JPH064946B2 - Deinking agent - Google Patents

Description

TECHNICAL FIELD The present invention relates to a deinking agent used for recycling used paper such as newspapers and magazines. More specifically, it relates to a deinking agent capable of obtaining deinked pulp having a high b value and less sticky (sticky substance) when deinking newspapers, magazines, etc. by a flotation method, a washing method and their eclectic method. .

[Problems to be Solved by Prior Art and Invention]

Recycling of newspapers, magazines, etc. has been carried out for a long time, but especially recently, the effective use of waste paper has become more important due to the shortage of pulp resources and the rising price thereof. Applications are also expanding to advanced applications. On the other hand, recently used paper is becoming more rigorous in terms of deinking, such as changes in printing technology, printing methods, changes in printing ink components, and the use of used paper that has not been collected and used in the past. Improvements have also been made to the device 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, sodium phosphate, hydrogen peroxide, hyposulfite and hypochlorite. Anion activity such as alkylbenzene sulfonate, higher alcohol sulfate ester salt, α-olefin sulfonate, dialkyl sulfosuccinate as deinking agent, together with bleaching agent such as acid salt, sequestering agent such as EDTA and DTPA Nonionic activators such as agents, higher alcohols, ethylene oxide adducts of alkylphenols and fatty acids, and alkanol amides have been used alone or in combination of two or more. However, these deinking agents have a large foaming property in the flotation process, but have a low ink-collecting ability, and the cleaning method has a weak cleaning power and a high foaming property, which causes foaming troubles in the drainage process. And resulted in only low grade deinked pulp. Furthermore, because of the dullness even with high whiteness, the use of deinked pulp is restricted (reduction in the amount of paper used underneath the board, reduction in the amount added to newsprint, etc.)
However, the amount of bleach used had to be increased in order to eliminate dullness. In order to obtain a deinked pulp which has no dullness and has a light color tone, the b value may be increased. As a method for increasing the b value, a large amount of alkalis may be used, but it has the drawbacks of increased sticky (sticky matter), increased drainage load and embrittlement of pulp, and an effective means is There wasn't.

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 a valence of 3 or more is used as a deinking agent (JP-A-60-239585).
Issue).

However, when the behavior in the deinking step is examined in detail, the compounds in which the mixing ratio of the natural fats and oils and the polyhydric alcohol having a valence of 3 or more in a molar ratio of 1: 0.5 to 1: 3 are in the flotation step, the dehydration step, It was found that foaming troubles often occur in the drainage process and the papermaking process, and the whiteness of the obtained deinked pulp is certainly high, but it has the drawback that dullness does not come off.

[Means for Solving the Problems]

The inventors of the present invention have shown that the flotation method, the washing method, and the eclectic method thereof have excellent ink removing ability, and there is no foaming trouble, no dullness (high b value), and low sticky (adhesive) deinked pulp. As a result of intensive research to develop a deinking agent that can be obtained, it was surprisingly found that a deinking agent containing a specific nonionic active agent as an essential component satisfies the above performances. Reached

That is, the present invention provides a natural oil or fat or a reaction product obtained by previously reacting a natural oil or fat with glycerin and a dihydric alcohol.
Ethylene oxide and propylene oxide were added to ethylene oxide with respect to an ester mixture having a hydroxyl value (OHV) of 10 to 78, which was obtained by reacting a polyhydric alcohol and glycerin in the natural fat and oil at a molar ratio of 0.05 / 1 to 0.48 / 1. / Propylene oxide = 1.8 to 2.2 (molar ratio), and a deinking agent containing an ester mixture added so that the ethylene oxide addition mole number becomes 20 to 200 as an active ingredient.

Examples of the dihydric alcohol used in the present invention include hexadecane-1,2-diol, octadecane-1,2-diol, eicosane-1,2-diol, and α such as ethylene glycol, propylene glycol, butanediol, and hexanediol. , Ω-glycol and the like can be mentioned.

The natural oils and fats used in the present invention include palm oil, palm oil, olive oil, soybean oil, rapeseed oil, linseed oil, castor oil, sunflower oil and other vegetable oils, lard, beef tallow, land oil such as bone oil, and sardines. Examples of the oil include marine animal oils such as oil and herring oil, hydrogenated oils and semi-hardened oils thereof, and recovered oils obtained in the refining step 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 dihydric alcohol used and glycerin in the natural fat / oil is 0.05 / 1 to 0.48 / 1,
Moreover, it is important that the hydroxyl value (OHV) of the ester mixture is 10 to 78.

