JP3422984B2 - 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 when recycling used paper such as newspapers and magazines.

[0002]

2. Description of the Related Art The effective use of waste paper is becoming more important in connection with global environmental issues such as forest resource protection and waste disposal. When using deinked pulp recycled from waste paper, it is necessary to obtain deinked pulp with higher quality, that is, less residual ink, in order to achieve a high blending ratio. Deinking is
It is necessary to efficiently perform deinking that separates ink from paper and removal of ink that separates the separated ink from pulp. With regard to deinking agents, deinking agents with good ink releasability and ink collecting properties, and deinking methods Development is desired.

The development of the deinking agent was initially due to the progress of printing technology,
Starting from the direction of strengthening the ink releasability due to the deterioration of waste paper in the recovery cycle of waste paper, and the combination of fatty acid, fatty acid alkylene oxide (hereinafter referred to as AO) adduct, higher alcohol AO adduct, alkyl group and AO adduct form. It has been. Among these, the fatty acid AO adduct is excellent in the ability to collect the peeled ink, and is currently used as a general deinking agent. For the examination of fatty acid AO adducts, see, for example, JP-A-3-146780 and JP-A 3-1.
No. 93986 discloses a deinking agent containing an adduct formed by adding 300 moles or less of AO to a dimer acid or a polymer acid or its ester as a main component. Further, JP-A-6-108390 discloses a deinking agent containing an ester mixture obtained by adding AO in a range of more than 300 and 1,000 or less to a mixture of polycarboxylic acid and alcohol.

However, JP-A-3-146780.
JP-A-3-193986, JP-A-6-10839
It has been found that the No. 0 deinking agent often causes deterioration of the quality of recycled paper depending on the conditions of used paper. Specifically, the peeling of the ink progresses under the influence of heat, ultraviolet rays, or long-term storage in the summer. For this reason, implement measures such as increasing mechanical power and adding alkali and deinking agent,
Although the amount of unpeeled ink is reduced, as a result, defective removal of ink occurs due to the miniaturization of the peeled ink, and in reality, it is not possible to sufficiently cope with the deterioration of quality due to dullness.

[0005]

The object of the present invention is to show sufficient ink-collecting property not only under normal operating conditions but also for fine ink generated when recycled deteriorated waste paper is regenerated. It is intended to provide a deinking agent that exhibits a high deinking effect.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have studied the deinking performance of the arrangement pattern of AO adducts according to the prior art, and as a result, in the case of containing two or more kinds of AO, the ink affinity and the defoaming property are improved. It has been found that a reaction product obtained by adding propylene oxide alone having the above formula in the final addition step is effective for solving the above problems.

That is, the present invention comprises a reaction product obtained by adding two or more kinds of AO to (a) a mixture or ester of a polycarboxylic acid or its acid anhydride and (b) an alcohol. A deinking agent, in which the AO is added in a two-step addition process, and the AO added in the first addition process is ethylene oxide (hereinafter referred to as EO) and propylene oxide (hereinafter referred to as PO) )
AO mixture of AO added in the last addition step
Relates to a deinking agent which is PO alone.

The present invention also includes a reaction product obtained by adding two or more kinds of AO to (a) a mixture or ester of a polycarboxylic acid or its acid anhydride and (b) an alcohol. The present invention relates to a deinking agent, wherein the AO is added in three or more adding steps, and the AO added in the last adding step is PO alone.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION (a) Polyvalent carboxylic acid or acid anhydride thereof used in the present invention includes oxalic acid, malonic acid, succinic acid, methylsuccinic acid, maleic acid, glutaric acid, adipic acid and phthalic acid. , Fumaric acid, itaconic acid, malic acid, tartaric acid, maleated oleic acid, citric acid, percitric acid, trimellitic acid, butanetetracarboxylic acid,
Pyromellitic acid, tetradecane hexacarboxylic acid, maleic anhydride, succinic anhydride, oxalic anhydride, itaconic anhydride, glutaric anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, stearyl succinic anhydride,
Further, dimer acid of higher fatty acid having 14 to 22 carbon atoms and /
Or polymeric acids are also included. The dimer acid and / or polymer acid referred to here is a method in which an unsaturated fatty acid monomer such as monoenoic acid or dienoic acid, specifically oleic acid, linoleic acid, or linolenic acid is reacted by thermal polymerization such as Diels-Alder reaction. Alternatively, it can be synthesized by another reaction method. Further, the polymer acid referred to here is a polycarboxylic acid having three or more carboxyl groups in one molecule and does not include dimer acid. An unreacted monomer acid may remain in the produced dimer acid and / or polymer acid as long as the effects of the present invention are not impaired. As (a), a dimer acid and / or polymer acid of an unsaturated fatty acid having 12 to 32 carbon atoms is preferable, and further, the carbon number of the unsaturated fatty acid is more preferably 16 to 22, and particularly preferably 18 to 21.

