CA2047183A1

CA2047183A1 - Deinking agent

Info

Publication number: CA2047183A1
Application number: CA 2047183
Authority: CA
Inventors: Hideaki Urushibata; Koji Hamaguchi; Hiroyoshi Hiramatsu; Yoshitaka Miyauchi
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 1990-10-24
Filing date: 1990-10-24
Publication date: 1992-04-25

Abstract

ABSTRACT OF THE DISCLOSURE
A deinking agent comprising an ester mixture as the active ingredient, wherein the ester mixture is obtained by adding ethylene oxide and propylene oxide to a mixture obtained by reacting a natural fat or a reaction product, obtained by preliminarily reacting a natural fat with glycerol, with a tetra- to dodecahydric alcohol in such a manner as to give a molar ratio of the alcohol to the glycerol in the natural fat of from 0.02/1 to 1/1. By using the deinking agent of the present invention, a deinked pulp contaminated with little unliberated ink can be obtained without any foaming troubles or dulling.

Description

Z0~183 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 contaminated with little unliberated ink can be obtained by deinking, for example, newspapers or magazines according to the flotation method, the washing method or a compromise between these 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, i~ 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 Z0~7183 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-olefinsulfonates 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 projerties in the flota~ion 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. Furthermo~e even when a pulp of a high whiteness is obtained, a dull color remains to restrict the utilization of the deinked ;~0~7~8~

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 is 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 has been known for solving these problems.
The present inventors proposed the use of a reaction product obtained by adding an alkylene oxide to a mixture of a natural fat and a trihydric or higher alcohol as a deinking agent (cf. Japanese Paten~ Laid-Open No. 239585/1985).
As the result of investigations on the behaviors of such a reaction product i~ 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, draining and papermaking stages. Further, the deinked pulp thus obtained was contaminated with a large amount of unliberated ink, though it had a high whiteness.
[Disclosure of the Invention]
The present inventors have conducted extensive studies in order to develop a deinking agent which shows a good deinking performance when used i~
deinking according to the flotation method, the washing method or a compromise between these methods and thus a deinked pulp free from foaming troubles and a dull color (a high b value) and contaminated with little unliberated ink can be obtained thereby. As a result, they have surprisingly found out that a deinking agent comprising a specific nonionic surfactant as the essential ingredient satisfies the above requirements, thus completing the present invention.
Accordingly, the present lnvention provides a deinking agent comprising an ester mixture as the essential 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 2047~83 a reaction product, preliminarily obtained by reacting a natural fat with glycerol, with an alcohol having 4 to 12 hydroxyl groups at a molar ratio of the alcohol to 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 (~HV) of from 6 to 2000, preferably from 6 to 1500, in such a manner as to give an addition mol number of the ethylene oxide of from ~0 to 2400, preferably from 30 to 1200, as an essential component.
As the alcohol to be used in the present invention, those having 4 to 24 carbon atoms may be cited. Examples thereof include tetrahydric alcohols such as erythrose, erythrulose, erythritol, trethreose and diglycerol, pentahydric alcohols such as arabinose, xylulose, xylose, deoxyribose, lyxose, ribulose, ribose, arabitol, ribitol, altrose, allose and galactose, hexahydric alcohols such as gulose, mannose, glycitol, inositol, mannitol, sorbitol and tetraglycerol, heptahydric alcohols such as heptose an~ heptutholose, octahydric alcohols such as octitol, octulose and nonulose, and nonahydric alcohols such as agarobiose, cellobiose, maltose, lactose, gentianose, stachyose and cellotriose.
Among these polyhydric alcohols, tetra-, penta-and hepta- to dodeca-hydric ones are particularly preferable.
As the natural 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 collec~ed during the refining procedure thereof 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 alcohol having 4 to 12 hydroxyl groups to the glycerol in the natural fat range from 0.05/1 to 0.48/1. It is also important that the hydroxyl value (OHV) of the ester mixture range from 6 to 1500.
In the calculation of the molar ratio of the alcohol having 4 to 12 hydroxyl groups to the glycerol, the term "glycerol in the natural fat" means the sum of the glycerol binding to fatty acids so as to constitute the natural fat and the glycerol which is further added in order to modify the fat.

20~7~8~

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 the molar ratio is outside this range, 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 additionj. 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 (preferably from 1.8 to 2.2) and that the addition mol number of ethylene oxide range from 30 to 1200. 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 foaming properties are deteriorated. In the case of the washing treatment, on the other hand, the ability to remove ink is deteriorated. A compound wherein these values fall within the above ranges is particularly effective in reducing unliberated ink. It is therefore essential to use a compound satisfying the 2047~83 above requirements in order to obtain a deinked pulp having a high b value and contaminated with little unliberated ink.
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 an alcohol having 4 to 12 hydroxyl groups. Next, the resulting mixture is reacted with ethylene oxide and propylene oxide at approximately 100 to 200C under 1 to 3 kg/cm2 (gauge) for several hours.
When used together with known deinking agents such as higher alcohol sulfates, alkylbenzene-sulfonates, higher alcoho~s 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-concentration bleaching and pre-flotation stages.
Alternately, It may be added in portions at each of 2047~8;:~

