JP3467474B2 - Deinking agent - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flotation method for producing recycled paper by recycling newspaper wastepaper, magazine wastepaper, OA wastepaper and colored wastepaper recovered from domestic and overseas.
The present invention relates to a deinking agent used in a deinking process by a cleaning method or an eclectic method thereof.

[0002]

2. Description of the Related Art Recycled waste paper is produced by removing ink from raw waste paper by deinking treatment to obtain recycled pulp and producing recycled paper. Therein, in addition to conventional fatty acid-based deinking agents, alkylamine-based deinking agents and higher alcohol-based nonionic deinking agents have been developed. As the alkylamine-based deinking agent, a compound having a block arrangement in which ethylene oxide is added to a primary amine (JP-A-63-233)
20) or a compound having a random arrangement in which ethylene oxide and propylene oxide are added (JP-A-57-254).
No. 89) and the like. However, these alkylamine-based deinking agents have insufficient ink releasability as compared with higher alcohol-based nonionic deinking agents.

On the other hand, newspaper waste paper collected from Japan and overseas,
The magazine old paper, the OA old paper, the colored old paper, and the like may contain sticky substances such as adhesives, and removal of these sticky substances has become a major technical issue. However, known fatty acid-based, alkylamine-based, and higher alcohol-based nonionic deinking agents are not satisfactory in removing sticky substances. As a method for removing these sticky substances, for example, a method using a cleaner (Japanese Patent Laid-Open No. 06-065882) is known. However, this method requires a step of removing sticky substances in addition to the deinking step, and improvement is desired in terms of equipment and workability.

[0004]

DISCLOSURE OF THE INVENTION The present invention has a deinking performance which is excellent in whiteness and ink releasability of the recycled paper when the recycled paper is obtained from the recycled paper containing a sticky substance such as an adhesive. It is an object of the present invention to provide a deinking agent capable of removing sticky substances in the same process as the above.

[0005]

That is, the present invention provides (I)
A compound obtained by adding two or more stages of one or more alkylene oxides selected from ethylene oxide, propylene oxide and butylene oxide to the compound represented by the general formula (1) or (2) and having a block arrangement and a random arrangement. A deinking agent containing R ¹ —NH ₂ (1) R ² —NH—R ³ (2) (wherein R ¹ and R ² are alkyl groups having 6 to 22 carbon atoms, alkenyl groups, Acyl group or aryl group, R ³ represents an alkyl group, an alkenyl group, an acyl group or an aryl group having 1 to 22 carbon atoms. (II) The compound represented by the general formula (1) or (2) is ethylene oxide, Addition form of at least a block arrangement is obtained by adding 3 to 5 stages of one or more alkylene oxides selected from propylene oxide and butylene oxide. Deinking containing a compound having, (II
I) A deinking method using the deinking agent according to any one of (I) and (II) above.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The deinking agent of the present invention is used to obtain recycled paper by recycling used newspapers, magazines, OA wastes, etc. collected from domestic and overseas. Specifically, it is used in the process of deinking by a flotation method, a cleaning method, or an eclectic method thereof. In particular, it has good deinking performance and sticky substance removal performance such as sticky substances such as adhesives in the flotation method in which ink is attached to bubbles and discharged together with bubbles.

One compound contained in the deinking agent of the present invention is a compound represented by the general formula (1) or (2) to which an alkylene oxide selected from ethylene oxide, propylene oxide and butylene oxide is added in two stages. It is a compound having an addition form of a block sequence and a random sequence. (Aspect 1) R ¹ —NH ₂ (1) R ² —NH—R ³ (2) (In the formula, R ¹ and R ² are an alkyl group having 6 to 22 carbon atoms, an alkenyl group, or an acyl group. Group or aryl group, and R ³ represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group, an acyl group or an aryl group) Hereinafter, the first embodiment will be described.

