JP2593766B2 - Flotation 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 for recycling used paper used in obtaining recycled pulp from used printed paper such as newspaper, magazine, high-quality paper, computer printout paper, copy paper and the like, and a method of using the same. It is. More specifically, it is suitable for performing a deinking treatment on used printing paper by a flotation method, and not only can obtain high-quality recycled pulp having high whiteness and low residual ink, but also obtain stable operability. And a method of using the same.

[0002]

2. Description of the Related Art It has long been practiced to recycle printed waste paper to make it into papermaking raw material again. In particular, in recent years, the recycling of printed waste paper has become increasingly important from the viewpoint of resource saving, energy saving, and environmental protection, and accordingly, recycled pulp is required to have high quality such as high whiteness and low residual ink. Generally, the deinking method of used printing paper is roughly classified into a cleaning method and a flotation method. These processing methods, deinking mechanism, and
Many documents and findings have been obtained so far regarding the difference in performance of the deinking agents used in these treatment methods. For example, Pulp & Paper, Nov. p59, (1986), Pulp & Paper,
Mar. p60, (1989), Pulp & Paper, Mar.p76, (1990), P
ulp & Paper, Mar. p97, (1989), Japanese Journal of
PaperTechnology, Aug. p37 (1980), 1989 TAPPI Pulp
ing Conference, p343, JapanTAPPI Journal Vol. 36,
p1029, Japan TAPPI Journal Vol. 39, p747 and US Pat. No. 4,483,741, US Pat. No. 4,518,459
And the like.

[0003] Summarizing these documents and the knowledge and experience obtained in the actual operation, the washing method is generally to repeat the dilution and dehydration of the pulp slurry or to use a washing device such as a screen or a centrifugal cleaner to remove and separate the pulp slurry. This is a method of separating the dispersed ink from the pulp slurry, and the separation of the ink largely depends on mechanical factors caused by a cleaning device such as a press, a screen, and a cleaner. In addition, in the cleaning method, a large amount of water is required, thus saving resources.
From the viewpoint of energy saving, it has many disadvantages. Further, in the cleaning method, operability is regarded as important in each process because mechanical factors are strong. Particularly when using a highly foaming agent, especially when using a deinking agent, troubles due to bubbles occur in each device and process, and operability is reduced and power consumption becomes significant. Foaming or foam suppressing properties are required. In addition, the peeled ink is finer to improve the removal efficiency of the ink,
And must be dispersed.

On the other hand, the flotation method is a method of separating the ink and the pulp by attaching the peeled ink to foam generated mainly in a flotator. In contrast to the washing method, the removal of the ink is mainly performed by a chemical method. This is based on factors, and the mechanism for removing the ink is completely different from the cleaning method. Although the deinking step using the normal flotation method may have a step called a washing or dehydration step, the removal of the ink is mainly performed in the flotation step. In addition, the flotation method is advantageous from the viewpoint of resource saving because it requires less water than the cleaning method. Furthermore, in order to improve the ink removal efficiency in the flotation method, the particle diameter of the separated ink at the time of flotation must be larger than that of the cleaning method and must be aggregated. Further, in the flotation method, since the peeled ink must be removed by foam, an appropriate foaming property is required during flotation. It is well known that this foaming property is insufficient with the foaming power required in the cleaning method. On the other hand, if the foaming properties of the chemicals, especially the deinking agent, are too strong, it will not be possible to remove bubbles especially by flotation, or troubles due to bubbles will occur frequently in each process,
It is impossible to perform a stable operation, for example, because the operation is stopped or the yield is reduced to cause a decrease in productivity, and in some cases, high-quality recycled pulp with high whiteness cannot be obtained. As described above, the deinking mechanism is completely different between the cleaning method and the flotation method, and thus the properties required for the chemicals used therein are also required to be completely different. The flotation method is especially popular in Japan and Europe because the regenerated pulp has higher whiteness than the washing method and is superior to the washing method from the viewpoint of resource saving and energy saving. The deinking method has shifted from the cleaning method to the flotation method.

[0005] A number of patents have been filed for deinking agents and their use. For example, USP-4,
No. 518,459, propylene oxide is added to a terminal hydroxyl group of an ethylene oxide adduct of an alcohol or an alkylphenol to a certain extent, or a hydroxyl terminal of an ethylene oxide adduct of an alcohol or an alkylphenol or an ethylene oxide / propylene oxide block adduct is benzyl etherified. There is a description of a deinking treatment method using the same. However, this U.S. patent is used for a cleaning method, and since the present invention is used for a flotation method, the functions and performance required for the deinking agent are completely different as described above. While the patent is a deinking agent suitable for a cleaning method requiring low foaming or foam suppressing properties, the present invention relates to a molecular deodorizing agent that can obtain a suitable foaming property to obtain stable operation by flotation. Different in design. DE-2143912 also describes a deinking method characterized by adding ethylene oxide and propylene oxide of alcohol or alkylphenol in a certain range, and performing flotation above the cloud point of the deinking agent. In this method, high-quality recycled pulp with high whiteness and low residual ink cannot be obtained.

