WO1992007997A1

WO1992007997A1 - Deinking agent

Info

Publication number: WO1992007997A1
Application number: PCT/JP1990/001368
Authority: WO
Inventors: Hideaki Urushibata; Koji Hamaguchi; Hiroyoshi Hiramatsu; Yoshitaka Miyauchi
Original assignee: Kao Corporation
Priority date: 1990-10-24
Filing date: 1990-10-24
Publication date: 1992-05-14
Also published as: KR920702877A

Abstract

A deinking agent comprising as an active ingredient an ester mixture prepared by reacting a natural fat or a reaction product between a natural fat and glycerol with a tetrahydric to dodecahydric alcohol in a ratio of 0.02/1 - 1/1 in terms of a molar ratio of the alcohol to the glycerol in the natural fat to prepare a mixture, and adding ethylene oxide and propylene oxide to the mixture. It gives a deinked pulp free from somberness and containing less unpeeled ink.

Description

Specification

Deinking agent

[Industrial applications]

More specifically, the present invention relates to a deinking agent used for recycling used paper such as newspapers and magazines.More specifically, the present invention relates to a high b value when performing deinking treatment on newspapers, magazines, etc. by a flotation method, a cleaning method, and a compromise method thereof. The invention also relates to a deinking agent capable of obtaining deinked pulp with a low level of uninked ink.

[Conventional technology]

Recycling of newspapers, magazines, etc. has been practiced for a long time, but in particular, the effective use of waste paper has become increasingly important in recent years due to the shortage of pulp resources and soaring prices. The use of this is also expanding to advanced use. On the other hand, recent waste paper is becoming more severe in terms of deinking, such as changes in printing technology, printing methods, changes in printing ink components, and the use of waste paper that has not been collected and used in the past. Improvements have been made to the equipment to promote deinking. Chemicals that have been conventionally used to separate and remove ink and other impurities from waste paper include alkaline agents such as caustic soda, sodium silicate, sodium carbonate, and sodium phosphate, hydrogen peroxide, and hyposulfite. Salts, hypochlorites and other bleaching agents, EDTA, DTPA and other metal ion sequestering agents, as well as deinking agents, alkylbenzene sulphonate, higher alcohol sulphate, monopoly Anionic activators such as sulfonates and dialkyl sulfosuccinates; nonionic activities such as higher alcohols, alkylphenols and ethylenoxide adducts of fatty acids, and alcohol amides Agents have been used alone or in combination of two or more. However, these deinking agents have a high foaming property in the flotation process, but have a low ink-collecting ability.The cleaning method has a low detergency and a high foaming property. It caused foam trouble and resulted in only low grade deinked pulp. Furthermore, because of the dullness of high-whiteness, there are restrictions on the use of deinked pulp (reduction in the amount of paperboard used below and below, and reduction in the amount used in newspapers), and use of bleach to eliminate dullness. The situation had to be increased. In order to obtain a deinked pulp with a dull color and a light color, the b value should be increased. As a method for increasing the b value, it is sufficient to use a large amount of alcohol, but it has the disadvantage of increasing stickiness (sticky material), increasing drainage load and embrittlement of pulp. There is no effective means.

The present inventor has previously proposed that a reaction product obtained by adding an alkylene oxide to a mixture of a natural fat and oil and a polyhydric alcohol having 3 or more valencies is used as a deinking agent (Japanese Patent Application Laid-Open No. 60-239585). ).

However, when the behavior in the deinking process is examined in detail, it is found that the compound in which the mixing ratio of natural fats and oils and trivalent or higher polyhydric alcohol is in a molar ratio of 1: 0.5 to 1: 3 is σ The drawbacks are that foaming problems often occur during the ionizing process, deicing process, draining process, and papermaking process, and that the deinked pulp obtained has high whiteness, but has many unseparated inks. It was found that they had.

[Disclosure of the Invention]

The present inventors have developed a flotation method, a cleaning method and a compromise between them. And demonstrating excellent deinking ability, without foaming trouble, without dullness (high b value), and deinking pulp with low unreleased ink. As a result, surprisingly, the present inventors have found that a deinking agent containing a specific nonionic surfactant as an essential component satisfies the above-mentioned performance, and reached the present invention.