In the compound represented by the general formula (1) or (2), R ¹ , R ² and R ³ are linear or branched alkyl groups, alkenyl groups, acyl groups or aryl groups, and R ¹ And R ² has 6 or more carbon atoms from the viewpoint of ink collecting ability and 22 or less from the viewpoint of ink releasability, and R ³ has 1 or more carbon atoms from the viewpoint of ink collecting ability and 22 or less from the viewpoint of ink releasability. Is. Further, R ¹ , R ² and R ³ preferably have 8 or more and 20 or less carbon atoms from the viewpoints of both the collecting property and the releasability, particularly R ¹ and R ² preferably have 12 or more and 20 or less, and R ³ has 12 or more and 20 or less. The following are preferred.

The compound of general formula (1) is a primary amine, and the compound of general formula (2) is a secondary amine. Specific examples of the general formula (1) include hexylamine, octylamine,
Examples include nonaamine, decaamine, undecaamine, dodecaamine, tetradecaamine, hexadecaamine, octadecaamine, eicosamine, docosylamine, 2-ethylhexylamine and the like. Specific examples of the general formula (2) include dihexylamine, dioctylamine, dinonaamine, didecaamine, diundecaamine, didodecaamine, ditetradecaamine, dihexadecaamine,
Examples thereof include dioctadecamine, dieicosiamine, didocosylamine and di2-ethylhexylamine.

When alkylene oxide is added to amine, a compound having two alkylene oxide chains of the same kind can be obtained in the case of the general formula (1). In the case of the general formula (2), a compound having one alkylene oxide chain is obtained. In the present application, the average number of moles of alkylene oxide added and the number of stages of random arrangement and block arrangement refer to one alkylene oxide chain. Further, one stage of the random arrangement and the block arrangement means a unit in which alkylene oxide is added with the same composition and the same arrangement.

From the viewpoint of ink collecting properties and foaming properties during flotation, it is preferable to add ethylene oxide to the alkylene oxide chain. The average addition mole number (l) of ethylene oxide in the alkylene oxide chain is preferably 2 or more and 100 or less, and particularly preferably 2 or more and 50 or less, from the viewpoint of adhesive removal performance. The average added mole number (m) of propylene oxide is preferably 2 or more and 100 or less, and particularly preferably 2 or more and 50 or less, from the viewpoint of adhesive removal performance. The average addition mole number (n) of butylene oxide is preferably 0 or more and 100 or less, and particularly preferably 0 or more and 50 or less. Also, the sum of l, m, and n (l + m +
From the viewpoint of foamability during flotation, n is preferably 6 or more and 200 or less, particularly preferably 10 or more and 170 or less in the case of the general formula (1), and 30 in the case of the general formula (2).
Above 170 and below are particularly preferable.

The ratio of the average number of moles of ethylene oxide added to the alkylene oxide chain (l / (l + m +
n)) is, from the viewpoint of foamability during flotation,
0.4 or more and 0.95 or less are preferable, and 0.5 or more and 0.9
The following are particularly preferred.

The addition form of alkylene oxide has two stages from the viewpoints of ink releasability, ink collecting property and sticky substance removability. And this addition form is a block sequence part formed by adding a single alkylene oxide selected from ethylene oxide, propylene oxide and butylene oxide, and any two or more kinds selected from ethylene oxide, propylene oxide or butylene oxide. It is composed of a random array portion in which alkylene oxide is randomly added. The order of introducing the block sequence and the random sequence does not matter, but it is preferable to introduce the block sequence in the first stage (nitrogen atom side) from the viewpoint of ink releasability.

The relationship between the average number of moles (B) of the block sequence portion of the alkylene oxide chain and the average number of moles (R) of the random sequence portion is the ratio (B) of the block sequence portion.
/ (B + R)) is preferably 0.2 or more and 0.8 or less, and particularly preferably 0.2 or more and 0.4 or less from the viewpoint of the ink collecting property.

From the viewpoint of foaming property during flotation, the ratio of the average addition mole number of ethylene oxide constituting one stage of the random arrangement is preferably 0.3 or more and 0.95 or less, and the average addition mole number of the alkylene oxide chain is Number (l + n
When + m) is less than 100, 0.4 or more and 0.8 or less are particularly preferable, and when 100 or more, 0.7 or more and 0.95 or less are particularly preferable.

The other compound contained in the deinking agent of the present invention is a compound represented by the general formula (1) or (2) containing an alkylene oxide selected from ethylene oxide, propylene oxide and butylene oxide in three stages. It is a compound in which five stages are added and at least a block arrangement is added. (Aspect 2) Aspect 2 will be described below.

