JPH08337987A - Deinking agent - Google Patents

Abstract

PURPOSE: To obtain a deinking agent giving deinked pulp having high whiteness and a slight residual ink from old news papers, magazines and old papers for OA. CONSTITUTION: This deinking agent is composed of following components (A) and (B). The component (A); an 8-24C fatty acid or its alkali metal salt, organic amine salt or ammonium salt. The component (B); a polyoxyalkylene compound expressed by the formula: HO (EO)m (PO)p (EO)n }H (EO is oxyethylene group, PO is oxypropylene group, (m) and (n) are each an average adding molar number of oxyethylene group, (p) is an average molar number of oxypropylene group, (m+n)=0-100, (p):10-100 and ((m+n)/(p)):0.1-1).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a deinking agent for recycling used paper. More specifically, when deinking newspaper, magazines, waste paper for OA, etc. by the flotation method, flotation-water washing eclectic method, washing method, etc., in order to obtain deinked pulp with high whiteness and very little residual ink. Deinking agent used for.

[0002]

2. Description of the Related Art Conventionally, for the purpose of effectively utilizing resources due to a shortage of pulp for making paper, it is widely practiced to deink the used waste paper such as used newspapers, magazines, OA waste paper and recycle it. Has been. Further, in recent years, from the viewpoint of measures against dust and environmental protection, it is required to further increase the utilization. At present, the deinking method is as follows: (1) Flotation in which waste paper is disintegrated by disintegrating it with an alkaline agent and a surfactant to remove the ink, and air is blown into the disintegrating liquid to adhere the ink to the bubbles for deinking. Method, (2) Flotation-water washing eclectic method in which a washing step is performed before and after the flotation, and (3) a washing method of washing with a large amount of water. Among these methods, the methods of (1) and (2) Is widely adopted. Conventionally, sodium hydroxide, sodium silicate, sodium carbonate, sodium phosphate, etc. have been used as alkali agents, and surfactants such as fatty acids or salts thereof, alkylbenzene sulfonates, higher alcohol sulfate ester salts, dialkyl sulfosuccinates, etc. Ionic surfactants: alkylene oxide adducts of higher alcohols, alkylphenols and fatty acids, or nonionic surfactants of block or random adducts of two or more alkylene oxides such as higher alcohols, alkylphenols and fatty acids are used. It has been. In addition, hydrogen peroxide solution, bleaching agents such as hypochlorite, sequestering agents such as EDTA,
It has also been conducted to enhance the deinking effect by using a recontamination inhibitor such as carboxymethyl cellulose and polyvinylpyrrolidone together.

