JP2931433B2 - 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 deinking agent used for recycling used paper such as newspapers, magazines and OA used paper. More specifically, a deinking agent that can obtain a deinked pulp having a high b value and a small amount of unstripped ink when deinking a newspaper, magazine, OA waste paper, etc. by a flotation method, a cleaning method or a compromise method thereof. About.

[0002]

BACKGROUND OF THE INVENTION Newspapers,
Recycling of magazines, OA waste paper, and the like has been practiced for a long time, but recently, in conjunction with global environmental issues such as protection of forest resources and garbage disposal, the effective use of waste paper is increasing in importance. In addition, the use of deinked pulp has been advanced to higher-grade pulp as seen in the example of used newspaper to medium-grade paper. On the other hand, recently used paper is becoming more severe from the viewpoint of deinking due to changes in printing technology, printing method, printing ink components, and the like. Therefore, in order to further promote deinking, improvements have been made to the apparatus. Chemicals conventionally used to separate and remove ink and other impurities from waste paper include alkaline agents such as caustic soda, sodium silicate, sodium carbonate, and sodium phosphate, hydrogen peroxide, hyposulfite, and hypochlorous acid. Bleaching agents such as salts, sequestering agents such as EDTA and DTPA, and anionic surfactants such as alkylbenzene sulfonates, higher alcohol sulfates, α-olefin sulfonates, and dialkyl sulfosuccinates as deinking agents. Nonionic activators such as ethylene oxide adducts of higher alcohols, alkylphenols and fatty acids, and alkanolamides have been used alone or in combination of two or more. However, these deinking agents have a high foaming property in the flotation process, but have a low ink collecting ability.The cleaning method has a low detergency. And resulted in only low grade deinked pulp. Furthermore, because there is dullness even with high whiteness,
The use of bleaching agents had to be increased in order to eliminate the use of deinked pulp (for example, reducing the amount of paperboard used below and below, and reducing the amount used in newspapers) and eliminating dullness. To obtain a deinked pulp having a dull color and a bright color tone, the b value of the Hunter color difference type Lab display system may be increased. The deinked pulp having a high b value has a high removal rate of fine ink of 4 μm or less. If the b value is high, the color tone of the pulp becomes bright, so that the use of bleaching agents such as hydrogen peroxide can be reduced, the deinked pulp can be highly blended, and it can be used for one-grade applications.

[0003] There are two methods for increasing the b value, such as a method of efficiently removing fine ink of 4 µm or less as described above or a method of using a large amount of alkalis.
However, the latter has the disadvantage that sticky (adhesive) increases, drainage load increases, and pulp becomes brittle. There are some examples of the former technique for collecting and removing fine ink of 4 μm or less, but none of them is effective.

[0004] Higher fatty acids have long been known as deinking agents having a large 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 having excellent ink collecting ability when used alone. Also, JP-A-51-13762, JP-A-53-130309, and JP-A-54-6840.
No. 3 discloses that more excellent effects can be obtained when used in combination with another surfactant.

[0005] Subsequently, with the development of technology, the invention of a high-performance deinking agent comprising a compound to which an alkylene oxide such as ethylene oxide or propylene oxide was added to improve the whiteness of deinked pulp remarkably was made. JP-A-58-109696, JP-A-59-13
0400, JP-A-63-303190).
However, even with the use of the deinking agents disclosed in these techniques, high-b-value deinked pulp could not be obtained. When a conventionally known higher fatty acid or a salt thereof is used,
There was a disadvantage that there were many unstripped inks.

[0006]

Means for Solving the Problems The present inventors have demonstrated excellent ink removing ability, good operability, especially high b-value and high whiteness in the flotation method, the washing method and their compromise method. As a result of intensive research to develop a deinking agent that can obtain deinked pulp with less unstripped ink, the surprisingly, the above-mentioned drawbacks were overcome by using a specific compound derived from rosin. They found what they could do and completed the present invention.

