JP2009270222A - Method for producing deinked pulp - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing deinked pulp with little of unreleased ink from printed waste paper. <P>SOLUTION: The method for producing deinked pulp comprises the preparation of a pulp slurry containing a nonionic surfactant (1) consisting of a compound having an average carbon number of ≤15 excluding oxyalkylene group and having a specific structure, a deinking agent (2) having an average carbon number of >15 excluding oxyalkylene group, a specific structure and a cloud point of 20-90°C and a specific ink release assisting agent (3), and the use of the slurry for the deinking of waste paper including neutral newsprint paper. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing deinked pulp produced using waste paper including a neutral newspaper.

  The use of waste paper is becoming more and more important not only in terms of environmental awareness but also in terms of reducing manufacturing costs. There are two types of waste paper pulp, one that only disaggregates waste paper and one that has undergone a deinking process, but in recent years the technological development of deinked pulp that can be blended into higher quality paper products has been remarkable.

  In order to produce deinked pulp, the printing ink must first be peeled from the pulp fibers. The fibers (black beard-like fibers) in which the unpeeled ink remains are not preferable because they eventually become a paper product dirt, which deteriorates the appearance and causes a decrease in whiteness. This causes the problem that it is difficult to raise. The peeled ink can be easily removed in a deinking process using a floatator, a washing device, etc., and there are few black whisker-like fibers, and a high white deinked pulp can be obtained.

  Therefore, various technical developments have been made in order to improve ink peelability and reduce black whisker-like fibers. For example, conventionally, ink peeling by a mechanical treatment using a mixer, a kneader, a disperser or the like, and ink peeling by using a deinking agent are generally performed.

  As an ink peeling technique by mechanical treatment, a method is disclosed in which an alkali soaking is performed for 3 hours or more and then a stirring process is performed with a mixer or a kneader (for example, see Patent Document 1). Also, add deinking agent and bleaching agent and use refiner, kneader, mixer or disperser at a pulp concentration of about 15% or more and an alkali concentration of 5.0 g / l (as NaOH) or more under heating. A method of performing mechanical stirring while applying a compressive force is disclosed (for example, see Patent Document 2). Furthermore, a method of performing a two-stage mechanical process before and after soaking is disclosed (for example, see Patent Document 3).

  Also, alcohol derivatives are known as deinking agents used in the production of deinked pulp. For example, Patent Document 4 discloses a deinking agent having a specific iodine value obtained by adding an alkylene oxide to an alcohol having a specific carbon number distribution, which can obtain a deinked pulp having good operability and low unpeeled ink. It is disclosed.

  Further, in Patent Document 5, a paper product having a high whiteness, a high L value, and a high b value is obtained, and an alkylene oxide is added to alcohol as a deinking agent composition having an excellent defoaming effect during the deinking process. A deinking agent composition containing a component and an oil derivative component is disclosed.

  On the other hand, neutral newspaper having performance equivalent to or better than that of conventional acid newspaper has been developed as newspaper (for example, Patent Document 6), and in recent years, neutral newspaper has been used instead of acid newspaper. Along with this, the content of neutral newspaper in waste paper is increasing.

However, in recent years, it has been found that this neutral newspaper waste paper is difficult to remove ink, which is a big problem. Although the cause is still unknown, the increase in residual unpeeled ink and the accompanying decrease in whiteness have occurred, making it difficult to blend deinked pulp into high-quality paper products.
Japanese Patent Laid-Open No. 54-120705 JP-A-55-40850 JP-A 63-28992 JP-A-5-25789 JP-A-10-292279 Japanese Patent No. 2889159

Conventional ink stripping techniques have insufficient ink stripping performance for such neutral newspapers. For example, in the case of mechanical treatment, a sufficient ink peeling effect cannot be obtained even if a conventional technique including two-stage mechanical treatment is used.
Therefore, there is a demand for a technique that is excellent in ink peeling performance with respect to neutral newspaper waste paper without using mechanical treatment. The subject of this invention is providing the method which can manufacture deinked pulp with few unpeeled inks from the used paper containing a neutral newspaper.

The present invention is a method for producing deinked pulp made from waste paper containing at least a neutral newspaper, and is one or more kinds selected from the group consisting of the following general formulas (1-1) to (1-5) The present invention relates to a method for producing deinked pulp having a step of deinking in the presence of an ionic surfactant (1), the following deinking agent (2), and the following ink peeling aid (3).
Nonionic surfactant (1):

[Wherein, R ¹ and R ² are each a linear alkyl group or alkenyl group having 1 to 13 carbon atoms, the total average carbon number of R ¹ and R ² is 7 to 14, and AO is the number of carbon atoms. 2 or 3 oxyalkylene groups, m is a number of 1 to 25 in terms of average added mole number. ]

[Wherein, R ³ and R ⁴ are each a linear alkyl group or alkenyl group having 1 to 12 carbon atoms, R ⁵ is a linear alkylene group having 1 to 12 carbon atoms, and R ³ and R ⁴ And R ^{5 has} a total average carbon number of 5 to 14, AO is an oxyalkylene group having 2 or 3 carbon atoms, and n is an average added mole number of 1 to 25. ]
_{^{R 6 O- (AO) p H}} (1-3)
[In the formula, R ⁶ is a linear alkyl group or alkenyl group having 6 to 15 carbon atoms on average, AO is an oxyalkylene group having 2 or 3 carbon atoms, and p is an average added mole number of 1 to 25. is there. ]

[Wherein, R ⁷ is a linear or branched alkyl group or alkenyl group having an average carbon number of 4 to 9, and R ⁸ and R ⁹ are a hydrogen atom or a glycerol group, respectively. ]

[Wherein, AO is an oxyalkylene group having 2 or 3 carbon atoms, and q and r are numbers of 1 to 25 in terms of the average number of added moles, respectively. ]
Deinking agent (2):
One or more deinking agents selected from the group consisting of the following (2-1) to (2-3), wherein the deinking agent has a cloud point of 20 to 90 ° C. and a compound having active hydrogen Obtained by adding an alkylene oxide to the compound, the average number of carbon atoms per active hydrogen excluding the oxyalkylene group is from 15 to 24, and the average number of moles of the oxyalkylene group added per mole of the compound having active hydrogen Deinking agent which is 10-500.
(2-1) Higher alcohol-based deinking agent (2-2) Fatty acid-based deinking agent (2-3) Oil / polyhydric alcohol-based deinking agent Ink peeling aid (3):
1 or more types of ink peeling adjuvant chosen from the compound represented by following General formula (3).