It is difficult to remove the ink from the waste paper efficiently with the conventionally known deinking agents. In particular, with respect to used paper that has been popularly used in recent years for offset printing, it is very difficult to remove the ink due to the properties of the ink components, and residual carbon due to recontamination and so-called “beard” that is unpeeled ink poses a problem. . In order to solve this problem, JP-A-3-
In JP279479, it has an alkyl or alkenyl alcohol having 3 to 24 carbon atoms, a phenol having 1 to 2 alkyl or alkenyl groups having 3 to 24 carbon atoms, and 1 to 2 alkyl or alkenyl groups having 3 to 24 carbon atoms. Aryl alcohol, bishydroxyphenylalkane having an alkyl or alkenyl group having 3 to 24 carbon atoms, biscyclohexylalkane having an alkyl or alkenyl group having 3 to 24 carbon atoms, or 3 to
It is disclosed that an ester of a compound obtained by adding ethylene oxide and propylene oxide to a phenol formaldehyde condensate having 1 or 2 24 alkyl or alkenyl groups and a polyvalent carboxylic acid is useful as a deinking agent. JP-A-3-287888 discloses that a reaction product of a compound obtained by adding ethylene oxide or propylene oxide to a higher fatty acid and a polycarboxylic acid is useful as a deinking agent. In JP-A-4-202877, a carboxylic acid modified product of an alkylene oxide adduct having 2 to 4 carbon atoms of a monohydric alcohol having an alkyl group or alkenyl group having 8 to 24 carbon atoms is useful as a deinking agent. Is disclosed. JP-A-4-20288
No. 0 discloses that a reaction product of a compound obtained by adding ethylene oxide or propylene oxide to rosin and a polyvalent carboxylic acid is useful as a deinking agent. JP-A-4-202881 discloses that a reaction product of a polycarboxylic acid and a compound obtained by adding ethylene oxide or propylene oxide to a hydroxy fatty acid or an ester of a hydroxy fatty acid and an alcohol is useful as a deinking agent. ing. In JP-A-5-71086, a block-shaped adduct of propylene oxide of a fatty acid having an alkyl group or an alkenyl group having 7 to 21 carbon atoms, an alkylene oxide having 2 to 4 carbon atoms and propylene oxide is useful as a deinking agent. Is disclosed. In JP-A-4-136288, propylene oxide of a hydroxy compound having an alkyl group or an alkenyl group having 8 to 22 carbon atoms, a block-shaped adduct of alkylene oxide having 2 to 4 carbon atoms and propylene oxide, or 7 carbon atoms. It is disclosed that a propylene oxide adduct of a phenolic hydroxyl group consisting of ~ 26 alkylphenol group and a block-shaped adduct of an alkylene oxide having 2 to 4 carbon atoms and propylene oxide are useful as a deinking agent. In JP-A-4-163387, the number of carbon atoms is 7.
To a fatty acid having an alkyl group or an alkenyl group, an alkylene oxide having 7 to 21 carbon atoms, and 2 to 3 carbon atoms
Useful as a deinking agent is a mixture of an adduct of the alkylene oxide with C8-C30 α-olefin oxide and an alkylene oxide adduct of a condensate of a natural fat and oil and an amine having two or more active hydrogens. Is disclosed. In JP-A-4-361681, a hydroxy compound having an alkyl group or an alkenyl group having 12 to 22 carbon atoms has an alkylene oxide having 2 to 3 carbon atoms and 8 to 3 carbon atoms.
Blocked adducts of 0 with α-olefin oxides are disclosed to be useful as deinking agents.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a deinking agent capable of obtaining a deinking pulp having a high whiteness and an extremely small number of residual inks.

[0005]

The present invention comprises the following components (A) and (B), the weight ratio of which is (A) /
(B) = A deinking agent having a ratio of 50/50 to 95/5. Component (A): a fatty acid having 8 to 24 carbon atoms or its alkali metal salt, organic amine salt or ammonium salt. Component (B); a polyoxyalkylene compound represented by formula (1). HO {(EO) m (PO) p (EO) n} H (1) (where EO is an oxyethylene group, PO is an oxypropylene group, m and n are oxyethylene groups, and p is an average of oxypropylene groups. The number of added moles, m + n is 0 to 100,
p is 10 to 100, and (m + n) / p is 0.1
~ 1. )

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As the component (A) fatty acid having 8 to 24 carbon atoms used in the present invention, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, Saturated fatty acids such as lignoceric acid; unsaturated fatty acids such as palmitooleic acid, oleic acid, elaidic acid, linoleic acid, and ricinoleic acid. Further, these fatty acids may be used alone or in combination. Specific examples of the fatty acid having 8 to 24 carbon atoms of the component (A) used in the present invention include avocado oil, linseed oil, olive oil, cocoa oil, kapok oil, mustard oil, tung oil, poppy seed oil, sesame oil, Rice oil, safflower oil, shea butter, soybean oil, camellia oil, corn oil,
Fatty acids derived from natural triglycerides such as rapeseed oil, palm oil, palm kernel oil, castor oil, sunflower oil, grape seed oil, jojoba oil, cottonseed oil, coconut oil, peanut oil, beef tallow, lard, fish oil, whale oil and the like can be mentioned. In addition, fatty acids obtained from recovered oil of these natural triglyceride waste oils can also be used.

