JPH09276605A - Flocculant in water-in-oil type emulsion state - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain water-in-oil type emulsion flocculant of an aqueous vinyl polymer with sufficiently high water filtering effect and good stability with the lapse of time. SOLUTION: This flocculant is a water-in-oil type emulsion containing aqueous vinyl copolymer (a1) consisting of 2- acryloyloxyethyldimethylbenzylammonium chloride A1 and mother vinyl monomer unit A2 as indispensable units, water (b), a hydrocarbon liquid (c), and a surfactant (d) as dispensable components, and the content of (c) in the emulsion is 10-40wt.% and the transmittance of the emulsion for light rays with 600nm wavelength is 60% or higher.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flocculant. More specifically, the present invention relates to an emulsion flocculant which is particularly excellent in the drainage improving effect for papermaking and the sludge dewatering effect, and has good separation stability over time.

[0002]

2. Description of the Related Art Conventionally, as a water-soluble polymer used as a drainage improving agent for papermaking among coagulants, a copolymer of dimethylaminoethyl methacrylate quaternary product and acrylamide, Mannich-modified polyacrylamide, etc. are known. (For example, Japanese Examined Patent Publication No. 59-40843, Japanese Patent Laid-Open No. Sho 5
8-183703). Further, a water-soluble polymer as a paper-making agent is industrially provided as a powder, a paste, or a water-in-oil emulsion product. Of these, the water-in-oil type emulsion product has advantages such as quick dispersion in water, quick dissolution, and easy continuation of dissolution equipment as compared with the former two, and has been attracting attention in recent years. ing. As such a water-in-oil type emulsion coagulant which is used as a drainage improving agent for papermaking, an acrylamide / dimethyldiallylammonium chloride copolymer or an acrylamide / sodium acrylate copolymer is known. (For example, JP-A-5
8-197398, JP-A-7-53827).

[0003]

However, the conventional emulsion-type flocculant composed of a water-soluble polymer as a drainage improving agent for papermaking has an insufficient effect of improving drainage and is not stable in separation over time.

[0004]

The present inventors have arrived at the present invention as a result of earnestly studying a water-in-oil type emulsion coagulant which has a sufficient drainage improving effect and is excellent in separation stability. That is, the present invention provides a water-soluble vinyl copolymer (a1), water (b), a hydrocarbon containing 2-acryloyloxyethyldimethylbenzylammonium chloride (A1) and another vinyl monomer (A2) as essential constituent units. A water-in-oil emulsion containing a liquid (c) and a surfactant (d) as essential components, wherein the content of (c) in the emulsion is 10 to 40% by weight, and the wavelength of the emulsion is 600 nm. Light transmittance of 60%
A coagulant characterized by the above; and a water-soluble vinyl (co) polymer having 2-acryloyloxyethyldimethylbenzylammonium chloride (A1) as an essential constituent unit and another vinyl monomer (A2) A water-in-oil emulsion containing a mixture (a2) of a water-soluble (co) polymer, water (b), a hydrocarbon liquid (c) and a surfactant (d) as essential components, wherein An aggregating agent characterized in that the content of c) is 10 to 40% by weight, and that the emulsion has a transmittance of light having a wavelength of 600 nm of 60% or more.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the other vinyl monomer (A2) constituting the water-soluble vinyl polymer (a1) or (a2) is limited as long as the obtained polymer is water-soluble. However, water-soluble monomers such as amide group-containing monomers [(meth) acrylamide, N-methylolacrylamide, N-vinylpyrrolidone, etc.], hydroxyl group-containing monomers [hydroxyethyl (meth) acrylate, triethylene glycol] (Meth) acrylate and the like], amino group-containing monomer [2-dimethylaminoethyl (meth) acrylate and salts thereof, 3-dimethylaminopropyl (meth) acrylamide and salts thereof,
N-vinylpyridine, dimethyldiallylammonium chloride, p-styryltrimethylammonium chloride, etc.], a weakly hydrophilic or oil-soluble monomer such as a (meth) acrylate vinyl monomer from alcohol [methyl (meth) acrylate, butyl ( (Meth) acrylate, etc.], aromatic hydrocarbon vinyl monomers [styrene, α-alkylstyrene, etc.], vinyl ester monomers [vinyl acetate, etc.], and nitrile monomers [(meth) acrylonitrile, etc.], etc. Is mentioned. Among these, preferred are amide group-containing monomers, and particularly preferred is acrylamide.

In (a1), the molar ratio of (A1) to (A2) is 5:95 to 30: 7 from the viewpoint of the drainage improving effect.
0 is preferable, and more preferably 5:95 to 20:80.
It is. Further, in the case of a mixture (a2) of a water-soluble vinyl (co) polymer having (A1) as an essential constituent unit and a water-soluble (co) polymer of another vinyl monomer (A2), (A1) and ( A
The molar ratio with 2) is also the same as the above range.

