JPH0324126A - Polymerized fatty acid ester and deinking of waste-paper by using same - Google Patents

Abstract

PURPOSE:To obtain a deinking agent which has an excellent ability to release an ink from wastepaper and an ability to agglomerate fine ink particles released by floatation and can give reclaimed waste paper of a high whiteness by using a specified polymerized fatty acid ester. CONSTITUTION:A deinking agent for wastepaper is obtained by using at least one polymerized fatty acid ester of the formula (wherein x is 0, 1 or 2; y is 1, 2 or 3; x+y=2 or 3; n is 0-25; m is 10-80; D is a 20-30 C alkyl or alkenyl; EO is an ethylene oxide residue; and PO is a propylene oxide residue). In this way, a deinking agent which has an excellent ability to release an ink from waste paper and a high ability to agglomerate fine ink particles released by floatation and can give a reclaimed waste paper of a high whiteness can be obtained.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a method for obtaining deinked pulp with high brightness when deinking recycled valves from used paper such as Shinkansen, magazines 9, books, etc. by the floatation method. The present invention relates to a deinking agent for deinking and a deinking method using the same.

[Conventional technology and problems]

The following method is known for deinking waste paper by treating it with deinking chemicals. After or at the time of finely pulverizing waste paper with 21 Gu, deinking chemicals consisting of bleaching agents such as alkali hydroxide and hydrogen peroxide, sodium chloride acid and surfactants as pH buffering agents and chelating agents are used. evil. At this time, in order to efficiently remove the ink from the valve, nonionic surfactants such as polyoxyalkylene alkyl ether and polyoxyalkylene alkyl pentol ether are used as the ink agent (deinking agent). These include oleic acid soap, higher alcohol sulfate salts, α
- Compatible with combinations of anionic systems such as olefin sulfonates. The ink was then kept at room temperature to 60=70°C under stirring for several hours to remove the ink adhering to the valve. In order to efficiently perform this deinking process, it is known that the concentration of the valves is increased as much as possible, and deinking is achieved through mechanical contact between the valves (Publication No. 56-6
3089). Next, the bulb solution is diluted to a concentration of around 1% and flotation is performed. At this time, the ink, filler, pigment, etc. that are released from the valve are entrained by air bubbles and removed from the system.

To efficiently carry out floatation, higher fatty acids such as oleic acid and stearic acid, bread oil, and rosin are used to coagulate the fine particles of paint separated during disintegration (newspaper). Investigation report on changes in fiber strength and de-ined beef quality during the distribution and storage stages of waste paper (S760.3 Clean Japan Center). The insolubilized metal soap becomes a floc, and at this time, the ink and pigment are removed and removed from the system along with air bubbles. If only a nonionic surfactant is used, the ink particles will be small (Fronck type or sometimes 6000 yen), but if a phosphorus fatty acid type or its soap is used, the aggregated ink particles will become larger, and the floatation effect will become larger. It becomes. Among fatty acids, oleic acid (C
MC Kanshi Paper Yakuhin ε Functional Materials for Paper p. 36) Stearic acid and palic acid are effective. Fatty acids are introduced in the free state or in the form of their soaps. When it is added in its free state, it functions as a soap due to the alkali added during disintegration.

In the case of fatty acids, liquid oleic acid is the most commonly used because it is easy to work with and has great effects. O1/inic acid has a high cohesive force against ink and can efficiently remove ink during printing. However, when oleic acid is used, foaming is poor, and the flocs in the coagulated and floated part of the ink have poor affinity with the foam. Sometimes they leaked out all at once, causing problems in the process. In addition, when trying to use stearic acid and valmitic acid as soap, they have low solubility in water, which inconveniences the need for new dissolving equipment.However, stearic acid and valmitic acid have a high cohesive force in ink, and are relatively inexpensive compared to sushi fatty acids. Despite its advantages, it had the disadvantage of being difficult to use. On the other hand, recently, due to the diversification of printing technology and printing ink in response to the diversification needs of printed materials, the proportion of printed materials that are difficult to deink has increased in the recovered waste paper. , Shinkaishi also transitioned from letterpress printing to offset printing.7
As the number of resin components in the ink increases, it is becoming difficult to remove ink from recovered newspapers. Against this background, much research has been carried out over the past few years, and patents have been issued.