In the compound represented by the general formula (1) or (2), R ¹ , R ² and R ³ are linear or branched alkyl groups, alkenyl groups, acyl groups or aryl groups, and R ¹ And R ² has 6 or more carbon atoms from the viewpoint of ink collecting property and 22 or less from the viewpoint of ink releasability, and R ³ has 1 or more carbon atoms from the viewpoint of ink collecting property and 22 or less from the viewpoint of ink releasability. . Furthermore, R ¹ , R ² and R ³ are
From the viewpoints of both releasability, the carbon number is preferably 8 or more and 20 or less, and particularly R ¹ and R ² are preferably 12 or more and 20 or less, and R
³ is preferably 12 or more and 20 or less.

As the compound of the general formula (1) or the general formula (2), the same compound as in the embodiment 1 can be used.

From the viewpoint of ink collecting properties and foaming properties during flotation, ethylene oxide is preferably added to the alkylene oxide chain. The average number of moles (l) of ethylene oxide added to the alkylene oxide chain is preferably 2 or more and 100 or less, and particularly preferably 2 or more and 50 or less, from the viewpoint of adhesive removal performance. The average added mole number (m) of propylene oxide is preferably 2 or more and 100 or less, and 2 or more and 5 or less from the viewpoint of sticking substance removal performance.
It is particularly preferably 0 or less. The average addition mole number (n) of butylene oxide is preferably 0 or more and 100 or less, and particularly preferably 0 or more and 50 or less. Also,
From the viewpoint of foamability during flotation, the total of l, m, and n (l + m + n) is preferably 6 or more and 200 or less, particularly preferably 10 or more and 170 or less in the case of the general formula (1), and the general formula (2) In the case of, 10 or more and 170 or less are particularly preferable.

The ratio of the average number of moles of ethylene oxide added to the alkylene oxide chain (l / (l + m +
n)) is, from the viewpoint of foamability during flotation,
0.4 or more and 0.95 or less are preferable, and 0.5 or more and 0.9
The following is particularly preferable.

The form of addition of the alkylene oxide is 3 from the viewpoint of ink releasability, ink collecting property and sticky substance removability.
It is in the form of 5 stages. Each stage has a block sequence formed by adding a single alkylene oxide selected from ethylene oxide, propylene oxide and butylene oxide, and any two or more kinds of alkylene selected from ethylene oxide, propylene oxide or cibutylene oxide. It is selected from a random array formed by randomly adding oxides. From the viewpoint of ink releasability, it is preferable that the block sequence formed by adding propylene oxide is in the first stage and the block sequence formed by adding propylene oxide is in the final stage. In the stage forming the alkylene oxide chain, two or more sequences having the same alkylene oxide composition and the same addition form may be present. However, when adjacent stages have the same alkylene oxide composition and the same type of addition form, both are combined into one stage.

The ratio of the average added mole number of each stage to the average added mole number of the first stage (on the nitrogen atom side) is (the average added mole number of the final stage) in the final stage from the viewpoint of sticking substance removal performance.
/ (Average number of moles added in the first step) is preferably 0.1 or more and 10 or less, and particularly preferably 0.2 or more and 5 or less. For each stage between the first stage and the final stage, (average added mole number of each stage between the first stage and final stage) / (average added mole number of blocks of the first stage) was 0. 2 or more and 15 or less are preferable, and 0.5 or more and 15 or less are especially preferable.

The ratio (B / (B + R)) of the average number of added moles of the block sequence portion in the alkylene oxide chain (total of all block sequences) is preferably 0.4 or more and 1.0 or less, and 0.7 or more and 1.0 or less. The following are particularly preferred.

When a random sequence is introduced, the ratio of the average number of moles of ethylene oxide constituting one stage of the random sequence is from the viewpoint of foamability during flotation.
0.3 or more and 0.95 or less are preferable, and 0.4 or more and 0.8 or less are especially preferable.