The intrinsic viscosity of (a1) or (a2) (in 0.1N-NaCl aqueous solution at 30 ° C.) is 5 or more, more preferably 6 or more, from the viewpoint of the effect of improving drainage.

The water (b) in the present invention is preferably distilled water or ion-exchanged water, but depending on the water quality, tap water,
Industrial water may be used. The (b) is usually 20 to 20 based on the total amount of the emulsion coagulant in the present invention.
70% by weight, preferably 20-60% by weight.

The hydrocarbon liquid (c) in the present invention is a hydrophobic aliphatic or aromatic hydrocarbon liquid, a vegetable or animal oil, or a modified oil of these oils (hydrogenated oil, polymerized oil, etc.) and the like. Is mentioned. Of these, preferred are aliphatic hydrocarbon liquids such as mineral oil, kerosene, naphtha, normal paraffin, and isoparaffin, and aromatic hydrocarbon liquids such as benzene, toluene, xylene, and particularly preferred are aliphatic hydrocarbon liquids. Among the hydrogen liquids are normal paraffin and isoparaffin. The (c) is usually 10 to 40% by weight, preferably 12 to 40% by weight based on the total amount of the emulsion coagulant in the present invention.
It is 29% by weight, more preferably 14 to 28% by weight.

In the present invention, the water-soluble vinyl polymer (a
The ratio of 1) or (a2) to the hydrocarbon liquid (c) is
Usually, (a1) or (a2) is 20 to 80% by weight based on the total weight of (a1) or (a2) and (c),
(C) is 80 to 20% by weight, preferably (a1) or (a2) is 40 to 70% by weight, and (c) is 60 to 30% by weight. When the proportion of the hydrocarbon liquid (c) is in the usual range, the emulsion has a particularly good stability over time.

The surfactant (d) in the present invention includes nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. Examples of nonionic surfactants include higher alcohol ethylene oxide adducts such as lauryl alcohol polyoxyethylene ether; higher fatty acid esters such as sorbitan diester stearate and sorbitan oleic acid monoester; polyoxyethylene nonyl phenyl ethers and the like. Polyoxyethylene alkyl ether;
Long-chain alkyl alkanolamides such as N, N-dihydroxyethyllaurylamide; fatty acid sorbitan ester ethylene oxide adducts such as oleic acid sorbitan ester ethylene oxide adducts. Among these, preferred are higher alcohol ethylene oxide adducts, higher fatty acid esters and long chain alkyl alkanolamides.

Examples of the anionic surfactant include carboxylate type such as oleic acid soap; sulfate ester type such as higher alcohol sulfate ester salt; sulfonate type such as sulfosuccinate diester; higher alcohol phosphate ester. Examples thereof include phosphate ester salt types such as salts.
Examples of the cationic surfactant include an amine salt type such as an aliphatic amine ethylene oxide adduct or a salt of a higher aliphatic amine; and a quaternary ammonium salt type such as a higher alkylamine ammonium salt. Examples of the amphoteric surfactant include amino acid type such as higher alkylaminocarboxylic acid salt; betaine type such as higher alkyldimethylbetaine. The (d) may be added during the polymerization of the above-mentioned monomer or after the polymerization.

The amount of the (d) used is usually 5 to 40% by weight, preferably 5 to 40% by weight based on the weight of the hydrocarbon liquid (c), from the viewpoint of apparent viscosity of the emulsion coagulant and dilution solubility in water. Is 10 to 30% by weight.

The water-in-oil type emulsion coagulant of the present invention may optionally contain a known pH buffer, polymer deterioration inhibitor, deodorant, preservative, rust preventive, decolorizer and the like. Good. These amounts are usually 5% by weight or less based on the weight of the emulsion coagulant.

The water-in-oil type emulsion coagulant of the present invention usually has a transmittance of light having a wavelength of 600 nm of 60% or more,
It is preferably at least 70%. If the transmittance is less than 60%, the stability of separation over time deteriorates. The transmittance was measured using a quartz cell with an optical path length of 10 mm and the emulsion temperature was 30 ° C.
Is a value measured by a spectrophotometer.

Illustrating the method for producing the water-in-oil type emulsion coagulant of the present invention, vinyl monomers (A1) and (A
It is obtained by mixing 2), water (b), a hydrocarbon liquid (c) and a surfactant (d) into a W / O type emulsion and emulsion polymerization. This emulsion polymerization can be carried out by a known method, for example, the methods described in JP-A-54-154437 and JP-A-54-102388. A chain transfer agent such as mercaptan, a pH buffering agent, and a chelating agent may be added to the polymerization system, if necessary. After emulsion polymerization, low volatile components such as water are distilled off under reduced pressure to remove the water-soluble vinyl polymer (a1), water (b),
The ratio of the hydrocarbon liquid (c) and the surfactant (d) may be adjusted.