[Wherein, R ¹⁰ represents a linear or branched alkyl group or alkenyl group having an average carbon number of 8 to 22. ]

  The present invention also provides a deinking additive (agent A) containing the nonionic surfactant (1) and the ink peeling aid (3), and a deinking agent containing the deinking agent (2). The present invention relates to an additive kit used for producing deinked pulp made from waste paper containing at least a neutral newspaper, which is composed of an additive for ink (B agent).

  The present invention also relates to a method for producing a deinked pulp made from waste paper containing at least a neutral newspaper, which is removed in the presence of the nonionic surfactant (1) and the ink peeling aid (3). The present invention relates to a method for producing deinked pulp having a step of performing ink.

  ADVANTAGE OF THE INVENTION According to this invention, the method which can manufacture deinked pulp with few unpeeled inks from the used paper containing a neutral newspaper is provided.

  The present invention relates to a method for producing a deinked pulp using a deinking agent with respect to a used paper containing at least a neutral newspaper as a raw material, and the unpeeled ink that cannot be removed only by the deinking agent (2) The non-ionic surfactant (1), which has excellent permeability, is used in combination with the ink peeling aid (3), or this combination is used in combination with the deinking agent (2) to remove the ink with little unpeeled ink. Ink pulp is produced. Conventionally, it has been considered that the nonionic surfactant (1) is inferior in deinking performance as compared with the deinking agent (2) (for example, the products 1 and 7 of the embodiment of Patent Document 1). Contrast etc.) is surprisingly found to be effective for the ink release of neutral newspapers by using the ink release aid (3) at the same time as the nonionic surfactant (1). It was. Although the manifestation mechanism of the effect is unknown, it is presumed that the nonionic surfactant (1) is excellent in permeability to neutral newspaper waste paper and has high ink peelability. Further, it is presumed that the deinking agent (2) has improved permeability to printed waste paper pulp and synergistically promotes ink peeling. Further, it is presumed that the use of the specific ink peeling aid (3) at the same time can further improve the permeability to the used waste paper pulp and further improve the quality of the deinked pulp.

  The nonionic surfactant (1) which concerns on this invention is a compound which has the osmotic power to the pulp of neutral newspaper waste paper. From the viewpoint of penetrating power, in the compounds of general formulas (1-1) to (1-3) and (1-5), compounds having an average carbon number of 15 or less excluding an oxyalkylene group (hereinafter abbreviated as AO) It is. Examples of AO include ethylene oxide (hereinafter abbreviated as EO) and propylene oxide (hereinafter abbreviated as PO), but the ratio of EO in the total number of AO addition moles is preferably 50 to 100 mol%, and further 100 Mole% is preferred. The average added mole number of AO is 25 moles or less from the viewpoint of penetrating power. In the case of an adduct of two or more types of AO, any addition form such as random or block may be used. In the case of introducing PO, the average addition mole number of PO is preferably 2 to 10 and more preferably 2 to 5 moles in the average addition mole of AO. The addition form of PO is preferably a block, and more preferably a terminal block. The nonionic surfactant (1) is at least one nonionic surfactant selected from the group consisting of the following (1-1) to (1-5).

(1-1) Nonionic surfactant represented by general formula (1-1)

[Wherein, R ¹ and R ² are each a linear alkyl group or alkenyl group having 1 to 13 carbon atoms, the total average carbon number of R ¹ and R ² is 7 to 14, and AO is the number of carbon atoms. 2 or 3 oxyalkylene groups, m is a number of 1 to 25 in terms of average added mole number. ]

In the present invention, for example, when R ¹ is the number 10, R ² carbons there are molecules of 1 carbon atoms, the carbon number of the sum of R ¹ and R ² of the molecule and 11, belonging to the (1-1) The average value of the total carbon number of R ¹ and R ² of all the molecules is defined as the total average carbon number of R ¹ and R ² . The average carbon number excluding the oxyalkylene group can be determined by ¹ H-NMR [hereinafter the same applies to the nonionic surfactants (1-2) and (1-3)].

  The average number of moles of AO added is the number of moles added per mole of the compound having active hydrogen, and can be calculated from the amount of AO charged at the time of AO addition [hereinafter, nonionic surfactants (1-2) and ( Same for 1-3)].

The average number of carbon atoms in the sum of R ¹ and R ² is preferably 9 to 14, 11 to 13 is more preferable. 1-16 are preferable, as for the average addition mole number m of AO, 1-10 mol is more preferable, and 1-5 mol is more preferable.

  Specific examples of the nonionic surfactant (1-1) include linear secondary alcohol AO adducts such as sec-octanol, sec-nonanol, sec-decanol, sec-undecanol, sec-dodecanol, Examples include AO adducts of sec-tridecanol, sec-tetradecanol, and sec-pentadecanol, and an AO adduct of 6-dodecanol and an AO adduct of 6-tetradecanol are preferred.

