JPH10195132A - Water-soluble polymer and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer flocculant by copolymerizing acrylonitrile, an N-vinylcarboxamide, and a dialkyldi(meth)allylammonium salt as a cationic vinyl monomer in a suitable molar ratio and hydrolyzing the resultant copolymer. SOLUTION: A specified amt. of water, 10-50mol% cationic diallyl monomer represented by the formula (R1 and R2 are each CH3 ; R3 and R4 are each 1-2C alkyl; and X<-> is an anionic counter ion) (e.g. dimethyldimethallylammonium chloride), 35-90mol% N-vinylcarboxamide (e.g. vinylformamide), and 0-55mol% acrylonitrile are mixed in a reactor. The monomer mixture is mixed with a compd. such as 2,2'-azobis-2-amidinopropane dihydrochloride and is then copolymerized under heating. Water and hydrochloric acid are added to the resultant copolymn. product, and the product is stirred under heating to be hydrolyzed, thus giving a hydrolyzate having an intrinsic viscosity (in an aq. 1-N NaCl soln.) of 0.1-10dl/g and a colloid equivalent value (at a pH of 3.0) of 3.0meq/g or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a novel cationic polymer useful as a polymer flocculant or a papermaking agent, having a diallyl ammonium salt structural unit, vinylamine structural unit or vinylamidine in the main chain. A sludge dehydrating agent comprising a novel cationic polymer having a structural unit,
The present invention relates to a paper strength enhancer, a retention improver such as a size and a filler, a drainage improver, and a coating agent used for coating base paper.

[0002]

2. Description of the Related Art Conventionally, a method of producing polyvinylamine by Hoffman decomposition of polyacrylamide is known. Further, it can be produced by hydrolyzing poly N-vinyl carboxylic acid amide obtained by polymerizing N-vinyl carboxylic acid amide (JP-A-58-23809).
Further, a water-soluble polymer having a vinylamino group can be produced by hydrolyzing a copolymer of N-vinylcarboxylic acid amide and vinyl acetate (Japanese Patent Application Laid-Open No. Sho 62-74902).
No.). N-vinyl carboxylic acid amide and acrylonitrile are copolymerized, and the copolymer is hydrolyzed,
Further, a water-soluble polymer which has been denatured at high temperature and converted into an amidine has also been proposed (JP-A-63-165412, JP-A-6-123096). A method of introducing a quaternary ammonium salt into a Hoffman degradation product by an addition reaction or the like is also known, but these known agents have still insufficient effects.

[0003]

An object of the present invention is to provide a polymer flocculant comprising a novel cationic water-soluble polymer which has not been known so far.

[0004]

According to the present invention, there is provided a cationic water-soluble polymer obtained by hydrolyzing a copolymer of a diallyl cationic monomer and a monomer containing N vinyl carboxylic acid amide. The present invention was found to be useful as a molecular coagulant and a papermaking agent, and completed the present invention. Until now, diallylic cationic monomers have never been selected as a copolymerization component with N-vinyl carboxylic acid amide.

The invention of claim 1 of the present invention provides the following formula (1)
10 to 50% by weight of a cationic vinyl monomer represented by
It is a water-soluble molecule obtained by copolymerizing a monomer containing 35 to 90 mol% of vinyl carboxylic acid amide and 0 to 55 mol% of acrylonitrile and then hydrolyzing it.

Embedded image (Where R ₁ and R ₂ are H or CH ₃ ; R ₃ and R
₄ represents an alkyl group having 1 to 2 carbon atoms; X ⁻ represents an anionic counter ion. )

A second aspect of the present invention is the water-soluble polymer according to the first aspect, wherein the hydrolyzate is a hydrolyzate with hydrochloric acid.

According to a third aspect of the present invention, the hydrolyzate has an intrinsic viscosity of 0.1 to 10 in 1N saline.
3. The method according to claim 1, wherein the weight ratio is dl / g.
The water-soluble polymer described in (1).

