JP2951737B2 - Deinking agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention 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 deinking agent capable of obtaining a deinked pulp having a high b value and a small amount of unstripped ink when performing deinking treatment on newspapers, magazines, etc. by a flotation method, a washing method and a compromise method thereof.

[0002]

BACKGROUND OF THE INVENTION Newspapers,
Recycling of magazines, etc. has been practiced for a long time, but recently, in particular, the effective use of waste paper has become increasingly important due to shortage of pulp resources and soaring prices. It is expanding to advanced use. On the other hand, recently used paper has changed in printing technology, printing method, printing ink component,
Furthermore, the situation is becoming more severe in terms of deinking, such as the use of waste paper that has not been collected and used in the past, and improvements have been made to devices for further promoting deinking. Chemicals 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, hyposulfite, and hypochlorite. Bleach such as acid salt, EDT
A, along with sequestering agents such as DTPA, as a deinking agent,
Nonionic activators such as alkylbenzene sulfonates, higher alcohol sulfates, α-olefin sulfonates, dialkyl sulfosuccinates, etc .; higher alcohols, ethylene oxide adducts of alkylphenols and fatty acids, and alkanolamides. They 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, and the cleaning method has a low detergency and a high foaming property. And resulted in only low grade deinked pulp. Furthermore, because of the dullness even at high whiteness, there are restrictions on the use of deinked pulp (reduction of the amount of paperboard used below and below, blending in newsprint, etc.) and the use of bleaching agents to eliminate dullness. Had to be increased. To obtain a deinked pulp having a dull color and a bright color tone, the b value may be increased. As a method for increasing the b value, it is sufficient to use a large amount of alkalis, but it has a drawback of increasing sticky (sticky substance), increasing drainage load and embrittlement of pulp. Did not.

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). No.). In addition, a natural oil or fat or a reaction product obtained by previously reacting natural oil or fat with glycerin and tetravalent, hexavalent,
It has been proposed that a reaction product obtained by adding an alkylene oxide to a mixture with a monohydric alcohol is used as a deinking agent (JP-A-2-293483, JP-A-2-293484,
JP-A-2-293485).

However, when the behavior in the deinking step is examined in detail, it is found that the compound in which the mixing ratio of the natural fats and oils and the polyhydric alcohol having a valency of 3 or more is 1: 0.5 to 1: 3 in the flotation step. It often causes foaming troubles in the dewatering process, drainage process, and papermaking process.Also, the resulting deinked pulp has high whiteness, but it has drawbacks such as lack of dullness and many unstripped inks. It turned out that it was. In addition, a natural oil or a reaction product obtained by reacting a natural oil or fat with glycerin in advance and a mixture of a tetravalent, hexavalent, or monohydric alcohol with an alkylene oxide is also a mustache ink, that is, a non-peeled ink. It was found that there was a drawback that there was a lot of ink.

[0005]

Means for Solving the Problems The present inventors have shown a further excellent ink removing ability in a flotation method, a washing method and a compromise method thereof, there is no foaming trouble, no dullness (high b value), and As a result of intensive research to develop a well-developed deinking pulp that can obtain deinked pulp with less unstripped ink, surprisingly, it was found that deinking pulp containing specific nonionic activator as an essential component The inventor has found that the black ink satisfies the above performance, and has reached the present invention.

That is, according to the present invention, natural oils and fats or a reaction product of natural oils and fats previously reacted with glycerin and a pentahydric alcohol are prepared by changing the molar ratio of the pentahydric alcohol to glycerin to 0.02 /
Ester oxide and propylene oxide are added to an ester mixture having a hydroxyl value (OHV) of from 8 to 800, particularly preferably from 8 to 400, obtained by reacting the mixture at a ratio of 1 to 1/1, particularly preferably 0.05 / 1 to 0.48 / 1. With ethylene oxide / propylene oxide = 0.5-4, particularly preferably 1.8
~ 2.2 (molar ratio) and 25% ethylene oxide
An object of the present invention is to provide a deinking agent containing as an active ingredient a product added with an amount of up to 1000 mol, particularly preferably 25 to 500 mol.

The pentahydric alcohol used in the present invention includes xylitol, arabitol, ribitol and the like.

