JP2594872B2 - 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 novel deinking agent for recycling used paper, and more specifically, to a method for printing used paper such as newspapers, magazines, leaflets, and information recording paper by a flotation method, a washing method, an earth pot method, and the like. The present invention relates to a deinking agent which is used for obtaining a regenerated pulp by deinking treatment and can produce a regenerated pulp having a high whiteness and a small amount of residual ink.

[0002]

2. Description of the Related Art In recent years, due to the shortage of pulp resources and soaring prices, the reuse of waste paper has become increasingly important. There is a need for the development of black ink processing technology and deinking processing technology for obtaining recycled pulp of excellent quality close to virgin pulp. Conventionally, a cleaning method, a flotation method, and the like are known as a deinking treatment method for recycling used paper. In the former cleaning method, after first disintegrating waste paper with a pulper or the like (defibration step), a deinking agent is acted together with an alkali and a bleaching agent to release ink from pulp fibers,
In this method, the pulp slurry is filtered and washed to remove ink components. On the other hand, the flotation method first disintegrates waste paper with a pulper or the like (defibration process), and then acts on a deinking agent together with an alkali and a bleaching agent.
In this method, ink is removed from the pulp fiber, and then air is blown into the pulp slurry to form bubbles, thereby causing ink to adhere to the bubbles and removing ink components together with the bubbles. Currently, as the deinking treatment method, the above-described cleaning method and the flotation method occupy most, but there are cases where this cleaning method and the flotation method are combined or performed by other methods. The deinking processing methods are different. In recent years, less water is required, and process machines can be made more compact.
The flotation method is increasing because of the small amount of ink drainage. Various surfactants have conventionally been used as a deinking agent used in such deinking treatment, and higher fatty acid soaps have long been known as representatives thereof. However, although this deinking agent has excellent ink coagulation performance, it is inferior in ink adhesion and foaming property to the equipment, so the removal of the ink that has coagulated and floated by flotation becomes incomplete, and the ink becomes in the pulp. It may remain, and in order to enhance foamability,
It has the disadvantage that other blowing agents must be used in combination. Therefore, in recent years, as a deinking agent, in addition to the higher fatty acid soaps, alkylbenzene sulfonates, higher alcohol sulfates, α-olefin sulfonates,
Anionic surfactants such as dialkylsulfosuccinates and nonionic surfactants such as alkylphenol oxides, higher alcohols, fatty acids, alkylene oxide adducts of polyhydric alcohols and fatty acid esterified products thereof have been used. However, such a deinking agent has insufficient ink aggregation and removal performance in flotation. That is, the ability of the ink to adhere to the foam during flotation is low, the ink alone cannot be efficiently removed, and the desired pulp with high whiteness and little residual ink cannot be obtained. In addition, necessary pulp has been removed, and the yield has been reduced. Regarding foaming properties during flotation, although there are few problems due to low foaming properties such as higher fatty acid soap, foaming does not disappear indefinitely even after foaming and removing ink components together with foam. The ink that has coagulated and adhered to the bubbles in the rotator cannot be removed forever and remains, which may cause an ink spot.

[0003]

SUMMARY OF THE INVENTION The present invention overcomes such disadvantages of the conventional deinking agent, has an excellent cleaning ability by a cleaning method, and has a low ink cohesive force in a flotation treatment in a flotation method. Excellent, high adhesion of ink to foam, efficient removal of ink only, has appropriate foaming properties for removing coagulated and floating ink, and removes foam that can easily disappear when removed from floatator It is an object of the present invention to provide a deinking agent for recycling used paper, which can generate recycled pulp having high whiteness and little residual ink when generated.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to develop a deinking agent having the above-mentioned preferable properties, and as a result, a compound having a specific structure obtained from a polyamine compound as a starting material. It has been found that a deinking agent containing as an essential component is suitable for the purpose, and based on this finding, the present invention has been completed. That is, the present invention relates to the general formula

[0005]

