JPH0726349B2 - Manufacturing method of deinking agent for recycled waste paper - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a deinking agent used for recycling printed waste paper such as newspapers, magazines and leaflets.

[0002]

2. Description of the Related Art Generally, deinking agents are roughly classified into dispersed deinking agents for the purpose of removing the desorbed ink outside the system in a finely dispersed state and the desorbed ink to some extent. There is an aggregating deinking agent intended for removal to the outside of the system in the state, and of these, an aggregating deinking agent capable of further increasing the whiteness of recycled pulp is widely used.
As the deinking agent, alkylbenzene sulfonate, higher alcohol sulfate, anion activator such as α-olefin sulfonate, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl allyl ether,
Nonionic activators such as fatty acid alkanol amides or higher fatty acids have been used alone or in combination of two or more. However, although the higher fatty acid type has a high ink aggregation effect, it has a problem that it cannot penetrate into the pulp, the ink peeling effect and the foamability are low, and a sufficient deinking effect cannot be obtained.

Therefore, a deinking agent for recycling used paper, in which an alkylene oxide is added to a monovalent higher fatty acid (JP-A-53-53)
130309), a deinking agent obtained by adding an alkylene oxide to a fatty acid (JP-A-58-109696), and a deinking agent for recycling used paper obtained by adding an ethylene oxide and a mixed alkylene oxide to a monovalent higher fatty acid (JP-A No. 59-
130400), a deinking agent containing a polyoxyalkylene glycol ester as a main component, which is obtained by adding an alkylene oxide to rosin which is also a monovalent carboxylic acid (JP-A-63-303190), natural fats and oils and polyhydric alcohols. A deinking agent for recycling used paper, which contains an addition reaction product of alkoxide with alkylene oxide, has been proposed (JP-A-1111086). However, these alkylene oxide adducts such as polyoxyalkylene alkyl ethers permeate pulp and ink. The peeling and dispersing effect is high, but the affinity for the ink is poor, and therefore the ink aggregating effect is still insufficient.

[0004]

In particular, recent waste papers have a change in ink composition due to improvement in printing technology, especially offsetting of printing inks, and a drying oil or a thermosetting resin is used. Was hardened, and it was difficult to remove the ink from the conventional deinking agent and separate it from the pulp, and it was not possible to obtain a high quality deinked pulp. Further, as the use of deinked pulp expands, there is a demand for deinked pulp with higher whiteness and less residual ink.

Therefore, the object of the present invention is to provide a deinking agent capable of easily highly deinking waste paper which has become difficult to be desorbed and separated, and further relates to the above higher fatty acid alkylene oxide adduct. In view of the fact that it is necessary to be a deinking agent that has a large ink peeling effect and a large ink aggregation effect and foaming property at the same time, as a result of intensive research, as a result, especially dimer acid or polymer acid of higher unsaturated fatty acid It was found that a polymer obtained by polymerizing a carboxyl group with polyoxyalkylene has the above-mentioned required physical properties. However, the method for binding polyoxyalkylene to the dimer acid and polymer acid of the higher unsaturated fatty acid is roughly classified into an esterification method through polyoxyalkylene glycol and an addition polymerization method in which alkylene oxide is directly addition-polymerized. The former esterification method is suitable for producing an addition polymer in which a polyoxyalkylene is bonded to a part of a carboxyl group and a fatty acid group is partially left, but the production cost is high and it is not suitable for industrial products. On the other hand, in the latter addition polymerization method, polyoxyalkylene is added to all carboxyl groups to leave no fatty acid group,
The inventors have found that an inexpensive addition polymer is suitable for mass production, and that it has deinking performance that is not inferior to the addition polymer obtained by the above-mentioned esterification method, and completed the present invention.

[0006]

That is, according to the present invention, at least one of a dimer acid and a polymeric acid of a higher unsaturated fatty acid having 16 to 20 carbon atoms is put in a pressure resistant reactor and heated to remove nitrogen gas after degassing. A method for producing a deinking agent for recycling used paper is characterized in that the deinking agent for recycling used paper is encapsulated and one or more kinds of alkylene oxides having 2 to 4 carbon atoms are simultaneously blown in or reacted in a stepwise manner.

The number of carbon atoms used in the present invention is 16 to 2
Higher unsaturated fatty acid dimer acid and polymer acid of 0 can be obtained by multimerization of higher fatty acid monoenoic acid or dienoic acid. Examples include those obtained by thermal polymerization of unsaturated fatty acid monomers such as oleic acid, linoleic acid, and linolenic acid, or by other methods.Currently commercially available and easily available are those of oleic acid and linoleic acid. Polymerized dimer acid having 36 carbon atoms and trimer acid having 54 carbon atoms, or a mixture thereof. Its molecular structure is not clear, and it is industrially provided as a mixture of various isomers, such as halidimer obtained by polymerization of tall oil fatty acid (manufactured by Harima Kasei Co., Ltd.) and that obtained by polymerization of soybean oil fatty acid. This is a suitable example. The present invention does not limit the incorporation of small amounts of monomeric acid.