Examples of the alcohol (b) used in the present invention include monohydric or polyhydric alcohols. The monohydric alcohol used in the present invention has 6 to 6 carbon atoms.
24 alcohol-1, alcohol-2, unsaturated alcohol, branched chain alcohol, cyclic alcohol can be mentioned, and specifically, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1- Dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1
-Heptadecanol, 1-octadecanol, 1-nonadecanol, 1-icosanol, 1-henicosanol, 1-docosanol, 1-tricosanol, 1-tetracosanol, 2-octanol, 2-nonanol, 2
-Decanol, 2-undecanol, 2-dodecanol, 2-tridecanol, 2-tetradecanol, 2-
Pentadecanol, 2-hexadecanol, 2-heptadecanol, 2-octadecanol, 2-nonadecanol, 2-icosanol, 2-octen-1-ol, 2
-Dodecen-1-ol, 2-undecen-1-ol, 2-tetradecen-1-ol, 2-pentadecen-1-ol, 2-hexadecen-1-ol, 2-octadecen-1-ol, 8-nonene -1-all, 1
0-undecen-1-ol, 11-dodecen-1-ol, 12-tridecen-1-ol, 15-hexadecen-1-ol, oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenyl alcohol, eleo Stearyl alcohol, ricinoyl alcohol, cyclononanol, cyclodecanol, cycloundecanol, cyclododecanol, cyclotridecanol, cyclotetradecanol, cyclopentadecanol, cyclohexadecanol, cycloheptadecanol, cyclo Octadecanol, cyclononadecanol,
Examples thereof include cyclocosanol, octylphenol, nonylphenol, isohexyl alcohol, 2-ethylhexyl alcohol, 3-methyl-pentanol, isooleyl alcohol and isostearyl alcohol.

The polyhydric alcohol has 2 carbon atoms.
And hexane-1,2-diol, diglycerin, polyglycerin, ethylene glycol, propylene glycol, trimethylene glycol, butylene glycol, 1,6. -Hexane glycol, 2-ethylbutane-1,2,3-triol, glycerin, trimethylolpropane, trimethylolethane, 1,2,4-butanetriol, 1,2,6-hexanetriol, 1,1,
1-trimethylolhexane, erythrose, erythrulose, erythritol, threose, pentaerythritol, arabinose, xylose, xylulose, deoxyribose, lyxose, ribulose, ribose,
Arabitol, ribitol, altrose, allose,
Galactose, growth, mannose, glycitol,
Inositol, mannitol, sorbitol, tetraglycerin, heptose, heptose, octitol, octulose, nonulose, agarobiose, cellobiose, maltose, lactose, gentianose,
Stachyose, cellotriose, etc. can be mentioned.

As (b), a monohydric alcohol having 6 to 22 carbon atoms is preferable, and a monohydric alcohol having 8 to 18 carbon atoms is particularly preferable.

In the present invention, the molar ratio of (a) polycarboxylic acid or its acid anhydride and (b) alcohol is (a) / (b) = 1 / from the viewpoint of the aggregation effect of the fine ink.
It is 0.02 to 1/5, preferably 1 / 0.1 to 1/3.

In the present invention, a mixture or ester of the polyvalent carboxylic acid (a) or its acid anhydride and the alcohol (b) can be used. The ester can be obtained, for example, by subjecting a mixture of (a) and (b) to a dehydration reaction under alkaline conditions.

