JP4260578B2 - Deinking agent - Google Patents

Description

  The present invention relates to a deinking agent.

In conjunction with global environmental issues such as forest resource protection and waste disposal, the effective use of waste paper has become increasingly important. In using deinked pulp regenerated from waste paper, it is necessary to obtain deinked pulp of higher quality, that is, less residual ink, in order to achieve a high blending ratio. Deinking requires efficient deinking that separates ink from paper and ink that separates the peeled ink from pulp. Deinking agents also have good ink-removing and ink-collecting properties. Development of a deinking method is desired. As a deinking agent, a reaction product obtained by adding alkylene oxide (hereinafter referred to as AO) to a mixture of fats and alcohols (for example, Patent Document 1), a reaction product obtained by adding AO to a fatty acid (for example, Patent Document 2). ), Reaction products obtained by adding AO to higher alcohols (for example, Patent Documents 3 and 4) and the like have been developed. Higher alcohol AO adducts are used as deinking agents that are economical and versatile. Yes.
Patent No. 1573380 Patent No. 2645208 Patent No. 2999363 Patent 3081120

  However, although higher alcohol AO adducts are excellent in ink releasability, they have strong ink dispersibility and inferior ink collecting properties. In order to obtain deinked pulp with higher quality, that is, less residual ink, an ink collector such as fatty acid is used in the flotation process and the previous process in order to supplement the ink collecting property, and the pulp yield is also increased. There are measures such as allowing a decrease and increasing the foamability in the flotation process to increase the amount of floss discharged. However, these measures have problems in terms of work, facilities, and cost because additional processing is performed. Therefore, it is desired to further improve the performance of the deinking agent itself.

The present invention contains a compound represented by the following general formula (Y), hydroxyl value (OHV), saponification value (SV), acid value (AV) is 0 to 0.3 in OHV / (SV-AV + OHV). Relates to deinking agents that are in the range of
X- [O- (AO) mR] n (Y)
[In the formula, each R is a hydrogen atom or an acyl group having 1 to 24 carbon atoms, at least one is an acyl group having 8 to 24 carbon atoms, and A is an alkylene group having 2 to 4 carbon atoms. A having different carbon numbers may be mixed, m × n is a number of 45 to 1000, X is a trivalent to 10 valent polyhydric alcohol group, and n is a valence of X Same number from 3 to 10. ]

  The polyhydric alcohol group is a residue obtained by removing hydrogen from the alcohol hydroxyl group of the polyhydric alcohol. Examples of the compound represented by the general formula (Y) include compounds in which the compound is represented by the following general formula (a).

[Wherein, R ^{1 to} R ³ are each a hydrogen atom or an acyl group having 1 to 24 carbon atoms, at least one of which is an acyl group having 8 to 24 carbon atoms, and A is a group having 2 to 4 carbon atoms. In the alkylene group, a plurality of A's having different carbon numbers may be mixed, and a + b + c is a number of 45 to 1,000. ]

  The present invention also relates to a deinking method using the deinking agent of the present invention in a deinking step.

  Further, the present invention includes a step of esterifying a compound obtained by adding an alkylene oxide to a mixture of a trivalent to 10-valent polyhydric alcohol and an oil and fat and a carboxylic acid at 100 ° C to 260 ° C. Y) containing a deinking agent, wherein the deinking agent has a hydroxyl value (OHV), a saponification value (SV) and an acid value (AV) of OHV / (SV-AV + OHV) = 0 to The present invention relates to a method for producing a deinking agent in the range of 0.3.

  Further, the present invention contains the above general formula (Y), which includes a step of esterifying a compound obtained by adding an alkylene oxide to a trivalent to 10-valent polyhydric alcohol and a carboxylic acid at 100 ° C to 260 ° C. A method for producing a deinking agent, wherein the hydroxyl value (OHV), saponification value (SV) and acid value (AV) of the deinking agent are in the range of OHV / (SV-AV + OHV) = 0 to 0.5. The present invention relates to a deinking agent production method and a deinking agent obtained by the production method.

  The deinking agent of the present invention can improve the ink collecting ability in the flotation process, and can obtain high-quality deinked pulp without reducing the pulp yield.

  The mechanism by which the ink collecting property of the deinking agent of the present invention is good is not clear, but as described below, the compound represented by the general formula (Y) of the present invention, preferably the general formula (a) Then, it is considered that the formation of a micelle structure connected by an AO chain contributes to an improvement in ink collecting ability.

