JPH10110010A - Water-soluble polymer and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-soluble polymer which exhibits excellent effect as a sludge dehydrating agent, a paper strength enhancing agent and the like by copolymerizing a monomer contg. an Nvinylcarboxylic acid amide, hydrolyzing the copolymer to obtain a water-soluble polymer, and reacting the water-soluble polymer with a predetermined amt. of a specified compd. SOLUTION: A monomer contg. 35 to 100mol% N-vinylcarboxylic acid amide (e.g. N-vinylformamide) and 0 to 65mol% acrylonitrile is copolymerized. The copolymer is then hydrolyzed to obtain a water-soluble polymer. The water-soluble polymer is reacted with 3-chloro-2-hydroxypropyltrimethylammonium chloride represented by formula I or 2-epoxypropyltrimethylammonium chloride represented by formula II in an amt. of 10 to 100mol% based on the N- vinylcarboxylic acid amide. Pref., the water-soluble polymer has an intrinsic viscosity in 1 N saline of 0.1 to 10dl/g and/or a colloid equivalent value at pH3.0 of not less than 3.0meq/g.

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, and has an acrylic 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]

SUMMARY OF THE INVENTION The present invention relates to a cationic water-soluble polymer obtained by hydrolyzing a (co) polymer of a monomer containing N-vinyl carboxylic acid amide. The inventors have found that a water-soluble polymer obtained by reacting trimethylammonium chloride or 3,2 epoxypropyltrimethylammonium chloride is useful as a polymer flocculant and a papermaking agent, and completed the present invention.

The invention of claim 1 of the present invention relates to a water-soluble polymer obtained by copolymerizing a monomer containing 35 to 100 mol% of N-vinyl carboxylic acid amide and 0 to 65 mol% of acrylonitrile and then hydrolyzing it. In the molecule, 3-chloro-2-hydroxypropyltrimethylammonium chloride represented by the following formula (1) or 3,2 epoxypropyltrimethylammonium chloride represented by the following formula (2) is added in an amount of 10 to 10% based on the charged amount of N-vinyl carboxylic acid amide.
A water-soluble polymer characterized by being reacted by 100 mol%.

Embedded image

Embedded image

According to a second aspect of the present invention, the water-soluble polymer has an intrinsic viscosity of 0.1 to 1 in 1N saline.
The water-soluble polymer according to claim 1, wherein the water-soluble polymer is 0 dl / g.

According to a third aspect of the present invention, the water-soluble polymer has a colloid equivalent value of 3.0 m at PH of 3.0.
3. The water-soluble polymer according to claim 1, wherein the water-soluble polymer is at least eq / g.

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

A fifth aspect of the present invention is a paper strength agent comprising the water-soluble polymer according to the first to third aspects.

[0010] A sixth aspect of the present invention is a yield improver comprising the water-soluble polymer according to the first to third aspects.

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

[0012] The invention of claim 8 of the present invention is a surface coating agent for papermaking, comprising the water-soluble polymer according to any one of claims 1 to 3.

According to a ninth 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 eighth aspect to the surface of a coated base paper.

[0014]

DETAILED DESCRIPTION OF THE INVENTION A first limitation of the present invention is that it is obtained by copolymerizing a monomer containing 35 to 100 mol% of N-vinyl carboxylic acid amide and 0 to 65 mol% of acrylonitrile, followed by hydrolysis. The water-soluble polymer is reacted with 3-chloro-2-hydroxypropyltrimethylammonium chloride or 3,2-epoxypropyltrimethylammonium chloride in an amount of 10 to 100 mol% based on the charged amount of N-vinyl carboxylic acid amide, and has a high water-solubility. Is a molecule. The hydrolyzate of the N-vinyl carboxylic acid amide (co) polymer forms an amino group or an amidine group, and reacts with 3 chloro 2-hydroxypropyltrimethyl ammonium chloride or 3,2 epoxy propyl trimethyl ammonium chloride to form an amino group or an amidine group. It has cationicity while reducing active hydrogen by one, and two cationic groups are expressed together with the trimethylammonium group at the end of the reactant. As a result, a water-soluble polymer having the most appropriate range of adsorption and ionic strength is provided. In some cases, a carboxyl group is formed as a by-product in the hydrolysis of the acrylonitrile copolymer, but if the amount is small, the effect is not affected.