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Wherein Y is a residue obtained by removing active hydrogen from a polyamine or polyalkyleneimine or a derivative thereof having (k + m + n) active hydrogens, A is an acyl group optionally having a hydroxyl group, and B is polyether group terminal oxygen atom is bonded to X ^1, X ¹ and X ² are each a hydrogen atom, an alkyl group, an acyl group optionally having an alkenyl group or a hydroxyl group, they the same as or different from each other K and m are each an integer of 1 to 50, and n is k
+ M + n = integer satisfying the relationship of 3 to 100. When k is 2 or more, a plurality of A may be the same or different. When m is 2 or more, a plurality of B and X ¹ may be the same or different. And when n is 2 or more, a plurality of X ² may be the same or different.] The present invention provides a deinking agent comprising a compound represented by the formula: Less than,
The present invention will be described in detail. The deinking agent of the present invention has a general formula

[0007]

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Wherein Y, A, B, X ¹ , X ² , k, m and n have the same meanings as described above as an essential component. Y in the general formula [1] is a residue obtained by removing active hydrogen from a polyamine, a polyalkyleneimine or a derivative thereof having (k + m + n) active hydrogens. A is an acyl group which may have a hydroxyl group, for example, of the general formula

[0009]

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An acyl group represented by the formula [R in the formula is an alkyl group or hydroxyalkyl group having 7 to 21 carbon atoms or an alkenyl group or hydroxyalkenyl group having 7 to 21 carbon atoms] is preferable. Further, B is a polyether group in which a terminal oxygen atom is bonded to X ^1.

[0011]

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Wherein each of a, b, c and d is 0 or an integer of 1 to 200, or a homopolymer residue comprising only oxyethylene units, or an oxyethylene unit and an oxypropylene unit. And a block and / or random copolymer or residue composed of oxybutylene units or oxystyrylene units. The oxypropylene unit and oxybutylene unit may be linear or branched. On the other hand, each of X ¹ and X ² is a hydrogen atom, an alkyl group, an alkenyl group or an acyl group optionally having a hydroxyl group, and an alkyl group, an alkenyl group or an acyl group optionally having a hydroxyl group is Those having 1 to 22, 2 to 22, and 2 to 22 carbon atoms are preferred. X ¹ and X ² may be the same or different. k and m are each 1 to
It is an integer of 50, and n is an integer that satisfies the relationship of k + m + n = 3-100. When k is 2 or more, a plurality of A may be the same or different, when m is 2 or more, a plurality of B and X ¹ may be the same or different, and when n is 2 or more, a plurality of A and X ² may be the same or different.

The compound represented by the general formula [1] is obtained by starting from a polyamine compound as a starting material, and (1) amidating one or more amino groups in the polyamine compound using a higher fatty acid or a reactive derivative thereof. Step, (2) using the amidated compound obtained in the above step (1) as an intermediate, and adding an alkylene oxide to the remaining active hydrogen of the compound, and optionally (3) step (2). Production by subjecting the obtained alkylene oxide adduct to a step of esterifying or etherifying a terminal hydroxyl group or (4) a step of alkylating, alkenylating, or acylating a group having a remaining active hydrogen other than the terminal hydroxyl group. can do. In the amidation step (1), one or more amino groups in the polyamine compound are subjected to a high-temperature dehydration amidation reaction with a higher fatty acid, or a dehydrochlorination with a higher fatty acid chloride using a catalyst such as an acid without using a catalyst. Amidation is carried out by a reaction or an ester exchange reaction with a lower alcohol higher fatty acid ester, or the like to produce an amidated intermediate. As the higher fatty acid or its acid chloride or lower alcohol ester used at this time, a general formula

R-COOH ... [4] wherein R is an alkyl group or hydroxyalkyl group having 7 to 21 carbon atoms, preferably 11 to 21 carbon atoms or 7 carbon atoms.
-21, preferably 11-21 alkenyl groups or hydroxyalkenyl groups], or acid chlorides and lower alcohol esters derived therefrom. In the step (2), an alkylene oxide is added to the remaining active hydrogen of the compound using a catalyst such as an alkali or an acid, using the amidated product thus obtained as an intermediate. At this time, as the alkylene oxide, ethylene oxide may be used alone, or propylene oxide, butylene oxide, or styrene oxide may be used together with ethylene oxide in some cases. The total number of moles of ethylene oxide added is desirably 1 to 1000, preferably 10 or more. The total number of added moles of propylene oxide, butylene oxide and styrene oxide is preferably in the range of 0 to 500. In the present invention, a random adduct and / or a block adduct obtained by adding the above-mentioned propylene oxide, butylene oxide, or styrene oxide together with ethylene oxide is preferable to ethylene oxide alone adduct, and such an adduct is preferably used for a product. It provides improved low-temperature stability.

