JPH04163387A - Deinking agent for recycling waste paper - Google Patents

Abstract

PURPOSE:To obtain a deinking agent capable of providing recycled pulp with a high whiteness and a low content of residual ink by mixing a specific compound with a reaction product prepared by adding an alkylene oxide to a mixture of natural fats and oils with an amine compound having plural active hydrogens at a specified ratio. CONSTITUTION:The objective deinking agent is obtained by mixing (A) a compound expressed by the formula (R is 12-22C alkyl or alkenyl; x is 2-3; y is 8-30; z is 2 or a mixture of 2 with 3; b is 0-30; c is an average equiv. of 0.2-5; d is 1-100) with (B) a reaction product prepared by subjecting a mixture of natural fats and oils (e.g. coconut oil) with an amine compound (e.g. ammonia) having >=2 active hydrogens at preferably (1:0.1)-(1:3) molar ratio to addition reaction with an alkylene oxide (e.g. ethylene oxide) in an amount of preferably 5-200mol based on 1mol mixture at (5/95)-(50/50), preferably (10/90)-(40/60) weight ratio of the components [(A)/(B)].

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a deinking agent used when recycling used printed paper such as newspapers, magazines, flyers, information writing paper, imitation paper, etc. More specifically, the present invention relates to a deinking agent that can produce recycled pulp with high whiteness and a small amount of residual ink when waste paper is deinked by a flotation method, a washing method, or the like. Conventional technology: With the diversification of used paper, efforts have been made to improve the deinking performance of deinking agents used in the recycling of printed waste paper such as newspapers, magazines, leaflets, information recording paper, imitation paper, etc. There is. For example, in recent years, the effective use of waste paper has increased due to the shortage of pulp resources and the rise in its price, and advanced use has been made for deinked recycled pulp. In addition, with the recent development of printing technology, printing methods and printing ink components have changed for used paper.
The situation is becoming more difficult when deinking waste paper. Under these circumstances, improvements have been made to equipment to promote deinking, and deinking separation methods using chemicals have been widely adopted in the recycling of waste paper. Chemicals include alkaline agents such as caustic soda, sodium silicate, soda carbonate, and sodium phosphate, bleaching agents such as hydrogen peroxide, hyposulfite, and hypochlorite, and sequestering agents such as EDTA and DTPA. A combination of auxiliary agents and deinking agents is used, and the deinking agents include alkylbenzene sulfonic acid Na salt, higher alcohol sulfate ester Na salt, dialkyl sulfosuccinate Na salt, ethoxylated higher alcohol sulfate ester ammonium salt, fatty acid Anionic activators such as Na salts, nonionic activators such as ethylene oxide and propylene oxide added to starting materials such as higher alcohols, fatty acids, alkylphenols, or ethylene oxide alone, or combinations of two or more of them. is used as.

[Problem to be solved by the invention]

However, such conventional deinking agents for waste paper recycling include, for example, alkylbenzene sulfonates, higher alcohol sulfate ester salts, and higher Although alcohol, ethylene oxide adducts of alkylphenols, and the dialkyl sulfosuccinates disclosed in Japanese Patent Publication No. 17476/1987 can provide ink dispersibility, they lack the ability to collect the detached ink, resulting in insufficient whiteness. . In addition, it is known that the fatty acid Na soap used in combination in Japanese Patent Publications No. 51-13762 and No. 61-1556 improves the removal of detachable ink during flotation and improves whiteness. When used alone or in hard water, the ink separated from the waste paper adheres to the equipment, and the ink that coagulates and surfaces due to flotation remains in the pulp again, causing problems with ink spots and reducing the deinking effect. . Furthermore, JP-A-55-51891 discloses random adducts of higher alcohols propylene oxide and ethylene oxide, and JP-A-58-109696 discloses random adducts of higher fatty acids propylene oxide and ethylene oxide. . All of these chemicals are used for deinking old newspapers, but high whiteness cannot be obtained because they lack ink stripping properties and detached ink removal properties. On the other hand, recently, in addition to newspapers and magazines, offset printing paper and information recording paper have been increasing in terms of used paper. Since these contaminated waste papers contain thermosetting resin vehicles and toner inks, the deinking agents described above cannot provide sufficient deinking effects, and in order to obtain high-quality recycled paper, additional steps are required. There is a demand for high-performance deinking agents. In view of the above circumstances, the present invention has high ink releasability and removability of detached ink regardless of the type of used printed paper, and also has high ink removability and removeability of detached ink in the flotation process. The present invention provides a deinking agent that can produce high quality recycled paper by reducing residual ink and unpeeled ink with high whiteness.

