JPH03152284A - Deinking agent for waste paper recycling - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a deinking agent used for recycling used printed paper such as newspapers, magazines, flyers, etc. More specifically, the present invention relates to a deinking agent that improves foamability and ink collection ability when deinking newspapers, magazines, etc. using the flow-chilled silane method, and can provide a deinking valve 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 deinking valves. 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 a valve and separate the desorbed ink from pulp by water washing or flowy silane treatment.

Deinking agents can be roughly divided into dispersion type deinking agents, which remove the detached ink from the system in a finely dispersed state, and dispersion deinking agents, which remove the detached ink from the system in a state where it has aggregated to some extent. There are agglomerated deinking agents whose purpose is to remove the white color of recycled pulp, and among these, agglomerated deinking agents that can further enhance 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,
Ion activators such as fatty acid alkanolamide or higher fatty acids have been used alone or in combination of two or more. However, conventional deinking agents such as higher fatty acids have a high ink aggregation effect, but have low penetration into the pulp and ink removal effect, making it difficult to obtain a sufficient deinking effect.Alkylene oxides such as polyoxyalkylene alkyl ether Adduct systems (e.g. Japanese Patent Publication No. 6411756, Japanese Patent Publication No. 63
-303190 and JP-A-1-111086) have high penetration into pulp and ink peeling and dispersion effects, but have poor affinity with ink, and therefore do not yet have a sufficient ink aggregation effect.

(Problems to be solved by the present invention) In particular, the ink composition of recent waste paper has changed due to improvements in printing technology, especially offset printing ink, and drying oil and thermosetting resin are used. 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 !IN) In order to achieve the above object, the present inventors found that it is necessary to have a deinking agent that has a large ink removal effect, an ink coagulation effect, and a suitable foaming property. In view of this, as a result of intensive research, it was discovered that a product obtained by adding an alkylene oxide to a specific dicarboxylic acid or dicarboxylic acid monoester has the above-mentioned necessary physical properties, and the present invention was completed.

That is, the present invention resides in a deinking agent for waste paper recycling, which is an alkylene oxide adduct of a dicarboxylic acid or dicarboxylic acid monoester of the following formula (I) (representing an alkyl group).

The basic skeleton dicarboxylic acid used in the present invention has the formula (n) (wherein, one of X is COO(A 0) nH, the other is H or CH, and n = 1 to 200, and AO is , Y is (AO)mH or R m-1~2
00, R is a carbon number of 1 to 1 day (X is a formula (same as the definition of υ))
No. 899476, generally known by the trade name DIA
CID-1550 (distributor: Harima Kasei Kogyo 90% dicarboxylic acid, 9% monocarboxylic acid, mixture of other unsaponifiables) can be used. ) and an alcohol represented by ROH (R is an alkyl group having 1 to 18 carbon atoms, preferably 1 to 15 carbon atoms), such as methanol, isopropanol, butanol, hexanol, It is possible to use octatool, lauryl alcohol, and various other synthetic alcohols, either alone or in combination, reacted by a known method. The present invention does not limit the incorporation of a small amount of heptamic acid.

Examples of the alkylene oxide used in the present invention include ethylene oxide, propylene oxide, and butylene oxide, and one or more types may be added,
The addition of two or more types can be carried out by random addition or block addition, but random or block addition is most preferred with a combination of ethylene oxide and propylene oxide. The number of moles of alkylene oxide added is 1 to 200 moles, and if it is more than 200 moles, the foamability of the flotation step during deinking will decrease, and the cohesiveness of the peeled ink will be impaired, making it difficult to obtain a high-quality regenerated valve. No, the number of moles of alkylene oxide added is 10 to 120
Moles are particularly preferred.

The addition reaction is not particularly limited (for example, an alkaline substance is added to the above dicarboxylic acid or dicarboxylic acid monoester as a catalyst,
An addition product can be obtained by blowing alkylene oxide at a rate of kg/c- 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 this deinking agent is sufficiently effective alone, it may also be used in combination with other deinking agents, such as anionic activators, nonionic activators such as polyoxyalkylene alkyl ether, and higher fatty acids. No problem.