That is, the present invention provides a mixture of natural fats and oils or a reaction product obtained by reacting natural fats and oils with glycerin in advance and any one of alcohols having 4 to 12 hydroxyl groups, wherein the natural molar ratio in the fat and glyceryl Li down _{0 S 02Z 1~:. IZ 1} , is properly particularly preferred are obtained by reacting a 0.05 / 1-0 48/1, a hydroxyl value (DP) Is preferably 6 to 2000, particularly preferably 6 to 1500, and, for an ester mixture, ethylene oxide and propylene oxide are substituted by ethylene oxide Ζ propylene oxide = 0.5 to 4 (molar ratio), particularly preferably. Is to provide a deinking agent containing as an active ingredient an ester mixture added so as to be 1.8 to 2.2, the number of moles of ethylene oxide added to be 20 to 2400, particularly preferably 30 to 1200. .

Examples of the alcohol used in the present invention include alcohols having any of 4 to 24 carbon atoms. Specifically, tetrahydric alcohols such as erythrose and Trolulose, erythritol, threose, pentaerythritol, diglyserin, and pentavalent as arabinose, xylulose, xylose, deoxysil Baud2, lyxose, ribulose, ribose, arabitol, revitol, altroth, alose, galactose, hexavalent , Mannose, glycitol, inositol, mannitol, sorbitol, tetraglycerin, heptose and heptrose as heptavalent, and octitol as octavalent , Occulose, nonulose, 9 ffi include agaro biose, cello biose, altose, light toe, gentianose, stachyose, cello triose and the like.

• ^, -SO

Of the above polyhydric alcohols, ¹ ^ "4, 5, 7 to 12 are preferable. Natural fats and oils used in the present invention include coconut, palm, olive, soybean, rapeseed Vegetable oils such as Amani Shanto, Himashi Shanto, Himamori Shanto, etc., marine animal oils such as terrestrial animals such as lard, tallow, bone bone, etc. Examples of oils include recovered oils obtained in the process of purifying these fats and oils, etc. Further, monoesters and diesters produced by previously reacting these natural fats and oils with glycerin can also be used. In the present invention, it is important that the molar ratio of any of the alcohols having 4 to 12 hydroxyl groups to be used and the glycerin in natural coconut oil is 0.055Z1 to 0.48Z1. In addition, the hydroxyl value (0HV) of the ester mixture is any of 6 to 1500. In the above calculation of the molar ratio of alcohol to glycerin having any of 4 to 12 hydroxyl groups, "glycerin in natural fats and oils" It means the sum of glycerin, which is combined with fatty acids to form natural fats and oils, and glycerin that has been further added and reacted to modify the fats and oils.o Compounds having the above molar ratio and hydroxyl value within these ranges are effective in removing fine ink, give a dull, bright color tone, and consequently give a high b value deinked pulp. If the molar ratio deviates from this range, the dullness remains.

In the present invention, the addition of ethylene oxide and propylene oxide can be performed by adding the two in a mixed manner (random addition) or by sequentially adding (block addition). Considering this, random addition is preferred.

The addition ratio between ethylene oxide and propylene oxide is ethylene oxide Z propylene oxide = 0.5 to 4, preferably 1.8 to 2.2 (molar ratio), and the number of moles of ethylene oxide added is small. It must be between 30 and 1200. If it is out of this range, the ability to remove ink from waste paper will decrease. Furthermore, the foaming property is reduced during the flotation treatment, and the ink removal property is reduced during the washing treatment. Compounds within this range are particularly effective in reducing unisolated ink. Therefore, a deinked pulp having a high b value and a low unseparated ink cannot be obtained unless a compound satisfying the above conditions is used.

In the present invention, the method of addition reaction between ethylene oxide and propylene oxide is not particularly limited, and it can be carried out under the conditions of a general alkylene oxide addition reaction to a compound having active hydrogen. it can. That is, a catalytic amount of a mixture of the above-mentioned natural fats and oils (tridalicelide) or a reaction product obtained by reacting the natural fats and oils with glycerin in advance and any alcohol having 4 to 12 hydroxyl groups is added to the mixture. This can be achieved by adding ethylene oxide and propylene oxide for several hours at about 100-200 at l-3 kg / cm ² (gauge).

The deinking agent of the present invention exhibits excellent performance even when used in combination with a known deinking agent, for example, a higher alcohol sulfate, an alkylbenzene sulfonate, a higher alcohol, or an ethylene oxide adduct of alkylphenol. Demonstrate. The deinking agent of the present invention may be added to any of the waste paper disintegration step, the high-concentration bleaching step, the pre-flotation step, and each of the steps. The amount of addition is preferably 0.03 to L0% by weight based on the raw waste paper.

