JPH0788638B2 - Method for producing cellulosic papermaking product - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a cellulosic papermaking product for the purpose of reducing the amount of cellulose components in waste water in a papermaking process and improving the yield of modifiers added. The obtained cellulose-based paper has excellent antibacterial, antifungal, deodorant, and biodegradable properties, so printing paper, wiping paper, food packaging paper, decorative paper,
Suitable for use as agricultural material paper.

[0002]

2. Description of the Related Art Cellulose-based paper products made from cellulose have been widely used for printing paper, wiping paper, food packaging paper, decorative paper, agricultural material paper and the like. And
Various modifiers suitable for these various uses are added to white water when producing a cellulosic papermaking product. However, when white paper containing a modifier is made into paper, these modifiers and cellulose components flow out into the wastewater, causing problems in wastewater treatment and poor yield of the modifier.

On the other hand, the wiping paper and the food wrapping paper are required to have a sanitary function, and some cellulosic paper products having antibacterial, antifungal and deodorant properties have been proposed. Therefore, it is said that the papermaking process solves the above-mentioned problems, and that the obtained papermaking product retains antibacterial performance, antifungal performance and deodorizing performance during use and is easily decomposed or disintegrated in soil after use. Development of a method for producing a cellulosic papermaking product having characteristics is desired.

In the case where chitosan is used to prevent the leakage of the cellulose component in the waste water in the paper making process of cellulose fiber, an aqueous solution of a water-soluble acid salt of chitosan is added to a suspension of cellulose fiber, and alkali is added with stirring. A method of adding and precipitating chitosan and then making a paper is disclosed (Japanese Patent Publication No. 4-47077). Further, an example of using chitosan to improve the yield of the modifier compounded in the cellulosic papermaking product is an aqueous suspension of cellulose fibers containing an adsorbent such as activated carbon or acid clay, and a solution of a water-soluble acid salt of chitosan. Is added, and an alkali is added with stirring to precipitate chitosan and then papermaking is disclosed (JP-A-55-70).
342). Furthermore, an example of using chitosan to prevent leakage of the cellulose component in the waste water and improve the yield of the modifier is a method of papermaking by adding an aqueous solution of a water-soluble acid salt of chitosan to an aqueous suspension of cellulose fibers. Is disclosed (JP-A-60-134097). However, a method of papermaking by adding a water-soluble acid salt of chitosan, a water-soluble polymeric substance, and an acid salt that makes chitosan insoluble to a water suspension containing cellulose fibers and a modifier as in the present invention is unknown.

[0005]

In the above-mentioned prior art, in the method disclosed in JP-A-60-134097, since the added chitosan makes the paper in the state of the water-soluble acid salt, the chitosan leaks to the waste water. There was a problem of doing. Further, in the method of Japanese Patent Publication No. 4-47077, since the water-soluble acid salt of chitosan is treated with an alkali to precipitate chitosan,
Although the leakage of chitosan to the wastewater has been greatly improved, it cannot be said that the level is still sufficient for the recovery of the cellulose component, and the method disclosed in JP-A-55-70342 is also disclosed in Japanese Patent Publication No. 4-4.
By the same operation as No. 7077, the yield of the adsorbent is improved, but there is a side inferior to the yield of the modifier other than the adsorbent, and since an alkali is used, depending on the type of the modifier used, It had the drawback of causing denaturation.

Therefore, the present invention improves the yield of the modifier added and the reduction of the cellulose component in the wastewater in the papermaking process, and the chitosan has antibacterial, antifungal, deodorant and biodegradable properties. The present invention provides a method for producing a cellulosic papermaking product which is excellent in these performances.

[0007]

The present invention relates to a water-soluble acid salt of chitosan in an aqueous suspension containing cellulose fibers and a modifier.
The present invention relates to a method for producing a cellulosic papermaking product, in which a water-soluble polymer substance and an acid salt that makes chitosan insoluble are added and stirred to make white water, and paper is made from this.