The natural oils and fats used in the present invention include vegetable oils such as coconut oil, palm oil, olive oil, soybean oil, rapeseed oil, linseed oil, castor oil and sunflower oil, and terrestrial oils such as lard, beef tallow and bone oil. Examples include marine animal oils such as animal oil, sardine oil and herring oil, and hardened and semi-hardened oils thereof, as well as recovered oils obtained in a purification process of these oils and fats. Further, monoesters and diesters produced by previously reacting these natural fats and oils with glycerin can also be used.

In the present invention, the molar ratio of the pentahydric alcohol used to glycerin in natural fats and oils is from 0.02 / 1 to
1/1 and the hydroxyl value (OHV) of the ester mixture is 8 to
It is important that it is 800.

In the above-mentioned calculation of the molar ratio between the pentahydric alcohol and glycerin, "glycerin in natural fats and oils" refers to glycerin which is combined with fatty acids to constitute natural fats and oils,
It means the sum with glycerin that has been further added and reacted to modify the fat or oil.

A compound having the above molar ratio and hydroxyl value within the above ranges is effective for removing fine ink, has a small amount of unstripped ink, gives a bright color tone, and consequently gives a high b-value deinked pulp. If the molar ratio is out of this range, the unstripped ink will remain.

In the present invention, ethylene oxide and propylene oxide can be added by mixing both (addition at random) or by sequentially adding (block addition). Addition is preferred.

The addition ratio of ethylene oxide and propylene oxide is as follows: ethylene oxide / propylene oxide =
It is necessary that the ratio is 0.5 to 4 (molar ratio) and the number of moles of ethylene oxide added is 25 to 1000. If it is out of this range, the ink releasability from the used paper decreases. Furthermore, foaming properties are reduced during the flotation process, and ink removal properties are reduced during the washing process. Compounds within this range are effective in reducing unstripped ink. Therefore, a deinked pulp having a high b value and a low number of unstripped inks 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 the addition reaction can be carried out under the conditions of an alkylene oxide addition reaction to a compound having active hydrogen which is generally performed. That is, a catalytic amount of an alkaline substance is added to a mixture of the above natural fats and oils (triglyceride) or a reaction product of natural fats and oils previously reacted with glycerin and a pentahydric alcohol. ² (gauge)
And reacting ethylene oxide and propylene oxide for several hours.

The deinking agent of the present invention is a known deinking agent such as higher alcohol sulfate, alkylbenzene sulfonate,
Even when used in combination with higher alcohols, alkylphenol ethylene oxide adducts and the like, excellent performance is exhibited.
The deinking agent of the present invention may be dividedly added to any of the waste paper disintegration step, the high-concentration bleaching step, the pre-flotation step, and each step. Further, the amount of addition is preferably 0.03 to 1.0% by weight based on the raw waste paper.

[0016]

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

Production Example 1 In a 1.5-liter autoclave, beef tallow and D-arabitol were respectively charged with 223.5 g and 7.8 g, and 100% KOH with 2.2%.
g, and the temperature was increased to 130 ° C. under the condition of a stirring speed of about 600 rpm. Then, 761.0 g of a mixture of ethylene oxide and propylene oxide at a molar ratio of 2: 1 was reacted. The reaction conditions at this time are as follows: temperature 130 ° C. to 140 ° C., pressure 1
３3 kg / cm ² (gauge). After the reaction,
After cooling to 75 ° C., the pH was adjusted to about 6 with acetic acid. The yield of the reaction product (the product of the present invention, No. 1 in Table 1) was 99%.

Production Example 2 160.4 g and 3.1 g of coconut oil and ribitol, and 1.6 g of 100% KOH were charged into a 10 liter autoclave, and the temperature was raised to 155 ° C. under a stirring speed of about 600 rpm. Then, 2646.1 g of ethylene oxide was added at a temperature of 1
The reaction was carried out little by little at 55 to 165 ° C under a pressure of 1 to 3 kg / cm ² (gauge). After the end of the ethylene oxide addition reaction,
Cool the temperature to 120-130 ° C, pressure 1-3kg / cm
3480.2 g of propylene oxide were reacted under ² (gauge). Thereafter, the mixture was cooled to 80 ° C., and the pH was adjusted to about 6 with acetic acid. The yield of the reaction product (the product of the present invention, No. 11 in Table 2) is
98%.