The alkylene oxide used in the present invention includes ethylene oxide, propylene oxide,
Butylene oxide may be mentioned. In the case of carrying out block addition polymerization, a stepwise blowing reaction in which one kind of alkylene oxide is blown in and then another kind of alkylene oxide is blown in is employed. On the other hand, when performing random addition polymerization, it is advisable to simultaneously blow two or more kinds of alkylene oxides for the reaction. In particular, random addition is most suitable in the combination of ethylene oxide and propylene oxide. The addition mole number of alkylene oxide is 300
When the amount is 300 mol or more, the foamability of the flotation step in deinking is deteriorated and the cohesiveness of the peeled ink is impaired, so that high quality recycled pulp cannot be obtained. The number of added moles of alkylene oxide is particularly preferably 10 to 200 moles. The addition mole number is preferably adjusted by adjusting the filling amount and the reaction time. The addition reaction is not particularly limited. For example, when an alkaline substance is added to the above dimer acid and / or polymer acid as a catalyst and alkylene oxide is blown at 100 to 200 ° C. and 1 to 5 kg / cm ² for several hours to react. Good.

[0009]

EFFECT OF THE INVENTION The deinking agent of the present invention employs an addition polymerization method in which an alkylene oxide is directly added upon binding polyoxyalkylene to a dimer acid of a higher unsaturated fatty acid or a carboxyl group of a polymer acid. Unlike the method, an addition polymer having an acid value of 0 in which a carboxyl group does not substantially remain can be mass-produced at low cost.
Therefore, it is possible to provide a deinking agent which is excellent not only in penetrating into ink and in releasability but also in foaming property and ink cohesiveness as compared with conventional deinking agents.

[0010]

EXAMPLES The present invention will be specifically described below based on examples.

[Example 1] 484 g of Haridimer 250 (manufactured by Harima Kasei Co., Ltd.) having a dimer acid of 79%, a trimer acid of 18%, a monomer acid of 3% and an acid value of 193 and an average molecular weight of 605, obtained by polymerization of tall oil fatty acid. Was placed in a pressure resistant reactor, 2.4 g of caustic potash was added, and the mixture was heated to 170 ° C. for degassing, and nitrogen gas was sealed therein.
The deinking agent of ethylene oxide 6 mol adduct was obtained by bubbling 1 g to 1 to 5 kg / cm ² for 3 hours.

Example 2 The reaction conditions were halider 25.
A deinking agent containing 40 mol of ethylene oxide was obtained in the same manner as in Example 1 except that 242 g of 0 (manufactured by Harima Kasei Kogyo Co., Ltd.), 1.2 g of caustic potash, and 704.8 g of ethylene oxide were used.

Example 3 121 g of Haridimer 250 (manufactured by Harima Kasei Kogyo Co., Ltd.) having 79% dimer acid, 18% trimer acid and 3% monomer acid, obtained by polymerization of tall oil fatty acid, and having an acid value of 193 and an average molecular weight of 605. Was placed in a pressure resistant reactor, 0.6 g of caustic potash was added, and the mixture was heated to 170 ° C. for deaeration, nitrogen gas was sealed therein, and ethylene oxide 176.2 was added.
g of 1-5 kg / cm ² for 3 hours over blowing reaction, and then removing the propylene oxide 232.3g of reacted blown over 3 hours at 1-5 kg / cm ² 20 moles of ethylene oxide and propylene oxide 20 mol adduct I got ink.

[Example 4] 352.4 g of ethylene oxide and butylene oxide 144.2 as alkylene oxides
A deinking agent of an adduct of 40 mol of ethylene oxide and 10 mol of butylene oxide was obtained in the same manner as in Example 3 except that g was used.

Example 5 As an alkylene oxide, 352.4 g of ethylene oxide and 23 of propylene oxide were used.
A deinking agent of an adduct of 40 mol of ethylene oxide and 20 mol of propylene oxide was obtained in the same manner as in Example 3 except that 2.3 g was used.

Example 6 As an alkylene oxide, 352.4 g of ethylene oxide and 46 of propylene oxide were used.
Ethylene oxide 40 was used in the same manner as in Example 3 except that 4.6 g was used and propylene oxide was blown in for 4 hours.
A deinking agent of 40 moles and 40 moles propylene oxide adduct was obtained.

Example 7 As an alkylene oxide, 352.4 g of ethylene oxide and 46 of propylene oxide were used.
Using 4.6 g, the reaction conditions were the same as in Example 3 except that ethylene oxide and propylene oxide were simultaneously blown in, and the reaction time was 6 hours, to obtain a deinking agent of random adduct of 40 mol of ethylene oxide and 40 mol of propylene oxide. Obtained.

Example 8 352.4 g of ethylene oxide and propylene oxide 46 as alkylene oxides
A deinking agent of 40 mol of ethylene oxide and 40 mol of propylene oxide was obtained in the same manner as in Example 6 except that 4.6 g of propylene oxide was blown into the reaction mixture and then ethylene oxide was blown into the reaction mixture.