In order to form a micelle structure linked by an AO chain, R of the compound represented by the general formula (Y), preferably R ¹ , R ² , R ^{3 of the} compound represented by the general formula (a) Is preferably a large proportion of acyl groups which are hydrophobic groups, and a small proportion of hydroxyl groups which are hydrophilic groups. In general, in the production of the compound represented by the general formula (Y), preferably the general formula (a), a mixture of compounds having different numbers of hydroxyl groups and acyl groups, and by-products having hydroxyl groups, acyl groups and carboxyl groups. Is obtained. OHV is the number of hydroxyl groups, SV is the total number of acyl groups and carboxyl groups, AV is an index of the number of carboxyl groups, and an acyl group (SV-AV) is an index of the ability to form micelle structures linked by AO chains. ) And the ratio of hydroxyl groups to the total of hydroxyl groups (OHV) [OHV / (SV-AV + OHV)] can be used.

  That is, the general formula (Y) of the present invention contained in the deinking agent satisfying the range where OHV / SV, AV is OHV / (SV−AV + OHV) is 0 to 0.3 (or 0 to 0.5 in a specific production method). ) Or the compound represented by the general formula (a), since most of the terminal OH groups of the AO chain are substituted with hydrophobic groups, when the micelle is formed, the hydrophobic portion of two adjacent micelles has an AO chain. One of the two hydrophobic groups at both ends is taken in, and sharing of the AO chain (EO / PO chain, etc.) between the hydrophobic groups occurs, and a three-dimensional network structure of micelles is formed.

  Here, the ink collecting property is a performance in which the ink particles dispersed with the deinking agent are adsorbed to the generated bubbles and float on the water surface, and the strength with which the dispersed ink particles are adsorbed to the bubbles is dispersed. It is determined by the strength of the hydrophobic bond between ink particles and bubbles.

There are two possible mechanisms for improving the ink collecting power according to the present invention.
1) In the deinking agent that forms micelles that are not linked by the AO chain (conventional), it is necessary to re-adsorb the hydrophobic group adsorbed on the ink particles to the air bubble. Of the linked micelle structures, the hydrophobic chains of micelles that are not adsorbed on the ink particles are adsorbed to the bubbles, and at the same time, the ink particles connected with the AO chain are also attracted and adsorbed. Can play that role independently.
2) Since such a structure is formed, it is difficult to cover the ink particles completely with hydrophobic chains due to three-dimensional crowding, so that hydrophobic surfaces may remain on the surface of the ink particles. It is considered to be a facilitating factor.

  In the deinking agent of the present invention, OHV / (SV-AV + OHV) is 0 to 0.3, preferably 0 to 0.2, more preferably 0 to 0.1. When OHV / (SV-AV + OHV) is 0.3 or less, the ink collecting power is improved. In addition to the compound represented by the general formula (Y) or the general formula (a) in the deinking agent, the value of OHV such as ethylene glycol, glycerin, lower alcohols having 7 or less carbon atoms, and these low AO addition mole compounds. When a high compound is added, in order to eliminate the influence of the compound having a high OHV value added later, OHV / (SV-AV + OHV) is measured for a fraction having a weight average molecular weight of 2000 or more, What satisfies said range is preferable. Further, foamability in the flotation process is also reduced, and the yield is improved.

Here, the weight average molecular weight means a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) under the following conditions.
Column: G4000HXL + G2000HXL (manufactured by Tosoh Corporation)
Eluent: THF (in 50mmol / l CH ₃ COOH)
Flow rate: 1.0mL / min
Column temperature: 40 ° C
Detector: RI
Sample size: 5mg / mL, 100μl

  Further, OHV (hydroxyl value), SV (saponification value), and AV (acid value) are measured by the test method described in JIS K 0070. Specifically, OHV is a potentiometric titration method (pyridine-acetic anhydride method), SV is a potentiometric titration method, and AV is a potentiometric titration method.

  The compound represented by the general formula (a) is obtained by using glycerin or a mixture of glycerin and oil as a raw material compound, ethylene oxide (hereinafter referred to as EO), propylene oxide (hereinafter referred to as PO), butylene oxide (hereinafter referred to as PO). , Expressed as BO), and a mixture of compounds having an ester bond to which one or more alkylene oxides (hereinafter referred to as AO) added.

  According to the present invention as described above, a reaction product obtained by adding a C2-C4 alkylene oxide to glycerin or a mixture of glycerin and oil and fat, and an esterification reaction product of a carboxylic acid, a hydroxyl value (OHV) A deinking agent having a saponification value (SV) and an acid value (AV) of OHV / (SV-AV + OHV) in the range of 0 to 0.3 is provided. In the esterification reaction product, the ratio of the compound represented by the general formula (Y) or (a) is preferably 50% by weight or more, more preferably 80% by weight or more, particularly preferably 90% by weight or more, and particularly preferably the weight average molecular weight is 2000 or more. The ratio of the compound is preferably 80% by weight or more, more preferably 90% by weight or more.