In the present invention, the AO to be added to the mixture (a) or (b) or the ester has 2 carbon atoms.
AO of 4 to 4 are preferable, and examples thereof include EO, PO, butylene oxide (hereinafter abbreviated as BO), and at least two of them are added.

The addition of AO to the mixture or ester of the above (a) and (b) is carried out by two or more steps, preferably three or more steps. Also, from the productivity, 5
Addition steps up to and including stages are preferred, and up to and including 4 steps are particularly preferred. Then, in the case where the addition step is two steps, the mixture of EO and PO is added to the first (first step) addition step, and PO is added in the last (second step) addition step. In addition, in the case where the number of addition steps is three or more, if PO is added in the last addition step, AO added in the previous addition step is not limited, and EO alone, PO alone, BO alone, EO A mixture of PO and PO (random addition), a mixture of EO and BO (random addition), a mixture of PO and BO (random addition), etc. can be added, but in the first addition step, EO and PO are added like two-step addition. It is preferred that a mixture of is added. When both EO and PO are added in the first addition step of two-step addition or in three or more addition steps, the molar ratio of both is EO / PO = 6/1 to 1/5, further 3.2 / 1. ~
1 / 1.9 is preferable. Further, the average number of added moles of both is preferably 9.5 to 700, and more preferably 49 to 350.

In the last addition step, PO is added alone, and the average number of added moles is preferably 0.5 to 300, more preferably 1 to 100, and most preferably 3 to 50.

In the AO adduct (reaction product) according to the present invention, the average number of added moles of all AO is preferably 10 to 1000, more preferably 20 to 600, and particularly preferably 50 to 400. Also,
The molar ratio of EO to PO in all AO is EO / PO = 10 /
1 to 1/10 is preferable, and more preferably 5/1 to 1 /
5, particularly preferably 2/1 to 1/2. The molar ratio of BO in all AO is BO / (EO + PO) = 5 / 10-0
/ 10 is preferable. The type of AO and the number of added moles used in each AO addition step are adjusted so as to fall within the above range. In each range of the above AO addition modes, the fine ink has an excellent aggregation effect, and the ink can be efficiently removed in the flotation step.

In the present invention, AO in each additional step
The addition reaction method is not particularly limited, and the addition reaction can be performed under the conditions of AO addition reaction to a compound having active hydrogen which is generally performed. That is, a catalytic amount of an alkaline substance is added to the mixture or ester of the polyvalent carboxylic acid or its acid anhydride and alcohol, and the mixture is added under an inert gas atmosphere at about 100 to 200 ° C. and 1 to 3 kg.
/ Cm ² (gauge) [98.1 to 294.2 kPa (gauge)] can be carried out by reacting AO for several hours.

The reaction product obtained by adding AO in a specific order to the mixture or ester of (a) polyvalent carboxylic acid or its acid anhydride and (b) alcohol of the present invention has a bulky skeleton. Moreover, since PO is added in the last addition step, the affinity for ink is stronger than that of the compound used in the conventional deinking agent, and the fine ink collecting property is large. It is possible to obtain deinked pulp having a low content.

The deinking agent of the present invention is a known deinking agent, for example, higher alcohol sulfate, alkylbenzene sulfonate, higher alcohol AO adduct, alkylphenol A.
It also exhibits excellent performance when used in combination with an O adduct. Also in that case, the deinking agent of the present invention is preferably used in an amount of 30% by weight or more and less than 100% by weight, and 50% by weight or more, based on the total weight of the deinking agent of the present invention and a known deinking agent. Is more preferable.

The deinking agent of the present invention may be added to any step before the flotation step. This provides a method for deinking used paper having a step of performing flotation in the presence of the deinking agent of the present invention. The place of addition is preferably a pulping process or a kneading process. Particularly preferably, the conditions for adding to the kneading step of a deinking system having two kneading steps are good. The amount added is not particularly specified,
Preferably, it is 0.03 to 1.0% by weight based on the raw waste paper.