(Effect) Since the deinking agent of the present invention has alkylene oxide added to a specific dicarboxylic acid or dicarboxylic acid monoester, it not only has excellent ink penetration and peelability, but also has foaming properties and ink aggregation. Since the deinking properties are far superior to those of conventional deinking agents, high-quality recycled valves with high whiteness and little residual ink can be easily obtained.

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

(Example 1) DIACI with an average molecular weight of 352.5 as a dicarboxylic acid
D-1550 (sold by: Shuma Kasei Kogyo ■) 352.5g
was placed in a pressure-resistant reaction vessel, 2.1 g of caustic potassium was added as a catalyst, heated to 170°C, the inside of the vessel was replaced with nitrogen gas, degassed under reduced pressure, and 264.3 g of ethylene oxide was reacted at a pressure of 1 to 5.
A deinking agent of 6 moles of ethylene oxide adduct was obtained by blowing reaction at kg/c- for 3 hours.

[Example 2] A deinking agent containing 20 moles of ethylene oxide was obtained in the same manner as in Example 1, except that 881.0 g of ethylene oxide was used as the reaction condition.

[Example 3] DIACID-1550 (distributor: Harima Kasei Kogyo ■) and an excess amount of methyl alcohol were reacted under methanol reflux using a sulfuric acid catalyst to form a monoester, and then the excess methyl alcohol was removed under reduced pressure. The monoester was purified by molecular distillation to obtain a monoester having an acid value of 113 and an average molecular weight of 367. 180.0 g of this monoester was placed in a pressure-resistant reaction container, 1.1 g of caustic was added as a catalyst, heated to 170°C, the inside of the container was replaced with nitrogen gas, and after degassing under reduced pressure, 649.0 g of ethylene oxide was added. Blow reaction at 1 to 5 kg/cd over 3 hours, then propylene oxide 285
．． A deinking agent containing 30 moles of ethylene oxide and 10 moles of propylene oxide was obtained by blowing and reacting 3 g at a pressure of 1 to 5 kg/cgi over 5 hours.

[Example 4] 200% of DIACID-1550 and octyl alcohol
After dehydration reaction at ~250°C to obtain a monoester, excess octyl alcohol was removed under reduced pressure to obtain a monoester having an acid value of 89 and an average molecular weight of 465. This monoester 18
0.0g was placed in a pressure-resistant reaction vessel, and 1 part of caustic potassium was added as a catalyst.
．． Add 1 g of ethylene oxide, heat to 170'C, heat the inside of the container to 1F nitrogen gas, degas under reduced pressure, and remove 682.5 ethylene oxide.
g was reacted by blowing at a pressure of 1 to 5 kg/c over 3 hours, and then 337.5 g of propylene oxide was reacted at a pressure of 1 to 5 kg/c.
A deinking agent containing 40 moles of ethylene oxide and 15 moles of propylene oxide was obtained by blowing reaction at kg/c- over 5 hours.

(Example 5) 200% of DIACID-1550 and lauryl alcohol
After reacting at ~250°C to form a monoester, excess lauryl alcohol was removed under reduced pressure to obtain a monoester with an acid value of 78 and an average molecular weight of 521.

Put 180.0 g of this monoester into a pressure-resistant reaction container,
1.1 g of caustic potassium was added as a catalyst, heated to 170'C, the inside of the container was replaced with nitrogen gas, degassed under reduced pressure, and 609.0 g of ethylene oxide was added at a pressure of I~5 kg/cd.
Blow reaction over time, then propylene oxide l
A deinking agent containing 7,140 moles of ethylene oxide and 5 moles of propylene oxide was obtained by blowing 0.4 g of O at a pressure of 1 to 5 kg/d over 5 hours to obtain a deinking agent (1).