[Examples and effects]

Hereinafter, the present invention will be described specifically with reference to Production Examples and Examples, but the present invention is not limited thereto.

Production Example 1

192.2 g and 19.23 g of coconut oil and pentaerythritol, respectively, and 2.5 g of 100% K0H were charged into a 1.5-pound autoclave, and the temperature was increased to 130 at a stirring speed of about 600 rpm. did.

Next, 786.1 g of a mixture of ethylene oxide and propylene oxide in a molar ratio of 1.8: 1 was reacted with the above reaction product. The reaction conditions at this time were as follows: temperature 130 to 0: pressure 1 to 3 kgZcrf (gauge).

After the completion of the reaction, the temperature was cooled to 80, and the pH was adjusted to about 6 with acetic acid. The yield of the reaction product (No. 1 in Table 1 of the present invention) was 98%.

Production Example 2

1.5 pounds of beef tallow and sorbitol 223.5 each g and 13.3 g, and 2.2 g of 100% KOH were charged, and the temperature was increased to 130 under the condition of a stirring speed of about 600 rpm.

Next, 761.0 g of a mixture of ethylenoxide and propylene oxide in a molar ratio of 2: 1 was reacted. The reaction conditions at this time were a temperature of 130 to 140 and a pressure of 1 to 3 kgZcnf (gauge).

After the completion of the reaction, the temperature was cooled to 75 ° C, and the pH was adjusted to about 6 with acetic acid. The yield of the reaction product (27 in Table 5 of the present invention) was 99%.

Production Example 3

In a 1.5 pound autoclave, 211.1 g and 50.2 g of bone oil and 2.1 g of 100% K0H were charged, respectively, and the temperature was raised to 150 under the condition of a stirring speed of about 600 rpm.

Then, 452.5 g of ethylenoxide was used at a temperature of 150-160. C. The reaction was performed little by little under a pressure of 1 to 3 kgZcnf (gauge).

After completion of the ethylene oxide addition reaction, the temperature was cooled to 120 to 130 ° C, and 331.9 g of propylene oxide was reacted under a pressure of 1 to 3 kgXcnf (gauge).

Thereafter, the mixture was cooled to 80, and the pH was adjusted to 6 with acetic acid. The yield of the reaction product (Na53 in Table 9 of the present invention) was 98%.

Example 1

After collecting used city waste newspaper Z magazine (50Z50wt%) into 2 x 5 cm pieces, put a certain amount of it into a tabletop disintegrator, where water and caustic soda (based on raw material) 0.8%, sodium silicate 3 (Based on raw material) Add 2.5%, 30% hydrogen peroxide (based on raw material) 2.8%, deinking agent shown on Table 1 (based on raw material) 0.2%, add pulp concentrate After 20 minutes of dissolution at 45% at 45 ° C, aging treatment was performed at 45t for 60 minutes. Then, water was added to dilute the pulp concentration to 1.0%. The pulp slurry after flotation was concentrated to a 6% concentration, and then diluted with water to a 1% concentration to prepare a pulp sheet using a tapping sheet machine.

The b value of the obtained pulp sheet was measured with a colorimeter and the number of inks not separated was measured with an image analyzer (X100). The b value here means the b value in the Lab color system of the Hunter color difference formula, and the relationship with the tristimulus value ΠΙ is as follows.

b = 7.0 (Y-0.) / T

As can be seen from this equation, the b value is a function of Y and Z. Positive values indicate yellowness, and negative values indicate bluish intensity.

Table 1 shows the tetravalent alcohol Z glycerin molar ratios of various deinking agents and the deinking performance results.

Molar ratio of quaternary alcohol / glycerin and deinking performance

CD

* 1 EO: ethylene oxide PO: provenoxide

0 Example 2

After chopping the city collection magazine into 2 x 5 cm pieces, put a certain amount of it into high-concentration pulper, containing 0.5% of water and caustic soda (based on raw material), sodium silicate 3 (based on raw material) 1 5%, 30% hydrogen peroxide (based on raw material) 1.0%, deinking agent shown in Table 2 (based on raw material) 0.05% was added, pulp concentration was 15%, and defibration treatment was performed at 45 ° C for 20 minutes. Was done. Thereafter, water was added to the mixture to dilute it to a pulp concentration of 4.0%, and then further added to adjust the pulp concentration to 1.0%. This was subjected to a flotation treatment at 30: for 10 minutes. After the flotation, the slurry was concentrated to a concentration of 6% and then diluted with water to a concentration of 1% to prepare a pulp sheet using a tapping sheet machine.

