JPH04327280A - Deiking agent - Google Patents

Abstract

PURPOSE:To obtain a deinking agent useful for deinking treatment in regenerating old paper such as newspaper and old paper of office automation, providing pulp having high b value and a small amount of unreleased ink, containing a specific compound as an essential component. CONSTITUTION:The objective deinking agent containing a compound shown by formula I or formula II (R is rosin skeleton; R<1> is 1-23C alkyl, alkenyl, aryl, rosin skeleton, etc.; AO is 2-4C alkylene oxide; n is 1-200) wherein AO in the compound consists of 2-3C ethylene oxide (EO) or propylene oxide (PO) in a mixed molar ratio of EO and PO of 0.5/1-5/1 as an essential component. The compound shown by formula I or formula II is obtained by adding an alkylene oxide to rosin alcohol in the presence of a catalyst.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deinking agent used for recycling used paper such as newspapers, magazines, and OA used paper. More specifically, a deinking agent that can obtain deinked pulp with a high b value and less unpeeled ink when deinking newspapers, magazines, OA waste paper, etc. by flotation, washing, or a combination thereof. Regarding.

0002

[Prior art and problems to be solved by the invention] Newspapers,
Recycling of magazines, OA waste paper, etc. has been carried out for a long time, but recently, the effective use of waste paper has become increasingly important, especially in conjunction with global environmental issues such as forest resource protection and garbage disposal. Furthermore, deinked pulp is increasingly being used to produce a higher grade of pulp, as seen in the use of waste newspapers to medium-quality paper. On the other hand, recently used paper is printed using printing technology.
Due to changes in printing methods, printing ink components, etc., the situation is becoming increasingly difficult from the standpoint of deinking. For this reason, improvements have been made to devices to further promote deinking. Chemicals traditionally used to separate and remove ink and other impurities from waste paper include:
As a deinking agent, along with 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. Anionic activators such as alkylbenzene sulfonates, higher alcohol sulfate ester salts, α-olefin sulfonates, dialkyl sulfosuccinates, nonionic activators such as higher alcohols, ethylene oxide adducts of alkylphenols and fatty acids, and alkanolamides. have been used singly or in combination of two or more. However, although these deinking agents have high foaming properties in flotation treatment, their ink collection ability is low, and in addition, their cleaning power is weak in washing methods, and their high foaming properties prevent foaming problems in wastewater treatment. As a result, only low grade deinked pulp was obtained. Furthermore, even with high brightness, it is dull, so there are restrictions on the use of deinked pulp (reducing the amount used under the surface of paperboard, reducing the amount added to newspapers, etc.), and bleaching agents are required to eliminate dullness. The situation forced us to increase usage. In order to obtain deinked pulp that is free from dullness and has a bright tone, it is sufficient to increase the b value of the Hunter color difference Lab display system. Deinked pulp with a high b value indicates a high removal rate of fine ink of 4 μm or less. The higher the b value, the brighter the color tone of the pulp.
It is possible to reduce the amount of bleaching agents such as hydrogen peroxide used, increase the content of deinked pulp, and use it for higher-grade applications.

There are two methods for increasing the b value: either by efficiently removing fine ink of 4 μm or less as described above, or by using a large amount of alkali. However, the latter has the drawbacks of increased stickiness, increased drainage load, and embrittlement of the pulp. Regarding the former technique of collecting and removing fine ink of 4 μm or less, several examples have been given, but none have been effective.

[0004] Higher fatty acids have been known for a long time as deinking agents with high ink collecting ability. For example, Japanese Patent Registration No. 80988, Japanese Patent Registration No. 82089, and Japanese Patent Registration No. 83901 disclose the use as a deinking agent with excellent ink collecting ability when used alone. Also, JP-A-51-13762, JP-A-53-130309, and JP-A-54-6840.
Publication No. 3 discloses that even more excellent effects can be obtained by combined use with other surfactants.

[0005] Subsequently, with the development of technology, a high-performance deinking agent was invented, which is made of a compound to which alkylene oxide such as ethylene oxide or propylene oxide is added, and which can significantly improve the whiteness of deinked pulp (
JP-A-58-109696, JP-A-59-130
400, JP-A-63-303190). However, even if the deinking agents disclosed in these techniques were used, it was not possible to obtain deinked pulp with a high b value. Furthermore, when conventionally known higher fatty acids or salts thereof are used, there is a drawback that there is a large amount of unreleased ink.