(Example 6) DIACI with an average molecular weight of 352.5 as a dicarboxylic acid
D-1550 l15. og was placed in a pressure-resistant reaction container, 0.7 g of caustic potassium was added as a catalyst, heated to 170°C, the inside of the container was replaced with nitrogen gas, and after degassing under reduced pressure, 862.3 g of ethylene oxide was added at a pressure of 1 to 5 kg/cj. Blow reaction over time, then propylene oxide 189.5
A deinking agent containing 60 moles of ethylene oxide and 10 moles of propylene oxide was obtained by blowing and reacting at a pressure of 1 to 5 kg/c over 4 hours.

(Example 7) A deinking agent was obtained in the same manner as in Example 6, except that the reaction conditions were that ethylene oxide was blown in after propylene oxide was blown in to react.

[Example 8] Example 6 except that the reaction conditions were that ethylene oxide and propylene oxide were simultaneously blown in for 6 hours.
In the same manner as above, a deinking agent was obtained by randomly adding 60 moles of ethylene oxide and 10 moles of propylene oxide.

[Example 9] A deinking agent containing 40 moles of ethylene oxide and 6 moles of butylene oxide was obtained in the same manner as in Example 6, except that the reaction conditions were 574.8 g of ethylene oxide and 141 Ig of butylene oxide.

(Example 10) The addition of 120 moles of ethylene oxide and 140 moles of pro and synoxy was carried out in the same manner as in Example 6, except that the reaction conditions were that 1724.5 g of ethylene oxide was blown in for 6 hours and 757.9 g of propylene oxide was blown in for 8 hours. A deinking agent was obtained.

[Comparative Examples 2 to 4] Oleic acid (
EO)z. (PO)10, stearic acid (EO)*. (
P.O.),. , lauryl alcohol (E O) 1s (P
O) +. I got it.

[Deinking test example]

J, TAPP Paper Valve Test Method No. 39-82, raw waste paper consisting of 80% offset printed newspaper waste paper and 20% flyer was shredded into 3 x 3 cm pieces, a certain amount was put into a valve disintegrator, and heated with hot water. of caustic soda per weight of waste paper. 5%, No. 3 sodium silicate 3.0%, 30%
3.0% hydrogen peroxide solution and 0.3% of each deinking agent shown in Table 1 were added, the bulb concentration was 4.0%, the mixture was decomposed at 50°C for 30 minutes, and then aged at 50°C for 1 hour. Thereafter, water was added to dilute the bulb concentration to 1.0%, and flotation treatment was performed at 30°C for 10 minutes. The valve slurry after flotation was dehydrated with an 80 mesh wire to 5% for 1 m, then water was added to dilute it to a pulp concentration of 1.0%, and a valve sheet with a basis weight of 100 g/rrr was made using a square sheet machine. Prepared.

The whiteness of the obtained valve seat is JIS P8123.
It was measured using a Hunter white photometer according to . To display the amount of carbon remaining in the pulp, use a simple method for measuring carbon in deinked pulp, and crush the obtained valve sheet with a household mixer.
This 10G+g was added to a mixture of acetyl bromide/acetic acid (l/3 volume ratio) to dissolve the cellulose at 65-70°C for 2 hours, filtered through a glass fiber filter (GS25, diameter 55 mm) manufactured by Atvanchik Toyo, and filtered. After air drying, it was measured using a color difference meter. The smaller the amount of residual ink on the obtained recycled valve seat, the greater the value of residual carbon L.

The results are also shown in Table 1. It can be seen that when the deinking agent of the present invention is used, the whiteness and residual ink are reduced compared to Comparative Examples 1 to 4.

Table 1 (u) EO is ethylene oxide, the circle is propylene oxide, and BOLt7'tyleneoxyP.

v4wilA, go to sashisai (I stands for Hisao Ishii)

Claims (1)

[Claims] The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, one of X is COO(AO)_nH, the other is H or CH_3, and n = 1 to 200 , AO is alkylene oxide, Y is (AO)_mH or R and m=1
~200, R represents an alkyl group having 1 to 18 carbon atoms) A deinking agent for recycling used paper, the main component of which is an alkylene oxide adduct of dicarboxylic acid or dicarboxylic acid monoester.