The alkylene oxide adduct thus obtained can be used as it is as a deinking agent. However, in some cases, the above-mentioned step (3) may be carried out to esterify or etherify the terminal hydroxyl group of the polyether group. And may be modified. For example, by using an esterification catalyst such as p-toluenesulfonic acid at the terminal hydroxyl group of the polyether group,
High-temperature dehydration esterification reaction with a fatty acid, dehydrochlorination reaction with a fatty acid chloride or transesterification with a lower alcohol fatty acid ester, may be esterified,
Alternatively, the terminal hydroxyl group may be subjected to a dehydrohalogenation reaction with an alkylating agent or an alkenylating agent such as an alkyl halide or an alkenyl halide to carry out alkyl etherification or alkenyl etherification. There is no particular limitation on the position or number of the hydroxyl groups to be esterified or etherified. The acyl group of the fatty acid or acid chloride or lower alcohol ester used for the esterification preferably has 2 to 22 carbon atoms, and may have a hydroxyl group. The alkyl group of the alkyl halide used for the etherification preferably has 1 to 22 carbon atoms,
The alkenyl group of the alkenyl halide has 2 to 22 carbon atoms.
Are preferred.

Further, in some cases, the above-mentioned step (4) is performed to convert the group having a residual active hydrogen other than the terminal hydroxyl group of the polyether group into an acyl group using a fatty acid or a reactive derivative thereof such as an acid chloride or a lower alkyl ester. Or alkylation or alkenylation using an alkyl halide or an alkenyl halide. There are no particular restrictions on the position or number of these active hydrogen-containing groups for acylation, alkylation and alkenylation. The acyl group in the fatty acid or its reactive derivative used for the acylation preferably has 2 to 22 carbon atoms, and may have a hydroxyl group. The alkyl halide used for the alkylation preferably has 1 to 22 carbon atoms, and the alkenyl halide used for the alkenylation has 2 carbon atoms.
To 22 are preferred.

In the present invention, the polyamine compound used as a starting material has at least three active hydrogens in the molecule, at least one of which has an amino group that can be amidated, and has two nitrogen atoms. And polyamines, polyalkylenimines and derivatives thereof. Examples of the polyamine include ethylenediamine, diethylenetriamine, triethylenetetramine,
Pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, propylenediamine,
Dipropylene triamine, tripropylene tetramine,
Alkylene polyamines such as hexamethylene diamine are exemplified. On the other hand, examples of the polyalkyleneimine include polyethyleneimine and polypropyleneimine, which have three or more active hydrogens in the molecule, and at least one of which has an amino group that can be amidated. In addition, as long as it has two or more nitrogen atoms, it may be a polymer having a linear structure or a polymer having a branched structure. In addition, a copolymer obtained by using allylamine, diallylamine, polyallylamine, or the like as a monomer, a derivative such as melamine or a resin thereof, or the like can also be used as a polyamine compound as a starting material.

Further, a compound obtained by adding an alkylene oxide to the above-mentioned alkylene polyamine or polyalkylene imine while leaving at least one amino group which can be amidated can also be used as a starting material. Specific examples of such a substance include aminoethylethanolamine (an ethylene oxide adduct of ethylenediamine) and a 1 mol ethylene oxide adduct of diethylenetriamine. When such a polyamine compound is used as a starting material, since there are an active group having an amino group and an active group having a hydroxyl group, when reacted with a fatty acid or the like, a reaction between an amidated compound and an esterified compound occurs. It is also conceivable that the mixture may be a mixture of different reacting positions or different numbers of moles, but this compound may be used as an intermediate as long as it contains amidated one. Also,
The number of moles and positions to be amidated and esterified are not particularly limited as long as the amidated one is included, and a compound reacted at any position and at any mole number may be used as an intermediate. .