According to a fourth aspect of the present invention, the hydrolyzate has a colloid equivalent value of 3.0 me at PH of 3.0.
The water-soluble polymer according to any one of claims 1 to 3, wherein the water-soluble polymer is q / g or more.

According to a fifth aspect of the present invention, there is provided a sludge dewatering agent comprising the water-soluble polymer according to the first to fourth aspects.

According to a sixth aspect of the present invention, there is provided a paper strength enhancer comprising the water-soluble polymer according to the first to fourth aspects.

A seventh aspect of the present invention is a yield improver comprising the water-soluble polymer according to the first to fourth aspects.

[0012] An eighth aspect of the present invention is a drainage improver comprising the water-soluble polymer according to the first to fourth aspects.

According to a ninth aspect of the present invention, there is provided a surface coating agent for papermaking, comprising the water-soluble polymer according to any one of the first to fourth aspects.

According to a tenth aspect of the present invention, there is provided a method for producing an ink jet recording paper, which comprises applying the surface coating agent of the present invention according to the ninth aspect to the surface of a coated base paper.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION As the diallyl cationic monomer represented by the above formula (1) to be copolymerized with vinylcarboxylic acid amide, a dialkyldi (meth) allylammonium salt, specifically, dimethyldiallylammonium Chloride, dimethyldimethallylammonium chloride, diethyldiallylammonium chloride, diethyldimethallylammonium chloride, and ethylmethyldiallylammonium chloride can be preferably used.
These have good stability against hydrolysis and can be preferably used without deterioration even when cations are revealed by hydrolysis of vinyl carboxylic acid amide. When acrylonitrile is used, a carboxyl group may be by-produced by hydrolysis, but the effect is not affected if the amount is small. The copolymerization ratio of the diallyl-based cationic monomer is suitably from 10 to 50 mol%, and if it is 10 mol% or less, the effect of the diallyl-based cationic monomer does not appear, and
If it is at least mol%, the effect of the vinyl carboxylic acid amide hydrolyzate will not appear. In the scope of the present invention, the vinyl carboxylic acid amide hydrolyzate generates an amino group or an amidine group, and together with the diallyl cationic monomer unit, gives a water-soluble polymer having the most appropriate range of adsorption and ionic strength.

The water-soluble polymer of the present invention hydrolyzes a vinylcarboxylic acid amide unit in a copolymer to generate an amino group, and when an nitrile group is adjacent, closes the ring to generate an amidine group. This hydrolysis is most preferably performed under hydrochloric acid acidity, and there is a possibility that a side reaction may occur under other hydrolysis conditions. Examples of the vinylcarboxylic acid amide monomer used in the present invention include vinylformamide and vinylacetamide, and vinylformamide is more preferably selected from the viewpoint of yield and difficulty of hydrolysis.

It is desirable that the water-soluble polymer of the present invention has an intrinsic viscosity in 1N saline in the range of 0.1 to 10 dl / g. Particularly preferably, 0.2 to 7 dl / g is used as a surface coating agent or a polymer flocculant according to the purpose. A conventionally known method can be used as it is as a sludge dewatering agent or a papermaking agent, and a low molecular weight agent is used as a coating agent and a high molecular weight agent is used as a polymer flocculant.

The colloid equivalent value of the water-soluble polymer of the present invention is 3.0 meq / g or more at pH 3.0, and below this value, satisfactory effects cannot be exhibited in various uses of the present invention.

The invention of claim 5 of the present invention relates to a sludge dewatering agent as a specific use of the above-mentioned water-soluble polymer. Raw sludge, excess sludge of the activated sludge method of various organic wastewaters (including sludge containing metal hydroxide) and the like, and sludge dewatering machines such as belt presses, decanters,
Examples include a filter press, a screw press, and a vacuum dehydrator. If necessary, it can be used in combination with an inorganic coagulant such as ferric chloride, polyiron sulfate, polyaluminum chloride, and a sulfuric acid band, and other organic polymer coagulants.