The water-in-oil emulsion flocculant of the present invention can be suitably used as a sludge dewatering agent, a wastewater treatment agent, etc., in addition to a drainage improving agent for papermaking.

The paper stock to which the drainage improving agent for papermaking using the water-in-oil type emulsion coagulant of the present invention is applied is not particularly limited, and pulp, filler, internal sizing agent, pH at the time of paper making,
It is not restricted by paper strengthening agents. For example, high-quality paper stock and coated base paper stock for acidic papermaking; medium-quality paper stock mixed with waste paper pulp and mechanical pulp; neutral or alkaline papermaking using an alkyl ketene dimer or alkenyl succinic anhydride as an internal sizing agent. High-quality paper stocks and coated paper stocks: white paperboard, core raw paper and liner and other paperboard stocks. The amount of the drainage improving agent for papermaking comprising the water-in-oil emulsion type flocculant of the present invention is usually 0.00 per solid content of the stock based on the weight of the polymer.
It is 3 to 1.5%, preferably 0.015 to 0.6%. When the amount used is in the usual range, the drainage improving effect is particularly good. The water-in-oil emulsion flocculant of the present invention is used for the paper-making drainage improving agent in an appropriate concentration with water (usually 0.01 to 2% in terms of polymer concentration, preferably 0.02 to 0.02%).
1%) and added to the stock at any stage of the papermaking process (fan pit or headbox). It may also be added to the recovered white water.

[0019]

The present invention will be further described with reference to the following examples, but the present invention is not limited by these examples. The tests described in the examples were carried out by the following method. Test method (1) Stability test 5 ° C. × 1 week and 40 ° C. × 1 week are repeated for 3 months to examine the separation rate and viscosity change of the emulsion. "Unmeasurable" means that it cannot be measured due to lumping due to separation. (2) Polymer intrinsic viscosity Measured at 30 ° C. in a 0.1 N NaCl aqueous solution. (3) Transmittance It is measured with a spectrophotometer manufactured by Shimadzu Corporation using a quartz cell having an emulsion temperature of 30 ° C. and an optical path length of 10 mm. (4) Freeness The freeness is measured by the Canadian standard freeness (CSF) measuring method.

Example 1 1L 4-neck separable Kolben equipped with a stirrer, a reflux tube, a nitrogen introduction tube and a thermometer (c) component: normal paraffin 200 g (d) component: pentaoxyethylene oleyl alcohol ether 25 g (〃 ) Component: 25 g of sorbitan monooleate was charged and mixed with stirring. Then, (A1) component: 2-acryloyloxyethyl dimethylbenzyl ammonium chloride 90 g (A2) component: acrylamide 210 g (b) component: water 450 g A mixed solution was adjusted to pH 3 with dilute sulfuric acid and added to the above mixture to emulsify. It was This was adjusted to 50 ° C. with stirring, and nitrogen gas was blown into the liquid for 30 minutes. Then, 1 g of a toluene solution containing 6% by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added while flowing nitrogen into the gas phase.
In addition, polymerization was carried out at 45 to 55 ° C for 8 hours. The obtained emulsion-type flocculant was a substantially transparent and stable emulsion.
The stability test results are shown in Table 1. The intrinsic viscosity of this polymer was 14.6 dl / g.

Examples 2 and 3 Implementation was carried out except that the proportions of the respective components of the water-soluble vinyl polymer (a1), water (b), hydrocarbon liquid (c) and surfactant (d) were changed as shown in Table 1. In the same manner as in Example 1, emulsions of Examples 2 and 3 were obtained. The stability test results of each emulsion are shown in Table 1. Example 4 1L 4-neck separable Kolben equipped with a stirrer, a reflux pipe, a nitrogen introduction pipe and a thermometer (c) component: normal paraffin 200 g (d) component: pentaoxyethylene oleyl alcohol ether 25 g (〃) component: 25 g of sorbitan monooleate was charged and mixed with stirring. Then, a mixed solution of (A1) component: 2-acryloyloxyethyldimethylbenzyl ammonium chloride 255 g (A2) component: acrylamide 45 g (b) component: water (450 g) is adjusted to pH 3 with diluted sulfuric acid and added to the above mixture to emulsify. It was This was adjusted to 50 ° C. with stirring, and nitrogen gas was blown into the liquid for 30 minutes. Then, 1 g of a toluene solution containing 6% by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added while flowing nitrogen into the gas phase.
In addition, it was polymerized at 45 to 55 ° C. for 8 hours (emulsion 1). Similarly, to a 1L 4-neck separable colben equipped with a stirrer, a reflux pipe, a nitrogen introduction pipe and a thermometer (c) component: normal paraffin 200 g (d) component: pentaoxyethylene oleyl alcohol ether 25 g (〃) component: sorbitan 25 g of monooleate was charged and mixed with stirring. Next, a mixed solution of (A2) component: 300 g of acrylamide and (b) component: 450 g of water was adjusted to pH 3 with dilute sulfuric acid and added to the above mixture to emulsify. This was adjusted to 50 ° C. with stirring, and nitrogen gas was blown into the liquid for 30 minutes. Then, 1 g of a toluene solution containing 6% by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added while flowing nitrogen into the gas phase.
In addition, it was polymerized at 45 to 55 ° C. for 8 hours (emulsion 2). Emulsions 1 and 2 obtained here are 1 /
The emulsion-like flocculant obtained by uniformly mixing at a weight ratio of 0.75 was a stable emulsion liquid which was almost transparent. The stability test results are shown in Table 1. The intrinsic viscosity of this polymer is 1
It was 2.8 dl / g.

