JPH0860573A - Deinking agent - Google Patents

Abstract

PURPOSE: To obtain deinked pulp having high whiteness from old paper by a flotation method. CONSTITUTION: This deinking agent comprises the below-cited components A and B. The component A is composed of an adduct of (a) an α, β-unsaturated dicarboxylic acid or its an anhydride and (b) a 3-36C unsaturated fatty acid or an ester containing at least one double bond in the molecule. The component B is one or more compounds selected from (c) a 1-26C monohydric alcohol, (d) a 2-20C polyhydric alcohol and (e) a compound of the formula, [(O((EO)k (PO)m (BO)n HH}]p (R is H, methyl or ethyl group; EO is oxyethylene group; PO is oxypropylene group; BO is oxobutylene group, the addition may be random or block, the molar ratio k:m:n:1:(0.2-1):(0-0.5), k++m+n is 5-100 and (p) is 1-10).

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deinking agent for recycling used paper. More specifically, when deinking newspaper, magazines, OA waste paper, etc. by the flotation method, flotation-water washing eclectic method, washing method, etc., it is used to obtain deinked pulp with very little residual ink and high whiteness. Regarding deinking agents. [0002] Used newspapers in order to effectively use paper industry resources in response to a shortage of pulp for papermaking,
It is widely practiced to deink and recycle printed waste paper such as magazines and OA waste paper. Further, in recent years, from the viewpoints of measures against dust and environmental protection, it is required to further increase the utilization. Currently, as a deinking method, a flotation method is used in which (a) waste paper is disintegrated by disintegrating it with an alkaline agent and a surfactant to separate the ink, and air is blown into the disintegrating liquid to adhere the ink to bubbles to remove ink. (I) Flotation-water washing eclectic method in which a washing step is performed before and after the flotation (u) There is a washing method of washing with a large amount of water, and of these, the method of (a) (i) is widely adopted. In the flotation method and the flotation-water washing eclectic method, if the surfactant used during flotation has too good foaming ability, the amount of froth removed from the system is too large and the yield of pulp deteriorates. Conventionally, sodium hydroxide, sodium silicate, sodium acid, sodium phosphate, etc. have been used as alkali agents, and surfactants such as fatty acids or salts thereof, alkylbenzene sulfonates, higher alcohol sulfate ester salts, dialkyl sulfosuccinates, etc. Ionic surfactants; alkylene oxide adducts of higher alcohols, alkylphenols, fatty acids and the like, nonionic surfactants such as block or random polymers of two or more alkylene oxides have been used. Further, the deinking effect is also enhanced by using a combination of a hydrogen peroxide solution, a bleaching agent such as hypochlorite, a sequestering agent such as EDTA, and a recontamination inhibitor such as carboxymethyl cellulose and polyvinylpyrrolidone. Came. It is difficult to remove the ink from the waste paper efficiently with the conventionally known deinking agents. In particular, in the waste paper by offset printing which has been popular in recent years, it is very difficult to remove the ink due to the properties of the ink component, and the residual carbon due to recontamination and the residual ink that is unpeeled ink, so-called “beard” has become a problem. There is. To solve this problem, the following techniques have been disclosed. In JP-A-3-279479, the number of carbon atoms is 3 to 24.
Alkyl or alkenyl alcohol of 3 to 2 carbon atoms
Phenol having 1 to 2 alkyl or alkenyl groups having 4 carbon atoms, aryl alcohol having 1 to 2 alkyl or alkenyl groups having 3 to 24 carbon atoms, and 3 to 24 carbon atoms
1 to 2 bishydroxyphenylalkanes having an alkyl or alkenyl group, biscyclohexylalkanes having an alkyl or alkenyl group having 3 to 24 carbon atoms, and alkyl or alkenyl groups having 3 to 24 carbon atoms.
It has been proposed to use, as a deinking agent, an ester of a compound obtained by adding ethylene oxide and propylene oxide to a phenol-formaldehyde condensate having a polycarboxylic acid and a polyvalent carboxylic acid. JP-A-3-287888 proposes a deinking agent such as a reaction product of a compound obtained by adding ethylene oxide or propylene oxide to a higher fatty acid and a polyvalent carboxylic acid. In JP-A-4-202877, the number of carbon atoms is 8 to 24.