The compound of Aspect 1 or 2 of the present invention can be produced by a conventional polymerization addition reaction of alkylene oxide. For example, in a nitrogen atmosphere, an alkaline substance is added as a catalyst to the compound of the general formula (1) or (2),
First, a predetermined amount of alkylene oxide (a mixture of a predetermined ratio in the case of random) added in the first step is subjected to an addition reaction,
Next, a predetermined amount of the second and subsequent alkylene oxides are sequentially subjected to an addition polymerization reaction.

The content of the compound of aspect 1 or aspect 2 in the deinking agent of the present invention is preferably 45 parts by weight or more and 100 parts by weight or less based on 100 parts by weight of the deinking agent, and the ink releasability is good. From the viewpoint of foaming power, it is particularly preferable to contain 60 parts by weight or more. The compounds of embodiment 1 and embodiment 2 may be used as a mixture, and the content in that case is calculated by the total amount of both. Further, from the viewpoint of matching with various individual deinking systems on the market, other known deinking agents, foaming agents, defoaming agents, etc. may be blended, but in that case also the effect of the present invention is impaired. In order to avoid this, for 100 parts by weight of the deinking agent after blending,
The amount of the compound of Aspect 1 and / or Aspect 2 of the present invention is preferably 45 parts by weight or more, and particularly preferably 60 parts by weight or more from the viewpoint of ink releasability and removal of sticky matters.

Examples of known deinking agents include fatty acid deinking agents, alkylamine deinking agents, higher alcohol nonionic deinking agents, and the like. Examples of the foaming agent include polyoxyalkyl ether sulfate and alkylbenzene sulfonate, and examples of the defoaming agent include mineral oil, fatty acids such as oleic acid and stearic acid, and silicone oil.

The place where the deinking agent of the present invention is used can be used collectively or dividedly in the ink peeling step, the ink removing step and the pulp washing step. Specifically, it can be added before or during the ink peeling process using a pulper, a kneader, a chemical mixer, etc., the ink removing process using a floater, etc., and the cleaning process using thickener, washer, extract, etc. In particular, it is preferable to float the deinking agent of the present invention in the pulp slurry, and it is preferable to add the deinking agent of the present invention in the ink removing step of the floater or before the step. Other steps can be performed according to a conventionally known deinking method, and each step can be performed multiple times. In addition to the conventionally known deinking step, the deinking agent of the present invention removes the tacky substance together with the ink without providing a process for removing the tacky substance.

The amount of the deinking agent of the present invention to be added is 10 from the viewpoint of stabilizing operability, ink releasability and sticky substance removability.
It is preferable to add 0.01 to 5 parts by weight with respect to 0 parts by weight. From the viewpoint of foaming power, workability, and cost, it is preferable to add 0.
It is particularly preferably from 01 to 1 part by weight.

The deinking agent of the present invention includes known alkaline agents such as caustic soda and sodium silicate, bleaching agents such as hydrogen peroxide, hypochlorite and hyposulfite, alkylbenzene sulfonates and higher alcohol sulfates. A foaming agent such as salt, a pitch control agent, a sequestering agent such as EDTA or DTPA can also be used in combination.

The waste paper to be deinked according to the present invention is not particularly limited, but it is applied to newspaper waste paper, magazine waste paper, OA waste paper or colored waste paper containing adhesive materials such as adhesives, and application to a mixture of various waste papers. Is suitable.

Although the mechanism for removing the sticky substance of the deinking agent of the present invention is not well understood, the alkylene oxide chain peels the ink from the pulp fiber, and at the same time, the sticky substance is also peeled off. It is thought that it is adsorbed to and prevents reattachment of sticky substances to pulp fibers. afterwards,
Adhesives aggregate to each other to some extent (approximately 10 μm)
Particles. Then, in an ink removing process such as flotation, these particles are discharged from the pulp slurry together with the ink together with the foam. Further, the selection of the alkylene oxide to be added and the addition form of the 2-stage or 3- to 5-stage random / block arrangement are necessary in order to promote the interaction with the ink, the adhesive and the pulp fiber. The oxyethylene group imparts hydrophilicity, and the oxypropylene group and oxybutylene group impart hydrophobicity. In addition, the random array has a bulky three-dimensional structure with low orientation,
It is considered that the block arrangement has a highly compact orientation and a relatively compact three-dimensional structure. It is considered that the appropriate hydrophilic / hydrophobic balance and the bulkiness due to the molecular orientation obtained by combining these give good deinking property and sticky substance removability.