[0006]

[Means for Solving the Problems] The present inventors have demonstrated excellent ink removal ability, good operability, particularly high b value, and high whiteness in the flotation method, washing method, and a hybrid method thereof. As a result of intensive research to develop a deinking agent that can produce deinked pulp with less unpeeled ink, it was surprisingly possible to overcome the above drawbacks by using a specific compound derived from rosin. They discovered what they could do and completed the present invention.

That is, the present invention provides general formula (1) or (2)
The object of the present invention is to provide a deinking agent containing the compound represented by the following as an essential component.

[0008]

[Case 2]

(In the formula, R represents a rosin skeleton. R' represents an alkyl group, alkenyl group, cycloalkyl group, or aryl group having 1 to 23 carbon atoms, or a rosin skeleton. AO represents a rosin skeleton having 2 to 4 carbon atoms. Indicates alkylene oxide, n
is 1-200. ) Necessary functions for a deinking agent include ■ ink removal properties due to a reduction in the interfacial tension between cellulose and ink, ■ ability to prevent ink from re-adhering after being peeled off from cellulose, ■ ability to adsorb ink to air bubbles, and ■ appropriate foaming. There are four types of gender. A deinking agent must have these four functions in a well-balanced manner. The compound of the present invention is particularly excellent in the above-mentioned (1) and (2).

General formula (1) or (2) according to the present invention
It is extremely important that the compound represented by the above formula satisfies the formula, and compounds that do not meet the formula cannot obtain the significant effects of the present invention.

In general formula (1) or (2), R
has a rosin skeleton derived from rosins such as wood rosin, gum rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin, and aldehyde-modified rosin. The rosin skeleton referred to in the present invention is a group derived from an acid in rosin, including abietic acid, dehydroabietic acid, neoabietic acid, isopimaric acid, parastric acid, pimaric acid, levopimaric acid, secodehydroabietic acid, and dihydroabietic acid. It shows a substituent derived from carboxylic acid alone or a mixture thereof. Particularly preferred rosins are wood rosin, gum rosin, tall oil rosin, hydrogenated rosin, and disproportionated rosin.

In the general formula (2), when R' is an alkyl group, alkenyl group, cycloalkyl group, or aryl group, it is important that the number of carbon atoms is in the range of 1 to 23. If the number of carbon atoms in R' is less than 1, a deinked pulp with high whiteness cannot be obtained. On the other hand, when the number of carbon atoms in R' exceeds 23, the releasability of ink from cellulose decreases, so that a large amount of unremoved ink remains, resulting in deinked pulp with poor appearance. R' is preferably an alkyl group or alkenyl group having 1 to 23 carbon atoms.

[0013] AO in the general formula (1) or (2) is ethylene oxide having 2 to 4 carbon atoms (hereinafter referred to as EO);
These are alkylene oxides (hereinafter referred to as AO) such as propylene oxide (hereinafter referred to as PO) and butylene oxide (hereinafter referred to as BO). Particularly preferred are EO and PO having 2 and 3 carbon atoms. More preferably, EO and PO
In that case, the molar ratio is EO/PO=0.
5/1 to 5/1 is preferred. Also, n is 1 to 200
It is important that Particularly preferably 10 to 12
It is 0. If n is less than 1, there will be a large amount of unreleased ink, resulting in a pulp with poor appearance. n is 2
If it exceeds 0.00, foaming will increase in the flotation step, the amount of pulp flowing out will increase, and the yield will decrease significantly. In order to maintain the yield, the amount of deinking agent added must be reduced, and as a result, deinked pulp with high whiteness cannot be obtained.

General formula (1) or (2) according to the present invention
An example of the compound represented by is shown below.

[0015]

[Chemical formula 3]

The compound represented by the general formula (1) according to the present invention can be obtained by addition reaction of alkylene oxide to rosin alcohol under an alkali catalyst by a known method. Here, the rosin alcohol used as a raw material can be obtained by catalytic reduction of methyl ester of rosin such as wood rosin, gum rosin, tall oil rosin, hydrogenated rosin, and disproportionated rosin at high temperature and high pressure.

Further, the ester compound represented by the general formula (2) according to the present invention can be produced by a dehydration reaction between the alkylene oxide adduct of the rosin alcohol and a carboxylic acid or rosin (acid component in the rosin), or It can also be obtained by a dehydration reaction between a carboxylic acid or an alkylene oxide adduct of rosin and rosin alcohol.

As a raw material for the ester compound represented by the general formula (2), a carboxylic acid having a moiety corresponding to R' in the general formula (2) or a rosin (the acid component in the rosin) is used.