In the above calculation of the molar ratio of dihydric alcohol and glycerin, "glycerin in natural fats and oils" means glycerin that is combined with fatty acids to form natural fats and oils, and further added and reacted to modify the fats and oils. Means the sum with glycerin. The compounds having the above molar ratio and hydroxyl value within this range are effective for removing fine ink, have no dullness and give a bright color tone, and as a result, give a deinked pulp having a high b value. If the molar ratio deviates from this range, dullness will still remain.

In the present invention, ethylene oxide and propylene oxide can be added by mixing both (random addition) or sequentially (block addition), but random addition is preferable from the viewpoint of foaming trouble reduction.

The addition ratio of ethylene oxide and propylene oxide is ethylene oxide / propylene oxide = 1.8 to 2.2 (molar ratio), and the ethylene oxide addition mole number is 20 to 20.
Must be 0. If it deviates from this range, the releasability of the ink from the waste paper will decrease. Further, the foaming property decreases during the flotation process, and the ink removability decreases during the cleaning process. Also, compounds within this range are effective in reducing stickiness, ie stickies. Therefore high b
A deinked pulp with high value and low stickiness cannot be obtained without using a compound satisfying the above conditions.

In the present invention, the method of addition reaction of ethylene oxide and propylene oxide is not particularly limited, and the addition reaction can be carried out under the condition of the commonly used alkylene oxide addition reaction to a compound having active hydrogen. That is, the natural fats and oils (triglycerides) or a reaction product obtained by previously reacting the natural fats and oils with glycerin, a dihydric alcohol,
Alternatively, a catalytic amount of an alkaline substance is further added to the mixture containing the glycerin ester derived from the fat and oil,
This can be done by reacting ethylene oxide and propylene oxide at 100 to 200 ° C. and 1 to 3 kg / cm ² (gauge) for several hours.

The deinking agent of the present invention also exhibits excellent performance when used in combination with a known deinking agent such as higher alcohol sulfate, alkylbenzene sulfonate, higher alcohol, and ethylene oxide adduct of alkylphenol. The deinking agent of the present invention may be added to any one of the used paper disaggregation step, the high-concentration bleaching step, the pre-flotation step, and each step.

Further, the addition amount thereof is preferably 0.03 to 1.0% by weight based on the used waste paper.

[Examples and effects]

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

Production Example 1 138.0 g and 2.0 g of beef tallow and ethylene glycol and 1.3 g of 100% KOH were charged into an autoclave of 1.5, and the temperature was raised to 130 ° C. under a stirring speed of about 600 rpm.

Then, the above reaction product was reacted with 858.4 g of a mixture of ethylene oxide and propylene oxide at a molar ratio of 1.8: 1. The reaction conditions at this time are as follows: temperature 135-140 ° C, pressure 1-
It was 3 kg / cm ² (gauge).

After completion of the reaction, the temperature was cooled to 80 ° C. 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 2 100.0 g and 2.4 g of coconut oil and ethylene glycol and 1.3 g of 100% KOH were charged into an autoclave of 1.5, and the temperature was raised to 150 ° C. under a stirring speed of about 600 rpm.

Next, 540.2 g of ethylene oxide was added at a temperature of 155-165 ° C.
The reaction was carried out little by little under a pressure of 1 to 3 kg / cm ² (gauge).

After completion of the ethylene oxide addition reaction, the temperature was cooled to 120 to 130 ° C., and 356.1 g of propylene oxide was reacted under a pressure of 1 to 3 kg / cm ² (gauge).

Then, it cooled to 80 degreeC and adjusted pH to 6 with acetic acid.
The yield of the reaction product (No. 11 in Table 2 of the present invention) was 99%.

Example 1 Waste newspaper / magazine (50/50 wt%) collected in the city was shredded into 2 × 5 cm pieces, and a certain amount thereof was put into a table disintegrator, in which water and caustic soda (against raw materials) 0.8%, silicate Soda No. 3 (to raw material) 2.5%, 30% hydrogen peroxide (to raw material) 2.8%, deinking agent (to raw material) 0.2% shown in Table 1 were added, pulp concentration 5%, 45
After the solution was separated at 20 ° C for 20 minutes, it was aged at 45 ° C for 60 minutes. After that, add water to dilute the pulp to 1.0%.
Flotation treatment was performed at 10 ° C for 10 minutes. The pulp slurry after flotation was concentrated to a concentration of 6%, water was added to dilute it to a concentration of 1%, and a pulp sheet was produced using a tappy sheet machine.

The b value of the obtained pulp sheet is measured with a colorimetric color difference meter,
The number of stickies (adhesives) was measured with an image analyzer (× 40 times). The amount of foam liquid during flotation (the amount of liquid required to form a foam layer) was also measured as a measure of foamability. If the amount of this foam liquid is large, the yield of pulp is lowered, and it is shown that the floss treatment in the wastewater treatment process cannot be performed smoothly.