For example, a nonionic surfactant such as polyoxyalkylene alkyl ether or polyoxyalkylene alkyl ether is used as the main agent, and an alkyl sulfate or alkyl sulfonate is added as a foaming agent or a foaming regulator. R from old paper
It is recommended to use a combination of a flocculant ε and a fatty acid in the ink. Even so, it is difficult to achieve the desired deinking property, and in order to solve this problem, various compounds have been proposed in patents, especially regarding nonionic surfactants.

As an example, a polyglycol-type ink-eluting deinking agent was proposed, and a factory experiment was conducted to remove ink from used paper for electronic copying, and considerable improvements were expected.Report from the Shizuoka Prefecture Paper Industry Experiment Station &40'88.12 ).

[Means for solving problems]

Therefore, the present inventors have solved the above problems, that is, it is possible to obtain recycled waste paper with excellent ink separation force from waste paper, high cohesive force of fine ink particles separated by flotation, and high whiteness. As a result of intensive research to develop a deinking agent, the present invention was successfully completed.

A compound that has both an anion and a nonion in one molecule, i.e., a polymerized fatty acid, in which some of the carboxyl groups are bonded to the hydrophilic groups of polyoxyethylene, polyoxyethylene, and polyoxypropylene, while leaving some fatty acid groups. It was discovered that the deinking effect was remarkable when using the above method, and the present invention was completed.

That is, the present invention can be represented by the following general formula (1).

(However, X is 0, 1 or 2, y is 1, 2 or 3, and x+
y is 2 or 3, m is 0 or a positive number less than or equal to 25, m is 10
(Positive number from 80 to 80, D is an alkyl or alkenyl group having 20 to 36 carbon atoms, EO is an ethylene oxide residue, PO is a propylene oxide residue) Deinking of polymerized fatty acid esters and used paper containing at least one of them This paper relates to a deinking agent and a method for deinking waste paper using the deinking agent. A mixture obtained by synthesis of natural products is sufficient as the polymerized fatty acid. The mixture is 2% to 70% monomer acid, 3% dimer acid.
0-95% trimer acid, 2-70% trimer acid. Dimer acid rich is preferable to trimer acid rich because the product becomes hard. There is no significant difference in deinking performance. The reaction molar ratio of polymerized fatty acid and polyoxyalkylene is 3
A range of :1 to 1:2 is desirable. Both polymerized fatty acids and polyoxyalkylenes are mixtures, so look at their average molecular weights. When the molar ratio of polymerized fatty acids is high, the number of moles of functional groups in one molecule is carboxyl group > polyoxyalkylene group, and the surfactant is an anionic surfactant as a whole. On the other hand, in the reverse case, all of the carboxyl groups of the polymerized fatty acid are blocked by polyalkylene oxide groups, so the entire product becomes a nonionic surfactant. When various ratios were investigated, fatty acids having an anionic to nonionic structure in approximately equimolar proportions showed the best results.

When using the compound of formula (1) as a deinking agent, it is mixed and used during disintegration when caustic soda, sodium silicate, soda carbonate, bleach, etc. are added. Compound (1) can be used in its free form, but it may also be used after being dissolved in advance as an aqueous solution of an alkali metal salt, ammonium salt, or ammonium salt. If a trimer-rich material is used as a raw material, the solubility of the salt in water will decrease. When used in free form, it can be heated to form a solution, or dissolved in water, alcohol, ketones, aromatic hydrocarbons, aliphatic hydrocarbons, liquid fatty acids, or other good solvents to improve handling. good. Alternatively, a surfactant having an HLB of 5 to 15 may be added to Compound (1) in an amount of 5 to 30%, and water may be added to emulsify or dissolve it.