That is, the present invention provides a deinking agent comprising a compound represented by the general formula (1) or (2) as an essential component.

[0008]

Embedded image

(Wherein, 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. Represents an alkylene oxide, wherein n is 1 to 20
0. ) Four functions necessary for the deinking agent are: ink releasability due to a decrease in the interfacial tension between cellulose and ink, prevention of re-adhesion of ink peeled from cellulose, ink absorption to air bubbles, and proper foaming properties. Can be mentioned. The deinking agent must have these four functions in a well-balanced manner. The compounds of the present invention are particularly excellent in the above.

It is very important that the compound represented by the general formula (1) or (2) according to the present invention satisfies the formula. Can not get.

In the general formula (1) or (2), R is derived from rosin such as wood rosin, gum rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin, aldehyde-modified rosin and the like. It has a rosin skeleton. The rosin skeleton referred to in the present invention is a group derived from an acid in rosin, and is abietic acid, dehydroabietic acid, neoabietic acid, isopimaric acid, parastolic acid, pimaric acid, levopimaric acid, secodehydroabietic acid, dihydroabietic acid. And the like, or a substituent derived from a 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, an alkenyl group, a cycloalkyl group or an aryl group, it is important that the number of carbon atoms is in the range of 1 to 23. If the carbon number of R ′ is less than 1, high-whiteness deinked pulp cannot be obtained. On the other hand, when the carbon number of R ′ exceeds 23, the ink releasability from cellulose becomes small, so that the remaining amount of unreleased ink is large and only deinked pulp with poor appearance can be obtained. R 'is preferably an alkyl group or an alkenyl group having 1 to 23 carbon atoms.

AO in the general formula (1) or (2) has 2 to 4 carbon atoms.
Of ethylene oxide (hereinafter referred to as EO), propylene oxide (hereinafter referred to as PO), and butylene oxide (hereinafter referred to as PO)
Alkylene oxide (hereinafter referred to as AO) such as BO)
It is. Particularly preferred are EO and PO having 2 and 3 carbon atoms. More preferably, it is a mixture of EO and PO, and the molar ratio in that case is preferably EO / PO = 0.5 / 1 to 5/1. It is important that n is 1 to 200. Particularly preferred is 10 to 120. When n is smaller than 1, the unstripped ink increases, and only pulp with poor appearance is obtained. n
If it exceeds 200, foaming will increase in the flotation step, the pulp flow will increase, and the yield will decrease significantly. In order to maintain the yield, the amount of the deinking agent added must be reduced, and as a result, deinked pulp with high whiteness cannot be obtained.

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

[0015]

Embedded image

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

The ester compound represented by the general formula (2) according to the present invention can be obtained by a dehydration reaction between the above-mentioned alkylene oxide adduct of rosin alcohol and carboxylic acid or rosin (acid component in 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 or a rosin (acid component in the rosin) having a portion corresponding to R ′ in the general formula (2) is used.