Modified carboxylic acid of an alkylene oxide adduct of a monohydric alcohol having 2 to 4 carbon atoms having an alkyl group or an alkenyl group, and an alkyl group or alkenyl having 8 to 24 carbon atoms obtained from a polyhydric alcohol and a monovalent fatty acid 2 to 4 carbon atoms of an ester having a group and at least one hydroxyl group
C24 to C24 obtained from a carboxylic acid modification product of an alkylene oxide adduct of the above, a polyhydric alcohol and a monovalent fatty acid
The carboxylic acid modified ester of an ester having at least one hydroxyl group with an alkyl group or alkenyl group of 2 to 2 carbon atoms
4 alkylene oxide adduct, polyhydric alcohol C 2-4 alkylene oxide adduct and an ester having an alkyl group or an alkenyl group having 8 to 24 carbon atoms and at least one hydroxyl group obtained from a monovalent fatty acid Modified carboxylic acids have been proposed as deinking agents. JP-A-4-202880 proposes, as a deinking agent, a reaction product of a compound obtained by adding ethylene oxide or propylene oxide to rosin and a polyvalent carboxylic acid. JP-A-4-202881 proposes a deinking agent such as a reaction product of a polyvalent carboxylic acid with a compound obtained by adding ethylene oxide or propylene oxide to a hydroxy fatty acid or an ester of a hydroxy fatty acid and an alcohol. . However, these deinking agents do not necessarily have sufficiently satisfactory performances in terms of pulp yield and pulp sheet whiteness. An object of the present invention is to provide a more excellent deinking agent having a small residual ink and a high whiteness. The present inventors have completed the present invention as a result of intensive investigations in view of the above problems. That is, the present invention is a deinking agent comprising the ester of the following components (A) and (B). Component (A); (a) α, β-unsaturated dicarboxylic acid, or an anhydride thereof, and (b) an unsaturated fatty acid having 3 to 36 carbon atoms or an ester having at least one double bond in the molecule. Addendum. Component (B); (c) monohydric alcohol having 1 to 26 carbon atoms (d) polyhydric alcohol having 2 to 20 carbon atoms, and (e) one or more compounds selected from compounds of the following formula (1) . R-[{O (EO) _k (PO) _m (BO) _n H}] p (1) (wherein R is a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, an alkenyl group or a divalent to 10 valent alcohol) Represents a residue, EO is an oxyethylene group, PO is an oxypropylene group, BO is an oxybutylene group, and k: m: n is a molar ratio of 1: 0.2 to 1: 0 to 0.5, And k + m
+ N is a number that becomes 5 to 100, and p is 1 to 10. The component (A) (a) α, used in the present invention,
Examples of β-unsaturated dicarboxylic acid include maleic acid and fumaric acid.
Acid, itaconic acid, mesaconic acid, citraconic acid, and the like, and the α, β-unsaturated dicarboxylic acid anhydride used in the present invention includes maleic anhydride, itaconic anhydride, citraconic acid, and the like. . Maleic acid and maleic anhydride are particularly preferable for improving various properties required for the deinking agent. These α, β-unsaturated dicarboxylic acids or their anhydrides may be used alone or in combination of two or more. The component (b) used in the present invention has 3 to 3 carbon atoms.