Compound (1) may be used alone or in combination with other surfactants.

Although the examples mainly show combinations of castor oil with ricinoleic acid, which is a fatty acid, the present invention is not limited to this. Other fatty acids, polyalkylene alkyl ethers, polyoxyalkylene alkylphenol ethers,
When used in combination with alkyl sulfates, alkyl sulfonates, etc., the floatation effect is improved and recovered waste paper with higher whiteness can be obtained. Although the mixing ratio is not particularly specified, the amount of foaming varies depending on the type of anion and nonion added during disintegration, pH, temperature, deinking equipment, type of waste paper, etc., so it is recommended to select an appropriate mixing ratio.

The addition of compound (1) depends on the type of waste paper, the deinking equipment,
Although it varies depending on the type of surfactant used in combination, it is 0.01 to 1.0% per dry waste paper. Owt%.

Examples will be described below, but the present invention is not limited thereto.

Example of synthesis of dimer acid ester Inumibanto 36 grams (0.06 mol) of a polymerized fatty acid consisting of 8% monomer acid, 74% dimer acid, and 18% trimer acid with a monoacid value of 194, a saponification value of 198, and an average molecular weight of 599. ), 60 g (0.03 mol) of polyoxyethylene glycol with an average molecular weight of 2000, and 50-1 mol of hydroxyethylene glycol, and using 180 g of p-toluenesulfonic acid as a catalyst, the mixture was heated at 170°C to 0.
．． The mixture was heated and refluxed for about 50 minutes until 0.6 moles of water came out. ■
After cooling to 00°C, add 0.442g of sodium bicarbonate equivalent to 0.442g of sodium p-toluenesulfonate to neutralize the catalyst. Thereafter, the temperature was raised from 40°C to 80°C under reduced pressure for about 1 hr (toluene was removed until the toluene odor disappeared, and the acid value was 34.
An ester with a molar ratio of polymerized fatty acid and polyoxyethylene glycol of 2=1 was obtained.

Practical basis L = Reaction was carried out in the same manner as in Example 1 using 30 grams (0.05 mol) of the same polymerized fatty acid as in Example 1 and 100 grams (0.05 mol) of polyoxyethylene glycol having an average molecular weight of 2,000. The mixture was heated and refluxed at 170°C for about 35 minutes until 0.05 mol of water was released. After the reaction was completed, the mixture was treated in the same manner as in Example 1, and a 1:1 combination of a hybrid fatty acid with an acid value of 21 and polyoxyethylene was carried out. A molar ratio of esters was obtained.

Example 1 Crushed 11 A reaction was carried out in the same manner as in Example 1ε using 15 g (0.025 mol) of the same polymerized fatty acid as in Example 1 and 100 g (0.05 mol) of polyoxyethylene glycol having an average molecular weight of 2,000. Approximately 60 minutes until 0.05 mol of water comes out at 170℃
The mixture was heated to reflux for a minute. After the reaction was completed, post-treatment was carried out in the same manner as in Example 1 to obtain an ester having a molar ratio of polymerized fatty acid having an acid value of 4 to polyoxyethylene in a molar ratio of 1:2.

30 grams (0.05 mol) of the same polymerized fatty acid as in Example 1 and the average molecule! 2 2 4 0 polyoxyethine polyoxypropylene glycol (the degree of polymerization of ethylene oxide and propylene oxide is 45 mol and 4 mol, respectively)
mol> The reaction and post-treatment were carried out in the same manner as in Example 2 except that 12 grams (0.05 mol) of i was used, and an ester of polymerized fatty acid with an acid value of 19 and bolyoxyethylene borioquipropylene glycol in a 1:1 molar ratio was prepared. I got it.