Specific examples of the carboxylic acid 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, and allyl Acid, caproic acid, 2-methylpentanoic acid, 3-methylpentanoic acid,
4-isocaproic acid, 2-hexynic acid, sorbic acid, 2
-Hexenoic acid, 3-hexenoic acid, 4-hexanoic acid, 5-
Hexenoic acid, heptanoic acid, 2-heptenoic acid, 3-heptenoic acid, 5-heptenoic acid, 6-heptenoic acid, 2-heptic acid, 6-heptic acid, caprylic acid, 2-ethylhexanoic acid, 2-octenoic acid, 3-octenoic acid, 2-octic acid, 7-octic acid, 2-methyl-2-heptenoic acid, cyclohexylacetic acid, 2-fluorovaleric acid, 2-fluorocaproic acid, 2-fluoroenanthic 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-hydroxy Caproic acid, 2-hydroxycaprylic acid, 2-hydroxypelargonic acid, 2-hydroxyundecanoic acid, 3-hydroxycaprylic acid, 6-hydroxycaproic acid, 7-hydroxyenanthic acid, 8-hydroxycaprylic acid, 2-methyl-hydroxy Enanthic 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 (eicosanoic acid ), Heneicosanoic acid, behenic acid, brassic acid, erucic acid, tricosanoic acid, tetracosanoic acid, coconut oil, fatty acids, tallow fatty acids,
Palm oil fatty acid, tall oil fatty acid, rapeseed oil fatty acid, fish oil fatty acid, or semi-hardened or hardened fatty acid thereof, cyclohexylpropionic acid, cyclohexylbutyric acid, cyclohexylvaleric acid, α-cyclohexylcaprylic acid, α-cyclohexylperargonic acid, α −
Cyclohexylcapric acid, α-cyclohexylundenic acid, α-cyclopentylcaprylic acid, α-cyclopentylcapric acid, benzoic acid, methylbenzoic acid and the like can be mentioned.

The rosin used in the production of the ester compound according to the present invention includes wood rosin, gum rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin, and aldehyde-modified rosin. Can be. Rosin is wood rosin,
Gum rosin and tall oil rosin are classified into three types, and they may be used as they are, or may be hydrogenated, disproportionated, polymerized, maleated, or aldehyde-modified. Hydrogenated rosin is generally a rosin compound obtained by hydrogenating rosin under a noble metal catalyst under high temperature and high pressure, and its main components are tetrahydroabietic acid and dihydroabietic acid. Disproportionated rosin is a rosin compound that can be heated at a high temperature using a noble metal catalyst or a halogen catalyst in order to eliminate conjugated double bonds that are unstable to radical species, and the main components are tetrahydroabietic acid and dihydroabietine. Is an acid. The polymerized rosin is obtained by treating under an acidic catalyst. Maleated rosin can be obtained by the Diels-Alder reaction between rosin and maleic acid. Aldehyde-modified rosin can be obtained by performing a Prince reaction between rosin and formaldehyde in the presence of an acid catalyst.

The deinking agent of the present invention has both ink cohesiveness and ink releasability which could not be obtained by a conventionally known compound, and can provide an excellent deinking effect 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 compounding ratio of the present invention / conventional product is preferably from 95/5 to 5/95, particularly preferably from 70/30 to 30/70 by weight. Conventionally known deinking agents include, for example, higher alcohol sulfates, polyoxyalkylene higher alcohol sulfates, alkylbenzene sulfonates, higher fatty acids and salts thereof, and alkylene oxide adducts of higher alcohols and alkylphenols.

When the deinking agent of the present invention is added to any of the steps, higher quality deinked pulp can be obtained. Generally, the deinking agent is added to either or both the mixing step and the flotation step. The deinking agent of the present invention conforms to this. When divided addition in each step, it can be added to each step of pulping, kneading, dispersing, chemical mixing, refining,
The split ratio of the deinking agent in the pre-process and post-process is 10/90 to 90/10
(Weight ratio) is preferred. Particularly preferably 40 / 60-60 /
40 (weight ratio). The amount of the deinking agent added should not be impaired in operability and should be economical.
0.03 to 1.0% by weight is preferred.

[0023]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

Production Example 1 316 g of hydrogenated methyl abietic acid (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 Bouvot-Bran reaction. Was. After filtration, the yield was 90%. This was charged into a 1.5 liter autoclave with 110 g of KOH, and reacted while pressing 576 g of ethylene oxide with a pump to obtain a target compound (product of the present invention, No. 1 in Table 1). The reaction conditions are temperature
The temperature was controlled at 150 ° C. and 3 atm.