Examples of the unsaturated fatty acid of 2 include acrylic acid, methacrylic acid, obtusylic acid, caproic acid, undecylenic acid,
Lindelic acid, tudus acid, fizeteric acid, myristoleic acid, palmitoleic acid, petroselinic acid, oleic acid,
Elaidic acid, asclepic acid, vaccenic acid, linoleic acid, α-eleostearic acid, β-eleostearic acid, linolenic acid, γ-linolenic acid, ricinoleic acid, gadoleic acid, gondoic acid, eicosapentaenoic acid, cetoleic acid, Examples thereof include erucic acid, brassic acid, docosahexaenoic acid, ceracoleic acid, ximene acid, and dimer acid. Further, these unsaturated fatty acids can be isomerized with a selenium catalyst or the like before use. These unsaturated fatty acids may be used alone or in combination of two or more. The unsaturated fatty acid used in the present invention preferably has 8 to 22 carbon atoms, and more preferably 12 to 20 carbon atoms. When the carbon number is more than 32, the foamability is lowered during flotation and the whiteness of the pulp sheet is deteriorated, which is not preferable. Examples of the ester having at least one double bond in the molecule of the component (b) used in the present invention include the following. That is, as the acid constituting the ester, (a-1) the unsaturated fatty acid shown in the above-mentioned examples of the component (A); (a-2) propionic acid, butyric acid, valeric acid,
Caproic acid, caprylic acid, 2-ethylhexanoic acid, 3,
Examples thereof include saturated fatty acids such as 5,5-trimethylhexanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid; and (a-3) polyvalent carboxylic acids such as adipic acid and sebacic acid. Further, as the alcohol constituting the ester, (b-1) methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methylpropanol, n-pentanol,
2-methylbutanol, 3-methylbutanol, n-hexanol, 4-methyl-2-pentanol, 2-ethylbutanol, n-heptanol, 2-ethylpentanol, n-octanol, 2-ethylhexanol, n
-Nonanol, 3,5,5-trimethylhexanol,
2,6-dimethyl-4-heptanol, n-decanol, n-undecanol, n-dodecanol, 2-butyloctanol, 2,6,8-trimethyl-4-nonanol, n-tridecanol, n-tetradecanol, 2
-Pentylnonanol, n-pentadecanol, n-hexadecanol, 2-hexyldecanol, n-octadecanol, 9-octadecenyl alcohol, 2-nonylnonanol, 2-heptylundecanol, 2-octyldodeca Nole, 2-decyltetradecanol, 2-
Monohydric alcohols such as undecyl pentadecanol and 3-methoxybutanol; (b-2) 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,3- Butanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethylpentane-1,3-propanediol, 1,8-octanediol, 2,2
4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,9-nonanediol, 2-methyl-1, 8-octanediol, glycerin, pentaerythritol, 3-methyl-1,3,5-
Polyhydric alcohols such as tripentanol, trimethylolpropane, sorbitol, dipentaerythritol;
(B-3) Unsaturated alcohols such as 9-octadecenyl alcohol may be mentioned. Especially among these ingredients,
(A-1) unsaturated fatty acid and (b-1) ester of monohydric alcohol, (a-1) unsaturated fatty acid and (b-
2) Polyhydric alcohol and (a-2) ternary ester of saturated fatty acid, (a-3) polycarboxylic acid and (b-3)
And an ester with an unsaturated alcohol. These esters are unsaturated fatty acids of (a-1) or (b-
Be sure to contain the unsaturated alcohol of 3). Among these esters, esters with glycerin are particularly preferred because they are easily available. The component (a) ester used in the present invention is
Although it can be obtained by the esterification reaction described below, in the case of an ester with glycerin, natural triglyceride,
In addition, recovered oil of waste oil of these natural triglycerides used in the food industry or household can also be used. Such natural triglycerides include avocado oil,
Linseed oil, olive oil, cacao oil, kapok oil, mustard oil, tung oil, poppy seed oil, sesame oil, rice oil, safflower oil, shea butter, soybean oil, camellia oil, corn oil, rapeseed oil, palm oil, palm kernel oil, Examples include castor oil, sunflower oil, grape seed oil, jojoba oil, cottonseed oil, coconut oil, peanut oil, beef tallow, lard, fish oil, whale oil and the like. These triglycerides may be used alone or in combination of two or more. In some cases, these triglycerides may be modified by slight hydrogenation, transesterification, fractionation, positional isomerization, geometric isomerization, or the like. These triglycerides may be used after being washed with water, treated with an acid such as phosphoric acid or sulfuric acid, further treated with clay, purified by steam deodorization, alkali deoxidation and the like. The component (C) used in the present invention has 1 to 2 carbon atoms.
Examples of the monohydric alcohol of 6 include the monohydric alcohols exemplified in the above (b-1). These monohydric alcohols may be used alone or in combination of two or more. The monohydric alcohol used in the present invention preferably has 1 to 1 carbon atoms.