(1-2) Nonionic surfactant represented by general formula (1-2)

[Wherein, R ³ and R ⁴ are each a linear alkyl group or alkenyl group having 1 to 12 carbon atoms, R ⁵ is a linear alkylene group having 1 to 12 carbon atoms, and R ³ and R ⁴ And R ^{5 has} a total average carbon number of 5 to 14, AO is an oxyalkylene group having 2 or 3 carbon atoms, and n is an average added mole number of 1 to 25. ]

The average carbon number of R ³ is preferably 2 to 5, and the average carbon number of R ⁴ is preferably 4 to 7. R ³ and R ⁴ and the average number of carbon atoms in the sum of R ⁵ is preferably 7 to 12, 8 to 10 is more preferable. The average carbon number of R ⁵ is preferably 1 to 3, and more preferably 1. 1-10 are preferable, as for the average added mole number n of AO, 3-7 are more preferable, and 4-6 are more preferable.

  The nonionic surfactant (1-2) is specifically an AO adduct of a branched alcohol, branched hexanol, branched heptanol, branched octanol, branched nonanol, branched decanol, branched undecanol, branched dodecanol, branched. Examples include AO adducts of tridecanol, branched tetradecanol, and branched pentadecanol, with an AO adduct of 2-propylheptanol and an AO adduct of 2-butylheptanol being preferred.

(1-3) Nonionic surfactant represented by the following general formula (1-3) R ⁶ O— (AO) _pH (1-3)
[In the formula, R ⁶ is a linear alkyl group or alkenyl group having 6 to 15 carbon atoms on average, AO is an oxyalkylene group having 2 or 3 carbon atoms, and p is an average added mole number of 1 to 25. is there. ]

The average number of carbon atoms of R ⁶ is 8 to 14 are preferred, 8 to 13 more preferred. 1-10 are preferable and, as for the average addition mole number of AO, 1-5 mol is preferable.

  The nonionic surfactant (1-3) is specifically a linear primary alcohol AO adduct, such as hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, Examples include an AO adduct of pentadecanol, and an AO adduct of octanol and an AO adduct of decanol are preferable.

(1-4) Nonionic surfactant represented by the following general formula (1-4)

[Wherein, R ⁷ is a linear or branched alkyl group or alkenyl group having an average carbon number of 4 to 9, and R ⁸ and R ⁹ are a hydrogen atom or a glycerol group, respectively. ]

The nonionic surfactant of (1-4) is glyceryl ether, and in the formula, the average carbon number of R ^{7, that} is, the group bonded through an ether bond is more preferably 5-8. The average carbon number of R ⁷ can be determined by ¹ H-NMR.

Specific examples of the nonionic surfactant (1-4) include pentyl glyceryl ether, octyl glyceryl ether, and 2-ethylhexyl glyceryl ether.

(1-5) Nonionic surfactant represented by the following general formula (1-5)

[Wherein, AO is an oxyalkylene group having 2 or 3 carbon atoms, and q and r are numbers of 1 to 25 in terms of the average number of added moles, respectively. ]

  In general formula (1-5), AO is preferably EO. q and r may be different from each other, and 5 to 15 are preferable.

The deinking agent (2) used in the present invention is one or more deinking agents selected from the group consisting of the following (2-1) to (2-3),
(2-1) Higher alcohol deinking agent (2-2) Fatty acid deinking agent (2-3) Oil / polyhydric alcohol deinking agent The cloud point of the deinking agent is 20 to 90 ° C, Obtained by adding alkylene oxide to a compound having active hydrogen, the average number of carbon atoms per active hydrogen excluding oxyalkylene groups is from 15 to 24, and the average number of added moles of oxyalkylene groups It is a deinking agent which is 10-500 per 1 mol of compound to have.

  The deinking agents (2-1) to (2-3) are obtained by adding AO to a compound having active hydrogen. The deinking agent is an active hydrogen excluding an oxyalkylene group (when it has an ester bond, the ester group is an active hydrogen and other groups are not active hydrogen). , Meaning this unless otherwise specified) is greater than 15-24. Moreover, it is preferable that the average addition mole number of an oxyalkylene group is 10-500 per mol of compounds containing active hydrogen (an ester bond is also made into active hydrogen). The reason why the ester bond is an active hydrogen is that the ester bond functions as a reaction point by the transesterification reaction.

  Moreover, from a viewpoint of deinking performance, the deinking agent of (2-1)-(2-3) has a cloud point of 20-90 degreeC, and 30-70 degreeC is more preferable. The cloud point is measured by once raising the 2% by weight aqueous solution to a temperature equal to or higher than the cloud point and then lowering the temperature, and the temperature at which the liquid becomes transparent is taken as the cloud point.

  In the deinking agent (2), the difference from the average carbon number of the nonionic surfactant (1) is preferably 1 or more, more preferably 3 or more, and even more preferably 5 or more.

  Hereinafter, the deinking agents (2-1) to (2-3) which are deinking agents (2) will be described.

(2-1) Higher alcohol deinking agent The deinking agent is a higher alcoholic deinking agent having an average carbon number of more than 15 to 24.

  Specific examples include AO adducts of primary alcohols having a saturated or unsaturated linear or branched alkyl group having an average carbon number of more than 15 to 24. As the constituent alcohol, palmityl alcohol and stearyl alcohol are preferable. Examples of AO added to alcohol include EO, PO, and butylene oxide (hereinafter abbreviated as BO), and it is particularly desirable to make EO essential. The average added mole number of AO is preferably 10 to 200 moles, more preferably 20 to 100 moles, and particularly preferably 40 to 80 moles per mole of alcohol. In this range, the deinking agent has particularly good ink releasability and easy liquefaction. Is obtained. The addition form may be either random addition or block addition. Specifically, any two of PO addition, EO addition, (EO / PO random addition) are added in stages, or any three of them are added. Examples include a three-stage addition in which steps are added, and a four-stage addition form in which any four are added in steps.

(2-2) Fatty acid-based deinking agents AO adducts of saturated or unsaturated higher fatty acids having an average carbon number of more than 15 to 24, AO adducts of polyvalent carboxylic acids or anhydrides, and ester compounds thereof. .

  Examples of higher fatty acids include saturated fatty acids such as palmitic acid, stearic acid, arachidic acid, and behenic acid. Examples of unsaturated fatty acids include palmitoleic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, erucic acid, ricinoleic acid and the like.

