JP3041146B2 - 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 for recycling used paper such as newspapers and magazines. More particularly, the present invention relates to a deinking agent capable of obtaining a high b-value deinked pulp when deinking a newspaper, a magazine, or the like by a flotation method, a cleaning method, or a compromise between them.

[0002]

BACKGROUND OF THE INVENTION Newspapers,
Recycling of magazines, etc. has been practiced for a long time, but recently, in particular, the effective use of waste paper has become increasingly important due to shortage of pulp resources and soaring prices. It is expanding to advanced use. On the other hand, recently used paper has changed in printing technology, printing method, printing ink component,
Furthermore, the situation is becoming more severe in terms of deinking, such as the use of waste paper that has not been collected and used in the past, and improvements have been made to devices for further promoting deinking. Chemicals conventionally used to separate and remove ink and other impurities from waste paper include alkaline agents such as caustic soda, sodium silicate, sodium carbonate, and sodium phosphate, hydrogen peroxide, hyposulfite, and hypochlorite. Bleach such as acid salt, EDT
A, along with sequestering agents such as DTPA, as a deinking agent,
Nonionic activators such as alkylbenzene sulfonates, higher alcohol sulfates, α-olefin sulfonates, dialkyl sulfosuccinates, etc .; higher alcohols, ethylene oxide adducts of alkylphenols and fatty acids, and alkanolamides. They have been used alone or in combination of two or more. However, these deinking agents have a high foaming property in the flotation process, but have a low ink collecting ability, and the cleaning method has a low detergency and a high foaming property. And resulted in only low grade deinked pulp. Furthermore, because of the dullness even at high whiteness, there are restrictions on the use of deinked pulp (reduction of the amount of paperboard used below and below, blending in newsprint, etc.) and the use of bleaching agents to eliminate dullness Had to be increased. To obtain a deinked pulp having a dull color and a bright color tone, the b value may be increased. As a method for increasing the b value, it is sufficient to use a large amount of alkalis, but it has a drawback of increasing sticky (sticky substance), increasing drainage load and embrittlement of pulp. Did not.

A deinking agent comprising a polycarboxylic acid derivative is disclosed in JP-A-3-24126, JP-A-3-146780, JP-A-3-152284 and JP-A-3-193986. Although the deinked pulp obtained using these deinking agents has good whiteness, it does not come off dullness, and also has a flotation step, a dehydration step, a drainage step,
It was found that it had a drawback such as causing foaming trouble in the paper making process.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have found that a deinked pulp having a better ink removing ability in a flotation method, a washing method and a compromise method thereof and having no foaming trouble and a dull color can be obtained. As a result of intensive studies to develop a deinking agent with a balanced balance as possible, the present invention has been completed.

That is, according to the present invention, an alkylene oxide is added to a reaction mixture comprising (a) a polycarboxylic acid or an anhydride thereof and (b) an alcohol in an average addition mole number of more than 300 moles and not more than 1000 moles. It is intended to provide a deinking agent characterized by containing an ester mixture obtained by the above method.

The (a) polyhydric carboxylic acid or its anhydride used in the present invention includes oxalic acid, malonic acid, succinic acid, methylsuccinic acid, maleic acid, glutaric acid, adipic acid, phthalic acid, fumaric acid, Itaconic acid, malic acid, tartaric acid, maleated oleic acid, citric acid, percitric acid,
Trimellitic acid, butanetetracarboxylic acid, pyromellitic acid, tetradecanehexacarboxylic acid, maleic anhydride, succinic anhydride, oxalic anhydride, itaconic anhydride, glutaric anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride Also included are acids, stearyl succinic anhydride, and dimer and / or polymeric acids of higher fatty acids having 14 to 22 carbon atoms. The dimer acid and / or polymer acid referred to herein is a method of reacting a monoenoic acid or a dienoic acid, specifically, an unsaturated fatty acid monomer such as oleic acid, linoleic acid, linoleic acid, etc., by thermal polymerization such as Diels-Alder reaction. Alternatively, it can be synthesized by other reaction methods. Further, the polymer acid referred to herein is a polycarboxylic acid having three or more carboxyl groups in one molecule, and does not include dimer acid. Unreacted monomer acid may remain in the formed dimer acid and / or polymer acid as long as the effect of the present invention is not impaired.