8 and even more preferably 1-8. When the carbon number is more than 26, the foamability during flotation is lowered and the whiteness of the pulp sheet is deteriorated, which is not preferable. Examples of the (d) polyhydric alcohol having 2 to 20 carbon atoms used in the present invention include the polyhydric alcohols exemplified in (b-2). These polyhydric alcohols may be used alone or in combination of two or more. The polyhydric alcohol used in the present invention preferably has 2 to 18 carbon atoms, and more preferably 2 to 8 carbon atoms. 20 carbons
If the amount is larger, the viscosity of the product increases, which is not preferable in practice. R in the formula (1) of the compound (1) used in the present invention is a hydrogen atom, an alkyl group having 1 to 24 carbon atoms or less, an alkenyl group, or a polyhydric alcohol having 10 to 10 valences. However, as specific examples, those corresponding to the specific examples of the above-mentioned component (c) and component (d) can be used, and preferably an alkyl group or an alkenyl group having 1 to 7 carbon atoms. And even more preferably a methyl group or an ethyl group. When the number of carbon atoms exceeds 24, the peelability of the ink is deteriorated, resulting in an increase in whiskers and a decrease in the whiteness of the pulp sheet, which is not preferable. In the formula (1), EO represents an oxyethylene group, PO represents an oxypropylene group, and BO represents an oxybutylene group, and the molar ratio of EO: PO: BO is 1: 0.2 to 1: 0 to 0. 0.5, and more preferably 1: 0.3 to 0.6: 0 to 0.2. When the molar ratio of the oxypropylene group is less than 0.2, the ink collecting property is deteriorated and, as a result, the whiteness of the pulp sheet is deteriorated, which is not preferable. In addition, foaming during flotation becomes too large, resulting in an increase in the amount of froth and a decrease in pulp yield, which is not preferable. If the molar ratio of oxypropylene groups exceeds 1, and if the molar ratio of oxybutylene groups exceeds 0.5, the amount of foaming during flotation is small and the ink cannot be removed from the system, resulting in a whiteness of the pulp sheet. It is not preferable because it decreases. K + m + n in Formula (1) is a number which becomes 5-100. It is preferably 5-70, and even more preferably 10-50. When it is less than 5, the peeling property and the collecting property of the ink are deteriorated, resulting in an increase in beard and a decrease in the whiteness of the pulp sheet, which is not preferable. On the other hand, when it exceeds 100, the foaming during flotation is small and the ink cannot be removed from the system as froth, and as a result, the whiteness is similarly lowered, which is not preferable. In order to obtain a recycled paper having a small number of residual inks and a high whiteness, a monovalent C1 to C26 of the component (B) (c) to be esterified with the adduct of the component (A) of the present invention. Alcohol and (d) a polyhydric alcohol having 2 to 20 carbon atoms,
Two or more compounds selected from the compounds represented by formula (1) in (e) are {residue of component (A)}: {residue of component (c)}: {residue of component (d)] Group}: {residue of component (e)}
= 1: 0 to 2: 0 to 4: 0 to 4, and it is preferable that the monohydric alcohol and the polyhydric alcohol do not become 0 at the same time. The molar ratio is {residue of component (A)}:
{Residue of component (c)}: {residue of component (d)}: {residue of component (e)} = 1: 0 to 1: 0 to 2: 0.5 to 2 and More preferably, the polyhydric alcohol and the polyhydric alcohol do not become 0 at the same time. When the molar ratio of the residue of the component (C) is more than 2, and when the molar ratio of the residue of the component (D) is more than 4, the peeling property and the collecting property of the ink are deteriorated, and as a result, the "beard" It is not preferable because it causes an increase and a decrease in the whiteness of the pulp sheet, and when the molar ratio of the residue of the component (e) is more than 4, foaming property is increased, and as a result, the yield of pulp during flotation is decreased, which is preferable. Absent. The adduct of the α, β-unsaturated dicarboxylic acid or its anhydride used in the present invention with an unsaturated fatty acid or an ester having at least one double bond in the molecule can be prepared by a conventionally known method. Can be synthesized. For example, it can be synthesized by a method described in US Pat. Nos. 2,188,882 and 2,188,883, which react at a high temperature of 150 ° C. or higher. Further, the silica described in JP-B-53-7412 and JP-B-53-12494,
It is also possible to synthesize using a catalyst such as alumina. Further, the phosphorus compound described in JP-A No. 61-157508 can be used to prevent coloration during the reaction. During the addition reaction, an α, β-unsaturated dicarboxylic acid is added to an unsaturated fatty acid, an ester of an unsaturated fatty acid and an alcohol, or a double bond in a triglyceride having at least one double bond in the molecule. Alternatively, it is preferable to add 0.3 to 2 equivalents of the anhydride thereof. If it is less than 0.3 equivalent, the yield of the adduct is decreased, which is not preferable.