Further, an addition reaction and a reaction with these polyamine compounds using guanidines such as urea and dicyandiamide, formalin, epihalohydrin, isocyanate compounds, glycidyl ether compounds, alkylene imines and alkyl halides are carried out. Compounds that have undergone crosslinking and / or cross-linked to form double and / or cross-linked molecules have at least three active hydrogens in the molecule, at least one of which has an amino group that can be amidated, and a nitrogen atom If it has two or more, it can be used as a substance to be emitted. In this case, the reaction procedure is changed, and a compound obtained by amidating a polyamine compound with a fatty acid or the like is subjected to an addition reaction and / or a cross-linking reaction using the compound, and the compound that has been subjected to dimerization and / or intramolecular cross-linking is interposed. It may be used as a substance, or after addition of the alkylene oxide, an addition reaction and / or a cross-linking reaction may be performed using the compound to form a dimer and / or an intramolecular cross-link.
Further, when the addition reaction and / or the cross-linking reaction is carried out using the compound, the position and the number of moles of addition or cross-linking are not particularly limited. They may be added and cross-linked with the same one, or may be added and cross-linked with different ones.

Some of the polyamine compounds, when amidated with a fatty acid or the like, form an imidazoline ring as the dehydration proceeds, and all of the imidazoline and some imidazoline rings are intermediate substances. And mixtures of these with those without an imidazoline ring can also be used as intermediates.
Furthermore, when two or more imidazoline rings are formed, the position and number of the imidazoline rings are not particularly limited, and any of them can be used as an intermediate. In the present invention, the starting polyamine compound is 1
Species may be used, or two or more may be used in combination. Similarly, an amidated compound as an intermediate before addition of an alkylene oxide may be used alone or in combination of two or more. A feature of the present invention is that a compound in which an amino group of a polyamine compound as a starting material is first amidated with a fatty acid or the like, and the resulting amidated product is used as an intermediate, and an alkylene oxide is added to the intermediate, or Is to further use an alkylated, alkenylated or acylated compound as a deinking agent.

The deinking agent of the present invention includes known agents conventionally used in the deinking process, for example, alkali agents such as sodium hydroxide, sodium silicate and sodium carbonate, hydrogen peroxide, sodium hypochlorite, Bleaching agents such as hydrosulfite, chelating agents, hydrogen peroxide stabilizers, other known deinking agents, foaming agents, pitch control agents, disaggregation accelerators, and the like can be added as desired. The deinking agent of the present invention can be used by dissolving, emulsifying or dispersing in water or an organic solvent. The deinking agent of the present invention is effective for the deinking treatment of any used paper. For example, newspapers, magazines, OA
It is effective for deinking of printed materials such as waste paper, handbills, books, heat-sensitive and pressure-sensitive recording paper, and for deinking of printed materials printed by any printing method, such as letterpress printing, offset printing, and gravure printing. . The amount of the deinking agent used in the present invention is usually 0.0 based on the dry weight of the used paper used.
It is selected in the range of 0.01 to 20% by weight, preferably 0.01 to 5% by weight.

[0022]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention. Production Example 1 Amidated polyamine compound (alkylene
Preparation of Intermediate Before Oxide Addition) Using the starting polyamine compound shown in Table 1, k in the above general formula [1] and R in the general formula [2]
Amidated polyamine compounds (intermediates before alkylene oxide addition) AK as shown in Table 1 were produced.

[0023]

[Table 1]

Examples 1 to 20, Comparative Examples 1 to 6 Amidated compounds A to A of the polyamine compound obtained in Production Example 1
Using K, deinking agents consisting of the compounds shown in Table 2 were prepared. In Table 2, the sum of a to d is the sum of each of a to d in the polyether group represented by the general formula [3], and X ¹ and X ² are the same as those of the general formula [1]. X ¹ and X ² in the compounds represented. For comparison, a deinking agent comprising the compounds shown in Table 3 was prepared.

[0025]

[Table 2]

[0026]

[Table 3]

(1) Performance test of deinking agent [1] The recovered paper in the city is shredded, put into a test pulper, and the weight of sodium hydroxide is 1.0 wt.
%, 35% by weight of aqueous hydrogen peroxide, 1.0% by weight of hydrogen peroxide, 3.0% by weight of sodium silicate No. 3, and 0.3% by weight of a deinking agent shown in Table 4 and uniformly mixed to give a pulp concentration of 5% by weight. After defibrating at 10 ° C. for 10 minutes, aging treatment was performed at 50 ° C. for 3 hours. Next, water was added to dilute the pulp concentration to 1.0 wt%, flotation treatment was performed at 30 ° C. for 10 minutes, and the obtained pulp slurry was hand-made into paper.
A pulp sheet was made. This pulp sheet was evaluated as follows, and the results are shown in Table 4.