these stages. It may be added prefera~ly in an amount of from 0.03 to 10% by weight based on the starting waste papers.
[Exàmples and Effect]
To further illustrate the present invention, and not by way of limitation, the following Production Examples and Examples will be given.
Production Example 1 192.2 g of coconut oil, 19.23 g of pentaery-thritol and 2.5 g of 100% KOH were fed into a 1.5-Q
autoclave and heated to 130C under stirring at approximately 600 rpm.
Next, the above mixture was reacted with 786.1 g of an ethylene oxide/propylene oxide mixture ~molar ratio: 1.8/1) at 130 to 140C under 1 to 3 kg/cm2 -(gauge).
After the completion of the reaction, the mixture was cooled to 80C 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 2 223.5 g of beef tallow, 13.3 g of sorbitol and 2.2 g of 100% KOH were fed into a l.S-Q autoclave and heated to 130C under stirring at approximately 600 _ g _ 20~17~La3 rpm.
Next, the above mixture was reacted with 761.0 g of an ethylene oxide/propylene oxide mixture (molar ratio: 2 : 1) at 130 to 140C under 1 to 3 kg/cm2 (gauge).
Then the mixture was cooled to 75C and the pH
value thereof was adjusted to approximately 6 with acetic acid. The yield of the reaction product (invention product No. 27 given in Table 5) was 99%.
Production Example 3 211.1 g of bone oil, 50.2 g of stachyose and 2.1 g of 100% KOH were fed into a 1.5-Q autoclave and heated to 150C under stirring at approximately 60 rpm.
Next, the above mixture was reacted with 452.5 g of ethylene oxide in portions at 150 to 160C under 1 to 3 kg/cm2 (gauge).
After the completion of the ethylene oxide a~dition reaction, the mixture was cooled to 120 to 130C and then reacted with 331.9 g of propylene oxide under 1 to 3 kg/cm2 (gauge).
Next, the reaction mixture was cooled to 80C and the pH value thereof was adjusted to approximately 6 with acetic acid. The yield of the reaction product (invention product No. 53 given in Table 9) was 98%.

;~04'7183 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 the starting waste papers) of sodium silicate No. 3, 2.8% (based on the starting waste papers) of ~0%
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 45C for 20 minutes, the mixture was aged at 45C for 60 minutes. Next, it was diluted with water to a pulp concentration of 1.0% and subjected to flotation at 30C 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 treatqd 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 while the unliberated ink spots were counted with an image analyzer (100 x magnification). The term "b value" as used herein means the value of b of the Lab~ color 2~)4~33 space in accordance with Hunter's color difference formula. The relation thereof with the tristimulus values (X, Y and Z) is as follows:
b = 7.0 (Y - 0.847z)/l~
As the above equation shows, the b 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 tetrahydric alcohol/glycerol ratio and de,inking performance of each deinking agent.

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~04718~

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 45C
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 flotatipn at 30C 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 differen¢e meter and the unliberated ink spots were counted with an image analyzer (100 x magnification).

Table 2 shows the molar ethylene oxide/propylene oxide ratio and deinking performance of each deinking agent.

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2 ~ ~ ' ,~ ~ c O

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~ C X ~

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2C)4718~

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 ~apers) 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% of a chelating agent (DTPA) and 0.06% (based on the starting waste papers) of each of the deinking agents listed in Table 3 were added thereto to conduct disintegration at a pulp concentration of 4% at 40C for 15 minutes.
Next, it was diluted with water to a pulp concentration of 1.0% and subjected to flotation at 30C 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 RAPPI 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 unliberated ink spots were counted with an image analyzer ~100 x magnification).
Table 3 shows the ethylene oxide addition mol 2047~8~

number and deinking performance of each deinking agent.

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Example 4 ~ recovered waste newspaper/magazine mixture t50/50 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 50C for 15 minutes and then aging at 50C for 2 hours. Next, it was diluted with water to a pulp concentration of 1.0% and subjected to flotation at 30C 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 a~nd the unliberated ink spots were counted with an image analyzer (100 x magnification).
- Table 4 shows the order of the addition of the alkylene oxides to the glycerol ester and deinking performance of each deinking agent.

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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 45C for 20 minutes and then aging at 45C for 60 minutes. Next, it was diluted with watar to a pulp concentration of 1.0% and subjected to flotation at 30C 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 unliberated ink spots were counted with an image analyzer (100 x magnification).
Table 5 shows the molar hexahydric 2047~83 alcohol/glycerol ratio and deinking performance of each deinking agent.

~.

~ ~a~ C Z047~33 C O N (~ N ~I rl N r~ N N N
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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 45C
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 30C 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 unliberated ink spots were counted with an image analyzer (100 x magnification).

Z047~33 Table 6 shows the molar ethylene oxide/propylene oxide ratio and deinking performance of each deinking agent.