Further, the b value referred to here is the b value in the Lab color system of the Hunter color difference formula, and the relationship with the tristimulus values XYZ is the following formula.

As can be seen from this equation, the b value is a function of Y and Z,
A positive value indicates yellowness, and a negative value indicates blueness.

The dihydric alcohol / glycerin molar ratio and the deinking performance results of various deinking agents are shown in Table 1.

Example 2 A 2 × 5 cm piece of a magazine collected in the city was shredded, and a fixed amount thereof was put into a high-concentration pulper, in which water and caustic soda (vs. raw material) were placed.
0.5%, sodium silicate No. 3 (for raw material) 1.5%, 30% hydrogen peroxide (for raw material) 1.0%, deinking agent (for raw material) 0.05 shown in Table 2
% Was added and pulp separation was performed at 20% at 45 ° C with a pulp concentration of 15%. Thereafter, water was added to this to dilute it to a pulp concentration of 4.0%, and then water was further added to adjust the pulp concentration to 1.0%. This was subjected to flotation treatment at 30 ° C. for 10 minutes. The pulp slurry after flotation was concentrated to 6% concentration, water was added to dilute it to 1% concentration, and a pulp sheet was produced by a tappy sheet machine.

The b value of the obtained pulp sheet is measured with a colorimetric color difference meter,
The number of stickies (adhesives) was measured with an image analyzer (× 40 times). The amount of foam liquid during flotation (the amount of liquid required to form a foam layer) was also measured as a measure of foamability.

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

Example 3 A 2 × 5 cm piece of a magazine collected in the city was shredded, and a fixed amount thereof was put into a low-concentration pulper, and water and caustic soda (against raw materials) were placed therein.
0.5%, sodium silicate No. 3 (against raw material) 1.0%, 30% hydrogen peroxide (against raw material) 0.8%, chelating agent (DTPA) 0.05%, Table 3
The deinking agent (compared to the raw material) 0.06% shown in Fig. 4 was added to give a pulp concentration of 4
%, And separated and treated at 40 ° C. for 15 times. Then, water was further added to adjust the pulp concentration to 1.0%. This was subjected to flotation treatment at 30 ° C. for 10 minutes. The pulp slurry after flotation was concentrated to 6% concentration, water was added to dilute it to 1% concentration, and a pulp sheet was produced by a tappy sheet machine.

The b value of the obtained pulp sheet is measured with a colorimetric color difference meter,
The number of stickies (adhesives) was measured with an image analyzer (× 40 times). The amount of foam liquid during flotation (the amount of liquid required to form a foam layer) was also measured as a measure of foamability.

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

Example 4 Recycled newspaper waste paper / magazine (50/50 wt%) was shredded into 2 × 5 cm pieces, and a certain amount thereof was put into a table disintegrator, in which water and caustic soda (against raw materials) 0.8%, silicate Soda No. 3 (to raw material) 2.0%, 30% hydrogen peroxide (to raw material) 1.5%, deinking agent (to raw material) 0.5% shown in Table 4 were added, pulp concentration 5%, 50
After the solution was separated at 15 ° C for 15 minutes, it was aged at 50 ° C for 2 hours. After that, add water to dilute the pulp concentration to 1.0%, and
The flotation treatment was performed at 0 ° C. for 10 minutes. The pulp slurry after flotation was concentrated to a concentration of 6%, water was added to dilute it to a concentration of 1%, and a pulp sheet was produced using a tappy sheet machine.

The b value of the obtained pulp sheet is measured with a colorimetric color difference meter,
The number of stickies (adhesives) was measured with an image analyzer (× 40 times). The amount of foam liquid during flotation (the amount of liquid required to form a foam layer) was also measured as a measure of foamability.

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

Claims (2)

[Claims] 1. A natural fat or oil or a reaction product obtained by previously reacting a natural fat or oil with glycerin and a dihydric alcohol, wherein the molar ratio of the dihydric alcohol and the glycerin in the natural fat or oil is adjusted.
To the ester mixture having a hydroxyl value (OHV) of 10 to 78 obtained by reacting 0.05 / 1 to 0.48 / 1, ethylene oxide / propylene oxide
A deinking agent containing propylene oxide = 1.8 to 2.2 (molar ratio) and an ester mixture added so that the ethylene oxide addition mol number becomes 20 to 200 as an active ingredient. 2. The deinking agent according to claim 1, wherein ethylene oxide and propylene oxide are randomly added.