JP-A-51-84905, JP-A-53-90505
31804, 55-51891, 55
JP-A-5-18992 and JP-A-56-79795 also disclose alkylene oxide adducts of alcohols or alkylphenols as deinking agents. However, these deinking agents also have a strong foaming property in each process, and cannot always achieve stable operation such as operation stoppage due to foam trouble and reduction in yield. It is difficult to achieve stable operation because it cannot be obtained. In addition, since the ink does not exhibit sufficient ink collecting properties during flotation, it is not always possible to obtain high-quality recycled pulp having high whiteness and low residual ink.

Japanese Patent Application Laid-Open No. 61-41386 discloses that an alkylene oxide adduct of alcohol and an ethylene oxide adduct of alcohol are used in combination. High-quality recycled pulp is also used in the flotation method because of the use of ethylene oxide adducts of highly alcohol
Stable operability cannot be obtained. In addition, Japanese Unexamined Patent Publication No.
Nos. 0-142804, 61-186592, 62-177291, 62-25029
No. 1 discloses a deinking agent used in combination with a higher fatty acid which improves ink collection during flotation, which is a drawback of an alkylene oxide adduct of alcohol, but although the ink collection is improved, It is difficult to control foam during flotation, and it is not easy to perform stable operation. JP-A-63-165591 also discloses a deinking agent which uses an alkylene oxide adduct of a fatty acid in combination in order to supplement the ink collecting property during flotation, which is a disadvantage of the alkylene oxide adduct of an alcohol. However, even if these deinking agents are used, it is not always possible to obtain stable operability in a deinking treatment step in which treatment is performed by a flotation method.

[0008] While the deinking agents described in the above-mentioned German and Japanese patents do not always provide high-quality recycled pulp with stable operability, high whiteness and low residual ink,
The deinking agent according to the present invention can be used in combination with two specific types of deinking agents of a specific limited type so that high-quality regenerated pulp with high whiteness and low residual ink can be obtained with stable operability. It is completely different in the point of molecular design. In addition, the above-mentioned known documents do not describe at all the effects of by-products on the deinking performance, and also differ from the present invention in that respect. Further, Canadian Patent No. 729,071 describes a deinking agent obtained by adding an alkylene oxide to an alkylphenol, but when this deinking agent is used in a flotation method, sufficient ink collecting properties are exhibited. Therefore, high-quality recycled pulp cannot be obtained, and the biodegradability of alkylphenol is poor, which is environmentally unfavorable. Also, U.S. Pat. Nos. 3,021,372 and 2,856,434,
Nos. 903,486 and 3,340,309, 3,444,
JP-A-242 and JP-A-3,625,909 disclose compounds obtained by adding an alkylene oxide to an alcohol or an alkylphenol, but these compounds have completely different structures and uses from the present invention. US Patent
No. 4,162,186 also discloses a deinking agent, but this US patent uses oil-soluble alcohol ethoxylate and water-soluble alcohol ethoxylate in combination and is completely different from the present invention. .

[0009]

The present invention relates to a deinking agent exhibiting good deinking performance in a flotation method and a method of using the same. It is an object of the present invention to provide a deinking agent capable of obtaining a high-quality recycled pulp having a low residual ink and achieving stable operability, and a method of using the same.

[0010]

DISCLOSURE OF THE INVENTION The present invention relates to a monoalkyl ether of an ethylene oxide-propylene oxide copolymer having different structures in which the average addition mole number m of ethylene oxide and the average addition mole number n of propylene oxide are within specific ranges. The present invention has been made based on the finding that the above problem can be effectively achieved as a deinking agent for flotation when used together with a specific amount of a polyalkylene oxide. That is, in the present invention, the average addition mole number m of ethylene oxide is 10 to 3
0, the average addition mole number n of propylene oxide is 8 to 35
Wherein the alkyl group of the compound represented by the general formula (A) has a carbon number of 12 to 22, and the alkyl group of the compound represented by the general formula (B) has a range of 16 to 24. Of the monoalkyl ethers (A) and (B)
9 to 97% by weight of a 10% by weight mixture and about 0.3 to about 3.0% by weight of a polyalkylene oxide selected from the group consisting of polyethylene oxide, polypropylene oxide and ethylene oxide-propylene oxide copolymer. The present invention provides a deinking agent for flotation characterized by the following.

R ¹ O- (PO) _n1 -[(EO) _m · (PO) _n2 ] H── (A) R ² O- (EO) _m1 -[(EO) _m2 · (PO) _n ] H ── (B) (wherein, R ¹ is an alkyl group having 12 to 22 carbon atoms, R ² is an alkyl group having 16 to 24 carbon atoms, m / (n1 + n2) =
0.5-1.5, (m1 + m2) /n=1.1-2.0, where m = m1 + m2 is 10-30, and n = n1 + n2 is 8
~ 35. EO and PO represent ethylene oxide and propylene oxide units, respectively.
PO bonds may be random or block. ) The ether compound (A) represented by the above general formula (A) is obtained by firstly adding propylene oxide to a higher alcohol having 12 to 22 carbon atoms in the alkyl group, and having a total addition molar ratio of ethylene oxide and propylene oxide of 0. .5-1.5,
It is preferably 0.5 to 0.9, and has a higher hydrophobicity than a known higher alcohol-based deinking agent. Therefore, the ink separated in the flotation can be efficiently separated and removed from the pulp by the foam, and as a result, a recycled pulp having a high whiteness can be obtained. When the added molar ratio exceeds 1.5, the hydrophilicity increases, so that the affinity for ink and the ink collecting property during flotation are weakened, so that it is not possible to obtain a recycled pulp having high whiteness. On the other hand, when the added molar ratio is less than 0.5, the foaming property at the time of flotation is weakened, bubbles are not sufficiently removed at the time of flotation, and sufficient ink collecting property is not exhibited at the time of flotation. Therefore, it is not possible to obtain recycled pulp having high whiteness. When the added molar ratio is 0.5 to 0.9, the ink collecting property is further improved.