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O O e N ~ ~D N N

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O E O O ~ ~ _ 1 J ~;~ ''''' C VV ~ ~ ~ ~ V X CO

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Example 7 Recovered waste magazines were cut into pieces (2 x S 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 0.06% (based on the starting waste papers) of each of the deinking agents listed in Table 7 were added thereto to conduct disintegrating at a pulp concentration of 4% at 40C for 15 minutes. Next, it was diluted with water to a pulp concentration of 1.0%
and subjected to flotation at 30C 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 unliberated ink spots were counted with an image analyzer (100 x magnification).

2047~83 Table 7 shows the ethylene oxide addition mol number and deinking performance of each deinking agent.

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O ~r ~ o c e ~ o 2047~83 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 N~. 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 8 were added thereto to conduct disintegration at a pulp concentration of 5% at 50C for 15 minutes and then aging at 50C for 2 hours. Next, it was diluted with water to a pulp concentration of 1.0~ and subjected to flotation at 30C 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 unliberated ink spots were counted with an image analyzer (100 x magnification).
Table 8 shows the order of the addition of the alkylene oxides to the glycerol ester and deinking performance of each deinking agent.

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C h 20471~33 Example 9 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%
hydrQgen peroxide and 0.2% (based on the starting waste papers) of each of the deinking agents listed in Table 9 were added thereto. After disintegrating at a pulp concentration of 5% at 45C for 20 minutes, the mixture was aged at 45C for 60 minutes. Next, it was diluted with water to a pulp concentration of 1.0% and subjected to flotation at 30C for 10 minutes. Aftèr 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 wi~h a color difference meter while unliberated ink spots were counted with an image analyzer (100 x magnification).
Table 9 shows the molar docecahydric alcohol/

glycerol molar ratio and deinking performance of each deinking agent.

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2~47183 Example 10 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 10 were added thereto to conduct disintegration at a pulp concentration of 15%
at 45C 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 30C 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 çolor difference meter and the unliberated ink spots were counted with an image analyzer (100 c magnification).

2047~83 Table 10 shows the molar ethylene oxide/propylene oxide ratio and deinking performance of each deinking agent.

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Example 11 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% of a chelating agent (DTPA) and 0.06% (based on the starting waste papers) of each of the deinking agents listed in Table 11 were added thereto to conduct disintegration at a pulp concentration of 4% at 40C for 15 minutes.
Next, it was diluted with water to a pulp concentration of 1.0% and subjected to flotation at 30C 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 RAPPI 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 unliberated ink spots were counted with an image analyzer (100 x magnification).
Table 11 shows the ethylene oxide addition mol Z04~83 number and deinking performance of each deinking agent.

~ ~0 r_ 2C)47183 N ~O o t''l ~I U) '~ ~ ~

= -O~ 00 ~_o N ~-- ~ N N

C ~

.,, e; ~ _ ~
N ~9 ~ n o o o o N ~ O O O O

S ~ ~ R r : I

_~ u e n, co c n n~ 'x 3 ~ ~D

93 o 2~47~33 Example 12 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 30%
hydrogen peroxide and 0.5% (based on the starting waste papers) of each of the deinking agents listed in Table 12 were added thereto to conduct disintegration at a pulp concentration of 5% at 50C for 15 minutes and then aging at 50C for 2 hours. Next, it was diluted with water to a pulp concentration of 1.0% and subjected to flotation at 30C 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 unliberated ink spots were counted with an image analyzer (100 x magnification).
Table 12 shows the order of the addition of the - - 204718~

alkylene oxides to the glycerol ester and deinking performance of each deinking agent.

o ~ a Z047~ 1~3 ! ! . , 1~
'x o o o _ ~ O ~ ~In o U ~
O a O O

O ~ o E~ ~ u u ~
X
z r ~o a c,l o 2047~133 Example 13 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 wlaste 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 13 were added thereto to conduct disintegration at a pulp concentration of 5% at 45C for 20 minutes and then aging at 45C for 60 minutes. Next, it was diluted with water to a pulp concentration of 1.0% and subjected to flotation at 30C 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 unliberated ink spots were counted with an image analyzer (100 x magnification).
Table 13 shows the deinking performance of each - Z047~83 deinking agent.

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o ~
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o I o I ~ ~ o o ~ o 1l ''I I o o O
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Claims

1. A deinking agent comprising an ester mixture as the active ingredient, said ester mixture being obtained by adding ethylene oxide and propylene oxide to a mixture obtained by reacting a natural fat or a reaction product, obtained by preliminarily reacting a natural fat with glycerol, with a tetra- to dodecahydric alcohol in such a manner as to give a molar ratio of said alcohol to the glycerol in said natural fat of from 0.02/1 to 1/1.

2. A deinking agent as claimed in Claim 1, wherein said mixture of said alcohol and said natural fat has a hydroxyl value of from 1.5N to 170N, wherein N represents the number of hydroxyl groups of the alcohol.

3. A deinking agent as claimed in Claim 1 or 2, wherein the molar ratio of ethylene oxide to propylene oxide ranges from 0.5 to 4.

4. A deinking agent as claimed in any of Claims 1 to 3, wherein the addition mol number of ethylene oxide ranges from 5N to 200N, wherein N represents the number of hydroxyl groups of the alcohol.

5. A deinking agent as claimed in any of Claims 1 to 4, wherein ethylene oxide and propylene oxide are added at random.