The b value of the obtained pulp sheet was measured with a colorimetric colorimeter, and the number of inseparable inks was measured with an image analyzer (× 100).

Table 2 shows the molar ratios of ethylene oxide and propylene oxide for various deinking agents and the deinking performance results.

Table Molar ratio of ethylene oxide to provenoxide and deinking performance

* 1 EO: ethylene oxide PO: provenoxide

Example 3

After chopping the city collection magazine into 2 x 5 cm, put a certain amount of it into a low-concentration pulper, in which water and caustic soda (based on raw material) 0.5%, sodium silicate 3 (号 raw material) 1.0 %, 30% hydrogen peroxide (based on raw material) 0.8%, chelating agent (DTPA) 0.05%, deinking agent shown in Table 3 (based on raw material) 0.06%, pulp concentration 4%, 15 separation and processing at 40 Was done. Next, water was further added to adjust the pulp concentration to 1.0%. This was subjected to a flotation treatment at 30 at 10 minutes. After the flotation, the pulp slurry was concentrated to a 6% concentration and then diluted with water to a 1% concentration to prepare a pulp sheet using a tape sheet machine.

The b value of the obtained pulp sheet was measured with a colorimetric colorimeter, and the number of uninked inks was measured with an image analyzer (× 100).

Table 3 shows the number of moles of ethylene oxide added to various deinking agents and the deinking performance results.

Table.Additional moles of ethylene oxide and deinking performance

CO

* 1 E0: Ethylene oxide P0: Propylene oxide

Example 4

Waste paper Z collected in the market (50 zo 50 wt%) was cut into 2 x 5 cm pieces, and a certain amount was put into a desktop disintegrator, in which water and caustic soda (based on raw material) 0.8%, sodium silicate No. 3 (based on raw material) 2.0%, 30% hydrogen peroxide (based on raw material) 1.5%, and deinking agent (based on raw material) 0.5% shown in Table 4 were added. Pal: 15% at 5% concentration and 50% After separating and dissolving, the mixture was aged at 5 (TC for 2 hours. After that, the pulp concentration was diluted to 1.0% by adding water, and subjected to a flotation treatment at 30 ° C for 10 minutes. After the pulp slurry was concentrated to a 6% concentration, water was added to dilute the pulp slurry to a 1% concentration, and a pulp sheet was prepared using a tapping machine.

Table 4 shows the order of addition of alkylene oxides of glycerin ester and deinking performance results for various deinking agents. '

Alkylene oxide addition order and deinking performance

Cn

* 1 E0: Ethylene oxide PO: Propylene oxide

Example 5

After collecting used city waste newspaper Z magazine (50Z50wt%) into 2 x 5 cm pieces, put a certain amount of it into a tabletop disintegrator, where water and caustic soda (based on raw material) 0.8%, sodium silicate 3 (Based on raw material) 2.5%, 30% hydrogen peroxide (based on raw material) 2.8%, deinking agent shown in Table 5 (based on raw material) 0.2%, pulp concentration 5%, disintegrated 20 at 45 ° C Thereafter, aging treatment was performed at 45 for 60 minutes. After that, the pulp concentration was diluted to 1.0% by adding elongation, and subjected to a flotation treatment at 30 ° C for 10 minutes. The pulp slurry after flotation was concentrated to a 6% concentration, and then diluted with water to a 1% concentration to prepare a pulp sheet using a tabby sheet machine.

Table 5 shows the hexavalent alcohol Z-glycerin molar ratios of various deinking agents and the deinking performance results.

Hexahydric alcohol Z glycerin molar ratio and deinking performance

* 1 E0: ethylene oxide PO: propylene oxide

Example 6

After chopping the city collection magazine into 2 x 5 cm pieces, put a certain amount of it into a high-concentration pulper, containing 0.5% of water and caustic soda (based on raw material), sodium silicate 3 (3raw material) 1 5%, 30% hydrogen peroxide (based on raw material) 1.0%, deinking agent shown in Table 6 (based on raw material) 0.05% was added, and pulp concentration was 15%, and defibration was performed for 20 minutes at 45. . Thereafter, water was added thereto to dilute the pulp concentration to 4.0%, and then water was further added to bring the pulp concentration to 1.0%. This was subjected to fate treatment at 30 ° C for 10 minutes. After the flotation, the slurry was concentrated to a 6% concentration and then diluted to a 1% concentration by adding elongate to prepare a pulp sheet using a tape sheet machine.