On the other hand, in the ether compound (B) represented by the general formula (B), ethylene oxide is first added to a higher alcohol, and the total addition molar ratio of ethylene oxide and propylene oxide is 1.1 to 2.2. The effect is exhibited when it is 0. In particular, the compound represented by the general formula (B) has an affinity for the ink printed on the paper surface, and is particularly excellent in the ink release property in the defibration and ripening steps. If the total molar ratio exceeds 2.0, not only does the foaming during flotation become too large to obtain a stable operation, but also the scraping of the foam is insufficient, and a high whiteness recycled pulp. Cannot be obtained.
Further, when the total added molar ratio is less than 1.1, the affinity for the ink printed on the paper surface in the disaggregation and ripening step is weakened, and the ink peeling ability is reduced.
Only recycled pulp with a large amount of residual ink can be obtained. It is important for the compound represented by the general formula (A) to add propylene oxide to the higher alcohol in an amount of 1 mol or more, preferably 1 to 5 mol, and to the propylene oxide adduct of the higher alcohol, ethylene oxide and propylene oxide are added. Are added at random or in blocks. When performing block addition, it is preferable to first add ethylene oxide and then add propylene oxide. Alternatively, it can be obtained by adding propylene oxide to the higher alcohol in an amount of 1 mol or more, then randomly adding ethylene oxide and propylene oxide, and further adding propylene oxide to the terminal.

On the other hand, it is important for the compound represented by the general formula (B) to add 1 mol or more, preferably 1 to 8 mol of ethylene oxide to the higher alcohol, and to add ethylene oxide and propylene oxide to the ethylene oxide adduct of the higher alcohol. Can be obtained by random or block addition. When performing block addition, it is preferable to first add ethylene oxide and then add propylene oxide. Further, as another preparation method, a method in which ethylene oxide and propylene oxide are directly added to a higher alcohol at random is exemplified. In this case, considering the reactivity of both, first, ethylene oxide is preferentially added to the higher alcohol. In the present invention, when the ether compound is produced, the water content in the reaction system is set to 0.3% or less, and a basic catalyst such as sodium hydroxide or potassium hydroxide or a magnesium oxide-aluminum solid catalyst used as a catalyst is used. Is added so as to always maintain 0.25% or less with respect to the intermediate product in each alkylene oxide addition step and the final product, and the by-products polyethylene glycol and polypropylene glycol contained in the obtained product are added. It is important that the content of polyalkylene glycol, which is a polymer of ethylene oxide and propylene oxide, is about 0.3 to about 3% by weight. However, it is also possible to add the polyalkylene glycol later in the above range.

The higher alcohol which forms the alcohol residue of R ¹ O has 12 to 22 carbon atoms, preferably 16 carbon atoms.
, More preferably 18 to 22 straight-chain higher alcohols, and the higher alcohols forming the alcohol residue of R ² O are those having 16 to 24 carbon atoms, preferably 18 to 22 carbon atoms.
Is a higher linear alcohol. Such higher alcohols include, for example, lauryl alcohol, myristyl alcohol, palmityl alcohol, heptadecanol, stearyl alcohol, nonadecanol, aralkyl alcohol, behenyl alcohol, tricosanol, tetracosanol, oleyl alcohol, and alcohols derived from animal and vegetable oil fatty acids For example, beef tallow alcohol, fish oil alcohol, tallow alcohol, and a cured product thereof can be mentioned. What is important in the above deinking agent is that the total number of moles of ethylene oxide to be added to the higher alcohol is 10 to 30 moles, preferably 12 to 28 moles per mole of the higher alcohol, and the number of moles of all propylene oxide added. Is 8 to 35 moles, preferably 9 to 30 moles per mole of higher alcohol, and the total addition molar ratio of ethylene oxide and propylene oxide is 0.5 to 1.5 in the general formula (A). , Preferably 0.5
-0.9, 1.1-2.0 in general formula (B) (A) (B)
And the number of carbon atoms of the alkyl group of the compound represented by formula (A) is from 12 to 22, and the number of carbon atoms of the alkyl group of the compound represented by formula (B) is from 16 to 24. When the carbon number of the higher alcohol in the deinking agent is shorter than the above range, the hydrophobicity is insufficient because the chain length of the alkyl group is short, and even if the ratio of the number of moles of ethylene oxide and propylene oxide added is within the above range. Insufficient foaming properties, and also lacks the ability to collect ink peeled off during flotation, preventing the ink from adhering to the foam,
High quality recycled pulp with high whiteness cannot be obtained.