  In the compound represented by the general formula (Y) or (a), the more the terminal OH group of the AO chain is substituted with a hydrophobic group, that is, the closer OHV / (SV-AV + OHV) approaches 0 Ink collecting ability is improved. It is a good deinking agent in deinking facilities that prefer low foaming in the flotation process.

  On the other hand, the foaming property increases as OHV / (SV-AV + OHV) increases from 0, but the pulp yield tends to decrease as the bubble property increases. From the viewpoint of pulp yield, OHV / (SV-AV + OHV) is preferably 0.5 or less.

  In the esterification reaction of a compound obtained by adding an alkylene oxide to a mixture of a trivalent to 10-valent polyhydric alcohol and an oil for a compound represented by the general formula (Y) or (a) and a carboxylic acid, When an alkylene oxide is added to a mixture of a monohydric alcohol and an oil and fat, a polyalkylene oxide compound containing no polyhydric alcohol is produced as a by-product. This compound is inferior in deinking performance. When using a compound in which an alkylene oxide is added to a mixture of a trihydric to 10 valent polyhydric alcohol and oil as a raw material for esterification, a by-product other than the compound represented by the general formula (Y) or (a) Therefore, OHV / (SV-AV + OHV) is preferably in the range of 0 to 0.3.

  On the other hand, when a compound obtained by adding an alkylene oxide to a trivalent to 10-valent polyhydric alcohol is used as a raw material for esterification and no fat or oil is mixed, a polyalkylene oxide compound containing no polyhydric alcohol is hardly produced. When a compound obtained by adding an alkylene oxide to a trivalent to 10-valent polyhydric alcohol is used as a raw material for esterification and no fats and oils are mixed, OHV / (SV-AV + OHV) is preferably in the range of 0 to 0.5.

  Thus, when using the deinking agent manufactured without mixing fats and oils, OHV / (SV-AV + OHV) is preferably from 0 to 0.5, more preferably from 0.1 to 0.5, from the viewpoint of foamability and pulp yield. 0.5, more preferably 0.2 to 0.5, particularly preferably 0.3 to 0.45. In particular, OHV / (SV-AV + OHV) is preferably 0.2 to 0.45 for deinking equipment that requires high foaming in the flotation process, and 0.1 to 0.3 for deinking equipment that requires low foaming. Is preferred.

  The temperature of the esterification reaction is preferably from 100 to 260 ° C., more preferably from 140 to 260 ° C., particularly preferably from 160 to 260 ° C. from the viewpoint of preventing the reaction rate and cleavage of the polyalkylene oxide chain. It is preferable to use a catalyst suitable for the reaction temperature.

  It is particularly preferred that OHV = 0, that is, the terminal OH group of AO is completely substituted with a hydrophobic group, but a part of the terminal OH group may be present.

  The average number of moles of AO added is in the range of 45 to 1000 per mole of the substance to which AO is added, more preferably 70 to 1000, still more preferably 100 to 1000, and particularly preferably 150 to 1000. Moreover, when handling property is considered, the range of 150-600 is the most preferable. When the average added mole number of AO is 45 or more, a connected micelle is formed and the effect of the present invention can be obtained satisfactorily.

  In the compound represented by the general formula (Y) or the general formula (a), the addition form in the case of containing two or more kinds of AO may be a block polymer chain or a random polymer chain, and is not particularly limited. In consideration of the amount of bubbles, the abundance ratio (molar ratio) of EO in AO is preferably EO / AO = 0.3-1. As AO, EO and PO are preferably used in combination, and the molar ratio in that case is preferably EO / PO = 10/0 to 3/7, more preferably 9/1 to 4/6.

R in the general formula (Y) or R ^{1 to} R ³ in the general formula (a) are each a hydrogen atom or an acyl group having 1 to 24 carbon atoms, and at least one of them is an acyl having 8 to 24 carbon atoms. More preferably two or more are acyl groups. These acyl groups may be unsaturated or saturated. Of all the groups of R and R ^{1 to} R ³ , the proportion of the acyl group having 8 to 24 carbon atoms and 12 to 24 carbon atoms is preferably 80% by weight or more.

The content of the compound represented by the general formula (Y) or the general formula (a) in the deinking agent is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, and particularly preferably 80 to 100% by weight.