The alcohol (b) used in the present invention includes monohydric or polyhydric alcohols. The monohydric alcohol used in the present invention has 6 to 24 carbon atoms.
Examples of alcohol-1, alcohol-2, unsaturated alcohol, branched alcohol, and cyclic alcohol include, but are not limited to, 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-hemicosanol, 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-
Eicosanol, 2-octen-1-ol, 2-dodecene-1-ol, 2-undecene-1-ol, 2-tetradecene-1-ol, 2-pentadecene-1-ol, 2-hexadecene-1-ol, 2-octadecene-1-ol, 8-nonen-1-ol, 10-undecene-1-ol, 11-dodecene-1-ol, 12-tridecene-1-ol, 15-hexadecene-1-ol,
Oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolen alcohol, eleostearyl alcohol, ricinoyl alcohol, cyclononanol, cyclodecanol, cycloundecanol, cyclododecanol, cyclotridecanol, cyclotetradeca Nol, cyclopentadecanol, cyclohexadecanol, cycloheptadecanol, cyclooctadecanol, cyclononadecanol, cyclocosanol, octylphenol, nonylphenol, isohexyl alcohol, 2-ethylhexyl alcohol, 3-methyl-
Pentanol, isooleyl alcohol, isostearyl alcohol and the like can be mentioned.

Further, polyhydric alcohols include those having 2 carbon atoms.
To 32, but specifically, 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, gulose, mannose, glycitol, inositol, mannitol, sorbitol, tetraglycerin,
Heptose, heptulose, octitol, octulose, nonulose, agarobiose, cellobiose, maltose, lactose, gentianose, stachyose, cellotriose and the like.

(A) a polycarboxylic acid or an acid anhydride thereof and
(b) The reaction mixture comprising the alcohol is obtained by heating the mixture under stirring in the presence of an alkali prior to the addition of the alkylene oxide.

In the present invention, the molar ratio of (a) a polycarboxylic acid or its anhydride to (b) an alcohol is (a) /
(b) = 1 / 0.02-5, preferably 1 / 0.1-3.
If the molar ratio of (a) / (b) is out of this range, there is no effect on the aggregation of the fine ink, and the ink is not efficiently removed in the flotation step, so that the whiteness of the deinked pulp is reduced.

In the present invention, the alkylene oxide (hereinafter abbreviated as AO) to be added to the reaction mixture of the above (a) and (b) includes ethylene oxide (hereinafter abbreviated as EO) and propylene oxide (abbreviated as PO hereinafter). ), Butylene oxide (hereinafter abbreviated as BO) and the like, and it is particularly preferable to add both EO and PO. EO / PO = EO / PO =
It is 0.2 to 4 (molar ratio), preferably 1 to 2 (molar ratio). The addition of EO and PO can be performed by mixing the two and adding (random addition) or by sequentially adding (block addition), but random addition is preferred in consideration of foaming trouble reduction.

The number of moles of AO added is more than 300 moles and 10 moles.
It is at most 00 mol, preferably from 320 to 515 mol. Also,
When the number of added moles of AO is out of this range, the releasability of the ink from the used paper decreases. In the case of the washing treatment, the ink removability decreases.

In the present invention, the method of addition reaction of AO is not particularly limited, and it can be carried out 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 reaction mixture of the polyhydric carboxylic acid or its anhydride and an alcohol, and the mixture is added thereto under an inert gas atmosphere.
It can be achieved by reacting AO for several hours at 0 ° C. and 1-3 kg / cm ² (gauge).

The reaction mixture of the present invention comprising (a) a polycarboxylic acid or an anhydride thereof and (b) an alcohol has a bulky skeleton, and therefore has a higher affinity than the compound used in a conventional deinking agent. It is strong and has a good ability to collect fine ink. Further, an ester mixture obtained by adding an alkylene oxide to such a reaction mixture gives an optimum foam amount at the time of flotation treatment, so that the collected ink is removed out of the system, and as a result, a high b value deinked pulp is obtained. Obtainable.

The deinking agent of the present invention also exhibits excellent performance when used in combination with a known deinking agent, for example, a higher alcohol sulfate, an alkylbenzene sulfonate, a higher alcohol, or an EO adduct of an alkylphenol. In this case, the combination ratio is as follows: deinking agent of the present invention / known deinking agent = 100/0
To 10/90, more preferably 80/20 to 30/70.