The b value of the obtained pulp sheet was measured with a colorimetric colorimeter, and the number of uninked inks was measured with an image analyzer (X100 times).

Table 6 shows the molar ratio of ethylene oxide to pi-pyrene oxide and the results of deinking performance for various deinking agents.

Molar ratio of ethylene oxide and provylene oxide and deinking performance

CD

* 1 E0: ethylene oxide P0: provenoxide

Example Ί

After chopping the city collection magazine into 2 x 5 cm, put a certain amount of it into low-concentration pulper, and add 0.5% water and caustic soda (based on raw material), 1.0% sodium silicate 3 (based on raw material), Add 30% hydrogen peroxide (based on raw material) 0.8%, chelating agent (DTPA) 0.05%, and deinking agent (based on raw material) 0.06% shown in Table 7; pulp concentration 4%; Was done. Next, water was further added to adjust the pulp concentration to 1.0%. This was subjected to a flotation treatment at 30 at 10 minutes. The pulp slurry after the rotation was concentrated to a concentration of 6%, and water was added to dilute it to a concentration of 1% to prepare a pulp sheet using a tape sheet machine.

Table 7 shows the number of moles of ethylene oxide added for each deinking agent and the deinking performance results.

Ethylene oxide addition mole number and deinking performance

N3

* 1 EO: Ethylene oxide PO: Propylene oxide

Example 8

After collecting used city waste newspaper Z magazine (50Z50wt%) into 2 x 5 cm pieces, put a certain amount of it into a tabletop disintegrator, where water and caustic soda (based on raw material) 0.8%, sodium silicate 3 (Based on raw material) 2.0%, 30% hydrogen peroxide (based on raw material) 1.5%, deinking agent shown in Table 8 (based on raw material) 0.5%, pulp concentration 5%, after dissolving 15 at 50 The mixture was aged at 50 "C for 2 hours. Then, water was added to dilute the pulp concentration to 1.0%, and the mixture was subjected to a lotion treatment at 30 for 10 minutes. After the pulp slurry was concentrated to a 6% concentration, water was added to dilute it to a 1% concentration, and a pulp sheet was prepared using a tapping machine.

Table 8 shows the order of addition of alkylene oxide of glycerin ester and the results of deinking performance for various deinking agents.

Alkylene oxide addition sequence and deinking performance

0

CO

* 1 ED: Ethylene oxide P0: Propylene oxide

Example 9

After collecting used city waste newspaper Z magazine (50Z50wt%) into 2 X 5 cm pieces, put a certain amount of it into a tabletop disintegrator, where water and caustic soda (对 raw material) 0.8%, sodium silicate No. 3 (for raw material) 2.5%, 30% hydrogen peroxide (for raw material) 2.8%, deinking agent shown in Table 9 (for raw material) 0.2%, pulp grade 5%, 20 separation at 45 ° C After disassembly, aging treatment was performed at 45 for 60 minutes. Thereafter, water was added to dilute the pulp concentration to 1.0%, and the mixture was subjected to a filtration treatment at 30 for 10 minutes. The pulp slurry after flotation was concentrated to a 6% concentration, diluted with water to 1% concentration, and pulp sheets were prepared using a tapping sheet machine.

The b value of the obtained pulp sheet was measured with a colorimeter and the number of inks not separated was measured with an image analyzer (X100).

Table 9 shows the molar ratio of dodecyl alcohol 12-glycol and the deinking performance of various deinking agents. '

Molar ratio of 12-hydric alcohol / daliseline and deinking performance

tc

* 1 EO: Ethylene oxide P0: P! ? Bilenoxide

Example 10

After chopping the city collection magazine into 2 x 5 era, put a certain amount of it into a high-concentration pulper, into which water and caustic soda (based on raw material) 0.5%, sodium silicate 3 (based on raw material) 1 5%, 30% hydrogen peroxide (based on raw material) 1.0%, 0.05% deinking agent (based on raw material) shown in Table 10 was added, pulp concentration was 15%, and defibration was performed at 45 ° C for 20 minutes. went. Thereafter, water was added thereto to dilute the pulp concentration to 4.0%, and then water was further added to bring the pulp concentration to 1.0%. This was subjected to a flotation treatment at 30 ° C for 10 minutes. The pulp slurry after flotation was concentrated to a 6% concentration and then diluted with water to a 1% concentration to prepare a pulp sheet using a tapping sheet machine.