On the other hand, if the alkyl group is longer than the above range, the deinking agent does not dissolve or disperse at the time of disaggregation, so that high-quality regenerated pulp having high whiteness and low residual ink cannot be obtained. If the ratio of the number of moles of ethylene oxide and propylene oxide to the number of moles of ethylene oxide and propylene oxide deviates from the above range, even if the number of carbon atoms of the alkyl group of the compound represented by the general formula (A) or (B) falls within the range described above, Even within this range, high-quality recycled pulp cannot be obtained and stable operation cannot be performed. In addition, it is important that the product of the present invention has sufficient nitrogen before the addition of the alkylene oxide at the time of production, that is, in order to reduce the water content when the alkylene oxide is added to the higher alcohol to about 0.3% or less. Substitution and dehydration under reduced pressure at a high temperature, and always keep the amount of the catalyst at 0.25% or less with respect to the product and the final product in each alkylene oxide addition step in the production of the ether compounds (A) and (B). As a result, the amount of by-products, polyethylene glycol, polypropylene glycol, and polyalkylene glycol, which is a polymer of ethylene oxide and propylene oxide, is reduced to about 0.3 to about 3% by weight.
It is to suppress. The amount of water and the amount of catalyst
The Japan Oil Chemist's Society Vol. 28, p88
1, (1979), it affects the amount of by-products in the product, especially the amount of polyethylene glycol, polypropylene glycol or polyalkylene glycol produced by polymerizing ethylene oxide and propylene oxide. Defining the amount and the amount of the catalyst is an indispensable condition for controlling the amount of by-products produced during the production to about 0.3 to about 3% by weight.

As a reason for suppressing these by-products to about 0.3 to about 3% by weight, polyethylene glycol, polypropylene glycol and polyalkylene glycol are well known as a dispersant and a compound having a high foaming property. Therefore,
When these compounds are present in an amount of more than about 3% by weight, the properties of these compounds disperse the ink and enhance the foaming property during flotation. This is particularly detrimental in the flotation method, which is required to have good properties. Further, since these compounds do not have a hydrophobic group such as an alkyl group, the ink-collecting property is not exhibited at all and the ink peeled off during flotation cannot be removed from the pulp slurry. Conversely, if the by-product is less than about 0.3% by weight, appropriate foaming properties cannot be obtained during flotation, and high whiteness results due to insufficient collection of the separated ink by bubbles. Recycled pulp cannot be obtained.

When the product of the present invention has a defibration step or a ripening step during the deinking step, it can be added to either or both of the defibration and ripening steps and used in a commonly used deinking treatment method. In order to obtain high-quality recycled pulp using the product of the present invention, the product of the present invention is added to the defibration step (pulpper). Alternatively, in order to obtain a higher quality regenerated pulp, it is preferable to perform an aging step after the defibration step. The deinking agent can be dividedly added to one or both of the disaggregation step and the ripening step, and a more preferred method of use is to add the deinking step and the ripening step separately. As described above, the deinking process is roughly divided into two. One is a cleaning method and the other is a flotation method. Usually, the deinking process is disaggregated,
Roughening, washing, or flotation are roughly classified, and defibration and aging are steps of finely separating and dispersing the ink. On the other hand, the washing step is performed in a state where the ink is dispersed as before, but in the flotation method, it is necessary to agglomerate the dispersed ink due to defibration and aging, and contradictory ink states are required. Therefore, the deinking agent required for the flotation method requires contradictory performances such as ink peeling, dispersion and agglomeration of the dispersed ink, and the cleaning method requires conversely the three steps of disaggregation, aging, and cleaning. The performance of the deinking agent is the same.

However, in the present invention, (A) and (B)
By using different types of deinking agents, the conventional problems were solved. The amount of the product of the present invention added to the disaggregation step and the aging step is 0.10
If the amount is less than this range, high-quality recycled pulp having high whiteness and low residual ink cannot be obtained, and ink is removed during flotation. The foaming properties necessary for the production cannot be obtained.
On the other hand, if the addition amount is larger than this range, the foam at the time of flotation becomes too large and stable operation cannot be obtained.
When adding to both the disaggregation step and the ripening step, the total amount of addition in both steps is 0.1 to 2.0% by weight, preferably 0.15%.
What is necessary is just to add so that it may be set to about 1.5 weight%. When deinking treatment is performed using the product of the present invention, a bleaching agent such as sodium hydroxide, sodium silicate, sodium carbonate or, depending on the case, hydrogen peroxide may be used in the disaggregation step in addition to the product of the present invention. Pulp concentration 4-25%, temperature 20-7
It is preferably used at 0 ° C. and pH = 7.5 to 11.5, preferably 8.0 to 11.5. If the pulp concentration is 4% or less or the temperature is 20 ° C. or less, the frictional force between the pulp fibers at the time of defibration is small, so that unpulled pulp increases and cannot be used as a raw material for papermaking, or ink residue increases. . On the other hand, when the pulp concentration is 25% or more and the temperature is 70 ° C. or more, the frictional force between the pulp fibers is too strong, or the paper strength of the regenerated pulp formed by heat is weakened, and a high-quality regenerated pulp can be obtained. Disappears. On the other hand, if the pH at the time of defibration is 7.5 or less, the degree of swelling of the pulp fibers at the time of defibration is low, so that the amount of unfiberized fibers increases, and the pulp fibers cannot be used as a raw material for papermaking. Quality recycled pulp cannot be obtained. If the pH is 11.5 or more, the pulp turns yellow due to alkali baking, causing a decrease in whiteness and a decrease in paper strength.