The water-soluble polymer of the present invention desirably has an intrinsic viscosity in 1N saline within a 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 not less than 3.0 meq / g at pH 3.0, and below this value, satisfactory effects cannot be exhibited in various uses of the present invention.

The invention of claim 4 of the present invention relates to a sludge dewatering agent as a specific use of the above-mentioned water-soluble polymer, wherein the target sludge is a mixture of anaerobic digested sludge and sewage by anaerobic digestion of organic substances. 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 5 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 6 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 7 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 invention of claim 8 of the present invention relates to a surface coating agent for paper making as a specific application of the water-soluble polymer, and the product of the present invention relates to other coating agents such as cationic starch and oxidized water. 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 ninth aspect 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.

[0023]

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 1-2) 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. The whole amount of the polymer was added to acetone to precipitate a polymer, which was dried under vacuum to obtain a solid granular polymer. Next, 25 g of the solid particulate polymer and 100 g of demineralized water were placed in a 200 ml three-necked flask equipped with a stirrer, a cooler and a thermometer,
8 g of a 10% aqueous solution of hydroxylamine and 110 mol% of caustic soda based on formyl groups were added and reacted at 60 ° C. for 3 hours with stirring, and then 70 mol% of 3-chloro-2-hydroxypropyltrimethylammonium based on formyl groups. Add chloride and stir with 60
The reaction was performed for 3 hours at ° C. The obtained reaction product solution was dropped into acetone to cause precipitation, and this was dried under vacuum to obtain a solid particulate polymer. The colloid equivalent value and the intrinsic viscosity were measured by a conventional method. The results are shown in Table 1.

(Synthesis Examples 3-4) 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. The whole amount of the polymer was added to acetone to precipitate a polymer, which was dried under vacuum to obtain a solid granular polymer. Next, 25 g of the solid particulate polymer and 100 g of demineralized water were placed in a 200 ml three-necked flask equipped with a stirrer, a cooler and a thermometer,
8 g of a 10% aqueous solution of hydroxylamine hydrochloride and 110 mol% of 35% hydrochloric acid based on formyl groups were added, and reacted at 70 ° C. for 3 hours with stirring.
After adjusting the pH to 5.5, then 70 mol% of 3,2 epoxypropyltrimethylammonium chloride based on the formyl group was added, and the mixture was reacted at 60 ° C. for 3 hours with stirring. The obtained reaction product solution was dropped into acetone to cause precipitation, and this was dried under vacuum to obtain a solid particulate polymer. 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) A sample obtained by performing the same operation as the synthesis example without using a cationizing agent (3chloro-2-hydroxypropyltrimethylammonium chloride / 3,2epoxypropyltrimethylammonium chloride). It was adjusted. The results are shown in Table 1.

[0027]

[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.

[0029]

[Table-2]

[Effect test-2] 300 ml of pulp slurry (pulp concentration 0.4%) 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.

[0031]

[Table-3]

[Effect test-3] Polymer of this example
A 2% aqueous solution was prepared, and this was mixed with a commercially available 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.

[0033]

[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.

[0035]

[Table-5]

[Effect test-5] A coating solution (6.8 g of fine powdered silica, PVA117 (manufactured by Kuraray)) was used as a support, using a high-quality paper having a basis weight of 70 g / m ² and a Steckigt sizing degree of 25 seconds.
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.