[0022]

[Table 1]

Test Example 1 Headbox stock in a white papermaking process (stock density 0.8
%), 0.05% of the emulsion drainage improver described in Examples 1 and 4 was added to the solid content of the stock, and then 500 r.p.m. p. m. The mixture was stirred at a peripheral speed of 2.0 m / sec for 30 seconds. The freeness of this stock is C.I. S. F. It was measured with a measuring instrument. Also SS of drainage
Was measured and the yield was checked. Table 2 shows the results.

[0024]

[Table 2]

Test Examples 2 and 3 To 1000 ml of headbox stock (paper concentration of 0.6%) in the high-quality papermaking process of neutral papermaking, the emulsion drainage improver of Examples 2 and 3 was stocked. 0.0 per solid
2% and then with a paddle type blade 500 r. p. m.
The mixture was stirred at a peripheral speed of 2.0 m / sec for 30 seconds. The freeness of this stock is C.I. S. F. It was measured with a measuring instrument. In addition, SS of filtered water was measured to check the yield. Table 3 shows the results.

[0026]

[Table 3]

[0027]

The water-in-oil type emulsion coagulant of the present invention has a high light transmittance and is almost transparent as compared with the conventional emulsion coagulant, is excellent in separation stability over time, and is used as a drainage improving agent for papermaking. When used, a sufficient drainage improving effect can be obtained. In particular, the effect is excellent for neutral or alkaline paper stocks, and the yield effect is also markedly excellent.
A satisfactory draining effect can be obtained with a smaller amount of use, and a significant cost reduction can be achieved.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tatsushi Iwase 1-11, Hitotsubashi Honcho, Higashiyama-ku, Kyoto Sanyo Kasei Kogyo Co., Ltd. (72) Yoshinobu Nakano 1-11, Hitotsubashi Honcho, Higashiyama-ku, Kyoto 1 Sanyo Kasei Industrial Co., Ltd. (72) Inventor Fukushima Gen 1 Sanyo Kasei Kogyo Co., Ltd. 1-11 Hitotsubashi Honcho, Higashiyama-ku, Kyoto City (72) Inventor Kimihiko Noda 1 11 Sanyo Kasei Kogyo Co., Ltd. 11 Hitotino-honcho, Higashiyama-ku, Kyoto

Claims (6)

[Claims] 1. A water-soluble vinyl copolymer (a1), water (b) and a hydrocarbon containing 2-acryloyloxyethyldimethylbenzylammonium chloride (A1) and another vinyl monomer (A2) as essential constituent units. A water-in-oil emulsion containing a liquid (c) and a surfactant (d) as essential components, wherein the content of (c) in the emulsion is 10 to 40% by weight, and the wavelength of the emulsion is 600 nm. An aggregating agent having a light transmittance of 60% or more. 2. A water-soluble vinyl (co) polymer containing 2-acryloyloxyethyldimethylbenzylammonium chloride (A1) as an essential constituent unit and a water-soluble (co) polymer of another vinyl monomer (A2). (A2), water (b), a hydrocarbon liquid (c) and a surfactant (d) as essential components, wherein the content of (c) in the emulsion is from 10 to 10. A coagulant, which is 40% by weight, and the emulsion has a transmittance of light having a wavelength of 600 nm of 60% or more. 3. The aggregating agent according to claim 1, wherein (A2) is acrylamide. 4. The molar ratio of (A1) to (A2) is 5:95.
The coagulant according to any one of claims 1 to 3, wherein the coagulant is -30: 70. 5. The aggregating agent according to claim 1, wherein the intrinsic viscosity of (a1) or (a2) (in 0.1N-NaCl aqueous solution, 30 ° C.) is 5 or more. 6. A drainage improving agent for papermaking, which comprises the aggregating agent according to any one of claims 1 to 5.