The invention of claim 6 of the present invention relates to a paper strength enhancer as a specific use of the water-soluble polymer. The paper strength enhancer is used for improving the compressive strength, tensile strength, burst strength, surface strength, delamination strength, etc. of paper.In addition to the method of adding to the pulp slurry when making paper,
A method of applying to a wet paper or a dry paper by a roll coater, a size press, a spray or a dipping machine is also employed. If necessary, a general paper strength enhancer such as a cationic starch and an anionic paper strength enhancer, and a sulfate band may be used in combination. The type of pulp is not particularly limited.
Used for P, SP, KP, DIP, etc.

The invention of claim 7 of the present invention relates to a retention improver as a specific use of the water-soluble polymer, and the product of the present invention is effective not only for improving the filler retention but also for improving the fixing retention of the size. This has the effect of improving the water repellency of the formed paper.

The invention of claim 8 of the present invention relates to a drainage improver as a specific use of the water-soluble polymer. The drainage improver is intended to improve the papermaking speed, and is mainly used in paperboard papermaking, and aims to increase the drying property by draining water on a wire and improving water squeezing.

The ninth aspect of the present invention relates to a surface coating agent for papermaking as a specific application of the water-soluble polymer, and the present invention relates to another coating agent such as cationic starch and oxidized starch. Water-soluble polymers such as starch and polyvinyl alcohol, and latex, or coating pigments such as colloidal silica, talc, kaolin clay, and calcium carbonate can be used in combination. The addition amount of these coating agents is usually 0.1.
05 to 10 g / m ^2, preferably 0.2 to 5 g / m ² . The base paper for coating is not particularly limited, and can be applied to base papers such as coated base paper of acid paper and neutral paper, newsprint, PPC paper and the like. A water-soluble polymer of the present invention alone or mixed with another coating agent is coated on a coating base paper with a size press, a gate roll coater, a blade coater, a calender, or the like, and the surface is coated. It can be.

The invention of claim 10 of the present invention relates to a surface coating agent for papermaking as a specific application of the water-soluble polymer, characterized in that the product of the present invention is applied to the surface of a coated base paper. Is a method for producing an ink jet recording paper. The present invention not only improves the printability of the coated base paper as described above, but also combines with an anionic water-soluble ink as an inkjet recording paper to make it water-insoluble, suppresses penetration into the paper, and performs inkjet printing. Maintains a vivid color tone in the expression of the color.

[0025]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

(Synthesis Examples 1-4) Stirrer, nitrogen inlet tube,
In a 300 ml four-necked flask equipped with a condenser and a thermometer, 40.0 g of a monomer having the composition shown in Table 1 and deionized water 14 were added.
3.0 g, 1% aqueous solution of hydroxylamine hydrochloride 7.0
g was added. After passing nitrogen gas under ice cooling, 50 ° C
To 2,2'-azobis-2-amidinopropane.
10.0 g of a 2% aqueous solution of dihydrochloride was added, and the mixture was maintained at 50 ° C. for 6 hours with stirring at 300 rpm. A part of the polymer was taken and added to acetone to precipitate a polymer, which was dried under vacuum to obtain a solid polymer. The polymer composition was analyzed by NMR, and it was confirmed that the charged amount of the monomer was copolymerized. Next, 100 g of the above polymer (liquid) was placed in a 200 ml three-necked flask equipped with a stirrer, a condenser and a thermometer, and 5.6 g of a 10% aqueous solution of hydroxylamine hydrochloride and 18.5 g of 35% hydrochloric acid (in the copolymer). (110 mol% based on formyl group), and the mixture was reacted at 70 ° C. for 3 hours with stirring, then heated to 90 ° C. and hydrolyzed for 3 hours. The obtained reaction product (hydrolyzate) solution was dropped into acetone to cause precipitation, and this was dried in vacuo to obtain a solid hydrolyzate. The colloid equivalent value and the intrinsic viscosity were measured by a conventional method. The results are shown in Table 1.