If it is more than the equivalent amount, the viscosity of the product becomes high, which is not preferable in practice. The ester having at least one double bond in the molecule used in the present invention can be synthesized by a conventionally known method. For example, unsaturated fatty acid and alcohol 50 to 25
It can be obtained by heating to 0 ° C. and, in some cases, removing water resulting from the reaction out of the system. The reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen. For the esterification reaction, a Bronsted acid catalyst such as p-toluenesulfonic acid or sulfuric acid, a Lewis acid catalyst such as zinc oxide, activated alumina, titanium oxide or titanic acid ester, sodium hydroxide, potassium hydroxide or the like. It is also possible to use the above alkali catalyst. The ester used in the present invention can also be obtained by a transesterification reaction. The ester of the present invention comprises an adduct and (C) 1 to 1 carbon atoms.
26 monohydric alcohols, (d) polyhydric alcohols having 2 to 20 carbon atoms, and (e) transesterification with one or more compounds selected from compounds of formula (1), and transesterification Although it can be obtained by a reaction, the acid value of the ester is preferably 30 or less, and more preferably 10 or less in order to obtain a recycled paper with a small residual ink number and high whiteness.
The following is more preferable. When the acid value is higher than 30, the whiteness decreases, which is not preferable. The compound represented by the formula (1) used in the present invention can be synthesized by a conventionally known method. For example, it can be obtained by adding ethylene oxide, propylene oxide, butylene oxide and the like to a monohydric alcohol in the presence of a catalyst. At this time, both random addition and block addition are possible, but random addition is preferable. Examples of the catalyst include alkali metal hydroxides and alkali catalysts such as alcoholates, Lewis acid catalysts such as metal halides, and acetic acid. The deinking agent of the present invention is preferably used by adding sodium hydroxide, potassium hydroxide or the like during disaggregation or kneading and adjusting the solution to be alkaline. The deinking agent of the present invention can also be used in combination with conventionally known deinking agents such as fatty acids and salts thereof, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, and higher alcohol sulfates. In that case, the blending ratio of the deinking agent of the present invention is preferably 5% by weight or more (based on the entire deinking agent), and more preferably 50% by weight or more. If the blending ratio of the deinking agent of the present invention is less than 5% by weight, the effect is not sufficiently exhibited, which is not preferable. The deinking agent of the present invention is a flotation method,
Flotation-in the washing eclectic method, washing method, etc.
It is added in the disaggregation step, the kneader processing step, the aging step, the flotation step, the washing step and the like. It is preferably added in the disaggregation step and the kneader treatment step. The addition amount of the deinking agent of the present invention is preferably 0.01 to 2% by weight, more preferably 0.05 to 1% by weight, based on the used paper. The present invention will be described in more detail below with reference to examples and comparative examples. Production Example A1; Production of Adduct of Maleic Anhydride and Methyl Oleate 294 g (1 mol) of methyl oleate and 98 g (1 mol) of maleic anhydride were charged in an autoclave having a capacity of 1 liter, and the amount was 190 to 200. 12 hours at ℃, 4-5kg
The reaction was performed at a pressure of / cm ² . Unreacted maleic anhydride is removed from the obtained reaction product at 90 to 100 ° C. for 4 to 5 mmH.
It was distilled off under reduced pressure of 2 g over 2 hours to recover 39 g, and unreacted methyl oleate was distilled off under the conditions of 190 to 200 ° C. and 4 to 5 mmHg for 2 hours to recover 117 g, and maleic anhydride and olein were collected. An adduct of methyl acid (1 mol of maleic anhydride adduct to 1 mol of methyl oleate was calculated). However, the methyl oleate used had a purity of about 70% by weight and an acid value of 11. Production Example B1: Production of a compound of CH ₃ {(EO) ₂₀ (PO) ₁₀ } H 32 g (1 mol) of methanol and 4 g of potassium hydroxide (weight of 0.3% charged) in an autoclave of 3 liter capacity. Charged in, ethylene oxide 924 g (21 mol), propylene oxide 605 g (10.5 mol)
120 to 1 while maintaining the pressure at ⁴ to 7 kg / cm ^2.