The aging step can be carried out under the same chemical conditions as in the defibration step. At this time, the pulp concentration is 10 to 30.
%, At a temperature of 30 to 80 ° C. for 1 hour or more. If the pulp concentration is 10% or less and the temperature is 30 ° C. or less, a sufficient aging effect cannot be obtained, and high-quality recycled pulp cannot be obtained. On the other hand, if the temperature is 80 ° C. or higher, there is a disadvantage that the paper strength is reduced by heat. The pulp concentration is 30
% Or more, it is not possible to obtain the ripening effect of ripening at a pulp concentration of 10 to 30%. Also, aged
Even when the pH is 8 or less, the aging effect cannot be obtained. On the other hand, when the pH is 12 or more, yellowing of the pulp due to alkali burning occurs, whiteness decreases, and paper strength decreases due to alkali. The peeled ink has a pulp concentration of 0.5 to 1.5% and a temperature of 2.
By performing the flotation at 0 to 45 ° C., the pulp slurry can be efficiently removed. Furthermore, even if the product of the present invention has processes that are usually used in the deinking process such as dilution dewatering, screen, disperser, and kneader processes, the quality and operability of the recycled pulp may vary. The present deinking agent may be added to a step of removing ink, for example, a kneader, a refiner, a disperser, etc., in addition to the above-described defibration and ripening steps.

When the present deinking agent is added to the deinking treatment step by a washing method, an adduct of ethylene oxide and propylene oxide of a higher alcohol described in a conventional method or a known patent publication is used. Compared to the case, stable operability without bubble trouble can be obtained, and high-quality recycled pulp with high whiteness and little residual ink can be obtained. Further, the present deinking agent can be used in combination with polyoxyalkylene alkyl ether sulfate, fatty acid or a salt thereof, or an alkylene oxide adduct of rosin acid.

[0021]

By using the deinking agent of the present invention in a flotation method, it is possible to obtain a high-quality recycled pulp having good deinking characteristics, high whiteness, and a small amount of remaining ink. In particular, according to the present invention, the whiteness of the waste paper is increased by one point or more, and the residual ink amount is reduced by 25% or more as compared with the case where (A) and (B) are not used together, and the whiteness is excellent in appearance. Can be obtained. Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0022]

【Example】

Production Example 1 108.2 g (0.4 mol) of stearyl alcohol and 1.01 g (0.20% based on the final product) of KOH as a catalyst were charged into a stainless steel autoclave, and the inside of the reaction system was sufficiently purged with nitrogen. Subsequently, after sufficient dehydration under reduced pressure at 135 ± 5 ° C. for 0.5 hour, 125 ± 5 ° C. and 1.0-1.0.
211.2 g of ethylene oxide to maintain 3.0 kg / cm ²
(4.8 mol) was added slowly. After completion of the addition, the mixture was aged at the reaction temperature for 2 hours, and unreacted ethylene oxide was removed under reduced pressure. Subsequently, 110 ± 5 ° C, 1.0
Propylene oxide to maintain a pH of about 3.0 kg / cm ² .
6 g (3.2 mol) were added slowly. After completion of the addition, aging was performed at the same temperature for 2 hours, and subsequently, unreacted propylene oxide was removed under reduced pressure. Then, pH = 6 with acetic acid
~ 8. (Sample No. 1) Sample Nos. 2 and 3 were prepared in the same manner as in Production Example 1 except for the conditions described in Table 1.

Production Example 2 Stearyl alcohol (108.2 g, 0.4 mol) and catalyst K
OH, 1.27 g (0.2% based on the final product) was charged into a stainless steel autoclave, the inside of the reaction system was sufficiently purged with nitrogen, and then dehydrated under reduced pressure at 120 ° C. for 2.0 hours. 35.2 g (0.8 mol) of ethylene oxide was added to 175 ±
The solution was gradually added at 5 ° C. while maintaining 1.0 to 3.0 kg / cm ² . After completion of the addition, after aging for 2 hours at the reaction temperature,
After removing unreacted ethylene oxide under reduced pressure, a mixture of 281.6 g (6.4 mol) of ethylene oxide and 200.8 g (3.6 mol) of propylene oxide was heated at 120 ± 5 ° C.
It was gradually added so as to maintain 1.0 to 3.0 kg / cm ² . After completion of the addition, the mixture was aged for 2 hours, and then unreacted ethylene oxide and propylene oxide were removed under reduced pressure. Subsequently, after cooling, 0.18 g (0.2% based on the product) of the catalyst KOH was further charged, and the inside of the reaction system was sufficiently purged with nitrogen, followed by dehydration at 120 ± 5 ° C. for 2 hours under reduced pressure. Was.
After dehydration, 92.8 g (1.6 mol) of propylene oxide
Was gradually added so as to maintain 1.0 ± 3.0 kg / cm ² at 115 ± 5 ° C. After the addition was completed, unreacted propylene oxide was removed under reduced pressure, and then cooled, and the pH was adjusted with acetic acid.
= 6-8. (Sample No. 4). Sample No. 5 was prepared in the same manner as in Production Example 2 except that ethylene oxide and propylene oxide were added in advance under the conditions shown in Table 1 and then propylene oxide was added.