Specific examples of the fatty acid salt include salts of alkali metals, ammonia, organic amines and the like. As the organic amine, methylamine, ethylamine, propylamine, butylamine, dimethylamine,
Monoamines such as diethylamine and dipropylamine;
Examples thereof include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine and diisopropanolamine, and polyamines such as ethylenediamine, propylenediamine and diethylenetriamine. As the alkali metal, sodium and potassium are more preferable. These salts may be partially neutralized or completely neutralized. When the deinking agent of the present invention is used at the time of disaggregation of used paper, it is preferably used together with sodium hydroxide, sodium silicate or the like to adjust the pH to 8 to 15, and further to pH 9
-12 are more preferable. Therefore, when disintegrating waste paper, p
When H is made alkaline and the fatty acid of the component (A) is added, an alkali metal salt of fatty acid is formed.

In the polyoxyalkylene compound represented by the formula (1) of the component (B) used in the present invention, m + n is 0 to 100, preferably 5 to 30. m +
When n exceeds 100, it tends to be solid and difficult to handle.
p is 10 to 100, preferably 15 to 60. If p is less than 10, the peeling property and the collecting property of the ink are deteriorated, resulting in an increase in beard and an increase in residual carbon and a decrease in whiteness, which is not preferable. Further, when p exceeds 100, the viscosity becomes high and it is difficult to handle. The molar ratio (m + n) / p of oxyethylene groups of EO to oxypropylene groups of PO is 0.1 to 1. When the molar ratio is more than 1, foaming during flotation is too much, the amount of froth increases, and the yield of pulp deteriorates, which is not preferable.

The weight ratio of the component (A) and the component (B) used in the present invention is preferably (A) / (B) = 50/50 to 95/5, more preferably (A) / (B). = 60/40
~ 85/15. If (A) / (B) is larger than 95/5, the foaming property is too small to remove the ink outside the system, so that the number of remaining inks is large and the whiteness tends to decrease.
If it is less than 50/50, the releasability and collecting property of the ink are deteriorated, the number of remaining inks is increased, and the whiteness is also likely to be decreased.

The deinking agent of the present invention is a fatty acid other than a fatty acid having 8 to 24 carbon atoms or a salt thereof, a conventionally known deinking agent such as polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, and higher alcohol sulfate ester salt. It can also be used in combination with. In that case, the content of the deinking agent of the present invention is preferably 5% by weight or more, and more preferably 50% by weight or more, based on the entire deinking agent. If the compounding ratio of the deinking agent of the present invention is less than 5% by weight, it is not preferable because the effect of high whiteness and a small number of residual ink does not appear.

The deinking agent of the present invention is a flotation method,
Flotation-in the washing eclectic method, washing method, etc.
It is added in the disaggregation step, the kneader treatment step, the aging step, the flotation step, the washing step, etc., but it is preferably added in the disaggregation step or the kneader treatment step. The amount of the deinking agent of the present invention added is preferably 0.01 to 2% by weight, more preferably 0.05 to 1% by weight, based on the used paper. If the addition amount of the deinking agent is less than 0.01% by weight, the effect as the deinking agent is small, and if it is more than 2% by weight, the foaming tends to be too much and the yield tends to decrease.

[0012]

INDUSTRIAL APPLICABILITY The deinking agent of the present invention is used in flotation method, flotation-water washing eclectic method, washing method, etc. to remove deinking ink from newspapers, magazines and waste paper for OA with high whiteness and little residual ink. Pulp can be obtained.

[0013]

EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples. Example 1 A deinking test shown below was carried out using the compound of component (A) 1-1 shown in Table 1 and the compound of component 2-1 (B) shown in Table 2 with the composition shown in Table 3. It was

[0014]

[Table 1]

[0015]

[Table 2]

[0016]

[Table 3]