Gradually added at 30 ° C. 120-130 ° C after addition
After aging for 2 hours at room temperature, while blowing nitrogen gas to remove unreacted ethylene oxide and propylene oxide, the mixture was cooled to 60 ° C., and the pH was adjusted to 7 with acetic acid at the same temperature. It was dehydrated for a period of time and filtered to obtain a random adduct (hydroxyl value 38) of methanol containing 20 mol of ethylene oxide and 10 mol of propylene oxide. Production of CH ₃ (EO) ₁₀ H Compound Ethylene oxide of methanol 10
A molar adduct was prepared. Production Example C1; Production of Compound of Example 1 97 g (0.25 mol) of an adduct of maleic anhydride and methyl oleate of Production Example A1, 20 mol of ethylene oxide of methanol and 10 mol of propylene oxide of Production Example B1. Random adduct of 369 g (0.25 mol), methanol ethylene oxide 10 mol adduct 114 g
(0.25 mol) and 1 g of P-toluenesulfonic acid
Was charged into a 1-liter four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen blowing tube, and the esterification reaction was carried out under nitrogen atmosphere at 180 ° C. for 12 hours while removing generated water out of the system. Example No. 1 (acid value 3) was obtained. Production Example A2: Production of maleic anhydride and oleic acid anhydride 98 g (1 mol) of maleic anhydride and 278 g of oleic acid
(1 mol) was charged into an autoclave having a volume of 1 liter, and the reaction was carried out at 190 to 200 ° C. for 12 hours under a pressure of 4 to 5 kg / cm ² . Unreacted maleic anhydride was distilled off from the obtained reaction product at 90 to 100 ° C. under a reduced pressure of 4 to 5 mmHg for 2 hours to recover 39 g, and further to 190 to 2
Unreacted oleic acid was distilled off under the conditions of 00 ° C. and 1 mmHg for 2 hours to recover 111 g of maleic anhydride and oleic acid adduct (calculated from 1 mol of oleic acid to 1 mol of maleic anhydride). Obtained. Production Example C2; Production of Compound of Example 2 Addition product 94 of maleic anhydride and oleic acid of Production Example A2
g (0.25 mol), 20 mol of ethylene oxide of methanol obtained in the same manner as in Production Example B1, 369 g (0.25 mol) of adduct of 10 mol of propylene oxide, 114 g of adduct of 10 mol of ethylene oxide of methanol (0.
25 mol) and 1 g of p-toluenesulfonic acid were charged into a 1-liter four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen blowing tube, and were charged under a nitrogen atmosphere at 1
The esterification reaction was carried out at 80 ° C. for 12 hours while removing the produced water out of the system, and Example No. 2 (acid value 25) was obtained. Production Example A3 In the same manner as in Production Example A1, the adduct of Production Example A3 shown in Table 1 was produced from maleic acid and methyl oleate. Production Examples A4 to A10 Production of adduct of maleic anhydride and 2-ethylhexyl oleate 98 g (1 mol) of maleic anhydride and 390 g (1 mol) of 2-ethylhexyl oleate were placed in a 1 liter autoclave. Charged at 190-200 ° C for 12 hours,
The reaction was carried out at a pressure of 4-5 kg / cm ² . Unreacted maleic anhydride from the obtained reaction product at 100 ° C, 5 mmH
39 g was distilled off under reduced pressure of 2 g over 2 hours, and an adduct of maleic anhydride and 2-ethylhexyl oleate (according to the calculation, 0.6 mol of maleic anhydride adduct to 2-mol of 2-ethylhexyl oleate was added). ) Production Example A4 was obtained.