Example 9 352.4 g of ethylene oxide and 92 of propylene oxide as alkylene oxides
A deinking agent of an adduct of 40 mol of ethylene oxide and 80 mol of propylene oxide was obtained in the same manner as in Example 6 except that 9.3 g was used.

Example 10 881.0 g of ethylene oxide and 11 of propylene oxide as alkylene oxides
Using 61.6 g, blowing ethylene oxide for 4 hours,
A deinking agent containing 100 mol of ethylene oxide and 100 mol of propylene oxide was obtained in the same manner as in Example 3 except that propylene oxide was blown in for 5 hours.

Example 11 Haridimer 300 (manufactured by Harima Kasei) having 97% dimer acid obtained by polymerization of tall oil fatty acid, 2% trimer acid, 1% monomer acid and an acid value of 195 and an average molecular weight of 566 was used. , 40 moles of ethylene oxide and 40 moles of propylene oxide in the same manner as in Example 6 except that 376.7 g of ethylene oxide and 496.7 g of propylene oxide were used as the alkylene oxide.
Molar adduct was obtained.

Example 12 Carrying out except that 413.2 g of ethylene oxide and 544.8 g of propylene oxide were used, which was an acid value of 190% consisting of 25% of dimer acid and 75% of trimer acid and Haridimer 500 having an average molecular weight of 774 (manufactured by Harima Kasei Co., Ltd.). An adduct of 60 mol of ethylene oxide and 60 mol of propylene oxide was obtained in the same manner as in Example 11.

Example 13 Ethylene oxide 619.8
g and propylene oxide of 272.4 g were obtained in the same manner as in Example 12 to obtain an adduct of 90 mol of ethylene oxide and 30 mol of propylene oxide.

[Comparative Examples 2-5] Oleic acid, stearic acid and lauryl alcohol were used in place of the above tall oil fatty acid polymers, and oleic acid (EO) ₂₀ (PO) ₁₀ and olein were prepared by the same reaction as in the examples. Acid (EO) ₂₀ (PO) ₂₀ , stearic acid (EO) ₂₀ (PO) ₂₀ , and lauryl alcohol (EO) ₂₀ (PO) ₂₀ were obtained.

[Deinking Test Example] TAPP paper pulp test method No. According to 39-82, raw waste paper consisting of 80% offset printed newspaper and 20% leaflet is shredded into 3 × 3 cm pieces, a certain amount of which is put in a pulp disintegrator, warm water is added, and caustic soda 1 is added to the weight of used paper. 0.5%, No. 3 sodium silicate 3.
Add 0%, 30% hydrogen peroxide 3.0%, each deinking agent 0.3% shown in Table 1, pulp concentration 4.0%, 3 at 50 ° C.
After the solution was separated into 0, it was aged at 50 ° C. for 1 hour. Thereafter, water was added to dilute the pulp to 1.0%, and a flotation treatment was performed at 30 ° C. for 10 minutes. The pulp slurry after flotation is dehydrated with an 80 mesh wire, concentrated to 5%, diluted with water to a pulp concentration of 1.0%, and a pulp sheet having a basis weight of 100 g / cm ² is prepared with a square sheet machine. did. The whiteness of the obtained pulp sheet is JIS P8.
According to 123, it was measured with a Hunter white photometer. The residual carbon is indicated by a simple measurement method of carbon in deinked pulp, the obtained pulp sheet is ground with a household mixer, and 100 mg of this is mixed with acetyl bromide / acetic acid (1/3).
(Volume ratio) The mixture was placed in a mixed solution, and the cellulose was dissolved at 65 to 70 ° C. for 2 hours, filtered with an Advantech Toyo glass fiber filter (GS25, diameter 55 mm), and the filter was air-dried and then measured with a color difference meter. The smaller the residual ink of the obtained recycled pulp sheet, the larger the residual carbon L value. The results are also shown in Table 1.

[0026]

[Table 1]

Claims (3)

[Claims] 1. A pressure-resistant reaction vessel is charged with at least one of dimer acid and polymer acid of higher unsaturated fatty acid having 16 to 20 carbon atoms, degassed and filled with nitrogen gas to have 2 to 4 carbon atoms.
1 to 5 k of one or more of the alkylene oxides of
At the same time, the reaction is performed by blowing at g / cm ² or having 2 to 2 carbon atoms.
No. 4, which is characterized in that one kind of alkylene oxide of 4 is blown and reacted at 1 to 5 kg / cm ² , and then a different kind of alkylene oxide is blown at 1 to 5 kg / cm ² , and the stepwise blowing reaction is performed. How to make ink. 2. The method for producing a deinking agent for recycling used paper according to claim 1, wherein the alkylene oxides are ethylene oxide and propylene oxide, and a blowing reaction is simultaneously performed to carry out random addition polymerization with respect to the dimer acid and the polymer acid. 3. The method for producing a deinking agent for recycling used paper according to claim 1, wherein an alkaline substance is added to the dimer acid or polymer acid as a catalyst.