When the deinking agent of the present invention is added to any step, a higher-quality deinked pulp can be obtained. In general, the deinking agent is added to either or both of the mixing step and the flotation step. It can be added to the process, and the splitting ratio of the deinking agent in the pre-process (pulping process) and the post-process (process after the pulping process) is 10
/ 90 to 90/10 (weight ratio) is preferred. Particularly preferably
40/60 to 60/40 (weight ratio). The amount of the deinking agent to be added is desirably in the economic range without impairing the operability, but is preferably 0.03 to 1.0% by weight based on the raw waste paper.

[0017]

EXAMPLES The present invention will now be described specifically with reference to Production Examples and Examples, but the present invention is not limited thereto.

Production Example 1 In a 2-liter autoclave, 10.0 g and 9.2 g of succinic anhydride and glycerin, respectively, and 0.1% of 100% KOH were added.
2 g was charged, and the temperature was increased to 130 ° C. at a stirring speed of about 600 rpm. Next, the molar ratio of EO and PO was added to the above reaction mixture.
1682.1 g of a 2.5: 1 mixture was reacted. The reaction conditions at this time were a temperature of 130 to 140 ° C. and a pressure of 1 to 3 kg / cm ² (gauge). After the completion of the reaction, the temperature was cooled to 80 ° C., and the pH was adjusted to about 6 with acetic acid. The yield of the reaction product (the product of the present invention, No. 3 in Table 1) was 98.8%.

Production Example 2 In a 2 liter autoclave, 8.3 and 9.1 g of phthalic acid and sorbitol, respectively, and 0.2 g of 100% KOH.
Charged, the temperature was raised to 140 ° C. at a stirring speed of about 600 rpm. Next, 903.0 g of EO was added to the above reaction mixture at a temperature of 140 ° C.
The reaction was carried out little by little at ℃ 150 ° C. and a pressure of 1 to 3 kg / cm ² (gauge). After the completion of the EO addition reaction, the temperature was cooled to 120 to 130 ° C., and 346.0 g of PO was reacted at a pressure of 1 to 3 kg / cm ² (gauge). Thereafter, the temperature was cooled to 80 ° C., and the pH was adjusted to about 6 with acetic acid. Reaction product (product of the present invention, No. 3 in Table 3)
The yield of 4) was 98.1%.

Example 1 This example is an example of batch addition of a deinking agent in a pulping step. After the used newspaper recovered in the city is cut into 2 x 5 cm pieces, a certain amount is placed in a tabletop disintegrator, in which 0.9% of water and caustic soda (based on raw materials), 2.4% of sodium silicate 3 (based on raw materials) and 30% are used. 3.0% of hydrogen peroxide (based on raw material) and 0.3% of deinking agent (based on raw material) shown in Tables 1 and 2 are added, pulp concentration is 15%, and 12 separations are performed at 45 ° C. Was done. afterwards,
Dehydration was performed to 23% with a high-speed dehydrator, and kneading treatment was performed with a biaxial lab kneader having a rotation speed of 300 rpm. Then, add water to dilute to 4%, and disintegrate again for 30 seconds using a tabletop disintegrator. After diluting the slurry to 1% with water,
Flotation treatment was applied for a minute. The pulp slurry after flotation was concentrated to 4% concentration with an 80 mesh wire, and then diluted to 1% concentration by adding water, and a pulp sheet was prepared using a tappy standard paper machine.

The hardness of the used water is 5 ° dH,
The hardness was adjusted using CaCl ₂ and MgCl _{2 so} that Ca / Mg = 8/2 (molar ratio). The b value of the pulp sheet obtained was measured with a colorimeter. Here, the b value refers to the b value in the Lab color system of the Hunter color difference meter, and the relationship with the tristimulus values X, Y, and Z is as follows.

[0022]

(Equation 1)

As can be seen from this equation, the b value is a function of Y and Z. A positive value indicates yellowish intensity, and a negative value indicates bluish intensity. Tables 1 and 2 show the polycarboxylic acids or their anhydrides and alcohols used in various deinking agents, their molar ratios, the types and molar ratios of AO, and the number of moles of AO added.
In Tables 1 and 2, the method of adding AO is random addition. In Tables 1 and 2, the dimer acids No. 12 and No. 24 are derived from oleic acid.

