JPH03193986A - Deinking agent for reclaiming waste paper - Google Patents

Abstract

PURPOSE:To obtain a deinking agent, composed of an adduct prepared by adding an alkylene oxide to a partial ester of a dimer acid, etc., of a higher unsaturated fatty acid and an alcohol, capable of enhancing foaming and ink capturing properties with high whiteness and hardly any residual ink. CONSTITUTION:The objective deinking agent consisting essentially of an adduct prepared by adding <=300mol, preferably 10-200mol alkylene oxide (preferably combination of ethylene oxide and propylene oxide) to a partial ester obtained from a dimer acid and/or polymer acid of a 16-20C higher unsaturated fatty acid and a 1-18C (preferably 5-12C) alcohol.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention is applicable to the recycling of printed waste paper such as newspapers, magazines, flyers, etc.
Regarding the deinking agent that can be used. More specifically, when deinking newspapers, magazines, etc. using the flow-chie silane method,
This invention relates to a deinking agent that can improve ink collection ability and produce deinked pulp with high whiteness and little residual ink.

(Conventional technology) Recycling of newspapers, magazines, etc. has been carried out for a long time, but in recent years, the effective use of waste paper has become increasingly important due to the protection of forest resources and the expansion of uses for deinked pulp. There is.

To recycle waste printed paper, it is usually treated in a disintegrating machine with an alkaline agent such as caustic soda or sodium silicate, a deinking agent, and, if necessary, a bleaching agent such as hydrogen peroxide or hyposulfite.
Disintegrates with sequestering agents such as DTA and DTPA,
A widely used method is to desorb ink from pulp and then separate the desorbed ink from the pulp by water washing or flow-free silane treatment.

Deinking agents can be roughly divided into *I[dispersion type deinking agents, which aim to remove the removed ink from the system in a finely dispersed state; There are agglomerated deinking agents whose purpose is to remove waste materials, and among these, agglomerated deinking agents that can further increase the whiteness of recycled pulp are widely used.

Examples of deinking agents include anionic activators such as alkylbenzene sulfonates, higher alcohol sulfates, α-olefin sulfonates, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl allyl ethers,
Nonionic surfactants such as fatty acid alkanolamides or higher fatty acids have been used alone or in combination of two or more. However, conventional deinking agents based on higher fatty acids have a high ink aggregation effect, but have the problem of poor penetration into pulp and ink removal effect, making it impossible to obtain a sufficient deinking effect. Alkylene oxide adduct systems (e.g., Japanese Patent Publication No. 11756/1983, 303190/1982, and 11108/1999)
No. 6) has a high ink penetration and ink removal and dispersion effect, but has poor affinity with the ink, so the ink aggregation effect is still insufficient.

(Problems to be solved by the present invention) In particular, in recent years, the ink composition of waste paper has changed due to improvements in printing technology, especially offset printing ink, and drying oil and thermosetting resin are used. As a result, the ink film is strongly cured, and it is difficult to remove the ink and separate it from the pulp using conventional deinking agents, making it impossible to obtain high-quality deinked pulp.

Additionally, as the uses of deinking valves expand, there is a demand for deinking valves with higher whiteness and less residual ink.

Therefore, it is an object of the present invention to provide a deinking agent that can easily remove high quality ink from waste paper that is difficult to remove and separate.

(Means for Solving the Problems) Therefore, in order to achieve the above object, the present inventors found that it is necessary to create a deinking agent that has a high ink removal effect, as well as a high ink coagulation effect and foaming property. In view of this, as a result of extensive research, it was discovered that alkylene oxide is added to partial esters of dimer acids and/or polymer acids of higher unsaturated fatty acids and alcohols, and the present invention completed.

That is, the present invention relates to a dimer acid and/or a polymer acid of a higher unsaturated fatty acid having 16 to 20 carbon atoms and a higher unsaturated fatty acid having 1 to 20 carbon atoms.
The deinking agent for waste paper recycling is characterized in that the main component is an adduct obtained by adding one or more alkylene oxides in an amount of 300 moles or less to a partial ester of No. 18 alcohol.

Dimer acids and polymer acids of higher unsaturated fatty acids having 16 to 20 carbon atoms used in the present invention are obtained by polymerizing higher fatty acid monoenoic acids or dienoic acids.
Examples include those obtained by thermal polymerization of unsaturated fatty acid monomers such as oleic acid, linoleic acid, and linoleic acid, or by other methods. It is a dimer acid having 36 carbon atoms and a trimer acid having 54 carbon atoms obtained by polymerization, or a mixture thereof. Its molecular structure is not clear;
It is commercially available as a mixture of various isomers,
Suitable examples include haridimer (manufactured by Harima Kasei Kogyo) obtained by polymerization of tall oil fatty acids and those obtained by polymerization of soybean oil fatty acids.The present invention does not limit the incorporation of small amounts of monomer acids.