<Deinking test> 70% by weight of Asahi Shimbun, Yomiuri Shimbun, and Nihon Keizai Shimbun newspaper (1 to 2 months after printing) and 30% by weight of leaflets were cut with a shredder. 350 g of the mixture, 1.75 g of sodium hydroxide (0.5% by weight based on the waste paper),
0.35 g of a deinking agent (0.1% by weight based on waste paper) and 10 liters of water were added, and disintegration was carried out for 10 minutes with a pulper having a volume of 10 liters. The disaggregated sample was dehydrated (2000 rpm, 5 minutes) with a centrifuge to reduce the waste paper concentration to 25-30.
% To 0.7% (0.2% by weight of waste paper), 1.75 g of sodium hydroxide (0.5% by weight of waste paper), 7.0 g of sodium silicate No. 3 ( After adding 2.0% by weight of waste paper) and 3.5 g of hydrogen peroxide solution (1.0% by weight of waste paper) and mixing well,
Needling treatment was performed with a 300-rpm dual-axis lab kneader. Take this sample in a polyethylene bag and
It was aged in a water bath at ℃ for 2 hours. Water is added to the sample after aging to dilute the waste paper concentration to 1%, disaggregated with a 2 liter pulper for 10 minutes, and this is poured into a 2 liter floatator (manufactured by Far East Co., Ltd.) and floated for 10 minutes. After removing the ink agglomerates in the upper layer, the pulp sheet was obtained by hand pulling with a Tappy standard sheet machine. With respect to the pulp sheet obtained by this method, the whiteness and the number of remaining inks were examined by the following measuring methods to evaluate the deinking effect. The results are also shown in Table 3.

<Measurement of whiteness> Photoelectric reflectometer {SM color computer ModelSM manufactured by Suga Test Instruments Co., Ltd.
-4} was used to measure the blue reflectance of the above-mentioned hand-skewed sample at 457 μm.

<Measurement of the number of remaining inks> Microscope (× 20)
The number of residual inks (whiskers and residual carbons) of the above-mentioned sample hand-skewed in (1) was counted at 5 positions in a visual field of 54 mm ² , and the average number was converted into a value per 1 cm ² .

Examples 2 to 11 In the same manner as in Example 1, 1-2 of the component (A) shown in Table 1
~ 1-11 and the corresponding corresponding compounds 2-2 to 2-11 of the component (B) shown in Table 2 were subjected to the deinking treatment test shown below with the composition shown in Table 3. . In addition, oleic acid in Table 1 is NAA-3 manufactured by NOF CORPORATION.
4 (industrial distilled oleic acid) was used. Lauric acid is manufactured by NOF CORPORATION NAA-122 (purity of lauric acid: 9
5%) was used. Extra linoleic 90 (linoleic acid purity 90%) manufactured by NOF Corporation was used as linoleic acid, and soybean oil fatty acid for paints manufactured by NOF Corporation was used as soybean oil fatty acid. As the plant recovered oil fatty acid, a hydrolyzed distilled fatty acid of a mixed vegetable oil containing soybean oil as a main component was used.

Comparative Examples 1-9 As comparative examples, Comparative Examples 1-1 to 1-9 of Table 1 and Table 2 are shown.
A deinking test was similarly performed using the compounds of Comparative Examples 2-1 to 2-9. The results are shown in Table 3. As the compound 2-8 in Comparative Example 8, NUREX R manufactured by NOF CORPORATION was used as the linear sodium dodecylbenzenesulfonate. As the compound 2-9 of Comparative Example 9, Parsoft SF manufactured by NOF CORPORATION was used as the sodium salt of lauryl sulfate.

As is clear from Table 3, the deinking agents of Examples Nos. 1 to 11 of the present invention are better than those of Comparative Examples 1 to 9 in comparison.
It can be seen that the number of remaining ink is small and the whiteness is high.

Claims (1)

[Claims] 1. A deinking agent comprising the following components (A) and (B) in a weight ratio of (A) / (B) = 50/50 to 95/5. Component (A): a fatty acid having 8 to 24 carbon atoms or its alkali metal salt, organic amine salt or ammonium salt. Component (B); a polyoxyalkylene compound represented by formula (1). HO {(EO) m (PO) p (EO) n} H (1) (where EO is an oxyethylene group, PO is an oxypropylene group, m and n are oxyethylene groups, and p is an average of oxypropylene groups. The number of added moles, m + n is 0 to 100,
p is 10 to 100, and (m + n) / p is 0.1
~ 1. )