Example 1 City waste newspaper / magazine (50/50 wt%) was cut into pieces of 2 × 5 cm, and a certain amount was put into a tabletop disintegrator, in which water and caustic soda (based on raw material) were 0.8%. , 2.5% sodium silicate 3 (based on raw material), 2.8% 30% hydrogen peroxide (based on raw material), 0.2% deinking agent (based on raw material) as shown in Table 1, 5% pulp concentration
After dissociation at 45 ° C for 20 minutes, aging treatment was performed at 45 ° C for 60 minutes. Then add water to dilute the pulp consistency to 1.0%,
A flotation treatment was performed at 10 ° C. for 10 minutes. After the pulp slurry after the flotation 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 tappy sheet machine. The b value of the obtained pulp sheet was measured with a colorimetric colorimeter, and the number of unstripped inks was measured with an image analyzer (× 100). The b value referred to here is the b value in the Hunter color difference formula in the Lab color system, and the tristimulus values X, Y,
The relationship with Z is as follows.

[0020]

(Equation 1)

As can be seen from this equation, the b value is a function of Y and Z. A positive value indicates yellowish intensity, and a negative value indicates bluish intensity. Table 1 shows the pentahydric alcohol / glycerin molar ratio of various deinking agents and the deinking performance results.

[0022]

[Table 1]

Example 2 A commercial collection magazine was cut into 2 × 5 cm pieces, and a certain amount was put into a high-concentration pulper, in which water and caustic soda (based on raw materials) were placed.
0.5%, sodium silicate No. 3 (based on raw material) 1.5%, 30% hydrogen peroxide (based on raw material) 1.0%, deinking agent (based on raw material) shown in Table 2
05% was added, pulp concentration was 15%, and 20 separation and dissolution treatments were performed at 45 ° C. 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 the flotation was concentrated to a 6% concentration and then diluted with water to 1% concentration to prepare a pulp sheet with a tappy sheet machine. The b value of the obtained pulp sheet was measured with a colorimetric color difference meter, and the image was analyzed using an image analyzer (× 100).
Times), the number of unstripped ink was measured. Table 2 shows the molar ratios of ethylene oxide and propylene oxide and the results of deinking performance for various deinking agents.

[0024]

[Table 2]

Example 3 A commercial collection magazine was cut into 2 × 5 cm pieces, and a certain amount was put into a low-concentration pulper, in which water and caustic soda (based on raw materials) were placed.
0.5%, sodium silicate No.3 (based on raw material) 1.0%, 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 3 , Pulp concentration 4
%, And 15 separation and dissolution treatments were performed at 40 ° C. Subsequently, water was further added to adjust the pulp concentration to 1.0%. This was subjected to a flotation treatment at 30 ° C. for 10 minutes. The pulp slurry after the flotation was concentrated to a 6% concentration and then diluted with water to 1% concentration to prepare a pulp sheet with a tappy sheet machine. The b value of the obtained pulp sheet was measured with a colorimetric colorimeter, and the number of unstripped 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 results of deinking performance.

[0026]

[Table 3]

Example 4 City-collected waste newspaper / magazine (50/50 wt%) was cut into 2 × 5 cm pieces, and a certain amount thereof was placed in a tabletop disintegrator, in which water and caustic soda (based on raw material) were 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, and the pulp concentration was 5%.
After 15 separation at 50 ° C., aging treatment was performed at 50 ° C. for 2 hours. After that, water is added to dilute the pulp concentration to 1.0%,
A flotation treatment was performed at 30 ° C. for 10 minutes. After the pulp slurry after the flotation 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 tappy sheet machine. The b value of the obtained pulp sheet was measured with a colorimetric colorimeter, and the number of unstripped inks was measured with an image analyzer (× 100). Table 4 shows the order of addition of alkylene oxide of glycerin ester and the results of deinking performance for various deinking agents.

[0028]

[Table 4]

Continuation of front page (58) Field surveyed (Int.Cl. ⁶ , DB name) D21C 5/02

Claims (2)

(57) [Claims] 1. A natural oil or fat or a reaction product obtained by reacting a natural oil or fat with glycerin in advance and a pentahydric alcohol obtained by reacting the pentahydric alcohol to glycerin at a molar ratio of 0.02 / 1 to 1/1. A product obtained by adding ethylene oxide and propylene oxide at a ratio of ethylene oxide / propylene oxide of 0.5 to 4 (molar ratio) and 25 to 1000 moles of ethylene oxide to an ester mixture having a hydroxyl value (OHV) of 8 to 800. Deinking agent as an active ingredient. 2. The deinking agent according to claim 1, wherein ethylene oxide and propylene oxide are added at random.