  The compound represented by the general formula (Y) or the general formula (a) can be obtained by esterifying a reaction product obtained by adding AO to glycerin or a mixture of glycerin and fat and oil and a carboxylic acid. The adjustment of OHV / (SV-AV + OHV) can be performed by setting the AV target value from the molar ratio of the charged raw materials and measuring AV by sampling.

  The compound represented by the general formula (a) is also present in a known reaction product obtained by adding AO to a mixture of fats and oils and alcohols. However, in these reactions, for example, by reacting with the formulation described in Japanese Patent No. 1573380, by-products such as AO copolymers are formed in addition to the compound represented by the general formula (a), the OHV value becomes large, and the entire mixture is increased. OHV / (SV + OHV-AV) is greater than 0.3.

  As the carboxylic acid used for the production of the compound represented by the general formula (Y) or the general formula (a), a carboxylic acid having 8 to 24 carbon atoms is used. Specific examples include lauric acid, stearic acid, oleic acid and the like. C1-C7 carboxylic acid can be used together as needed.

  The deinking agent of the present invention is a known deinking agent, for example, a higher alcohol AO adduct, a fatty acid AO adduct, an AO adduct of a mixture of fats and alcohols, an AO addition of a mixture of a polyvalent carboxylic acid and an alcohol. You may use together. In addition, for the purpose of increasing the yield of deinked pulp, for example, higher fatty acids, higher fatty acid salts, etc., and higher alcohol sulfates, glycerin, etc. in consideration of operational improvements such as control of foaming and foam suppression in the flotation process. These polyhydric alcohols and these AO adducts may be used together.

  If the deinking agent of the present invention is added to any step before the flotation step, a higher-quality deinked pulp can be obtained. Generally, the deinking agent of the present invention is added to any or all of the pulping process, mixing process, and flotation process. The amount of addition is not particularly limited, but is preferably 0.03 to 1.0% by weight based on the raw paper.

Production Example 1-1
A 2 liter autoclave was charged with 230.3 g and 16.8 g of glycerin and 100% KOH, respectively, and heated to 135 ° C. at a stirring speed of about 600 rpm. Next, 1753 g of a mixture having a molar ratio of EO and PO of 228: 102 was reacted with the above reaction mixture (corresponding to 10 mol of EO and 4.5 mol of PO with respect to 1 mol of glycerin). The reaction conditions at this time were a temperature of 135 ° C. and a pressure of 1 to 3 kg / cm ² (98 to 294 kPa) (gauge pressure). After completion of the reaction, the temperature was cooled to 80 ° C. to obtain an intermediate product 1 (reaction product corresponding to 10 mol of EO and 4.5 mol of PO per 1 mol of glycerin).

Next, 290 g of intermediate compound 1 was charged into a 2 liter autoclave and heated to 135 ° C. at a stirring speed of about 600 rpm to react 1678 g of a mixture having a molar ratio of EO and PO of 228: 102. The reaction conditions at this time were a temperature of 135 ° C. and a pressure of 1 to 3 kg / cm ² (98 to 294 kPa) (gauge pressure). After completion of the reaction, the temperature was cooled to 80 ° C. to obtain an intermediate product 2 (reaction product corresponding to 76 mol of EO and 34 mol of PO for 1 mol of glycerin) with AV = −1.1, OHV = 35.7, and SV = −1.1.

  Next, the intermediate compound 2, stearic acid (AV = 202.7) obtained in a 200 ml four-necked flask, was calculated from the molar ratio ((a) / (b ) Reaction ratio) is 1: 1.2. Charged 124.4g and 26.3g, respectively, and allowed to react at 215 ° C for 8 hours under nitrogen, AV = 6.5, OHV = 2.8, SV = 34.7, OHV / (SV-AV A compound having a + OHV) of 0.09 (Test No. 7 in Table 1) was obtained.

Production Example 1-2
Into a 2 liter autoclave, 668 g of the intermediate compound 2 synthesized in Production Example 1-1 was charged, the temperature was raised to 135 ° C. at a stirring speed of about 600 rpm, and 1311 g of a mixture having a molar ratio of EO and PO of 228: 102 was obtained. Reacted. The reaction conditions at this time were a temperature of 135 ° C. and a pressure of 1 to 3 kg / cm ² (98 to 294 kPa) (gauge pressure). After completion of the reaction, the temperature was cooled to 80 ° C. to obtain an intermediate compound 3 (reaction product corresponding to 228 mol of EO and 102 mol of PO with respect to 1 mol of glycerin) of AV = −0.3, OHV = 16.3, SV = −0.38.