[0033]

[Example] [Deinking treatment] Waste paper raw material (newspaper / flyer ratio =
6/4) 100 parts by weight (absolute dry weight) was put into a table disintegrator, 0.5 parts by weight of caustic soda, 0.3 parts by weight of the compounds shown in Tables 2 to 4 and 2000 parts by weight of warm water at 40 ° C. were added, 1
The disaggregation treatment was performed at 3000 rpm for 0 minutes. Then
After concentrating the pulp concentration to 15% using a stainless steel wire of 80 mesh, 0.5 parts by weight, 1.5 parts by weight of caustic soda, sodium silicate No. 3 and hydrogen peroxide, respectively,
0.5 part by weight was added, and bleaching treatment was performed at 60 ° C. for 120 minutes. Then, it was diluted with warm industrial water at 40 ° C. to a pulp concentration of 5% and re-disintegrated at 3000 rpm for 1 minute to obtain a pulp slurry. Then, the slurry (diluted with a pulp concentration of 1%, 300 g) before being charged into a floater, which was obtained by diluting the slurry with industrial water at 40 ° C. to a pulp concentration of 1%, was collected and used as a sample before sticky substance removal (Sample A). Meanwhile, put the pulp slurry diluent 4500Cm ³ lab flotation cell volume 5000 cm ^3, was performed for 6 minutes flotation in feed amount of diluent 1.50 liters per minute per liter. During that time, an operation of removing the foam containing the ink and the sticky matter accumulated on the flotation cell was carried out every one minute. A pulp slurry (pulp concentration: about 1%, 300 g) immediately after the floatator treatment was collected and used as a sticky substance amount evaluation sample (Sample B). After that, the pulp slurry was concentrated to a pulp concentration of 13%, diluted again to 1% with industrial water, and a handsheet having a basis weight of 150 g / cm ² was produced with a 150 mesh wire according to JIS P8209-1994 to prepare Sample 1. . Further, 25.4 g of the slurry concentrated to a pulp concentration of 13% after the flotation treatment was diluted with 200 times the amount of industrial water, and the operation of concentrating the pulp concentration to 13% was repeated 4 times. A sheet having a basis weight of 150 g / cm ² was prepared and used as Sample 2.

[Performance Evaluation] In the above deinking method, the following evaluations (1) to (3) were performed. The results are shown in Tables 5-7.

(1) Whiteness The whiteness of Sample 1 was measured according to JIS P8123-1961.

(2) Unpeeled Ink Area Ratio The ink area on the surface of Sample 2 was measured with an image analyzer (Luzex F, manufactured by Nireco) at a magnification of 20 and calculated by the following formula. Unstripped ink area ratio (%) = (S / F ) × 100 S; 100 field ink area measured during (mm ²⁾ F; 100 field total area 15000 ² (1 viewing area 150 mm ²⁾ of the.

(3) Adhesive Removal Rate Samples A and B were dried at 105 ° C. under a reduced pressure of 60 mmHg 48.
Let stand for an hour to obtain a dried product. Next, 2 g was accurately weighed, Soxhlet extraction was performed for 8 hours using 1,2-dichloroethane, and the sticky substance removal rate was calculated from the weight of the sticky substance extracted by the following formula. Adhesive removal rate = 100 × {(1- (extracted weight of sample B dry solid / extracted weight of sample A dry solid)}.

Table 1 shows the criteria for performance evaluation. Generally, there is a positive correlation between (1) whiteness and (2) unpeeled ink area ratio, so the deinkability evaluation value is (1) whiteness and (2) unpeeled ink area ratio evaluation value. The lower one was adopted.