[0024]

[Table 1] Table 1 RO ・ (EO)-[(EO) (PO)] H ----- (B) component ━━━━━━━━━━━━━━━━━━━━墨 Deinking agent No. Alkyl group Total EO, PO Addition form in [] EO / PO by-product ━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━ 1 C18 12, 8 blocks 1.50 1.25 2 C18 / C22 18, 9 blocks 2.00 2.15 = 70/30 (wt%) 3 C16 / C18 18, 16 random 1.13 1.15 = 40/60 (wt%) 4 C18 18, 10 random, 1.80 2.25 block * 1 5 C16 / C18 16, 13 random, 1.23 2.15 = 30/70 (wt%) block * 1 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ * 1; After random addition of EO and PO, additional propylene oxide . Sample No. 4 has 4 moles of terminal PO addition mole Sample No. 5 has 5 moles of terminal PO addition mole

Production Example 3 An autoclave was charged with 108.2 g (0.4 mol) of stearyl alcohol and 1.20 g (0.18% based on adduct of stearyl alcohol propylene oxide (1 mol)) of KOH as a catalyst. After sufficiently purging the system with nitrogen,
After sufficiently dehydrating under reduced pressure at 140 ± 5 ° C. for 1 hour, 23.2 g (0.4 mol) of propylene oxide was added to 115
The solution was gradually added so as to maintain ± 5 ° C and 1.0 to 3.0 kg / cm ² . After completion of the addition, the mixture was aged for 2 hours, and then unreacted propylene oxide was removed under reduced pressure. Subsequently, after cooling, 0.3 g of KOH was added (total amount of catalyst; 0.20% based on the product), and the inside of the reaction system was sufficiently purged with nitrogen.
A mixture of 176 g (4 mol) of ethylene oxide and 440.8 g (7.6 mol) of propylene oxide was mixed with 120 ± 5.
C and 1.0 to 3.0 kg / cm ² was gradually added.
After completion of the addition, aging, and removal of unreacted ethylene oxide and propylene oxide were performed.
= 6-8. (Sample No. 6) Sample Nos. 7, 10 and 11 were also prepared in the same manner as in Production Example 3 except for the conditions described in Table 3. When the addition form of ethylene oxide and propylene oxide is block addition, first after adding ethylene oxide,
Propylene oxide was added.

Production Example 4 Stearyl alcohol (108.2 g, 0.4 mol) and catalyst K
After charging 1.67 g of OH (0.23% with respect to the adduct of stearyl alcohol propylene oxide (5 mol) / ethylene oxide (15 mol) / propylene oxide (10 mol)) in the autoclave, the reaction system was sufficiently purged with nitrogen. After the replacement, dehydration was performed at 125 ± 5 ° C. for 1.5 hours under reduced pressure. After the completion of the dehydration, 116 g (2 mol) of propylene oxide was gradually added so as to maintain the temperature at 115 ± 5 ° C. and 1.0 to 3.0 kg / cm ² . After completion of the addition, aging was performed for 2 hours, after which unreacted propylene oxide was removed. Subsequently, a mixture of 270 g (6.1 mol) of ethylene oxide and 232 g (4 mol) of propylene oxide was added to 115 ± 5.
C. and gradually added so as to maintain 1.0 to 3.0 kg / cm ² , followed by aging and removal of unreacted ethylene oxide and propylene oxide. Subsequently, cooling is performed and the catalyst K
0.44 g of OH (total amount of catalyst added; 0.25
%), Followed by nitrogen replacement in the reaction system and dehydration at high temperature under reduced pressure, and then 116 g (2 mol) of propylene oxide was added to 1
The solution was gradually added at 15 ± 5 ° C. while maintaining 1.0 to 3.0 kg / cm ² . After aging and removal of unreacted propylene oxide, the mixture was cooled and adjusted to pH 6 to 8 with acetic acid.
(Sample No. 8) Sample No. 9 was prepared in the same manner as in Production Example 4 except for the conditions described in Table 2.

[0027]

[Table 2] Table 2 RO ・ (PO) n1-[(EO) m (PO) n2] H ━━━━━━━━━━━━━━━━━━━━━━━━━墨 Deinking agent No. Alkyl group n1, m, n2 [] Addition form in [] EO / PO by-product ━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━ 6 C18 1,10,19 random 0.50 1.53 7 C16 / C18 3,16,15 block 0.67 2.30 = 30/70 (wt%) 8 C18 5, 15,15 random, 0.75 2.53 block * 1 9 C18 / C22 7,18,14 random, 0.86 2.85 = 70/30 (wt%) block * 1 10 C12 2,18,10 block 1.50 2.34 11 C16 / C18 3, 18,12 blocks 1.20 2.45 = 20/80 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ * 1; ethylene oxide and propylene Sample No. 8 was 5 moles of terminal PO addition mole, and Sample No. 9 was terminal PO Addition molar number 6 mol

Comparative Production Example 1 In Production Example 1, ethylene oxide (1) was added such that the total addition molar ratio of ethylene oxide and propylene oxide added to 1 mol of stearyl alcohol was 1.0.
(8 mol) and propylene oxide (18 mol) were prepared under the same conditions except that block addition was carried out. (Sample N
o.12)