  Next, the intermediate compound 3, stearic acid (AV = 202.7) obtained in a 200 ml four-necked flask is set to have a molar ratio of 1: 1.2 calculated from OHV of the intermediate compound 3 and AV of stearic acid. 136.8g and 13.2g were charged at 215 ° C for 8 hours under nitrogen injection, and AV = 2.3, OHV = 0.7, SV = 17.8, OHV / (SV-AV + OHV) 0.04 (Table) Test No. 1) in No. 1 was obtained.

Production Example 1-3
A 2 liter autoclave was charged with 151.1 g and 4.8 g of beef tallow and glycerin (0.3 mol of glycerine with respect to 1 mol of beef tallow) and 1.2 g of 100% KOH, respectively, and heated to 135 ° C. at a stirring speed of about 600 rpm. Next, 1834.4 g of a mixture having a molar ratio of EO and PO of 148: 66 was reacted with the above reaction mixture (equivalent to 148 mol of EO and 66 mol of PO per mol of beef tallow). The reaction conditions at this time were a temperature of 135 ° C. and a pressure of 1 to 3 kg / cm ² (98 to 294 kPa) (gauge pressure). After completion of the reaction, the temperature is cooled to 80 ° C, and a compound with AV = 0.52, OHV = 18.9, SV = 16.7, OHV / (SV-AV + OHV) is 0.54 (equivalent to EO148 mol, PO66 mol per mol of tallow) The reaction product, test No. 17) in Table 1, was obtained.

Production Example 1-4
In the 200 ml four-necked flask, the molar ratio of the compound synthesized in Production Example 1-3, stearic acid (AV = 202.7), calculated from the synthetic OHV and stearic acid AV is 1: 1.2. 134.9g and 15.1g, respectively, were reacted at 215 ° C for 8 hours under nitrogen filling, and OHV = 0, OHV / (SV-AV + OHV) was 0 (Test No. 14 in Table 1) Got.

  Test No. 18 in Table 1 was synthesized in the same manner as in Production Example 3, and Test Nos. 2-6, 8-13 and Test Nos. 15, 16 were the same as Production Example 1-1 or 1-2. In the same manner, AO was added to glycerin, and the compound before the esterification reaction was synthesized as an intermediate product. Then, the intermediate product and carboxylic acid were charged and esterified.

note)
* 1: The (a) / (b) reaction ratio is the ratio of the esterification reaction, and is represented by the molar ratio calculated from OHV in (a) and AV in (b) (the same applies hereinafter).
* 2: Average number of moles of AO added to the glycerin skeleton
* 3: Deinking agent OHV / (SV-AV + OHV) (the same applies hereinafter)

Example 1
Using the deinking agents shown in Table 1, the deinking process was performed according to the following procedure, and the deinking performance was evaluated. The results are shown in Table 2.

[Deinking]
City-collected newspaper waste paper (raw material) is deteriorated at 80 ° C for 5 hours and cut to 2cm x 5cm, and then a certain amount of it is put into a desktop disintegrator, in which 0.5% by weight of hot water and caustic soda (raw material), deinking agent (Raw material) 0.3% by weight was added, and the pulp concentration was 4% by weight, and the disaggregation treatment was performed at 3,000 rpm for 10 minutes at 45 ° C. Next, it is concentrated to a pulp concentration of 17% by weight, caustic soda (vs. raw material) 1.0% by weight, sodium silicate No. 3 (vs. raw material) 2.0% by weight, hydrogen peroxide (vs. raw material) 0.3% by weight, warm water added to pulp concentration 15% by weight As follows, bleaching was performed for 2 hours in a high-temperature water bath at 55 ° C, and the pulp slurry was diluted with hot water to a pulp concentration of 1.0% by weight, and then subjected to flotation treatment at 40 ° C for 6 minutes (Flotator manufactured by Kyokuto Shinko Co., Ltd.) use).

Add 10% by weight of aluminum sulfate to the pulp slurry after flotation and stir, then, according to JIS P8209, 150g / m ² basis paper with 150 mesh wire (mesh size 109μm) (deinking treatment) Sheet).

In addition, the pulp slurry obtained by the deinking treatment was concentrated to a pulp concentration of 10% by weight with # 80 mesh wire (aperture 180 μm) and diluted with tap water to a pulp concentration of 1% by weight. Hand-washed sheet with a basis weight of 150 g / m ² with a 150 mesh wire (aperture 109 μm) according to JIS P8209, after adding 10% by weight of aluminum sulfate as a fully washed pulp slurry and stirring. ) Was produced.

[Deinking performance]
(1) Whiteness About the above deinking treatment sheet, Hunter whiteness was measured using SPECTRO COLOR METER PF-10 (MGO standard) manufactured by Nippon Denshoku Industries Co., Ltd., and the average value of the front and back sides was obtained. The significant difference in whiteness in this example is 0.5% or more.