Specific examples of carboxylic acids include acetic acid, propionic acid, propic acid, butyric acid, isobutyric acid, tetrolic acid, valeric acid, α-methylbutyric acid, isovaleric acid, trimethylpropanoic acid, 2-pentylic acid, allyl acid, caproic acid, 2-methylpentanoic acid, 3-methylpentanoic acid,
4-isocaproic acid, 2-hexic acid, sorbic acid, 2
-hexenoic acid, 3-hexenoic acid, 4-hexenoic acid, 5-
Hexenoic acid, heptanoic acid, 2-heptenoic acid, 3-heptenoic acid, 5-heptenoic acid, 6-heptenoic acid, 2-heptonic acid, 6-heptonic acid, caprylic acid, 2-ethylhexanoic acid, 2-octenoic acid, 3-octenoic acid, 2-octinoic acid, 7-octinoic acid, 2-methyl-2-heptenoic acid, cyclohexyl acetic acid, 2-fluorovaleric acid, 2-fluorocaproic acid, 2-fluoroenantoic acid, 2-chlorocaprylic acid , 2-bromovaleric acid, 2-bromocaproic acid, 2-
Bromoenanthic acid, 2-bromocaprylic acid, 5-chlorovaleric acid, oxalic acid, malonic acid, succinic acid, glutaric acid,
Adipic acid, pimelic acid, suberic acid, ethylmalonic acid, 2-hydroxyvaleric acid, 2-hydroxycaproic acid,
2-hydroxycaprylic acid, 2-hydroxypelargonic acid, 2-hydroxyundecanoic acid, 3-hydroxycaprylic acid, 6-hydroxycaproic acid, 7-hydroxyenantoic acid, 8-hydroxycaprylic acid, 2-methyl-hydroxyenantoic acid, 2-hydroxy-3-pentenoic acid, 4-hydroxy-3-pentenoic acid, 4-hydroxy-
4-pentenoic acid, 5-hydroxy-2,4-pentadienoic acid, 2,3-dihydroxycaproic acid, 2,3
-dihydroxyenanthic acid, 2,3-dihydroxycaprylic acid, pelargonic acid, capric acid, undecanoic acid,
Lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, elaidic acid, linoleic acid, linoleic acid,
stearolic acid, ricinoleic acid, ricinoelaidic acid,
nonadecanoic acid, arachidic acid (icosanoic acid),
Heneicosanoic acid, behenic acid, brassic acid, erucic acid, tricosanoic acid, tetracosanoic acid, coconut oil, fatty acids, tallow fatty acids, palm oil fatty acids, tall oil fatty acids, rapeseed oil fatty acids, fish oil fatty acids, or semi-hardened or hardened fatty acids thereof , cyclohexylpropionic acid, cyclohexylbutyric acid, cyclohexylvaleric acid, α-cyclohexylcaprylic acid, α-cyclohexylpelargonic acid, α-cyclohexylcapric acid, α-cyclohexylundecanoic acid, α-cyclopentylcaprylic acid, α
- Cyclopentyl capric acid, benzoic acid, methylbenzoic acid, etc. may be mentioned.

[0020] Examples of the rosin used in the production of the ester compound according to the present invention include wood rosin, gum rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin, and aldehyde-modified rosin. Can be done. Depending on the manufacturing method, rosin is wood rosin,
They are classified into three types: gum rosin and tall oil rosin, and they may be used as they are, or may be hydrogenated, disproportionated, polymerized, maleated, or modified with aldehyde. Hydrogenated rosin is generally a rosin compound obtained by hydrogenating rosin under a noble metal catalyst at high temperature and high pressure, and the main components are tetrahydroabietic acid and dihydroabietic acid. Disproportionated rosin is a rosin compound that can be heated at high temperatures using a noble metal catalyst or a halogen catalyst in order to eliminate conjugated double bonds that are unstable to radical species.The main components are tetrahydroabietic acid and dihydroabietic acid. It is an acid. Polymerized rosin is obtained by treatment under an acidic catalyst. Maleated rosin can be obtained by the Diels-Alder reaction of rosin and maleic acid. Aldehyde-modified rosin can be obtained by subjecting rosin and formaldehyde to a Prince reaction under an acid catalyst.

The deinking agent of the present invention has both ink cohesion and ink releasability, which conventionally known compounds could not have, and excellent deinking effects can be obtained even when used alone.
If necessary, a conventionally known deinking agent can be used in combination. When a conventionally known deinking agent is used in combination, the weight ratio of the inventive product/conventional product is preferably 95/5 to 5/95, particularly preferably 70/30 to 30/70. Conventionally known deinking agents include, for example, higher alcohol sulfates, polyoxyalkylene higher alcohol sulfates, alkylbenzene sulfonates, higher fatty acids and their salts, alkylene oxide adducts of higher alcohols and alkylphenols, and the like.