  The polyvalent carboxylic acid or acid anhydride thereof includes a dimer acid and / or polymer acid of a higher fatty acid having 20 to 40 carbon atoms, and further an esterified product thereof. The dimer acid and / or polymer acid referred to here is a method of reacting a monoenoic acid or a dienoic acid, specifically, an unsaturated fatty acid monomer such as oleic acid, linoleic acid, linolenic acid, etc. by thermal polymerization such as Diels-Alder reaction. Alternatively, it can be synthesized by other reaction methods. In addition, polycarboxylic acids such as dimer acid and polymer acid can be used in a mixture with alcohol.

  Examples of AO added to higher fatty acids, polyvalent carboxylic acids or anhydrides thereof include EO, PO, and BO, and it is particularly desirable to make EO essential. The average added mole number of AO is preferably 50 to 450 moles, more preferably 100 to 400 moles per mole of higher fatty acid or polyvalent carboxylic acid or anhydride thereof. The addition form may be either random addition or block addition. The polyvalent carboxylic acid may contain a compound partially esterified by adding AO in the presence of alcohol. The average carbon number includes the carbon number of the ester-bonded alcohol.

(2-3) Oil / Fat / Polyhydric Alcohol Deinking Agent As the oil / polyhydric alcohol deinking agent of (2-3), a saturated or unsaturated fatty acid having an average carbon number of 15 to 24 and glycerin An AO adduct of a mixture of an oil and fat comprising an ester and a 2 to 10 valent polyhydric alcohol can be mentioned. Examples of the fatty acid include those exemplified in (2-2) above. As a 2-10 valent polyhydric alcohol, it is effective to raise reaction efficiency when adding AO to fats and oils, and ethylene glycol, propylene glycol, glycerin, polyglycerin, sorbitol, sorbitan, sucrose, etc. are mentioned. . In the mixture, the ratio of the fat / oil to the polyhydric alcohol is preferably fat / oil / polyhydric alcohol = 10/1 to 1/1 (molar ratio). Examples of AO added to the mixture include EO, PO, and BO, and it is particularly desirable to make EO essential. The average added mole number of AO is preferably 10 to 200 moles, more preferably 20 to 80 moles, based on 1 mole of oil and fat and polyhydric alcohol. The addition form may be either random addition or block addition.

  The ink peeling aid (3) used in the present invention is at least one ink peeling aid selected from compounds represented by the following general formula (3).

[Wherein, R ¹⁰ represents a linear or branched alkyl group or alkenyl group having an average carbon number of 8 to 22. ]

Average carbon number of R ¹⁰ is from 8 to 22, preferably 12 to 22, 12 to 18 is more preferable. R ¹⁰ is a linear or branched alkyl group or alkenyl group, preferably a linear alkyl group. Examples of R ¹⁰ include hydrocarbon groups derived from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, and the like.

  These nonionic surfactant (1), deinking agent (2) and ink stripping aid (3) are for deinking containing nonionic surfactant (1) and ink stripping aid (3), respectively. Used for the manufacture of deinked pulp made from waste paper containing at least a neutral newspaper composed of an additive (agent A) and a deinking additive (agent B) containing a deinking agent (2) Additive kit.

  Further, these nonionic surfactant (1), deinking agent (2), and ink peeling aid (3) are deinking additive (C agent) containing nonionic surfactant (1). The deinking additive (B agent) containing the deinking agent (2) and the deinking additive (D agent) containing the ink peeling aid (3) are at least neutral. It can be set as the additive kit used for manufacture of the deinking pulp which uses the waste paper containing a newspaper as a raw material.

  It is preferable to adjust the combination of the nonionic surfactant (1) and the deinking agent (2) and the concentration in water in the pulp slurry so that the permeation time of these aqueous solutions into the neutral newspaper is shortened. When 5 μL is dropped onto neutral newspaper, the penetration time from dripping until it is completely absorbed by neutral newspaper is preferably 40% or less in terms of relative penetration time when water penetration time is 100%, 25% The following is more preferable. In addition, the nonionic surfactant (1), the deinking agent (2), and the ink peeling aid (3) are also combined with pulp slurry so that the permeation time of these aqueous solutions into the neutral newspaper is shortened. It is preferable to adjust the concentration in water. When 5 μL is dropped onto neutral newspaper, the permeation time from dripping until it is completely absorbed by neutral newspaper is preferably 40% or less in terms of relative permeation time when water permeation time is 100%, 30% The following is more preferable.

  The method for producing deinked pulp of the present invention uses waste paper containing at least a neutral newspaper as a raw material. The content of the neutral newspaper in the used paper raw material is preferably 10% by weight or more, and more preferably 20 to 100% by weight, from the viewpoint of developing the ink peelability effect. Waste paper materials other than neutral newspaper waste paper include acid paper waste paper, flyer waste paper, magazine waste paper, colored waste paper, OA waste paper, and mixed waste paper thereof.

  The production method of the deinked pulp of the present invention is used when producing recycled paper using waste paper or the like as a raw material, specifically, the flotation method, the washing method, and the deinking process using its compromise method, Specifically, it can be used in a method for producing pulp by appropriately combining steps such as disaggregation, dust removal, dilution, dehydration, ink peeling, bleaching, ink removal and washing. Among these steps, the step of deinking is a step of disaggregating or peeling the ink and a step of removing the ink, and includes a step of disaggregation, dilution, dehydration, ink peeling, bleaching, ink removal and washing. In the present invention, at least one of these steps is performed in the presence of the nonionic surfactant (1) and the ink stripping aid (3), or the nonionic surfactant (1), the deinking agent (2), and the ink stripping. It is carried out in the presence of auxiliary agent (3).