[Table 3] Table 3 RO ・ (EO)-[(EO) (PO)] H ━━━━━━━━━━━━━━━━━━━━━━━━━━━━墨 Deinking agent No. Alkyl group Total EO, PO Addition form in [] EO / PO by-product ━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━ 12 C18 18, 18 block 1.0 2.56 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━

Production Example 5 In Production Example 3, first, 4 mol of propylene oxide was added to 1 mol of stearyl alcohol, and then ethylene oxide (16 mol) and propylene oxide were added to (1 mol).
2 mol), and prepared under the same conditions except that the total addition molar ratio of ethylene oxide and propylene oxyoxide was changed to 1.0. (Sample No.13)

[Table 4] Table 4 RO ・ (PO) n1-[(EO) m (PO) n2] H ━━━━━━━━━━━━━━━━━━━━━━━━━墨 Deinking agent No. Alkyl group n1, m, n2 [] Addition form in [] EO / PO by-product ━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━ 13 C18 4,16,12 Random 1.0 2.48 ━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━

Example 1 After cutting the used raw paper (offset-printed newspaper / magazine = 7/3 weight ratio) into 3 × 3 cm, put it in a pulp disintegrator (manufactured by Kumagaya Riki Kogyo) and add hot water or water. After adjusting the temperature and pulp concentration, the pH was adjusted using sodium hydroxide and sodium silicate.
Was prepared, and 1.0% of hydrogen peroxide (active ingredient) and 0.35% of various deinking agents were added. Subsequently, pulp disintegrator 7
Disintegration was performed for a minute. The obtained pulp slurry was used for 8
After centrifugal dehydration using a 0 mesh filter cloth and concentration to 15%, the pulp concentration was adjusted to 5% again using water. Subsequently, the pulp was defibrated with a pulp disintegrator for 3 minutes.
Next, after adjusting the pulp concentration to 1% with warm water, a flotation treatment was performed for 7 minutes using a Denver-type flotator (manufactured by Far East Shinko Co., Ltd.). Next, the pulp slurry was concentrated to 10% using an 80-mesh filter cloth, then diluted to 1% with water, and the pulp sheet obtained during preparation of the pulp sheet using a TAPPI sheet machine was evaluated for whiteness according to JIS P.
According to the method of -8123, it was determined by measuring with a colorimetric colorimeter (manufactured by Nippon Denshoku Industries Co., Ltd.), and the residual ink amount was determined by using an image analyzer (Luzex, manufactured by NIRECO) to determine the residual ink area ratio. The results are shown in Table 5. In the table, the operability (foam) during the flow was evaluated according to the following criteria. Also, with deinking agent No.3
Table 6 shows the effect of the amount added when No. 8 was used in combination. A: Good operability B: Slightly high foam but no operability problem C: Slightly low foam but no operability problem D: Too much foam to disable operation E: Too little foam to disable operation

[0031]

[Table 5] Table ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Experiment Disintegration conditions No deinking agent ( wt%) PC Temp pH Whiteness Residual ink Operability ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 1 No. 1 / No.7 = 40/60 5 25 9.5 58.4 0.250 B 2 No.2 / No.6 = 10/90 15 40 10.9 57.7 0.275 C 3 No.3 / No.8 = 20/80 5 40 9.8 58.1 0.258 A4 No.4 / No.9 = 70/30 25 65 10.5 58.2 0.254 B5 No.5 / No.7 = 55/45 15 30 11.5 58.4 0.251 A6 No.1 / No.8 = 33/67 15 40 10.9 58.0 0.260 A7 No.2 / No.10 = 40/60 15 40 11.2 57.4 0.280 B8 No.3 / No.7 = 70/30 15 40 11.3 59.2 0.214 A9 No.3 / No.11 = 70/30 15 40 11.1 58.6 0.233 A10 No.2 15 40 10.9 55.6 0.376 B11 No.6 15 40 10.9 55.7 0.380 E12 No.12 15 40 10.9 55.3 0.391 A13 No.13 15 40 10.9 55.4 0.388 B14 No. 7 15 40 10.8 55.9 0.363 A ━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━ Experiment No. 1 to 9; Example, experiments No. 10 to 14; comparative example

[0032]

[Table 6] Table 6 墨 Deinking agent (wt /%) Addition during disaggregation Amount Whiteness Residual ink Operability ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ No.3 / No.8 = 20/80 0.08 57.0 0.293 E 0.10 57.5 0.276 C 0.35 58.1 0.258 A 1.00 58.7 0.232 A 2.00 59.1 0.221 B 2.50 58.4 0.235 D ━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━ Disintegration conditions; PC = 5%, Temp; 40 ° C., pH = 9.8