Evaluation method: The obtained pulp sheet was measured for whiteness using an SM color computer manufactured by Suga Test Instruments Co., Ltd. Further, the number of remaining inks and the residual ink area ratio were measured by an image analyzer “EXCEL” (manufactured by Olympus Corporation) for an image obtained by copying the pulp sheet at a magnification of 100 with an optical microscope. The measured ink particles had a size of 1.25 μm or more, and the area of one measurement was 0.3.
The total area was 84 mm ² , and the total number of inks obtained at 10 locations and the ink area ratio were measured.

[0029]

[Table 4]

As can be seen from Table 4, the examples using the deinking agent of the present invention exhibited higher whiteness than the comparative example and lower values in the number of remaining inks and the remaining ink area ratio. In particular, the residual ink area ratio was remarkably low, indicating that the size of the residual ink particles was small. (2) Performance test of deinking agent [2] After chopping waste paper collected in the city, put it into a test pulper and add 0.5% by weight of sodium hydroxide to water and dry weight of waste paper.
Was added, and the pulp concentration was adjusted to 5 wt%, and after defibration at 50 ° C. for 10 minutes, the pulp concentration was adjusted to 25 wt%. Next, 1.0 wt% of sodium hydroxide based on the dry weight of waste paper
%, 35% by weight of hydrogen peroxide, 1.0% by weight of aqueous hydrogen peroxide, 3.0% by weight of sodium silicate No. 3, and 0.3% by weight of a deinking agent shown in Table 5 and mixed uniformly. After one pass (about 2 minutes) of kneading treatment at 60 ° C. using a Yamamoto-type kneader manufactured by Kobe Steel, aging treatment was performed at 50 ° C. for 3 hours. Next, water is added to dilute the pulp to a concentration of 1.0 wt%, followed by a flotation treatment at 30 ° C. for 10 minutes, and a pulp sheet is prepared by hand-making the obtained pulp slurry. did. About this pulp sheet,
The whiteness, the number of remaining inks, and the remaining ink area ratio were measured according to the above (1). Table 5 shows the results.

[0031]

[Table 5]

As can be seen from Table 5, the examples using the deinking agent of the present invention exhibited higher whiteness and lower values in the number of remaining inks and the remaining ink area ratio than the comparative examples. In particular, the residual ink area ratio was remarkably low, indicating that the size of the ink particles was small.

[0033]

By using the deinking agent of the present invention,
Regardless of the type of the used printing paper and the method of the recycling process, it is possible to obtain a high-value-added recycled paper having a high whiteness and a small remaining ink amount. According to the present invention, it is possible to contribute to global environmental problems and industry by providing an excellent deinking agent that can collect and use all kinds of used paper as recycled paper.

Claims (4)

(57) [Claims] 1. A compound of the general formula [Wherein Y is a polyamine having (k + m + n) active hydrogens, a residue obtained by removing active hydrogens from polyalkyleneimine or a derivative thereof, A is an acyl group which may have a hydroxyl group, B is a terminal oxygen atom there polyether group bonded to X ^1, X ¹ and X ² are each a hydrogen atom, an alkyl group, an acyl group optionally having an alkenyl group or a hydroxyl group, even if they are the same with or different from each other Well, k
And m are each an integer of 1 to 50, and n is k + m + n = 3
An integer that satisfies the relationship of ~ 100, and when k is 2 or more, a plurality of A may be the same or different, and when m is 2 or more, a plurality of B and X ¹ may be the same or different; When n is 2 or more, a plurality of X ² may be the same or different]. 2. The acyl group of A which may have a hydroxyl group is represented by the general formula: The deinking agent according to claim 1, wherein R is an alkyl group or hydroxyalkyl group having 7 to 21 carbon atoms or an alkenyl group or hydroxyalkenyl group having 7 to 21 carbon atoms. 3. The polyether group of B has a general formula: Wherein a, b, c and d are each 0 or 1 to 200
The deinking agent according to claim 1 or 2, which is a single, block and / or random polymer residue represented by the following formula: 4. An alkyl group of X ¹ and X ² , an alkenyl group or an acyl group which may have a hydroxyl group has 1 to 22, 2 to 22, and 2 to 22 carbon atoms, respectively.
Or the deinking agent according to 3.