  The method for producing deinked pulp of the present invention can be carried out in accordance with the conventional method for producing deinked pulp, and includes a nonionic surfactant (1), a deinking agent (2), and an ink peeling aid (3). Is a process for producing deinked pulp from raw waste paper, for example, waste paper disaggregation step such as pulper, ink peeling step such as kneading, bleaching step such as soaking, ink removal step such as flotation treatment, or Added in multiple steps. The nonionic surfactant (1), the deinking agent (2), and the ink peeling aid (3) may be added in the same step as long as the three agents coexist and can come into contact with the used printing paper. May be added. When adding in the same step, a mixture of the nonionic surfactant (1), the deinking agent (2), and the ink peeling aid (3) may be prepared in advance, and the mixture may be added.

  In any step of deinked pulp production other than the step of adding three agents of nonionic surfactant (1), deinking agent (2) and ink peeling aid (3), deinking agent (2) It is more preferable to add. That is, a step of deinking by adding a nonionic surfactant (1), a deinking agent (2), and an ink peeling aid (3), and a deinking agent (2) are added for deinking. A method for producing a deinked pulp having other steps to be performed is preferred. For example, a nonionic surfactant (1), a deinking agent (2), and an ink peeling aid (3) are added in the disaggregation step, and a deinking agent (2) is further added in the kneading step after that step. To do. Moreover, it is preferable to perform a dehydration process between several processes which add a deinking agent (2). For example, after the process of adding the deinking agent (2) for the first time, the dehydration process is performed before the kneading process of adding the second time in view of the effect of the deinking agent (2) for the second time. preferable. It is preferable to select and add different deinking agents (2) to be added in each step from the viewpoint of achieving both ink releasability and ink collecting properties. When the deinking agent (2) is added twice, the cloud point of the deinking agent (2) added for the first time is preferably 20 to 70 ° C, more preferably 30 to 60 ° C. The cloud point of the deinking agent (2) added the second time is preferably 30 to 90 ° C, more preferably 40 to 70 ° C.

  When the nonionic surfactant (1) is at least one selected from the group consisting of the general formulas (1-1) to (1-3), water 100 in the pulp slurry in the deinking step The content of the nonionic surfactant (1) with respect to parts by weight is preferably 0.03 parts by weight or more. Hereinafter, the weight part of the nonionic surfactant (1) with respect to 100 parts by weight of water in the pulp slurry is defined as the aqueous solution concentration. From the viewpoint of pulp slurry addition amount and permeability effect, the aqueous solution concentration of these nonionic surfactants (1) is preferably 0.03 to 10 parts by weight, more preferably 0.03 to 1 part by weight, and 0.04. -0.3 weight part is further more preferable. When adding in several times, it is preferable that the total of each addition amount is the said range.

  Moreover, the addition amount in case a nonionic surfactant (1) is 1 or more types chosen from the group which consists of general formula (1-1)-(1-3) is 100 weight part of pulp in a pulp slurry. 0.05 parts by weight or more, more preferably 0.1 to 5 parts by weight, based on (absolute dry weight).

  The addition amount of the deinking agent (2) is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1 part by weight, with respect to 100 parts by weight (absolute dry weight) of the pulp in the pulp slurry. When adding in several times, it is preferable that the total of each addition amount is the said range. A step of adding the deinking agent (2) together with the nonionic surfactant (1) and the ink peeling aid (3) (first addition), and a step of adding the deinking agent (2) (second time) In the case of having (addition), the weight ratio [(first time) / (second time)] of the deinking agent (2) is preferably 3/1 to 1/2.

  Moreover, 0.001 weight part or more is preferable for content of the deinking agent (2) with respect to 100 weight part of water in the pulp slurry in the process of performing deinking. Hereinafter, the weight part of the deinking agent (2) with respect to 100 parts by weight of water in the pulp slurry is defined as the aqueous solution concentration. 0.001-0.5 weight part is preferable, as for the aqueous solution density | concentration of a deinking agent (2), 0.005-0.5 weight part is more preferable, and 0.05-0.1 weight part is further more preferable.

  The amount of the ink stripping aid (3) added is preferably 0.003 parts by weight or more, and more preferably 0.006 to 0.03 parts by weight with respect to 100 parts by weight (absolute dry weight) of the pulp in the pulp slurry. When adding in several times, it is preferable that the total of each addition amount is the said range.

  Moreover, as for content of the ink peeling adjuvant (3) with respect to 100 weight part of water in the pulp slurry in the process of performing deinking, 0.0002 weight part or more is preferable. The aqueous solution concentration of the ink peeling aid (3) is preferably 0.0002 to 0.1 parts by weight, more preferably 0.001 to 0.1 parts by weight, and still more preferably 0.01 to 0.02 parts by weight.

  In the present invention, the total amount of the nonionic surfactant (1), the deinking agent (2), and the ink peeling aid (3) used in all the steps is 100 parts by weight of pulp (absolute dry weight). On the other hand, it is preferable to add so that it may become 0.01-5 weight part, and 0.02-3 weight part is still more preferable. The ratio (weight ratio) between the nonionic surfactant (1) and the deinking agent (2) is as follows: nonionic surfactant (1) / deinking agent (2) = 1/100 to 500/1, 1/10 to 100/1 is preferable, and 1/5 to 10/1 is particularly preferable. The ratio (weight ratio) between the nonionic surfactant (1) and the ink peeling aid (3) is as follows: nonionic surfactant (1) / ink peeling aid (3) = 1/8 to 20/1. Further, 1/4 to 10/1, particularly 1/2 to 8/1 is preferable.

