected to flotation at 30°C for 10) minutes. After
the completion of the flotation, the obtained pulp
slurry was concentrated until the pulp concentration
reached 6~ and then diluted with water so as to give a
concentration of 1~. Then it was treated with a TAPPI
sheet machine to thereby give a pulp sheet.
The b value of the obtained pulp sheet was
measured with a color difference meter and the
percentage defoaming of the flotation reject was
determined.
Table 8 shows the order of the addition of the
- 33 -
~04"718~
alkylene oxides to the glycerol ester and deinking
performance of each deinking agent.
- 34 -
a 204'18:
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