The deinking agent of the present invention can be added to any process to obtain deinked pulp of higher quality. Generally, a deinking agent is added to either the mixing step or the flotation step, or both. The deinking agent of the present invention also conforms to this. If added separately to each process, it can be added to each process of pulping, kneading, dispersing, chemical mixing, and refining.
The dividing ratio of the deinking agent in the front process and the back process is 10/90 to 90.
/10 (weight ratio) is preferable. Particularly preferably 40/
60 to 60/40 (weight ratio). The amount of deinking agent added should preferably be within an economical range without impairing operability.
It is preferably 0.03 to 1.0% by weight based on the raw material waste paper.

[0023]

[Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

Production Example 1 Hydrogenated methyl abietate (trade name "Hercolyn")
(manufactured by Hercules Powder Co., Ltd.) was stirred and reacted at 50°C in the presence of 92 g of sodium and 296 g of t-butyl alcohol based on the Bouveau-Blanc reaction. When filtered, the yield was 90%. This is 1
．． 110g of KOH in a 5 liter autoclave
The reaction was carried out while 576 g of ethylene oxide was introduced under pressure using a pump, and the target compound was obtained (product of the present invention, No. 1 in Table 1). The reaction conditions are temperature 15
The temperature was controlled at 0°C and 3 atm.

Example 1 This example is an example of adding a deinking agent all at once during the pulping process. After shredding municipally collected newspapers into 2 x 5 cm pieces, put a certain amount of them into a tabletop disintegrator, and add water, caustic soda (based on raw materials) 0.8% (based on weight, the same applies hereinafter), and sodium silicate.
(based on raw materials) 2.2%, 30% hydrogen peroxide solution (based on raw materials) 3
．． 5%, various deinking agents shown in Table 1 (based on raw materials) 0.5%
was added and disintegrated at 45°C for 12 minutes at a pulp concentration of 15%, and then aged at 55°C for 120 minutes. The material was dehydrated to 23% using a high-speed dehydrator, and kneaded using a twin-screw lab kneader at a rotation speed of 300 rpm. After that, add water to dilute the pulp to 4%, and use a tabletop disintegrator again for 30% pulp.
It disintegrated for seconds. Then, water was added to dilute the pulp to a concentration of 1%, and 0.5% of calcium chloride (based on raw materials) was added.
Flotation treatment was performed at 30°C for 10 minutes. Next, the pulp slurry after flotation was concentrated to a concentration of 4% using an 80 mesh wire, water was added to dilute the slurry to a concentration of 1%, and a pulp sheet was created using a TAPPI sheet machine. The hardness of the water used was 5°dH, and the hardness was CaCl2 and MgCl2, with Ca/Mg=
Adjustment was made so that the molar ratio was 8/2. The b value of the obtained pulp sheet was measured using a side color difference meter (diffuse reflection type),
The number of unpeeled inks was measured using an image analyzer (×100). The results are shown in Table 1. The b value here refers to the b value in the Hunter color difference Lab color system, and the tristimulus value
The relationship with YZ is as shown below.

[0026]

[Math 1]

As can be seen from this equation, the b value is a function of Y and Z, and a positive value indicates the intensity of yellowness, and a negative value indicates the intensity of bluishness.

[0028]

[Table 1]

[0029]

[Table 2]

Example 2 This example is an example in which a deinking agent is added separately in the pulping process and the chemical mixing process. 2 x 5 recycled newspapers collected in the city
After shredding into cm pieces, put a certain amount of it into a tabletop disintegrator, and add water, 0.2% of caustic soda (based on the raw material), and 0.1% of the various deinking agents shown in Table 2 (based on the raw material). After disintegration at 50°C for 15 minutes at a pulp concentration of 5%, the pulp was dehydrated to a pulp concentration of 18%, and 0.6% of caustic soda (based on the raw material) was added.
%, sodium silicate (based on the raw material) 2.2%, 30% hydrogen peroxide solution (based on the raw material) 3.5%, various deinking agents shown in Table 2 (based on the raw material) 0.2% were added, and water was added. The pulp concentration was adjusted to 15% and mixed for 1 minute using a tabletop disintegrator. 55℃, 120
Aging treatment was performed for 15 minutes at a pulp concentration of 15%. After that, water was added so that the pulp concentration was 4%, and the pulp was disintegrated for 3 minutes using a tabletop disintegrator.Water was then added to dilute the pulp concentration to 1%, and 0.5% calcium chloride (based on the raw material) was added. ,
Flotation treatment was performed at 30°C for 10 minutes. Next, the pulp slurry after flotation was concentrated to a concentration of 6% using an 80 mesh wire, water was added to dilute it to a concentration of 1%, and a pulp sheet was created using a TAPPI sheet machine. The hardness of the water used was 5°dH, and the hardness was CaCl2 and MgCl2, with Ca/Mg=
Adjustment was made so that the molar ratio was 8/2. The b value of the obtained pulp sheet was measured using a colorimeter (diffuse reflection type),
The number of unpeeled inks was measured using an image analyzer (×100). The results are shown in Table 2.