[Means to solve the problem]

The present invention relates to a compound represented by the following general formula (1) (hereinafter (a)
) and a reaction product (hereinafter referred to as component (b)) obtained by addition reaction of an alkylene oxide to a mixture of natural oil and fat and an amine compound having two or more active hydrogens, in a weight ratio of (a)/(b). ) = 5/95 to 50150 is a deinking agent for recycling used paper. RO(C,+(2,O)l,fCyH2yO),(C2
H,,O), H-・-・(1) (in the formula, R has 12 to 12 carbon atoms
22 alkyl group or alkenyl group, X is 2 to 3
, y is an integer of 8 to 3 degrees, 2 is 2 or a mixture of 2 and 3, b is 0 or an integer of 1 to 30, C is an average equivalent of 0.2 to
5, and d represents an integer of 1 to 100. ) [Requirements constituting the means] The natural fats and oils as component (b) used in the present invention include coconut oil,
Vegetable oils such as palm oil, olive oil, soybean oil, rapeseed oil, linseed oil, sunflower oil, animal oils such as liver fat, beef tallow, bone tallow, tallow, and fish oils, or hydrogenated oils of these natural oils and fats,
Examples include semi-curable oils, refined oils and recovered oils obtained in the refining process of these oils and fats. The amine compound having two or more active hydrogens used in the present invention includes ammonia, an oxyalkylamine compound having 2 to 30 carbon atoms, and an alkylamine compound having 1 to 20 carbon atoms. Without specifying one of the above compounds, oxyalkylamine compounds include monoethanolamine obtained by reacting ammonia with ethylene oxide; monoisopropanolamine, diisopropanolamine, triisopropanolamine obtained by reacting ammonia with butylene oxide, jetanolamine,
Tributanolamine. In addition, ammonia
-Oxyalkylamines such as mono-, di-, and tri-mixed 1-decanolamine and octadecanolamine obtained by reacting olefin oxides are mentioned. The alkylamine compounds include methylamine, ethylamine, propylamine, ocdylamine, coconut fatty amine, tallow fatty amine, ethylenediamine, propylene diamine, and mixtures of the above-mentioned amine compounds. Examples of the alkylene oxide used in component (b) of the present invention include ethylene oxide, propylene oxide, butylene oxide, and α-olefin oxide having 8 to 30 carbon atoms. In the alkylene oxide addition reaction described above, the catalyst used is usually a trace amount of any of alkaline substances, alkali metal hydroxides, carbonates, etc. used in these reactions. The compound represented by the general formula (1) as the component (a) used in the present invention is a higher alcohol having 12 to 22 carbon atoms and 8 carbon atoms.
~3[1] A long chain alkylene oxide is added as an essential component, and a short chain alkylene oxide having 2 to 3 carbon atoms is further added. Furthermore, ethylene oxide and/or propylene oxide may be added prior to the addition of the long-chain alkylene oxide. Such a structure is particularly preferable because of its ink releasability, ink collection and bubble properties.The short chain alkylene oxide is ethylene oxy
Single addition and random addition with propylene oxide,
Block (=1 may be added, but in order to improve water solubility, it is preferable that the amount of ethylene oxide is 10 moles or more. Also, the average number of moles of alkylene oxide added is 10
~100 mol is preferred. The present invention uses a reaction product obtained by directly reacting an alkylene oxide with a mixture of natural fats and oils and an amine compound having two or more active hydrogen atoms (component (b)), and a polymeric acid containing a higher alcohol represented by the general formula (1). This relates to a deinking agent containing a chain alkylene oxide adduct, and the reaction product of the component (b) is obtained by mixing an amine compound having two or more active hydrogen atoms with a natural oil or fat that does not contain active hydrogen atoms. This is based on the knowledge that when oxy 1~ is added, the alkylene oxide