[0037]

[Table-6]

[0038]

The cationizing agent (3 chloro-2-hydroxypropyltrimethylammonium chloride and 3,2 epoxypropyltrimethylammonium chloride) of the N-vinylcarboxylic acid amide (co) polymer hydrolyzate reacts with the cationizing agent. It exerts an excellent effect as a sludge dewatering agent and a papermaking agent on hydrolyzed N-vinylcarboxylic acid amide (co) polymer which is not allowed to be used, and has high product stability. It is difficult to infer such an effect from conventionally known techniques.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Procedure amendment]

[Submission date] February 25, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction contents]

(Synthesis Examples 1-2) 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 and an appropriate amount of 2-mercaptoethanol were added.
After passing nitrogen gas under ice cooling, the temperature was raised to 50 ° C.
2'-azobis-2-amidinopropane dihydrochloride 2%
Add 10.0 g of the aqueous solution and mix at 300 rpm 50 ° C
For 6 hours. The whole amount of the polymer was added to acetone to precipitate a polymer, which was dried under vacuum to obtain a solid granular polymer. Next, the solid particulate polymer 25
g, 100 g of demineralized water in a 200 ml three-necked flask equipped with a stirrer, a condenser and a thermometer, and 8 g of a 10% aqueous solution of hydroxylamine and 11
Add 0 mol% of caustic soda and stir at 60 ° C
For 3 hours, and then 70 mol% of 3-chloro-2-hydroxypropyltrimethylammonium chloride based on the formyl group was added. The mixture was reacted at 60 ° C. for 3 hours with stirring. The obtained reaction product solution was dropped into acetone to cause precipitation, and this was dried under vacuum to obtain a solid particulate polymer. The colloid equivalent value and the intrinsic viscosity were measured by a conventional method. The results are shown in Table 1.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0025

[Correction method] Change

[Correction contents]

(Synthesis Examples -3 to 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 and an appropriate amount of 2-mercaptoethanol were added.
After passing nitrogen gas under ice cooling, the temperature was raised to 50 ° C.
2'-azobis-2-amidinopropane dihydrochloride 2%
Add 10.0 g of the aqueous solution and stir at 300 rpm at 50 ° C.
For 6 hours. The whole amount of the polymer was added to acetone to precipitate a polymer, which was dried under vacuum to obtain a solid granular polymer. Next, the solid particulate polymer 25
g and 100 g of demineralized water were placed in a 200 ml three-necked flask equipped with a stirrer, a condenser and a thermometer, and 8 g of a 10% aqueous solution of hydroxylamine hydrochloride and 110 mol% of 35% hydrochloric acid based on formyl groups were added thereto and stirred. While 7
After reacting at 0 ° C. for 3 hours and further reacting at 90 ° C. for 3 hours, the pH was adjusted to 5.5, and then 70 mol% of 3,2 epoxypropyltrimethylammonium chloride based on formyl groups was added and stirred. 3 at 60 degrees C
Allowed to react for hours. The obtained reaction product solution was dropped into acetone to cause precipitation, and this was dried under vacuum to obtain a solid particulate polymer. The colloid equivalent value and the intrinsic viscosity were measured by a conventional method. The results are shown in Table 1.

Claims (9)

[Claims] 1. N-vinylcarboxylic acid amide 35-100
Mol% and a monomer containing 0 to 65 mol% of acrylonitrile and then hydrolyzed to give a water-soluble polymer obtained by adding 3 chloro-2-hydroxypropyltrimethylammonium chloride represented by the following formula (1) or A water-soluble polymer obtained by reacting 3,2 epoxypropyltrimethylammonium chloride represented by the following formula (2) with 10 to 100 mol% based on the charged amount of N-vinylcarboxylic acid amide. Embedded image Embedded image 2. The water-soluble polymer according to claim 1, wherein the water-soluble polymer has an intrinsic viscosity in 1N saline of 0.1 to 10 dl / g. 3. The water-soluble polymer according to claim 1, wherein the water-soluble polymer has a colloid equivalent value at pH 3.0 of 3.0 meq / g or more. 4. A sludge dewatering agent comprising the water-soluble polymer according to claim 1. 5. A paper strength enhancer comprising the water-soluble polymer according to claim 1. Description: 6. A yield improver comprising the water-soluble polymer according to claim 1. Description: 7. A drainage improver comprising the water-soluble polymer according to claim 1. 8. A coated paper surface coating comprising the water-soluble polymer according to claim 1. Description: 9. A method for producing an ink jet recording paper, comprising applying the surface coating agent for papermaking according to claim 8 to the surface of a coated base paper.