However, 2-ethylhexyl oleate having a purity of 70% by weight and an acid value of 1 was used. In the same manner, Production Examples A5 to 10 shown in Table 1 were produced. Production Examples B3 to B10 Production by blending 30 moles of ethylene oxide, 10 moles of propylene oxide, 2 moles of butylene oxide and glycerin shown in Table 2. A formulation of Example B3 was obtained. Similarly, the formulations shown in Table 2 were obtained in Production Examples B4 to B10. Production Examples C3 to C10 (Examples 3 to 10) From the component (A) shown in Table 1 and the component (B) shown in Table 2, the example Nos. Shown in Table 3 were obtained. Three to ten esters were prepared. Comparative Production Examples 1 to 8 Similarly, as Comparative Production Examples, Comparative Example Nos. Shown in Table 3 were obtained from the component (A) shown in Table 1 and the component (B) shown in Table 2. 1-8 esters were prepared. [Table 1] [Table 2] Next, the above production example No. 1 to 10, Comparative Example No. A deinking treatment test was carried out by the following method using each of the deinking agents 1 to 8. <Deinking test> Asahi, Yomiuri, and Nikkei newspapers (1 to 2 months after printing) 70% by weight of waste paper and 30% by weight of leaflets cut with a shredder and mixed to 350 g Add 1.84 g of sodium (0.5% by weight to used paper), 1.4 g of deinking agent (0.4% by weight to used paper), and 10 liters of water to a volume of 1
Disaggregated with a 0 liter pulper for 10 minutes. The disaggregated sample is dehydrated (2000 rpm, 5 minutes) with a centrifuge to concentrate the waste paper concentration to 25 to 30%, and hydrogen peroxide solution is added.
5g (1.0% by weight based on waste paper), 0.35g deinking agent
After adding (0.1% by weight to waste paper) and mixing well, the sample was placed in a vinyl bag and aged in a water bath at 60 ° C. for 2 hours. Water is added to the sample after aging to dilute the concentration of waste paper to 1%, and disintegrated with a 2 liter pulper for 10 minutes, and this is mixed with a 2 liter floatator (Far East Co., Ltd.).
It was poured into a product) and floated for 10 minutes to remove carbon aggregates (ink) in the upper layer, and then hand-pulled by a tappy standard sheet machine to obtain a pulp sheet. The weight of bubbles discharged to the outside of the system during the flotation treatment was measured as the amount of froth. With respect to the pulp sheet obtained by the above method, the whiteness and the number of remaining inks were examined by the following methods to evaluate the deinking effect. [Table 3] <Measurement of whiteness> Photoelectric reflectometer {SM color computer Model manufactured by Suga Test Instruments Co., Ltd.
The blue reflectance of the above-mentioned hand-skewed sample was measured at 457 μm using SM-4}. <Measurement of the number of remaining inks> Microscope (× 200
The number of residual inks (whiskers) of the above-mentioned sample, which was hand-drawn, was counted and converted into a value per 1 cm ² . As is clear from Table 3 above, Comparative Example No. 1 having a high acid value. The deinking agent of the present invention having an acid value of 30 or less has excellent whiteness as compared with 6 to 8. Also, in Comparative Example No. 2,
5 and 8 have a large amount of froth and the yield of pulp is poor, while the product of the present invention has a good yield of pulp. The deinking agent of the present invention is used in the flotation method, flotation-water washing eclectic method, and washing method.
Deinked pulp with little residual ink and high whiteness can be obtained from newspapers, magazines, and waste paper for office automation.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Fujio Takahashi             1-1-13-207 Higashi-Naruo-cho, Nishinomiya-shi, Hyogo

Claims (1)

Claims: A deinking agent comprising an ester of the following components (A) and (B). Component (A); (a) Addition of α, β-unsaturated dicarboxylic acid or anhydride thereof and (b) unsaturated fatty acid having 3 to 36 carbon atoms or ester having at least one double bond in the molecule. Stuff. Component (B); (c) monohydric alcohol having 1 to 26 carbon atoms (d) polyhydric alcohol having 2 to 20 carbon atoms, and (e) one or more compounds selected from the compounds of the following formula (1). R-[{O (EO) _k (PO) _m (BO) _n H}] _p (1) (wherein R is a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, an alkenyl group, or a divalent to 10-valent group). Represents an alcohol residue, EO is an oxyethylene group, PO is an oxypropylene group, BO is an oxybutylene group, and k: m: n is 1: 0.2 to 1: 0 to 0.5 in a molar ratio. , And k +
m + n is a number of 5 to 100, and p is 1 to 10. )