Example 1 This example is an example of batch addition of a deinking agent in a pulping step. After the used newspaper collected in the city is cut into 2 x 5 cm pieces, a certain amount is placed in a table disintegrator, in which water and caustic soda (based on raw materials) 0.8% (by weight, the same applies hereinafter), sodium silicate (based on raw materials) 2.2%, 30% hydrogen peroxide solution (based on raw material) 3.5%, various deinking agents shown in Table 1 (based on raw material) 0.5%, and pulp concentration
After fibrillating at 15% at 45 ° C for 12 minutes, it was aged at 55 ° C for 120 minutes. Dehydrate to 23% with high-speed dehydrator, rotation speed 30
The kneading process was performed by a 2-axis lab kneader at 0 rpm. Thereafter, water was added to dilute the pulp to a pulp concentration of 4%, and the mixture was defibrated with a desktop disintegrator for 30 seconds. Thereafter, water was added to dilute the pulp to a concentration of 1%, and calcium chloride (based on raw material) 0.5
%, And a flotation treatment was performed at 30 ° C. for 10 minutes. Next, the pulp slurry after flotation is concentrated to a concentration of 4% with an 80 mesh wire, and water is added to the pulp slurry to form a 1% concentration.
The pulp sheet was diluted to a concentration and a pulp sheet was prepared using a TAPPI sheet machine. The hardness of the water used was 5 ° dH, and the hardness was CaCl ₂ or MgCl ₂ , and Ca / Mg = 8/2.
(Molar ratio). The b value of the obtained pulp sheet was measured by a side color difference meter (diffuse reflection type), and the number of unstripped ink was measured by an image analyzer (× 100). Table 1 shows the results. Here, the b value refers to the b value in the Lab color system of the Hunter color difference formula, and the relationship with the tristimulus value XYZ is as follows.

[0026]

(Equation 1)

As can be seen from this equation, the b value is a function of Y and Z, with a positive value representing yellowish intensity and a negative value representing blueish intensity.

[0028]

[Table 1]

[0029]

[Table 2]

Example 2 This example is an example of the divisional addition of the deinking agent in the pulping step and the chemical mixing step. 2 x 5 used newspapers collected in the city
After chopping into pieces, a certain amount was put into a tabletop disintegrator, into which water and caustic soda (based on raw materials) 0.2%, and various deinking agents (based on raw materials) 0.1% shown in Table 2 were added. %, 50 ℃,
After fibrillation for 15 minutes, dehydrate the pulp to 18% concentration, and add 0.6% of sodium hydroxide (based on raw material), 2.2% of sodium silicate (based on raw material), 3.5% of 30% hydrogen peroxide (based on raw material), Table 2
Each of the various deinking agents (based on the raw material) shown in (1) was added at 0.2%, the pulp concentration was adjusted to 15% with water, and mixed for 1 minute using a desktop disintegrator. 55
The ripening treatment was performed at a pulp concentration of 15% at 120 ° C for 120 minutes. Then add water to a pulp concentration of 4%, and add 3
Disintegration treatment for 1 minute, further adding water to reduce the pulp concentration to 1%
And add 0.5% of calcium chloride (based on raw material)
A flotation treatment was performed at 30 ° C. for 10 minutes. Then
The pulp slurry after flotation was concentrated to 6% concentration with an 80 mesh wire, and then diluted to 1% concentration by adding water, and a pulp sheet was prepared using a TAPPI sheet machine. The hardness of the used water was 5 dH and the hardness was Ca
It was adjusted so that Ca / Mg = 8/2 (molar ratio) using Cl ₂ and MgCl ₂ . The b value of the obtained pulp sheet was measured with a colorimeter (diffuse reflection type), and an image analyzer (× 10
In 0), the number of unstripped inks was measured. Table 2 shows the results.