Example 2 After cutting the used printing paper (offset-printed newspaper / magazine = 7/3 weight ratio) as a raw material into 3 × 3 cm, put it in a pulp disintegrator (manufactured by Kumagaya Riki Kogyo) and use hot water or water. After adjusting the temperature and pulp concentration, the pH was adjusted with sodium hydroxide and sodium silicate.
Was prepared. Next, 0.15% of the deinking agent listed in Table 1 was used.
After the addition, a disintegration treatment was performed for 7 minutes. The obtained pulp slurry was subjected to centrifugal dehydration using an 80 mesh filter cloth to adjust the pulp concentration, and then the pH was adjusted using sodium hydroxide and sodium silicate. Subsequently, 1.7% of hydrogen peroxide,
0.1% of a deinking agent was added, and ripening was performed in a thermostat. After aging, adjust the pulp concentration to 5% again with water,
Disintegration treatment was performed for 3 minutes with a pulp disintegrator. Next, after adjusting the pulp concentration to 1% with warm water, a flotation treatment was performed at 30 ° C. for 7 minutes using a Denver type flotator (manufactured by Far East Shinko Co., Ltd.). Then the pulp slurry was added to 8
After concentrating to 10% using a 0 mesh filter cloth, 1%
And a pulp sheet was prepared using a TAPPI sheet machine. The whiteness of the obtained pulp sheet was measured according to JIS P
According to the method of -8123, it was determined by measuring with a colorimetric colorimeter (manufactured by Nippon Denshoku Industries Co., Ltd.), and the residual ink amount was determined by using an image analyzer (Luzex, manufactured by NIRECO) to determine the residual ink area ratio. The results are shown in Table 7. Table 8 shows the effect of the amount of addition of the deinking agents No. 2 and No. 6 in combination.

[0034]

[Table 7] Table 7 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Experiment Disintegration conditions Aging conditions No Deinking agent (Wt%) PC, Temp, pH PC, Temp, pH ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 1 No .1 / No.9 = 30/70 25 55 10.4 25 55 10.5 2 No.2 / No.6 = 20/80 20 65 10.1 30 60 9.6 3 No.3 / No.7 = 60/40 5 35 9.8 20 55 10.8 4 No.4 / No.8 = 45/55 15 55 10.3 20 55 10.9 5 No.5 / No.7 = 90/10 5 35 10.8 25 60 11.2 6 No.4 / No.7 = 29/71 15 55 10.3 20 55 10.9 7 No.3 5 35 9.8 20 55 10.8 8 No.8 15 55 10.3 20 55 10.9 9 No.12 5 35 9.8 20 55 10.8 10 No.13 15 55 10.3 20 55 10.9 ━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

━━━━━━━━━━━━━━━━━━ Whiteness Residual ink Operability ━━━━━━━━━━━━━━━━━━ 59.0 0.231 A 58.8 0.235 A 59.3 0.223 A 58.9 0.233 A 59.3 0.222 A 59.4 0.221 A 56.5 0.341 B 56.8 0.339 A 56.3 0.346 A 56.4 0.341 A ━━━━━━━━━━━━━━━━━━ Experiment Nos. 1 to 6; Example No. 7 to 10; Comparative Example

[0036]

[Table 8] Table 8 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Deinking agent (wt%) Disintegration When ripening Whiteness Residual ink Operability Addition amount Addition amount ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ No. 2 / No.6 = 20/80 0.15 No addition 58.0 0.251 C 〃 0.08 58.5 0.245 A 〃 0.10 58.8 0.235 A 〃 0.35 59.3 0.223 A 〃 1.50 60.2 0.203 B 〃 2.50 59.7 0.218 D 0.10 No addition 57.4 0.275 C 〃 0.10 58.3 0.240 A 〃 0.30 58.9 0.230 A 〃 1.50 60.1 0.201 B 〃 2.20 59.8 0.215 D ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━

Claims (3)

(57) [Claims] An average number of moles of ethylene oxide added, m, is 10 to 30, an average number of moles of propylene oxide added, n is 8 to 35, and a compound represented by formula (A) has an alkyl group having 12 carbon atoms. To 22, monoalkyl ethers (A) and (B) of the following ethylene oxide-propylene oxide copolymers in which the alkyl group of the compound represented by formula (B) has a carbon number in the range of 16 to 24:
Mixture 99.7-9 of 0 / 90-90 / 10 (weight ratio)
A deinking agent for flotation, comprising 7% by weight and about 0.3 to about 3.0% by weight of a polyalkylene oxide selected from the group consisting of polyethylene oxide, polypropylene oxide and ethylene oxide-propylene oxide copolymer. R ¹ O- _{(PO) n1} - _{[(EO) m · (PO)} n2 ] ^{H - (A) R 2 O-} (EO) m1 - _{[(EO) m2 · (PO)} n) H - ( B) (wherein, R ¹ is an alkyl group having 12 to 22 carbon atoms, R ² is an alkyl group having 16 to 24 carbon atoms, m / (n1 + n2) =
0.5-1.5, (m1 + m2) /n=1.1-2.0
Where m = m1 + m2 is 10 to 30, and n = n1 + n
2 is 8-35. EO and PO represent ethylene oxide and propylene oxide units, respectively, and the addition form of EO and PO in [] may be random or block. ) 2. A method for deinking printed waste paper, comprising: disintegrating printed waste paper in the presence of the deinking agent according to claim 1; and separating and removing the separated ink from the pulp slurry by flotation. . 3. A method for removing used printed paper, comprising: aging the printed waste paper in the presence of the deinking agent according to claim 1; and separating and removing the separated ink from the pulp slurry by flotation. Ink method.