[0031]

[Table 3]

Example 3 This example is an example in which a deinking agent is added separately in the pulping process and the kneading process. After shredding municipally collected newspaper waste into 2 x 5 cm pieces, put a certain amount of it into a tabletop disintegrator, and add water, 0.2% caustic soda (based on the raw material), and various deinking agents (based on the material) shown in Table 3. Raw materials) Add 0.2%, pulp concentration 5%, 5
After disintegration at 0°C for 15 minutes, the pulp was dehydrated to a pulp concentration of 28%, and the pulp was mixed with 0.6% caustic soda (based on raw materials), 2.2% sodium silicate (based on raw materials), and 30% hydrogen peroxide solution. (
3.5% (based on raw materials) and 0.2% of various deinking agents (based on raw materials) shown in Table 3 were added, and the pulp concentration was adjusted to 25% with water.
Kneading treatment was performed using a two-screw lab kneader with a rotation speed of 300 rpm. After that, aging treatment was carried out at 55℃ for 120 minutes at a pulp concentration of 25%, and then at a pulp concentration of 4%.
Water was added to the pulp and disintegrated for 3 minutes using a bench-top disintegrator.Water was further added to dilute the pulp to 1%, and flotation was carried out at 30°C for 10 minutes. Next, the pulp slurry after flotation was concentrated to a concentration of 6% using an 80 mesh wire, and then water was added to dilute it to a concentration of 1%.
A pulp sheet was created using a TAPPI sheet machine. The hardness of the water used was 10°dH, and the hardness was Ca
Using Cl2, MgCl2, Ca/Mg=8/2
(molar ratio). The b value of the obtained pulp sheet was measured using a colorimeter (diffuse reflection type), and the number of unpeeled inks was measured using an image analyzer (x100). The results are shown in Table 3.

[0033]

[Table 4]

Example 4 This example is an example in which a deinking agent is added separately in the pulping process and the flotation process. Municipally collected newspaper waste 2 x 5 cm
After shredding, put a certain amount of it into a tabletop disintegrator, add water and 0.2% of caustic soda (based on the raw material), and 0.2% of the various deinking agents shown in Table 4 (based on the raw material). Pulp concentration 15%
After disintegrating at 45°C for 12 minutes, the mixture was aged at 55°C for 120 minutes. After that, it was dehydrated to 23% using a high-speed dehydrator.
Caustic soda (based on raw materials) 0.6%, sodium silicate (based on raw materials) 2.2%, 30% hydrogen peroxide (based on raw materials) 3.5%
% was added, the pulp concentration was adjusted to 22% with water, and the mixture was mixed for 1 minute using a tabletop disintegrator. After that, the rotation speed is 300 rpm.
Kneading treatment was performed using a shaft-type lab kneader. Thereafter, water was added to dilute the pulp to a concentration of 4%, and the mixture was disintegrated again for 30 seconds using a tabletop disintegrator. Thereafter, 0.3% of various deinking agents (based on raw materials) shown in Table 4 were added, the pulp concentration was diluted to 1% with water, and then flotation treatment was performed at 30° C. for 10 minutes. Next, the pulp slurry after flotation was concentrated to a concentration of 4% using a 60 mesh wire, water was added to dilute the slurry to a concentration of 1%, and a pulp sheet was prepared using a TAPPI sheet machine. The hardness of the water used was 4.
The hardness was adjusted to Ca/Mg=8/2 (molar ratio) using CaCl2 and MgCl2. The b value of the obtained pulp sheet was measured using a colorimeter (diffuse reflection type), and the number of unpeeled inks was measured using an image analyzer (x100). The results are shown in Table 4.

[0035]

[Table 5]

Claims (2)

[Claims] 1. A deinking agent containing a compound represented by the general formula (1) or (2) as an essential component. [Formula 1] (In the formula, R represents a rosin skeleton. R' has 1 to 2 carbon atoms.
3 represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a rosin skeleton. AO represents alkylene oxide having 2 to 4 carbon atoms, and n is 1 to 20
It is 0. ) [Claim 2] R in general formula (2)
2. The deinking agent according to claim 1, wherein ' is an alkyl group or an alkenyl group having 1 to 23 carbon atoms.