[0031]

[Table 3]

Example 3 This example is an example of adding the deinking agent in the pulping step and the kneading step separately. The used newspaper collected in the market is cut into 2 x 5 cm pieces, and a certain amount is placed in a tabletop disintegrator, in which water and caustic soda (based on raw materials) are 0.2%, and various deinking agents shown in Table 3 (based on raw materials). Add 0.2%, defibrate for 15 minutes at 50 ° C, pulp concentration of 5%, dehydrate to a pulp concentration of 28%, and add caustic soda (based on raw material) 0.6% and sodium silicate (based on raw material) 2.
2%, 30% aqueous hydrogen peroxide (based on raw material) 3.5%, various deinking agents shown in Table 3 (based on raw material) 0.2%, and pulp concentration in water
It was adjusted to 25%, and kneading treatment was performed using a biaxial lab kneader having a rotation speed of 300 rpm. After that, aging treatment is performed at 55 ° C for 120 minutes at a pulp concentration of 25%, and then a pulp concentration of 4%
Was added to the mixture, and the mixture was subjected to a defibration treatment for 3 minutes using a desktop disintegrator, further diluted with water to a pulp concentration of 1%, and subjected to a flotation treatment at 30 ° C. for 10 minutes. Next, the pulp slurry after flotation was treated with 80 mesh wire for 6 hours.
After concentrating to 1% concentration, add water to dilute to 1% concentration,
A pulp sheet was prepared using a PPI sheet machine. still,
The hardness of the water used was 10 ° dH, the hardness was CaCl ₂ , Mg
It was adjusted to be Ca / Mg = 8/2 (molar ratio) using Cl ₂ . The b value of the obtained pulp sheet was measured by a colorimeter (diffuse reflection type), and the number of unstripped ink was measured by an image analyzer (× 100). Table 3 shows the results.

[0033]

[Table 4]

Embodiment 4 This embodiment is an example in which the deinking agent is added separately in the pulping step and the flotation step. The used paper collected in the market is shredded to 2 x 5 cm, and a certain amount is placed in a tabletop disintegrator, in which 0.2% of water and caustic soda (based on raw materials), various deinking agents shown in Table 4 (based on raw materials) 0.2% was added, pulp concentration was 15%, defibration was performed at 45 ° C for 12 minutes, and ripening was performed at 55 ° C for 120 minutes. After that, dehydrate to 23% with high-speed dehydrator, and use caustic soda (based on raw material) 0.6
%, Sodium silicate (based on raw material) 2.2%, and 30% aqueous hydrogen peroxide (based on raw material) 3.5%. The pulp concentration was adjusted to 22% with water, and the mixture was mixed for 1 minute using a desktop disintegrator. After that, rotation speed 300r
The kneading process was performed using a two-axis lab kneader of pm.
Thereafter, water was added to dilute the pulp to a pulp concentration of 4%, and the mixture was defibrated with a desktop disintegrator for 30 seconds. Thereafter, 0.3% of various deinking agents (based on raw materials) shown in Table 4 were added, and the pulp concentration was adjusted to 1% with water.
And then subjected to a flotation treatment at 30 ° C. for 10 minutes. Next, the pulp slurry after flotation was
After concentrating to 4% concentration with a mesh wire, add water and add
%, And a pulp sheet was prepared using a TAPPI sheet machine. The hardness of the water used was 40 ° dH, and the hardness was CaCl ₂ or MgCl ₂ , and Ca / Mg = 8/2.
(Molar ratio). The b value of the obtained pulp sheet was measured by a colorimeter (diffuse reflection type), and the number of unstripped ink was measured by an image analyzer (× 100). Table 4 shows the results.

[0035]

[Table 5]

Claims (2)

(57) [Claims] 1. A deinking agent comprising a compound represented by the general formula (1) or (2) as an essential component. Embedded image (Wherein, R represents a rosin skeleton; R ′ represents an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group having 1 to 23 carbon atoms, or a rosin skeleton. AO represents an alkylene oxide having 2 to 4 carbon atoms. And n is 1 to 200.) 2. The deinking agent according to claim 1, wherein R ′ in the general formula (2) is an alkyl or alkenyl group having 1 to 23 carbon atoms.