In addition, alcohols having 1 to 18 carbon atoms for partial esterification include ordinary primary, secondary, and tertiary alkyl alcohols such as methanol, ethanol, isopropanol, n-
Butanol, isobutanol, 5ec-butanol, t
Examples include ert-butanol, amyl alcohol, hexyl alcohol, lauryl alcohol, oxo-synthesized and other synthetic alcohol mixtures, and stearyl alcohol.

In view of esterification reactivity and properties after addition of alkylene oxide, carbon atoms having 5 to 12 carbon atoms are particularly preferred.

As partial esters, dimer acids and polymer acids 1
Preferably, the amount of esterification is such that at least one carboxylic acid remains per molecule.

A known method can be used for partial esterification of dimer acid and polymer acid with the above alcohol.

Furthermore, the alkylene oxide used in the present invention includes ethylene oxide, propylene oxide, and butylene oxide, and one or more types may be added, and the addition of two or more types can be performed by random addition or block addition. However, random or block addition with a combination of ethylene oxide and propylene oxide is most preferred. The number of moles of alkylene oxide added is 300 moles or less; if it is more than 300 moles, the foamability of the flotation step during deinking will decrease, and the cohesiveness of the peeled ink will be impaired, making it impossible to obtain high-quality recycled pulp. . The number of moles of alkylene oxide added is 10~
200 mol is particularly preferred. The addition reaction is not particularly limited (it can be carried out in a conventional manner, for example, by heating the partial ester of the dimer acid and/or polymeric acid to 100 to 200°C in the presence of an alkali as a catalyst). An addition product can be obtained by blowing alkylene oxide at a rate of 1 to 5 kg/cd and reacting for several hours.

The deinking agent of the present invention is preferably added before the pulper or aging tower, but it can also be added to the floatator. Although the wood deinking agent alone is sufficiently effective, other deinking agents such as anionic activators, nonionic activators such as polyoxyalkylene alkyl ether, higher fatty acids, etc. may be used in combination.

(Effect) The deinking agent of the present invention has an alkylene oxide added to a partial ester of dimer acid and/or polymer acid of higher unsaturated fatty acid and alcohol, so it has excellent ink penetration and releasability. Furthermore, since the ink collection property is much better than that of conventional deinking agents, high-quality recycled pulp can be easily obtained.

(Example) Hereinafter, the present invention will be specifically explained based on Examples.

[Example 1] Polymer acids include 79% dimer acid, 118% trimer, and 3 monomer acids obtained by polymerization of tall oil fatty acids.
%, acid value 193, average molecular weight 605 Hallidimer 25
0 (manufactured by Yokoma Kasei Kogyo) and n amyl alcohol from 130 to
The reaction was carried out at 160°C to obtain a partial ester with an acid value of 90 and an average molecular weight of 675. Put 675 g of this ester into a pressure-resistant reaction vessel, add 3.4 g of caustic potassium as a catalyst, and
Heating to 0''C, degassing the inside of the container and purging it with nitrogen gas, and adding 440.5g of ethylene oxide at a pressure of 1 to 5 kg/cd.
The reaction was carried out by blowing over 3 hours to produce 1 ethylene oxide.
A deinking agent with 0 mole addition was obtained.

[Example 2] Haridimer 250 and lauryl alcohol 200-2
The reaction was carried out at 50°C to obtain a partial ester having an acid value of 79 and an average molecular weight of 773. 386.5 g of this ester was placed in a pressure container, 1.9 g of caustic potassium was added as a catalyst, and the mixture was heated to 170°.
The inside of the container was degassed and replaced with nitrogen gas, and 881 g of ethylene oxide was heated at a pressure of 1 to 5 kg/cd.
A deinking agent containing 40 moles of ethylene oxide was obtained by blowing and reacting over a period of time.

[Example 3] Ethylene oxide was blown into the partial ester obtained in Example 2 in the same manner as in Example 2, and then 580.8 g of propylene oxide was blown into the partial ester obtained in Example 2 at a rate of 1 to 5 kg/cd for 5 hours to react. A deinking agent containing 40 mol and 20 mol of propylene oxide was obtained.

(Example 4) 1.0 g of caustic potash was added as a large container catalyst to a large container catalyst, 193.3 g of Halidimer 250 lauryl alcohol ester obtained in the same manner as in Example 2, and the container was degassed. After the air was replaced with nitrogen gas, 881 g of ethylene oxide was blown into the reactor at a rate of 1 to 5 kg/c4 over 5 hours, and then 290 g of propylene oxide was added.
．． 4 g was blown into the solution over a period of 3 hours and reacted to obtain a deinking agent containing 80 moles of propylene oxide and 20 moles of propylene oxide randomly added.