addition reaction easily occurs even in natural oils and fats whose reaction is considered a national problem. The reaction consists of three reactions: amidation reaction, transesterification reaction, and addition reaction of alkyleneoxy) to active hydrogen. In other words, an amidation reaction or transesterification reaction first proceeds between the used amine compound having two or more active hydrogens and the natural fat ester, and alkylene oxide is detected in the hydroxyl group of the natural fat produced here. . Alkylene oxide is also added to one of the amine compounds, but since the reaction is a mixed system, the alkylene oxide (-1 adduct) obtained here is further processed by amidation reaction with the raw material amount and transesterification reaction. This is followed by an alkylene oxide addition reaction to increase the ether chain length.In this way, the alkylene oxide addition reaction to both the natural fat and the amine compound is repeated. In the end, a mixture of alkylene oxide adducts of natural oils and fats and alkylene oxide adducts of amine compounds is obtained.Additionally, as by-products, polyalkylene glycols and alkylene oxide adducts of fatty acids are also partially produced. The number of moles of alkylene oxide added to the product can be changed freely, but it is preferably 5 to 200 moles per mole of the mixture of natural oil and fat and amine compound having two or more active hydrogen atoms. The addition reaction of 10 to 150 moles of alkylene oxide is good.When using ethylene oxide and propylene oxide as the alkylene oxide of component (b), the addition reaction can be carried out by a mixture of block or random addition, or by using ethylene oxide alone. Good. Furthermore, derivatives in which the terminal hydroxyl groups of some of the above compounds are converted into alkyl ethers, fatty acid esters, phosphoric esters, and sulfuric esters are also effective. Also, derivatives having two or more active hydrogens per mole of natural oil or fat are also effective. The molar ratio of the amine compound used can be adjusted over a wide range, but is preferably 1:0.1 to 1:3, preferably 1:03 to 1.
:2 is good. In carrying out the production of the deinking agent of the present invention, the reaction temperature may be any temperature that allows the amidation reaction and transesterification reaction to occur quickly, but specifically, it is 140 to 200°C.
is suitable. In addition, the catalyst (alkali hydroxide, etc.) is 0.0% relative to the product. The use of about 1 to 0.3% by weight of O is
In order to increase the reactivity of the alkylene oxide, it is preferable, and more preferably carried out under a pressure of 1 kg/cm2 or less than at normal pressure. In the deinking agent of the present invention, components (a) and (b) The weight ratio of (a)/(b) is from 5/95 to 50,150, preferably from 10/90 to 40/60.If it is out of this range, the cohesive flotation of the separated ink becomes unstable. The operation is followed by a waste paper disintegration process, a high-concentration bleaching process, and a flotation process, and the deinking agent of the present invention may be added to each process dividedly or added at a time.The preferred amount of addition is based on the raw material. The amount is 0.2 to 10% by weight based on the waste paper.The deinking agent of the present invention contains known deinking aids such as caustic soda,
It may be used in combination with an alkaline agent such as sodium silicate or soda carbonate, a bleaching agent such as hydrogen peroxide or sodium hypochlorite, a degrading enzyme such as cellulase, or a known deinking agent. The target printed waste paper on which the deinking agent of the present invention is applied are, for example, printed materials such as newspapers, magazines, books, copy OA waste paper, imitation paper, leaflets, etc., and printed materials produced by printing methods such as letterpress printing, offset printing, and gravure printing. It can also be applied to