(2) Ink collection performance Using the ERIC950 of Technidyne for the above deinking treatment sheet and complete washing treatment sheet, the residual ink effect density is measured, and the residual ink effect of the complete washing treatment sheet as an index of ink collection performance Evaluation was based on the difference between the density (I) and the residual ink effect density (II) of the deinked sheet. The smaller the difference, the higher the ink collecting property. The significant difference is 20 ppm.

(3) Pulp yield In the above deinking process, the difference between the weight of the pulp before deinking (A) and the weight of the pulp discharged from the flotator by the deinking process (B) is calculated as the pulp before deinking. The value divided by the weight (A) was multiplied by 100 [ie, [(A)-(B)] / (A) × 100) to obtain the pulp yield (%). The significant difference in yield in this example is 0.5% or more.

Production Example 2-1
A 2 liter autoclave was charged with 250.0 g and 18.3 g of glycerin and 100% KOH, respectively, and heated to 135 ° C. at a stirring speed of about 600 rpm. Next, 1416 g of a mixture having a molar ratio of EO and PO of 210: 90 was reacted with the above reaction mixture (equivalent to 7.5 mol of EO and 3.2 mol of PO with respect to 1 mol of glycerin). The reaction conditions at this time were a temperature of 135 ° C. and a pressure of 1 to 3 kg / cm 2 (98 to 294 kPa) (gauge pressure). After completion of the reaction, the temperature was cooled to 80 ° C., and extracted from the 1434.3 g autoclave to leave 250 g in the autoclave. The autoclave containing 250 g of the intermediate product was heated to 135 ° C. at a stirring speed of about 600 rpm, and 1416 g of a mixture having a molar ratio of EO and PO of 210: 90 was reacted. The reaction conditions at this time were a temperature of 135 ° C. and a pressure of 1 to 3 kg / cm ² (98 to 294 kPa) (gauge pressure). After completion of the reaction, the temperature was cooled to 80 ° C., extracted from the 1166 g autoclave, and 500 g remained in the autoclave. An autoclave containing 500 g of the intermediate product (equivalent to 58.7 mol of EO and 15.1 mol of PO per 1 mol of glycerin) was heated to 135 ° C. at a stirring speed of about 600 rpm, and the molar ratio of EO and PO was 210: 1264 g of 90 mixtures were reacted. The reaction conditions at this time were a temperature of 135 ° C. and a pressure of 1 to 3 kg / cm ² (98 to 294 kPa) (gauge pressure). After completion of the reaction, the temperature was cooled to 80 ° C. to obtain a reaction product (a1) with AV = −0.13, OHV = 15.2, and SV <1.

  Next, the reaction product (a1) and stearic acid (AV = 202.7) obtained in a 1-liter four-necked flask were converted to the moles of both calculated from the OHV of the reaction product (a1) and the AV of stearic acid (b1). 905.9 g and 88.3 g were charged so that the ratio ((a) / (b) reaction ratio) was 1 / 1.3, and dibutyltin oxide was further charged as a catalyst. ) Esterification reaction was carried out while blowing nitrogen at 225 ° C. ± 5 ° C.

  A compound (Test No. 1 in Table 3) having AV = 5.7, OHV = 3.2, SV = 18.4, and OHV / (SV-AV + OHV) of 0.20 was obtained after 4 hours of reaction.

  A compound (Test No. 2 in Table 3) having AV = 5.2, OHV = 2.7, SV = 18.4, and OHV / (SV-AV + OHV) of 0.17 was obtained after 5 hours of reaction.

  A compound (Test No. 3 in Table 3) having AV = 4.2, OHV = 1.2, SV = 18.3, and OHV / (SV-AV + OHV) of 0.08 was obtained after 6 hours of reaction.

Production Example 2-2
The reaction product (a1) and stearic acid (AV = 202.7) are mixed in a 1 liter four-necked flask with the molar ratio of (A) between the OHV of the reaction product (a1) and the AV of stearic acid (b1). ) / (B) reaction ratio) of 1 / 2.2 and 321.8 g and 28.9 g, respectively, and dibutyltin oxide as a catalyst and 0.5 wt% (1.8 g) of the total weight. The esterification reaction was carried out while blowing nitrogen at a temperature of ± 5 ° C.

  A compound (Test No. 4 in Table 3) having AV = 8.5, OHV = 6.3, SV = 17.4, and OHV / (SV-AV + OHV) of 0.41 was obtained after 4 hours of reaction.