(Comparative Synthesis Examples 1-4) Samples prepared by performing the same operations as in the Synthesis Examples without using diallylic cationic monomers were prepared. The results are shown in Table 1.

[0028]

[Table-1]

[Effect test-1] Anaerobic digestion sludge of sewage (PH; 7.1, S) under the polymer addition conditions shown in Table-2
S: 15200 mg / l, loss on ignition; 69.5%, M alkalinity: 3200 mg / l)
A 2% aqueous solution was added, transferred in a 300 ml glass beaker, and stirred 15 times. A PVC cylinder having an inner diameter of 50 mm was placed in a funnel covered with a nylon filter cloth, and coagulated sludge was poured into the cylinder, and 10 seconds later. Of the filtrate was weighed.
Next, the coagulated sludge remaining on the filter cloth was replaced with a polyester filter cloth for a belt press, and pressed at 2.0 kg / cm ² for 1 minute, and the cake on the filter cloth was scraped with a spatula to measure the water content. Sludge adhering to the filter cloth was visually evaluated for filter cloth releasability. The results are shown in Table-2.

[0030]

[Table-2]

[Effect Test-2] 300 ml of a pulp slurry (0.4% pulp concentration) of LBKP [CSF (Canadian Standard Freeness) = 400 ml] was added to 5
In a 00 ml glass beaker, 0.3% emulsion rosin size to pulp, 0.2% polymer to pulp of this example, and 3% liquid band to pulp of this example were added and mixed at an interval of 20 seconds while stirring at 600 rpm. ,
Target paper weight of 60 with Tappy Standard handmade paper machine
g / m ² paper, roll-dried at 105 ° C. for 5 minutes, and then conditioned in a constant temperature and humidity room at a temperature of 20 ° C. and a humidity of 60%.
Burst strength and Stekigt sizing degree were measured. The bursting strength was based on JIS P-8112, and the Stechig sizing degree was based on JISP-8122. The results are shown in Table-3.

[0032]

[Table-3]

[Effect test-3] Polymer of this example
A 2% aqueous solution was prepared, and this was commercialized medium paper [basis weight 55 g /
m ² , manufactured by Daishowa Paper Co., Ltd.] using a coating rod and roll-dried at 105 ° C. for 5 minutes to obtain a coated paper. The coating amount is 0.1 g / m ² and 0.2 g / m ²
It is. Table 4 shows the results of the burst strength test.

[0034]

[Table-4]

[Effect test-4] LBKP of effect test-2
Then, 1000 ml of a 0.3% slurry was added, and 2% of the liquid band was added to the pulp while stirring at 300 rpm. After 20 seconds, the polymer of the present example was added in the indicated amount. After stirring for 20 seconds, the mixture was charged into a Canadian Standard Freeness Tester. The amount of drainage was measured. The results are shown in Table-5.

[0036]

[Table-5]

[Effect test-5] Coating solution [6.8 g of fine powdered silica, PVA117 (manufactured by Kuraray)] using a high-quality paper having a basis weight of 70 g / m ² and a Steckigt sizing degree of 25 seconds as a support.
2.7 g, 0.5 g of the polymer of this example and 40 g of water
Was mixed with a coating rod at a solid content of 5.0 g / m ² on one side to obtain a coated paper. After color printing of this coated paper, the water resistance and lightfastness of the print were measured as follows. Color printing is provided by Canon Inc.
Solid printing was performed for each color of magenta (M), cyan (C), yellow (Y), and black (BL) using a color bubble jet printer manufactured by BJC600. The results are shown in Table-6. (Water resistance) The solid printed image was immersed in running water of 3 liter / min for 10 minutes, and the image density before and after the test was evaluated on a 5-point scale. <Judgment> A: No change B: Color slightly exudes. C: Discoloration is recognized. D: Large discoloration. E: Almost decolorization. (Light fastness) The solid printed image is 24
Irradiation was performed for a period of time, and the image density before and after the irradiation was evaluated in four stages. <Judgment> A: No change B: Slight fading. C: Fading. D: Extremely fading.