  In addition, the combination of the nonionic surfactant (1) and the ink stripping aid (3) is excellent in ink stripping property against neutral newspapers even when used alone without being used together with the deinking agent (2). Deinking can be performed effectively. That is, deinked pulp can be obtained by a production method having a step of deinking in the presence of the nonionic surfactant (1) and the ink peeling aid (3). In this case, the addition amount of the nonionic surfactant (1) is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 7 parts by weight, with respect to 100 parts by weight (absolute dry weight) of the pulp in the pulp slurry. . Also in this method, when the nonionic surfactant (1) is at least one selected from the group consisting of the general formulas (1-1) to (1-3), the nonionic surfactant ( The aqueous solution concentration of 1) is preferably 0.03 parts by weight or more. From the viewpoint of pulp slurry addition amount and permeability effect, the aqueous solution concentration of these nonionic surfactants (1) is preferably 0.03 to 10 parts by weight, more preferably 0.03 to 1 part by weight, and 0.04. -0.3 weight part is further more preferable. When adding in several times, it is preferable that the total of each addition amount is the said range. Moreover, in this method, the addition amount of the ink peeling aid (3) is 0.01 to 2 parts by weight, and further 0.02 to 1.4 parts per 100 parts by weight (absolute dry weight) of the pulp in the pulp slurry. Part by weight is preferred. Furthermore, from the viewpoint of deinking properties, the aqueous solution concentration of the ink peeling aid (3) is preferably 0.006 to 2 parts by weight, more preferably 0.006 to 0.2 parts by weight, and 0.008 to 0.06. Part by weight is more preferable, and 0.04 to 0.3 part by weight is further preferable. When adding in several times, it is preferable that the total of each addition amount is the said range.

  In the production method of the present invention, if necessary, a known deinking agent other than the conventionally used nonionic surfactants, for example, higher alcohol sulfates, polyoxyalkylene higher alcohol sulfates, alkylbenzene sulfones, and the like. It is also possible to use acid salts, higher fatty acids or salts thereof as deinking agents. Furthermore, in the production method of the present invention, known alkaline agents such as caustic soda and sodium silicate, hydrogen peroxide, bleaching agents such as hypochlorite and hyposulfite, scale inhibitors, pitch control agents, antifoaming agents, A slime control agent or the like can also be used in combination.

(Neutral newspaper and acid newspaper sorting method)
A piece of newspaper was wrapped around a pH electrode and wetted with a small amount of ion-exchanged water, and the pH after 1 minute was measured. Newspapers having a pH of over 6.0 were selected as neutral newspapers, and newspapers having a pH of 6.0 or less were selected as acidic newspapers.

(Deinking method)
Disaggregation process (pulper process): 100 parts by weight of raw paper raw material (neutral newspaper, acid newspaper, flyer) cut into 5 cm square (absolutely dry weight), 1.0 part by weight of caustic soda, nonionic surfactants in Tables 1 to 3 (1) The deinking agent (2) and the ink peeling aid (3) were put into a disaggregator and made up to 2857 parts by weight with water (pulp concentration: 3.5% by weight). At this time, the nonionic surfactant (1), the deinking agent (2), and the ink peeling aid (3) are calculated as an aqueous solution concentration with respect to 100 parts by weight of water in the pulp slurry (parts by weight), Furthermore, the addition amount of the deinking agent (2) was also calculated in parts by weight with respect to the pulp weight (absolute dry weight). Disaggregation was performed at 40 ° C., 2500 rpm, and 5 minutes.
Dehydration process: Concentrated with 80 mesh stainless wire until the pulp concentration was 25% by weight.
Ink peeling process (kneading process): 100 parts by weight of pulp (absolute dry weight), 0.5 parts by weight of caustic soda, 1.0 part by weight of sodium silicate 3, 0.5 parts by weight of hydrogen peroxide, and Table 2 The deinking agent (2) was added and further disaggregated 300 times using a PFI mill manufactured by Kumagaya Riki Kogyo Co., Ltd. as a kneading treatment.
Bleaching step: Bleached at 60 ° C. for 120 minutes.
Dilution step: Water was added so that the pulp concentration was 1% by weight, and the pulp was well dispersed to obtain a pulp slurry.

(Ink peelability evaluation method)
The pulp slurry obtained in the disaggregation step and the dilution step was collected in an absolute dry weight of 2.5 g, diluted with 4 L of water, and then concentrated with an 80 mesh wire to a pulp concentration of 13% by weight. The operation of further diluting it with 4 L of water and concentrating it with 80 mesh wire to a pulp concentration of 13% by weight was repeated three times to obtain a pulp slurry from which free ink was completely removed.

A handsheet was prepared according to JIS P8209-1994 so that the basis weight was 150 g / cm ² with a 150 mesh wire.

This sheet was measured using an image analysis paper dust measuring device DF-1000 manufactured by Oji Scientific Instruments Co., Ltd., and the number of colored materials having a thickness of 0.01 mm ² or more mainly composed of ink remaining in the pulp sheet. Was counted as the number of unreleased inks. Tables 4 to 6 show the sheet prepared using the pulp after the disaggregation process as the number of unpeeled ink after the pulper, and the sheet consisting of the dilution process as the number of unpeeled ink after the PFI mill.

(Permeation time evaluation)
Prepare an aqueous solution so that the content of the nonionic surfactant (1), the deinking agent (2) and the ink peeling aid (3) is the aqueous solution concentration in the pulper shown in Tables 4 to 6, and neutralize it. 5 μL was dropped on the surface of used newspaper. The time from dripping to complete water absorption was visually observed and used as the permeation time (drip water absorption). The water penetration time was 133 seconds. Tables 4 to 6 show the relative permeation time when the water permeation time is 100%.

(Average carbon number)
A 2% by weight deuterated chloroform solution is prepared from the target nonionic surfactant, deinking agent or ink peeling aid, and oxyalkylene groups are removed from the ¹ H-NMR spectrum using a nuclear magnetic resonance apparatus MMERCURY400 manufactured by VARIAN. The average number of carbon atoms per active hydrogen (when the ester bond is present, the ester group is defined as active hydrogen and the other groups are not active hydrogen) was determined and used as the average carbon number. For the AO adduct of polyvalent carboxylic acid of deinking agent (2), a 30% by weight deuterated chloroform solution was prepared, and from the ¹³ C-NMR spectrum, active hydrogen excluding oxyalkylene groups (when having an ester bond) (Ester group is defined as active hydrogen, and other groups are not defined as active hydrogen.) The average number of carbon atoms per one was determined and used as the average number of carbon atoms.