[Example 5] A deinking agent with random addition of 80 moles of ethylene oxide and 20 moles of propylene oxide was obtained in the same manner as in Example 4, except that the reaction conditions were that ethylene oxide and propylene oxide were reacted simultaneously over 8 hours.

[Example 6] A deinking agent of an adduct of 20 moles of propylene oxide and 80 moles of ethylene oxide was obtained in the same manner as in Example 4, except that the reaction conditions were that propylene oxide was blown into the reactor and then ethylene oxide was blown into the reactor.

[Example 7] The reaction conditions were the same as in Example 4 except that 881 g of ethylene oxide and 90.1 g of butylene oxide were used.
A molar addition deinking agent was obtained.

(Example 8) Halidimer 250 and stearyl alcohol are mixed at 200~
A partial ester having an acid value of 71 and an average molecular weight of 858 was obtained by reacting at 250"C. 171.6g of this ester was placed in a pressure vessel, 0.9g of caustic potassium was added as a catalyst,
After heating to 0'C and purging with nitrogen gas, 1321.5g of ethylene oxide was blown in at a rate of 1 to 5 kg/d for 7 hours, and then 58g of propylene oxide was added.
By blowing 0.8 g over 7 hours and causing a reaction, a deinking agent containing 150 moles of ethylene oxide and 60 moles of propylene oxide was obtained.

(Example 9) Acid value 19 consisting of 25% dimer acid and 75% trimer acid
0, Haridimer 500 (manufactured by Yokoma Kasei Kogyo) with an average molecular weight of 774 and n-amyl alcohol of 130 to 160'
A partial ester having an acid value of 72 and an average molecular weight of 1,879 was obtained by reacting with C. This ester 175.8g, caustic potassium 0.9
A deinking agent containing 150 moles of ethylene oxide and 50 moles of propylene oxide was obtained by reacting in the same manner as in Example 8, except that g was used.

[Example 10] Haridimer 500 and lauryl alcohol 200-2
The reaction was carried out at 50°C to obtain a partial ester having an acid value of 97 and an average molecular weight of 942. A deinking agent containing 80 moles of ethylene oxide and 20 moles of propylene oxide was obtained in the same manner as in Example 4, except that 235.5 g of this ester and 1.2 g of caustic potash were used.

[Comparative Examples 2 to 4] Oleic acid, stearic acid,
Olein # (EO), i., was obtained by the same reaction as in Example using lauryl alcohol. (PO)+6, stearic acid (Eo)z. (po),. , lauryl alcohol (EO) 2°(PO)+o was obtained.

[Example of deinking test] According to J, TAPP Paper Pulp Test Method No. 39-82, raw material waste paper consisting of 80% offset printed newspaper waste paper and 20% flyer was shredded into 3 x 3 cya, and a certain amount was cut into pieces by valve. Place in a disintegrating machine, add hot water, and add 1.5% caustic soda, 3.0% No. 3 sodium silicate, 3.0% hydrogen peroxide solution, and 0 each deinking agent shown in Table 1 based on the weight of the waste paper. .3% was added, the bulb concentration was 4.0%, and the mixture was dissolved at 50°C for 30 minutes, and then aged at 50°C for 1 hour. The drained water was added to dilute the bulb concentration to 1.0%, and a flotation treatment was performed at 30° C. for 10 minutes. The valve slurry after flotation was dehydrated with an 80 mesh wire to 5.0%, after 4 m, water was added to dilute it to a valve concentration of 1.0%, and a valve with a basis weight of 100 g/rrr was prepared using a square sheet machine. A sheet was prepared.

The whiteness of the obtained valve seat is JIS P8123.
It was measured using a Hunter white photometer according to .

In addition, to display the remaining carbon, use a simple method for measuring carbon in deinking valves.The resulting valve sheet is ground in a household mixer, and 100 ml of this is mixed with acetyl bromide/acetic acid (1/3 volume ratio) mixture. The cellulose was dissolved at 65 to 70° C. for 2 hours, and the mixture was filtered using a glass fiber filter (GS25, diameter 55 m+a) manufactured by Atobanchiku Toyo Co., Ltd. After air-drying the filter, measurement was performed using a color difference meter. The smaller the residual ink on the obtained recycled valve seat, the larger the residual carbon L value.

The results are also shown in Table 1.

Claims (1)

[Claims] (1) A partial ester of a dimer acid and/or a polymeric acid of a higher unsaturated fatty acid having 16 to 20 carbon atoms and an alcohol having 1 to 18 carbon atoms is added with 1 of alkylene oxide.
A deinking agent for waste paper recycling whose main component is an adduct obtained by adding 300 moles or less of a species or two or more species.