  A compound (Test No. 5 in Table 3) having AV = 7.6, OHV = 5.4, SV = 17.5, and OHV / (SV-AV + OHV) of 0.35 was obtained after 5 hours of reaction.

Production Example 2-3
A 2 liter autoclave was charged with 244.2 g and 5.3 g of beef tallow and glycerin (0.2 mol of glycerine with respect to 1 mol of beef tallow) and 3.6 g of 100% KOH, respectively, and heated to 135 ° C. at a stirring speed of about 600 rpm. Subsequently, 1604 g of a mixture having a molar ratio of EO and PO of 206: 83 was reacted with the above reaction mixture (69 mol of EO and 28 mol of PO corresponding to 1 mol of glycerin skeleton). The reaction conditions at this time were a temperature of 135 ° C. and a pressure of 1 to 3 kg / cm ² (98 to 294 kPa) (gauge pressure). After completion of the reaction, the temperature was cooled to 80 ° C. and extracted from the 1396 g autoclave, leaving 460 g in the autoclave. The autoclave containing 460 g of the intermediate product was heated to 135 ° C. at a stirring speed of about 600 rpm, and 786 g of a mixture having a molar ratio of EO and PO of 206: 83 was reacted. The reaction conditions at this time were a temperature of 135 ° C. and a pressure of 1 to 3 kg / cm ² (98 to 294 kPa) (gauge pressure). After completion of the reaction, the temperature is cooled to 80 ° C. (equivalent to 206 mol of EO and 83 mol of PO for 1 mol of glycerin skeleton), AV = 0.06, OHV = 13.8, SV = 8.4, OHV / (SV-AV + OHV) = 0.62. A composite (Test No. 19 in Table 3) was obtained.

Production Example 2-4
In a 200 ml four-necked flask, the reaction product (a1) and stearic acid (AV = 202.7) were mixed with the molar ratio of (a) between the OHV of the reaction product (a1) and the AV of stearic acid (b1). ) / (B) reaction ratio) is 1/2, respectively, 148.0 g and 22.2 g are charged, and dibutyltin oxide is charged as a catalyst, and 0.5% by weight (0.86 g) is charged with respect to the sum of the weights. A compound with AV = 14.8, OHV = 2.8, SV = 26.0, OHV / (SV-AV + OHV) of 0.20 obtained by performing esterification reaction while blowing nitrogen at ℃ ± 5 ℃ stearin at 5.2 kPa. The acid was distilled off under reduced pressure to obtain a compound (Test No. 6 in Table 3) in which AV = 4.3, OHV = 3.0, SV = 16.3, and OHV / (SV-AV + OHV) was 0.20.

Production Example 2-5
In a 200 ml four-necked flask, the reaction product (a1) and stearic acid (AV = 202.7) were mixed with the molar ratio of (a) between the OHV of the reaction product (a1) and the AV of stearic acid (b1). ) / (B) reaction ratio) is 1 / 1.2, 145.4 g and 13.1 g are charged, respectively, and dibutyltin oxide is charged as a catalyst. Perform esterification reaction while blowing nitrogen at ℃ ± 5 ℃, AV = 1.1, OHV = 2.9, SV = 17.4, OHV / (SV-AV + OHV) is 0.15, (SV **-AV ** + OHV * *) Compound with 19.2, (SV * -AV * + OHV *) = 14.1, (SV **-AV ** + OHV **) / (SV * -AV * + OHV *) = 1.36 (table Test No. 20) in No. 3 was obtained. Here, SV **, AV **, OHV **, SV *, AV *, and OHV * are defined as follows. When either (a) or (b) is charged and the smaller number of moles is completely consumed, the theoretical values of SV, AV, and OHV after the reaction are SV *, AV *, and OHV *, and the actual reaction When SV, AV, and OHV are later measured as SV **, AV **, and OHV **, some of the cleaved polyalkylene oxide volatilizes (SV **-AV ** + OHV Since the value of **) / (SV * -AV * + OHV *) increases, it can be estimated that it is not easy to obtain the deinking agent of the present invention. The value of (SV **-AV ** + OHV **) / (SV * -AV * + OHV *) is preferably smaller than 1.25.

Production Example 2-6
Test No. 7 in Table 3 shows that the reaction product (a1) and stearic acid (AV = 202.7) were calculated from the molar ratio of the reaction product (a1) calculated from the OHV of the reaction product (a1) and the AV of stearic acid (b1) (( a) / (b) reaction ratio) is the same as the reaction ratio in the table, and the same esterification reaction as in Production Example 2-1 was performed except that the esterification reaction was carried out for 3 hours while blowing nitrogen at 250 ° C. at 5 ° C. Obtained by the esterification method.