  In Table 1, the average carbon number of the nonionic surfactants (1-1) to (1-3) is the average carbon number per active hydrogen excluding the oxyalkylene group by NMR measurement. The average carbon number of the alkyl group of the nonionic surfactant (1-4) is the average carbon number of the alkyl group by NMR measurement. In Table 2, the average carbon number of the deinking agent (2) is the active hydrogen excluding the oxyalkylene group by NMR measurement (the ester group is the active hydrogen when it has an ester bond, and the other groups are not active hydrogen) The average number of carbon atoms per unit does not include the carbon atoms constituting the polyhydric alcohol. Moreover, the average addition mole number of AO of the nonionic surfactant (1) and the deinking agent (2) is the average addition mole number of all AOs per mole of the compound having active hydrogen (including an ester bond). . Moreover, in Tables 4-6, "medium / acid / chi" is a mixed old paper of neutral newspaper / acid newspaper / flyer = 30/30/40 (weight ratio).

Moreover, the nonionic surfactant (1) of Tables 1-3, the deinking agent (2), and the ink peeling adjuvant (3) are as follows.
Nonionic surfactant A: 1 mol of EO adduct (6-dodecanol / 6-tetradecanol mixture (50/50 wt%)) of 6-dodecanol / 6-tetradecanol mixture (50/50 wt%) (3 moles of EO added)
Nonionic surfactant B: 6-dodecanol / 6-tetradecanol mixture (50/50 wt%) EO / PO adduct (6-dodecanol / 6-tetradecanol mixture (50/50 wt%) 1 EO addition mole number 5 mole, PO addition mole number 3.5 mole, block addition)
Nonionic surfactant C: EO / PO adduct of 6-dodecanol / 6-tetradecanol mixture (50/50 wt%) (6-dodecanol / 6-tetradecanol mixture (50/50 wt%) 1 EO addition mol number 7 mol, PO addition mol number 8.5 mol, block addition)
Nonionic surfactant D: EO / PO adduct of 6-dodecanol / 6-tetradecanol mixture (50/50 wt%) (6-dodecanol / 6-tetradecanol mixture (50/50 wt%) 1 9 moles of EO addition mole, 15 moles of PO addition mole, block addition)
Nonionic surfactant E: EO adduct of 2-propylheptanol (4 mol of EO added to 1 mol of 2-propylheptanol)
Nonionic surfactant F: EO adduct of 2-propylheptanol (5 mol of EO added to 1 mol of 2-propylheptanol)
Nonionic surfactant G: EO adduct of 2-propylheptanol (6 mol of EO added to 1 mol of 2-propylheptanol)
Nonionic surfactant H: EO / PO adduct of 2-ethylhexanol (1 mol of PO added, 2 mol of EO added, 2 blocks added to 1 mol of 2-ethylhexanol)
Nonionic surfactant I: EO / PO adduct of 2-ethylhexanol (6 mol of PO addition, 3 mol of EO addition, block addition per 1 mol of 2-ethylhexanol)
Nonionic surfactant J: PO addition product of octanol (PO mole number of 2.7 moles per mole of octanol)
Nonionic surfactant K: mol of EO added to 1 mol of EO / PO adduct of lauryl alcohol / myristyl alcohol mixture (70/30 wt%) (lauryl alcohol / myristyl alcohol mixture (70/30 wt%)) 2.5 mol / PO addition mol number 1.5 mol / EO addition mol number 3.0 mol, 3-stage block addition)
Nonionic surfactant L: 2-ethylhexyl glyceryl ether Nonionic surfactant M: EO adduct of acetylenic diol represented by general formula (1-5) (average EO addition mole number 5 per active hydrogen) Mol (10 mol of EO added moles per mole of acetylenic diol))
Nonionic surfactant N: isodecyl glyceryl ether

Deinking agent A: EO / PO adduct of stearyl alcohol (4 mol of PO added per mol of stearyl alcohol / (3 mol of EO / PO random added mol / 3 mol) / mol of EO added) 24 mol / PO added mole number 20 mol, 4-stage block added Cloud point 37 ° C :)
Deinking agent B: EO / PO adduct of stearic acid (19 mol of EO addition, 9 mol of PO addition, block addition, cloud point 56 ° C. per 1 mol of stearic acid)
Deinking agent C: EO / PO adduct of dimer acid / 2 ethylhexanol (molar ratio 1/1) mixture (235 mol of EO addition, 105 mol of PO addition, 1 mol per mol of dimer acid) , Cloud point 60 ° C)
Deinking agent D: EO / PO adduct of beef tallow / glycerin (molar ratio 1 / 0.3) mixture (1 mol of beef tallow and 0.3 mol of glycerin (1.3 mol of compound having active hydrogen) Addition mole number 40 mol, PO addition mole number 20 mol, random addition, cloud point 52 ° C.)

Ink peeling aid A: R ¹⁰ in the general formula (3) is a lauryl group (R ¹⁰ is a linear alkyl group having 12 carbon atoms)
Ink peeling aid B: R ¹⁰ in the general formula (3) is a myristyl group (R ¹⁰ is a linear alkyl group having 14 carbon atoms)
Ink peeling aid C: R ¹⁰ in the general formula (3) is a palmityl group (R ¹⁰ is a linear alkyl group having 16 carbon atoms)
Ink peeling aid D: R ¹⁰ in the general formula (3) is an oleyl group (R ¹⁰ is a linear alkenyl group having 18 carbon atoms)
Ink peeling aid E: R ¹⁰ in the general formula (3) is a stearyl group (R ¹⁰ is a linear alkyl group having 18 carbon atoms)
Ink peeling aid F: R ¹⁰ in the general formula (3) is a behenyl group (R ¹⁰ is a linear alkyl group having 20 carbon atoms)