[0038]

[Table-6]

[0039]

EFFECTS OF THE INVENTION By copolymerizing a diallyl cationic monomer, excellent effects are exhibited as a sludge dehydrating agent and a papermaking agent. These are N-vinyl carboxylic acid containing no diallyl cationic monomer. This is an unexpected performance from a (co) polymer hydrolyzate.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

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[Procedure amendment]

[Submission date] February 25, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction contents]

(Synthesis Examples 1-4) An agitator, a nitrogen inlet tube,
In a 300 ml four-necked flask equipped with a condenser and a thermometer, 40.0 g of a monomer having the composition shown in Table 1 and deionized water 14 were added.
3.0 g, 1% aqueous solution of hydroxylamine hydrochloride 7.0
g was added. After passing nitrogen gas under ice cooling, 50 ° C
To 2,2'-azobis-2-amidinopropane.
10.0 g of a 2% aqueous solution of dihydrochloride was added, and the mixture was maintained at 50 ° C. for 6 hours with stirring at 300 rpm. A part of the polymer was taken and added to acetone to precipitate a polymer, which was dried under vacuum to obtain a solid polymer. The polymer composition was analyzed by NMR, and it was confirmed that the charged amount of the monomer was copolymerized. Next, 100 g of the above polymer (liquid) was placed in a 200 ml three-necked flask equipped with a stirrer, a cooler and a thermometer, and hydroquinylamine hydrochloride 100%
5.6 g of an aqueous solution and 18.5 g of 35% hydrochloric acid (110 mol% based on formyl groups in the copolymer) were added, and the mixture was reacted with stirring at 70 ° C. for 3 hours, and then heated to 90 ° C. Hydrolyzed for 3 hours. The obtained reaction product (hydrolyzate) solution was dropped into acetone to cause precipitation, and this was dried in vacuo to obtain a solid hydrolyzate. The colloid equivalent value and the intrinsic viscosity were measured by a conventional method. The results are shown in Table 1.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 133/20 C09D 133/20 133/24 133/24 139/00 139/00 D21H 17/34 D21H 3/38

Claims (10)

[Claims] 1. A monomer containing 10 to 50 mol% of a cationic vinyl monomer represented by the following formula (1), 35 to 90 mol% of N-vinyl carboxylic acid amide and 0 to 55 mol% of acrylonitrile. And then hydrolyzed. Embedded image (Where R ₁ and R ₂ are H or CH ₃ ; R ₃ and R
₄ represents an alkyl group having 1 to 2 carbon atoms; X ⁻ represents an anionic counter ion. ) 2. The water-soluble polymer according to claim 1, wherein the hydrolyzate is a hydrolyzate with hydrochloric acid. 3. The water-soluble polymer according to claim 1, wherein the hydrolyzate has an intrinsic viscosity in 1 N saline of 0.1 to 10 dl / g. 4. The water-soluble polymer according to claim 1, wherein the hydrolyzate has a colloid equivalent value at pH 3.0 of 3.0 meq / g or more. 5. A sludge dewatering agent comprising the water-soluble polymer according to claim 1. 6. A paper strength agent comprising the water-soluble polymer according to claim 1. Description: 7. A yield improver comprising the water-soluble polymer according to claim 1. Description: 8. A drainage improver comprising the water-soluble polymer according to claim 1. Description: 9. A coated paper surface coating agent comprising the water-soluble polymer according to claim 1. Description: 10. A method for producing an ink jet recording paper, comprising applying the surface coating agent for papermaking according to claim 9 to the surface of a coated base paper.