Table 10 shows the molar ratios of ethylene oxide and propylene oxide for various deinking agents and the deinking performance results.

Table 10 Molar ratio of tylene oxide and provenoxide and deinking performance

C

-

* 1 EO: Ethylene oxide P0: Propylene oxide

Example 11

After chopping the city collection magazine into 2 x 5 cm, put a certain amount of it in low-concentration pulper, and add 0.5% of water and caustic soda (based on raw material), 1.0% of sodium silicate 3 (based on raw material), 30% hydrogen peroxide (based on raw material) 0.8%, chelating agent (DTPA) 0.05%, and deinking agent (based on raw material) 0.06% shown in Table 11 were added, and pulp concentration was 4%. Was. Next, water was further added to adjust the pulp concentration to 1.0%. This was subjected to a flotation treatment at 30 tons for 10 minutes. The pulp slurry after the flotation was concentrated to a 6% concentration and then diluted with water to a 1% concentration to prepare a pulp sheet using a tape sheet machine.

Table 11 shows the number of moles of ethylene oxide added to each deinking agent and the deinking performance results.

Table 11 1 Number of moles of ethylene oxide added and deinking performance

C

* 1 E0: Ethylene oxide P0: Provylene aged oxide

Example 12

After collecting used city waste newspaper Z magazine (50Z50wt%) into 2 x 5 cm pieces, put a certain amount of it into a tabletop disintegrator, where water and caustic soda (based on raw material) 0.8%, sodium silicate 3 (对 raw material) 2.0%, 30% hydrogen peroxide (based on raw material) 1.5%, deinking agent shown in Table 12 (based on raw material) 0.5%, and pulp concentration 5% , 50: for 2 hours. Thereafter, water was added to dilute the pulp concentration to 1.0%, and subjected to a flotation treatment at 30 * C for 10 minutes. The pulp slurry after flotation was concentrated to a 6% concentration, then diluted with water to a 1% concentration, and pulp sheets were prepared using a tapping machine.

Table 12 shows the order of addition of alkylene oxide of glycerin ester and the results of deinking performance for various deinking agents.

Table 12 Order of addition of alkylene oxide and deinking performance

* 1 E0: Ethylene oxide P0: Propylene oxide

C

Example 13

巿 After collecting used waste paper Z magazine (50Z50wt%) into 2 x 5 era pieces, put a certain amount of it into a tabletop disintegrator, where water and caustic soda (based on raw material) 0.8%, sodium silicate No. 3 (based on raw material) 2.5%, 30% hydrogen peroxide (based on raw material) 2.8%, deinking agent shown in Table 13 (based on raw material) 0.2%, pulp concentration 5%, 20 separation at 45 at 45% After that, aging treatment was performed at 45 for 60 minutes. Thereafter, water was added to dilute the pulp concentration to 1.0%, and subjected to a lotion treatment at 30 at 10 minutes. After flotation, the pulp slurry was concentrated to a 6% concentration, and water was added to dilute it to a 1% concentration to prepare a pulp sheet using a tape sheet machine.

The b value of the obtained pulp sheet was measured with a colorimetric colorimeter, and the number of inseparable inks was measured with an image analyzer (X10Q).

Table 13 shows the deinking performance results of various deinking agents.

Table 13 Results of deinking performance of various deinking agents

O

* 1 E0: Ethylene oxide P0: Propylene oxide

Claims

The scope of the claims

1. A natural oil or a reaction product obtained by reacting a natural oil or fat with glycerin in advance and a tetrahydric to 12-hydric alcohol are prepared by adjusting the molar ratio of the alcohol to glycerin in the natural oil or fat to 0. 02 / 1-1 ~ 1 Deinking agent containing an ester mixture obtained by adding ethylene oxide and propylene oxide to the ester mixture obtained by reacting as Z 1 <

2. The deinking according to claim 1, wherein the hydroxyl value (0HV) of the mixture of the alcohol and glycerin in the natural fat or oil is 1.5N to 170N when the valence (N) of the alcohol is used. Agent.

3. The deinking agent according to claim 1, wherein the molar ratio of ethylene oxide to propylene oxide is 0.5 to 4.

4. The deinking agent according to any one of claims 1 to 3, wherein the addition mole number of ethylene oxide is 5N to 200N when the valence (N) of the alcohol is used.

5. The deinking agent according to claim 1, wherein ethylene oxide and propylene oxide are added at random.