[Examples 5 to 21] Basically Japan TAPPI llh39-82
This was implemented with some changes. The used paper used was Asahi Shimbun, which was published in Tokyo for three months. 1800a+j! 1. Caustic soda for dried waste paper in hot water of just over 50℃. 5%, No. 3 sodium silicate 3.0%, specified amounts of compound (1) as a deinking agent and other deinking aids shown in the table, 1.0% of 30% hydrogen peroxide solution, and pulverized with Schlegoo. Put 75g of old newspapers into a standard disintegrator manufactured by Toyo Tester ■ and disintegrate them at 50°C for 10 minutes.
After being left to stand and warm for 60 minutes, it is similarly disintegrated in a disintegrator for 5 minutes.

1) Take 50 g of the disintegrating solution, dilute it with water, dilute it to a pulp concentration of 1 pulse, set the temperature to 34-36°C, and float it for 10 minutes using a floatator manufactured by Kumagai Riki ■.

Add 38 ppl of calcium chloride during stirring before starting air supply.
1? ! While adding the foam to a certain degree and removing the foam at 3, 7, and 10 minutes during the flow test, track the amount of foam flowing out during the flow test, as well as changes in foam height and foam color over time. do. After flotation 1. Take the ol and squeeze it on a 60 mesh sieve,
About 90 to 95 g, diluted with furnace liquid to make 100 g,
Dilute with water 1. Return to Ol.

Dissolve the disintegration liquid, flotation completion liquid, and finishing liquid uniformly on 3.0 g of waste paper. JIS P
8209 was prepared for the test. The whiteness was measured according to Hunter Whiteness JIS P 8123.

The results of each example are shown in Table 1. D of compound 1 in Table 1
A and DB are abbreviations for polymerized fatty acids, and have the combination shown in the note in the table.
). , with a molar ratio of 2:l, DA- (RO), with a molar ratio of 1:1, (R○),l-DA- (RO
). means that DA and (RO) are combined in a molar ratio of 1:2. R represents ethylene or propylene.
The contents of the example are explained below. As in Comparative Examples (1) and (2), C.I. The nonionic surfactant, which is made by adding ethylene oxide to the fatty acid of )) was as small as 0.1 to 0.2, and almost no deinking effect was observed.On the other hand, these nonionic surfactants and C. Examples in which the ratio of the molecular weight equivalent to fatty acid and the molecular weight of polyoxyethylene were the same l1
For the compound, the amount of foam flowing out is also 1). 7%, and the deinking effect with floatation also increased from 0.1 to 0.2 to 3.9, and a large deinking effect was observed with polymerized fatty acids as lipophilic groups. 9 Examples 5.6.7 and 8,9,1/ have a molar ratio of dimer acid and polyoxyethylene of 2:1.1:1.1), and are classified as ordinary surfactants. Accordingly, they are classified into anion, anion/nonion, and nonion, respectively, and this is an example of using these together with ricinoleic acid.

Among these, the anionic and nonionic types were superior.

Claims (3)

[Claims] (1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, x is 0, 1 or 2, y is 1, 2 or 3, and x +
y is 2 or 3, m is 0 or a positive number less than or equal to 25, m is 10
A positive number from 80 to 80, D is an alkyl group or alkenyl group having 20 to 36 carbon atoms, EO is an ethylene oxide residue, and PO is a propylene oxide residue). (2) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, x is 0, 1 or 2, y is 1, 2 or 3, and x +
y is 2 or 3, m is 0 or a positive number less than or equal to 25, m is 10
D is an alkyl group or alkenyl group having 20 to 36 carbon atoms, EO is an ethylene oxide residue, and PO is a propylene oxide residue). A deinking agent for used paper. (3) In the process of deinking waste paper using a deinking chemical, the following general formula (I) ▲ mathematical formula,
There are chemical formulas, tables, etc.▼(I) (However, x is 0, 1 or 2, y is 1, 2 or 3, and x+
y is 2 or 3, m is 0 or a positive number less than or equal to 25, m is 10
A positive number from 80 to 80, D is an alkyl group or alkenyl group having 20 to 36 carbon atoms, EO is an ethylene oxide residue, and PO is a propylene oxide residue). A method for deinking waste paper, which is characterized by using an ink agent.