[0024]

[Table 1]

[0025]

[Table 2]

Example 2 This example is an example of the divisional addition of the deinking agent in the pulping step and the kneading step. After shredding the city collection newspaper into 2 x 5 cm pieces, put a certain amount of it into a tabletop disintegrator, and add 0.3% of water and caustic soda (based on raw materials) and 0.15% of the deinking agent (based on raw materials) shown in Table 3. In addition, pulp concentration was 15%, and after 12 separation at 45 ° C, aging treatment was performed at 55 ° C for 120 minutes. After that, dehydrate to 23% with high-speed dehydrator, and use caustic soda (based on raw material) 0.6
%, Sodium silicate No. 3 (based on raw material) 2.4%, 30% hydrogen peroxide (based on raw material) 3.0%, deinking agent shown in Table 3 (based on raw material) 0.15%
Was adjusted to a pulp concentration of 22% with water, and mixed for 1 minute using a desktop disintegrator. Thereafter, kneading treatment was performed by a biaxial lab kneader having a rotation speed of 300 rpm. Then, add water to dilute to 4%, and disintegrate again for 30 seconds using a tabletop disintegrator. After diluting the slurry to 1% with water,
Flotation treatment was applied for a minute. The pulp slurry after flotation was concentrated to 4% concentration with an 80 mesh wire, and then diluted to 1% concentration by adding water, and a pulp sheet was prepared using a tappy standard paper machine.

The hardness of the water used was 10 ° dH,
The hardness was adjusted using CaCl ₂ and MgCl _{2 so} that Ca / Mg = 8/2 (molar ratio). The b value of the pulp sheet obtained was measured with a colorimeter. Table 3 shows the polyvalent carboxylic acids or their anhydrides and alcohols used in various deinking agents, their molar ratios, the types and molar ratios of AO, and the number of moles of AO added. In Table 3, the method of adding AO is No. 34
Up to 39 are block additions, and others are random additions. In Table 3, the dimer acids No. 31 and No. 42 are derived from linoleic acid.

[0028]

[Table 3]

Example 3 This example is an example of the divisional addition of the deinking agent before the pulping step and the flotation step. After chopping the city collection newspaper into 2 x 5 cm pieces, put a certain amount of it in a tabletop disintegrator, and add 0.3% of water and caustic soda (based on raw materials) and 0.1% of the deinking agent (based on raw materials) shown in Table 4. In addition, pulp concentration was 15%, and after 12 separation at 45 ° C, aging treatment was performed at 55 ° C for 120 minutes. After that, dehydrate to 23% with a high-speed dehydrator, caustic soda (based on raw material) 0.6%,
Sodium silicate No. 3 (based on raw material) 2.4%, 30% hydrogen peroxide (based on raw material) 3.0% were added, the pulp concentration was adjusted to 22% with water, and the mixture was mixed with a desktop disintegrator for 1 minute. Thereafter, kneading treatment was performed by a biaxial lab kneader having a rotation speed of 300 rpm. afterwards,
Add water to dilute to 4%, and disintegrate again for 30 seconds using a desktop disintegrator. After adding 0.2% of the deinking agent (based on raw material) shown in Table 4 to the pulp slurry, the slurry was diluted to 1% with water, and then subjected to a flotation treatment at 30 ° C. for 10 minutes to remove bubbles from the flotation reject. The properties were measured. The pulp slurry after flotation was concentrated to a concentration of 4% with an 80-mesh wire, and then diluted with water to a concentration of 1% to prepare a pulp sheet using a tappy standard paper machine.

The water used had a hardness of 15 ° dH,
The hardness was adjusted using CaCl ₂ and MgCl _{2 so} that Ca / Mg = 8/2 (molar ratio). The b value of the pulp sheet obtained was measured with a colorimeter. Table 4 shows the polycarboxylic acids or their anhydrides and alcohols used in various deinking agents, their molar ratios, the types and molar ratios of AO, and the number of moles of AO added. In Table 4, the method of adding AO is random addition. The number in parentheses of the comparative product 51 means the average number of moles added.

[0031]

[Table 4]

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-370285 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D21C 5/02

Claims (2)

(57) [Claims] 1. An alkylene oxide is added to a reaction mixture comprising (a) a polycarboxylic acid or its anhydride and (b) an alcohol in an average addition mole number of more than 300 moles and not more than 1000 moles. A deinking agent comprising an ester mixture. (2) a polycarboxylic acid or an acid anhydride thereof;
2. The deinking agent according to claim 1, wherein the molar ratio of (b) the alcohol is (a) / (b) = 1 / 0.02 to 5.