[0023]

EXAMPLE A mixture of (a) polycarboxylic acid or its acid anhydride [represented by component (a) in the table] and (b) alcohol [represented by component (b) in the table] shown in Table 1, The following deinking treatment and performance evaluation were performed using the reaction product to which AO was added as a deinking agent.

The dimer acid in Table 1 is derived from oleic acid, linoleic acid and linoleic acid, and the composition ratio is dimer acid / monomer acid / trimer acid = 80/4/16 (weight ratio). All addition moles are average addition moles.

[Deinking treatment] After the newspaper collected in the city is shredded into 2 x 5 cm pieces, a certain amount thereof is put into a table disintegrator, in which tap water and caustic soda (against used raw paper) 0.3% by weight, a table 0.1% by weight of the deinking agent (against used waste paper) shown in 1 was added, and a disintegration treatment was performed at a pulp concentration of 5% at 45 ° C. for 10 minutes at 3000 rpm. Then, it was dehydrated to a pulp concentration of 28% with a centrifugal dehydrator, and caustic soda (against used waste paper) 1.5% by weight, sodium silicate No. 3 (against used wastepaper) 3.5% by weight, hydrogen peroxide (used wastepaper) 2 0.0% by weight, 0.2% by weight of the deinking agent shown in Table 1 (against used waste paper) were added, and the pulp concentration was 2 with tap water.
After adjusting to 5%, a kneading process was performed with a two-axis type lab kneader (manufactured by Yamamoto Hyakuma Seisakusho) having a rotation speed of 300 rpm. Then, after performing a bleaching process in a high temperature water tank at 50 ° C. for 2 hours, a kneading process was performed again with a biaxial type lab kneader having a rotation speed of 300 rpm. Then, tap water was added to dilute it to a pulp concentration of 4%, and disintegrated with a table disintegrator for 1 minute. The pulp slurry is tap water with a pulp concentration of 1
After diluting to 100%, it was subjected to a flotation treatment at 40 ° C. for 10 minutes with a flotator (manufactured by Kyokuto Shinko). From the pulp slurry before flotation and the pulp slurry after flotation, according to JIS P8209-1976,
A handsheet having a basis weight of 150 g / m ² was produced with a 150 mesh wire.

[Performance Evaluation] With respect to each of the handsheets obtained by the above deinking treatment, the whiteness and the Eric number were measured with a colorimetric color difference meter (Spectro Photometer Eric 950, Technodyne Co., Ltd.). did. The Eric number used here is a value for calculating the residual ink from the absorbance by applying infrared rays of 950 nm, and is the area ratio of the fine residual ink of usually 10 μm or less in the paper, and the unit is expressed in ppm. Further, the fine residual ink removal rate in the flotation process is calculated by the following formula.

[0027]

[Equation 1]

The results are shown in Table 2. When the fine residual ink removal rate is 70% or more, the quality of deinked pulp is good.

[0029]

[Table 1]

[0030]

[Table 2]

Continuation of front page (56) Reference JP-A-11-131380 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) D21C 5/02

Claims (4)

(57) [Claims] 1. (a) Dimer acid, phthalic acid and anhydrous fluorine
Two or more kinds of alkylene oxides (hereinafter referred to as AO) in a mixture or ester of a polyvalent carboxylic acid selected from taric acid or an acid anhydride thereof and (b) alcohol.
A deinking agent containing a reaction product obtained by adding AO, wherein the AO is added by a two-step addition process, and the AO added in the first addition process is an AO mixture of ethylene oxide and propylene oxide. The deinking agent in which AO added in the final addition step is propylene oxide alone. 2. (a) Dimer acid, phthalic acid and anhydrous phthalic acid
A deinking agent containing a reaction product obtained by adding two or more kinds of AO to a mixture or ester of a polyvalent carboxylic acid selected from taric acid or an acid anhydride thereof and (b) an alcohol, A deinking agent in which the AO is added in three or more addition steps and the AO added in the final addition step is propylene oxide alone. 3. The deinking agent according to claim 2, wherein the AO added in the first addition step is a mixture of ethylene oxide and propylene oxide. 4. A deinking method using the deinking agent according to any one of claims 1 to 3 in a deinking step.