Claims (4)

A method for producing deinked pulp using at least waste paper containing a neutral newspaper as a raw material, and one or more nonionic surfactants selected from the group consisting of the following general formulas (1-1) to (1-5) (1) The manufacturing method of the deinked pulp which has the process of deinking in presence of the following deinking agent (2) and the following ink peeling adjuvant (3).
Nonionic surfactant (1):

[Wherein, R ¹ and R ² are each a linear alkyl group or alkenyl group having 1 to 13 carbon atoms, the total average carbon number of R ¹ and R ² is 7 to 14, and AO is the number of carbon atoms. 2 or 3 oxyalkylene groups, m is a number of 1 to 25 in terms of average added mole number. ]

[Wherein, R ³ and R ⁴ are each a linear alkyl group or alkenyl group having 1 to 12 carbon atoms, R ⁵ is a linear alkylene group having 1 to 12 carbon atoms, and R ³ and R ⁴ And R ^{5 has} a total average carbon number of 5 to 14, AO is an oxyalkylene group having 2 or 3 carbon atoms, and n is an average added mole number of 1 to 25. ]
_{^{R 6 O- (AO) p H}} (1-3)
[In the formula, R ⁶ is a linear alkyl group or alkenyl group having 6 to 15 carbon atoms on average, AO is an oxyalkylene group having 2 or 3 carbon atoms, and p is an average added mole number of 1 to 25. is there. ]

[Wherein, R ⁷ is a linear or branched alkyl group or alkenyl group having an average carbon number of 4 to 9, and R ⁸ and R ⁹ are a hydrogen atom or a glycerol group, respectively. ]

[Wherein, AO is an oxyalkylene group having 2 or 3 carbon atoms, and q and r are numbers of 1 to 25 in terms of the average number of added moles, respectively. ]
Deinking agent (2):
One or more deinking agents selected from the group consisting of the following (2-1) to (2-3), wherein the deinking agent has a cloud point of 20 to 90 ° C. and a compound having active hydrogen Obtained by adding an alkylene oxide to the compound, the average number of carbon atoms per active hydrogen excluding the oxyalkylene group is from 15 to 24, and the average number of moles of the oxyalkylene group added per mole of the compound having active hydrogen Deinking agent which is 10-500.
(2-1) Higher alcohol-based deinking agent (2-2) Fatty acid-based deinking agent (2-3) Oil / polyhydric alcohol-based deinking agent Ink peeling aid (3):
1 or more types of ink peeling adjuvant chosen from the compound represented by following General formula (3).

[Wherein, R ¹⁰ represents a linear or branched alkyl group or alkenyl group having an average carbon number of 8 to 22. ]   The method according to claim 1, further comprising the steps of adding three agents, a nonionic surfactant (1), a deinking agent (2), and an ink peeling aid (3), and further adding a deinking agent (2). A method for producing deinked pulp.   Deinking is performed using a pulp slurry containing at least one nonionic surfactant (1) selected from the group consisting of general formulas (1-1) to (1-3) and an ink peeling aid (3). The content of the nonionic surfactant (1) with respect to 100 parts by weight of water in the pulp slurry is 0.03 parts by weight or more, and the ink peeling aid (3) is 0.003 parts by weight or more. Or the manufacturing method of the deinked pulp of 2. Deinking additive (1) containing at least one nonionic surfactant (1) selected from the group consisting of the following general formulas (1-1) to (1-5) and an ink peeling aid (3) ( A additive) and an additive for use in the manufacture of deinked pulp made from waste paper containing at least a neutral newspaper, comprising a deinking additive (B agent) containing the following deinking agent (2) kit.
Nonionic surfactant (1):

[Wherein, R ¹ and R ² are each a linear alkyl group or alkenyl group having 1 to 13 carbon atoms, the total average carbon number of R ¹ and R ² is 7 to 14, and AO is the number of carbon atoms. 2 or 3 oxyalkylene groups, m is a number of 1 to 25 in terms of average added mole number. ]

[Wherein, R ³ and R ⁴ are each a linear alkyl group or alkenyl group having 1 to 12 carbon atoms, R ⁵ is a linear alkylene group having 1 to 12 carbon atoms, and R ³ and R ⁴ And R ^{5 has} a total average carbon number of 5 to 14, AO is an oxyalkylene group having 2 or 3 carbon atoms, and n is an average added mole number of 1 to 25. ]
_{^{R 6 O- (AO) p H}} (1-3)
[In the formula, R ⁶ is a linear alkyl group or alkenyl group having 6 to 15 carbon atoms on average, AO is an oxyalkylene group having 2 or 3 carbon atoms, and p is an average added mole number of 1 to 25. is there. ]

[Wherein, R ⁷ is a linear or branched alkyl group or alkenyl group having an average carbon number of 4 to 9, and R ⁸ and R ⁹ are a hydrogen atom or a glycerol group, respectively. ]

[Wherein, AO is an oxyalkylene group having 2 or 3 carbon atoms, and q and r are numbers of 1 to 25 in terms of the average number of added moles, respectively. ]
Deinking agent (2):
One or more deinking agents selected from the group consisting of the following (2-1) to (2-3), wherein the deinking agent has a cloud point of 20 to 90 ° C. and a compound having active hydrogen Obtained by adding an alkylene oxide to the compound, the average number of carbon atoms per active hydrogen excluding the oxyalkylene group is from 15 to 24, and the average number of moles of the oxyalkylene group added per mole of the compound having active hydrogen Deinking agent which is 10-500.
(2-1) Higher alcohol-based deinking agent (2-2) Fatty acid-based deinking agent (2-3) Oil / polyhydric alcohol-based deinking agent Ink peeling aid (3):
1 or more types of ink peeling adjuvant chosen from the compound represented by following General formula (3).

[Wherein, R ¹⁰ represents a linear or branched alkyl group or alkenyl group having an average carbon number of 8 to 22. ]