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

[Table 3]

[0042]

[Table 4]

[0043]

[Table 5]

[0044]

[Table 6]

[0045]

[Table 7]

[0046]

INDUSTRIAL APPLICABILITY According to the present invention, in addition to good deinking performance when obtaining recycled paper from waste paper containing sticky substances such as adhesives,
There is provided a deinking agent capable of removing sticky substances in the same step.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hamaguchi Koji 1334 Minato Minato, Wakayama City, Wakayama Prefecture Research Institute (56) Reference JP-A-57-25489 (JP, A) JP-A-5-51887 (JP, A) JP-A-4-163384 (JP, A) JP-A-7-3681 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) D21C 5/02

Claims (8)

(57) [Claims] 1. A block arrangement and a random arrangement in which two or more alkylene oxides selected from ethylene oxide, propylene oxide and butylene oxide are added in two stages to the compound represented by the general formula (1) or (2). met deinking containing a compound having an additional form
In each alkylene oxide chain, ethylene
Average number of moles of oxide added (l), propylene oxa
Average number of moles of added oxide (m), average of butylene oxide
Average addition mole number (n), average addition mole of block array part
Number (B) and average number of added moles of random sequence part (R)
Is a deinking agent satisfying the formulas (6) and (8) . R ¹ —NH ₂ (1) R ² —NH—R ³ (2) (wherein R ¹ and R ² are an alkyl group, an alkenyl group, an acyl group or an aryl group having 6 to 22 carbon atoms, R ^{2 3} represents an alkyl group, an alkenyl group, an acyl group or an aryl group having 1 to 22 carbon atoms) 6 ≦ l + m + n ≦ 200 (6) 0.2 ≦ B / (B + R) ≦ 0.8 (8) 2. In each alkylene oxide chain,
Average addition mole number of ethylene oxide (l), average addition mole number of propylene oxide (m), average addition mole number of butylene oxide (n), average addition mole number of block sequence portion (B) and average of random sequence portion The number of added moles (R) is one of formulas (3) , (4), (5) and (7)
The deinking agent according to claim 1, which satisfies the above . 2 ≦ l ≦ 100 (3) 2 ≦ m ≦ 100 (4) 0 ≦ n ≦ 100 (5) 0.4 ≦ l / (l + m + n) ≦ 0.95 (7) 3. A general formula (1) or ethylene oxide to the compound represented by (2), one or more alkylene oxides selected from propylene oxide and butylene oxide is pressurized with 3 stages will be, at least block arrangement Deinking agent containing a compound having an addition form (however,
The compound represented by the general formula (1) has ethylene oxide in the first stage.
Keyside, propylene oxide in the second step, and d in the third step
Excluding those added with thylene oxide] . R ¹ —NH ₂ (1) R ² —NH—R ³ (2) (wherein R ¹ and R ² are alkyl groups having 6 to 22 carbon atoms, and
Kenyl group, acyl group or aryl group, R ³ is carbon number
1 to 22 alkyl group, alkenyl group, acyl group or
Represents an aryl group) 4. The first step is the addition of propylene oxide.
A compound containing a block sequence formed by
The deinking agent according to item 3 . 5. The final stage is the addition of propylene oxide.
A compound containing a block sequence formed by
The deinking agent according to 3 or 4 . 6. A compound represented by formula (1) or (2)
Ethylene oxide, propylene oxide and
One or more alkylene oxides selected from lenoxide
Add 4 to 5 sides,
Deinking agent containing a compound having an additional form of a Cuk sequence. R ¹ —NH ₂ (1) R ² —NH—R ³ (2) (wherein R ¹ and R ² are alkyl groups having 6 to 22 carbon atoms, and
Kenyl group, acyl group or aryl group, R ³ is carbon number
1 to 22 alkyl group, alkenyl group, acyl group or
Represents an aryl group) 7. In each alkylene oxide chain,
Average number of moles of ethylene oxide added (l), propylene
Average number of moles of added oxide (m), butylene oxa
Average number of added ids (n), average of block array part
Addition mol number (B) and average addition mol of random sequence part
The number (R) is, claim satisfy equation (9) to (14) 3-6
The deinking agent according to any one of items. 2 ≦ l ≦ 100 (9) 2 ≦ m ≦ 100 (10) 0 ≦ n ≦ 100 (11) 6 ≦ l + m + n ≦ 200 (12) 0.4 ≦ l / (l + m + n) ≦ 0.95 (13) 0.4 ≦ B / (B + R) ≦ 1.0 (14) 8. A deinking agent according to any one of claims 1 to 7.
Deinking method used.