[Effect]

The deinking agent of the present invention is composed of (a) a compound obtained by adding a long-chain alkylene oxide and a short-chain alkylene oxide to a higher alcohol having 12 to 22 carbon atoms, and (b) a mixture of natural oils and fats and an amine compound; It is a deinking agent with excellent ink stripping properties and floating ink separation properties because it is made of a mixture of a special composition containing a reaction product with added oxide. The reaction product of component (b) is a medium molecular weight drug with a special molecular structure to which ethylene oxide, propylene oxide, etc. are appropriately added. For this reason, when used as a deinking agent during disintegration in waste paper recycling, even hard-to-remove ink derived from offset printing waste paper and information recording paper can be used as a deinking agent.
It has excellent ability to promote detachment from valve fibers and disperse into liquids through the action of hydrophobic groups. Furthermore, the combined use of component (a) helps the agglomeration of release ink particles in the floatator, increasing the ability to collect separated ink, resulting in high-quality pulp with high whiteness and a small amount of residual ink. be able to.

【Example】

Hereinafter, the present invention will be explained in detail with reference to examples, but the present invention is not limited to the examples. Component (b) of the present invention used here is shown in Table 1, and (a,
) Ingredients are shown in Table 2. In addition, % in the examples is weight %.
means. Example 1 70% of the raw material waste newspaper (offset/letterpress = 872, both 1-2 months old after printing) and 30% of the flyers were shredded and put into a pulp disintegrator (JIS P-8209) to decompose the waste paper. Based on the weight, 15% caustic soda, 40% No. 3 sodium silicate 3%, 30% hydrogen peroxide solution 3%, and Table 1,
04% of the deinking agent listed in Table 2 was added, warm water was added so that the raw material concentration was 5%, and decomposition treatment was performed at about 50° C. for 20 minutes. The disintegrated pulp slurry was aged at 50°C for 60 minutes, diluted with water so that the pulp concentration was 1.0%, added with 21.0% CaCl (based on waste paper), and subjected to a floatator. Flotation treatment was performed using - at 30°C for 10 minutes. After flotation, the valve slurry was concentrated to a concentration of 6%, then water was added to dilute it to a concentration of 1%, and the p and H values were adjusted to 5. After that, the slurry was run on a Kutsbee standard sheet machine to produce recycled paper with a basis weight of IHg/m2. Prepared. The recycled paper obtained here was measured using a colorimetric colorimeter (JISP-812).
The amount of remaining ink on this recycled paper was measured by measuring the number of unpeeled ink and remaining ink using an image processing device (x 12b times), and the results were calculated using It is shown in Table 3. Example 2 60% of raw materials used newspaper (offset/letterpress = 872. Both are from 1 to 2 months after printing), 20% of flyers,
Shred 10% of magazines and 10% of used copy OA paper, put it into a pulp disintegrator (JIS P-8209), and add 15% of caustic soda, 3% of No. 3 sodium silicate,
Add 30% hydrogen peroxide solution and 04% deinking agent listed in Tables 1 and 2, add hot water to make the raw material concentration 5%, and perform decomposition treatment at approximately 50'C for 20 minutes. I did it. After that, the same treatment as in Example 1 was performed, and the basis weight was 100 g.
/m2 of recycled paper was obtained. The whiteness, number of remaining inks, and number of unpeeled inks of the recycled paper obtained here were measured, and the results are shown in Table 4.

【Effect of the invention】

With the combination formulation of the present invention, recycled paper with high whiteness and less residual ink can be obtained regardless of the type of used printed paper,
In addition, we provide an excellent deinking agent that can be widely recycled even if used paper that is difficult to recycle gets mixed in, or even if there are changes in printing technology. It contributes widely to industry.

Claims (1)

[Claims] 1. A reaction obtained by adding an alkylene oxide to (a) a compound represented by the following general formula (1) and (b) a mixture of a natural oil and fat and an amine compound having two or more active hydrogen atoms. Product weight ratio (a)/(b) = 5/95 to 5
A deinking agent for waste paper recycling made by mixing at a ratio of 0/50. RO(C_xH_2_xO)_b(C_yH_2_yO
)_c(C_2H_2_zO)_cH・・・・・・(1
) (In the formula, R represents an alkyl group or alkenyl group having 12 to 22 carbon atoms, x is an integer of 2 to 3, y is an integer of 8 to 30, z is 2 or a mixture of 2 and 3, and b is 0 or (An integer of 1 to 30, C indicates an average equivalent of 0.2 to 5, and d indicates an integer of 1 to 100.) 2. The reaction product is a mixture of natural oil and fat and an amine compound having two or more active hydrogen atoms. 5 to 2 per mol of the sum of
2. The deinking agent according to claim 1, which is obtained by addition reaction of 00 moles of alkylene oxide. 3. The deinking agent according to claim 1 or 2, wherein the mixing ratio of the natural oil and fat and the amine compound having two or more active hydrogen atoms is in a molar ratio of 1:0.1 to 1:3.