Production Example 2-7
Test Nos. 8 to 18 and 22 to 23 in Table 3 produce the reaction product (a) in the same manner as in Production Example 1 in the table, and then the reaction product (a) and carboxylic acid (b) in the table. It was obtained by the same esterification method as in Production Example 2-1, except that it was charged at a reaction ratio of (a) / (b).

  In Test No. 21, the reaction product (a1) and stearic acid (AV = 202.7) were calculated from the molar ratio of (OH) of the reaction product (a1) and AV of stearic acid (b1) ((a) / (B) It is blended and made uniform so that the reaction ratio) becomes 1 / 1.3.

Example 2
Using the deinking agents in Table 3, the same deinking treatment as in Example 1 was performed, and the deinking performance was evaluated. The results are shown in Table 4. However, MT flotator manufactured by Ishikawajima Industrial Machinery Co., Ltd. was used for the flotation treatment. Moreover, the deinking agent addition rate in Table 4 is% by weight of the raw material.

  In the evaluation of the deinking agent, the strength of the deinking agent affects the pulp yield, but the level of the pulp yield greatly affects the whiteness and the ink collecting property. That is, when the pulp yield is low, the whiteness and the ink collecting property are increased. There are various characteristics in the deinking process, and there are those that prefer a low-foaming deinking agent and others that prefer a high-foaming deinking agent. For the above reasons, it is difficult to compare the deinking ability with respect to the whiteness and ink collecting ability for different pulp yields. Therefore, the deinking property was evaluated by the whiteness and the ink collecting ability (deinking efficiency) for the same pulp yield.

  In Test No. 24 and Test No. 25, a known deinking agent was used in an amount of 0.3% by weight and 0.2% by weight, respectively, based on the raw material.

  Note that the pulp yield is plotted on the X-axis, the whiteness is plotted on the Y-axis, the pulp yield (100%) and the whiteness before deinking treatment are used as the starting points, and the plots of the present invention products are No.24 to No.25. If these curves are estimated, it is unlikely that these curves intersect, and it can be estimated that the deinking efficiency of the product group of the present invention is high.

  No. 20 is not preferable as a product form in terms of promoting blackening and handling properties at the same time as the performance is lower than the deinking agent of the present invention.

Claims (6)

It contains a compound represented by the following general formula (a), and has a hydroxyl value (OHV), saponification value (SV), and acid value (AV) in the range of 0 to 0.12 as OHV / (SV-AV + OHV). A deinking agent,
An esterification reaction product of a reaction product obtained by adding an alkylene oxide to glycerin or a mixture of glycerin and oil and a carboxylic acid selected from lauric acid, stearic acid, and oleic acid, the compound represented by the general formula (a) Is a deinking agent .

[Wherein, R ^{1 to} R ³ are each a hydrogen atom or an acyl group derived from a carboxylic acid selected from lauric acid, stearic acid and oleic acid , and at least one of them is derived from lauric acid, stearic acid and oleic acid. It is an acyl group derived from a selected carboxylic acid, A may be an alkylene group having 2 to 4 carbon atoms, a plurality of A may have different carbon numbers, and a + b + c is a number from 330 to 600. ] The hydroxyl value (OHV), saponification value (SV), and acid value (AV) of the fraction having a weight average molecular weight of 2000 or more are in the range of 0 to 0.12 in terms of OHV / (SV-AV + OHV). Deinking agent. A deinking method using the deinking agent according to claim 1 or 2 in a deinking step. The general formula according to claim 1, comprising a step of esterifying the compound obtained by adding an alkylene oxide to a mixture of glycerin and fat with a carboxylic acid selected from lauric acid, stearic acid, and oleic acid at 100 ° C to 260 ° C. A method for producing a deinking agent comprising the compound represented by (a) , wherein the hydroxyl value (OHV), saponification value (SV) and acid value (AV) of the deinking agent are determined by OHV / (SV-AV + OHV) = 0. A method for producing a deinking agent in the range of 0.12 . Table with a compound obtained by adding an alkylene oxide to glycerin and lauric acid, the general formula of claim 1 having the step of esterification with a carboxylic acid selected from stearic acid and oleic acid at 100 ℃ ~260 ℃ (a) A method for producing a deinking agent containing a compound to be used, wherein the hydroxyl value (OHV), saponification value (SV) and acid value (AV) of the deinking agent are OHV / (SV−AV + OHV) = 0 Method for producing deinking agent in the range of ~ 0.12 . A deinking agent obtained by the production method according to claim 4 or 5 .