As a result of intensive studies to solve the conventional drawbacks, the inventors of the present invention have found that a water-soluble salt of chitosan and a high water-soluble salt of chitosan are added to a water suspension containing cellulose fibers and a modifier before papermaking. By adding and stirring a molecular substance and an acid salt that insolubilizes chitosan, the cellulose fiber, the insolubilized chitosan salt, and the water-soluble polymer substance are physically and ionically bound to each other, and by these three factors, A molecular matrix is formed, and the modifier is firmly retained inside, and the insolubilized chitosan salt and the water-soluble polymeric substance also bind between the cellulose fibers, which allows the cellulose fibers to flow into the wastewater. It has been found that the outflow of water can be greatly reduced, and the present invention has been completed.

The cellulose fibers used in the present invention are not particularly limited, and may be fibers capable of ordinary papermaking such as linter, cotton, hemp, wood pulp, waste paper pulp, rayon staple and the like.

The modifier used in the present invention has been conventionally added for the purpose of improving the physical properties and imparting functionality of the cellulosic papermaking product. For example, anionic size of maleated rosin, fumarized rosin, etc. Agents, neutral size agents such as alkyl ketene dimer and alkenyl succinic anhydride,
Emulsion type wax sizing agent, melamine resin, urea resin, polyamide polyamine resin and other wet paper strength agents, fluorine and other oil resistant agents, titanium oxide, talc, clay, kaolin, calcium carbonate and other fillers, activated carbon, silica gel, acid clay , Zeolite, diatomaceous earth, adsorbents such as activated alumina, cellulase, chitinase, chitosanase, and biodegradation promoters such as microorganisms that produce them, or a mixture containing them, or a mixture of two or more thereof. Can be mentioned.

The water-soluble acid salt of chitosan referred to in the present invention is
When chitosan forms a salt, it exhibits water solubility, and examples thereof include chitosan formate, hydrochloride, acetate, propionate, lactate, butyrate, salicylate, tartrate,
Examples thereof include adipate, acrylate, anthranilate, mandelate, glutamate and malate. These acid salts of chitosan used in the present invention are usually obtained by adding chitosan to an aqueous solution of these acids in an amount of 1% by weight or more and dissolving them.
Further, a powdered product obtained by drying this can also be used. The chitosan used here is not particularly limited, but it is preferable to deacetylate the chitin derived from the cereals that can be mass-produced, and in view of solubility, the molecular weight is 1,000. It is desirable that the degree of deacetylation is 70% or more within the range of up to 200,000. Further, the shape thereof may be any one such as flakes, powder or granules.

The water-soluble polymer substance used in the present invention is
Polyvinyl alcohol, casein, starch, cationized starch, gelatin, alginic acid, κ-carrageenan, polyacrylamide, polyacrylic acid, carboxymethyl cellulose, carboxymethyl chitin, carboxymethyl chitosan, sulfated chitin, sulfated chitosan, etc. The mixture to be contained, or a mixture of two or more of these may be mentioned.

The acid salt which makes chitosan insoluble in the present invention is an acid salt which insolubilizes the above-mentioned water-soluble acid salt of chitosan in an aqueous solution. For example, molybdic acid, tungstic acid, phosphomolybdenum Examples thereof include acids, phosphotungstic acid, picric acid, chromic acid, phosphoric acid, sodium salts such as sulfuric acid, potassium salts, magnesium salts, calcium salts, aluminum salts and the like.

According to the present invention, the concentration of cellulose fiber is 0.01.
After suspending in water so as to be not less than 1% by weight, 0.01% by weight or more of a modifier is added to the cellulose fiber, and then 0.01% by weight or more to the cellulose fiber in terms of chitosan. , Preferably 0.1% by weight or more of a water-soluble acid salt of chitosan or an aqueous solution thereof, and 0.01% by weight or more, preferably 0.1% by weight or more of a water-soluble polymeric substance, chitosan A sufficient amount of insoluble acid salt of chitosan to insolubilize the water soluble acid salt is added with stirring. The order of addition is not particularly limited, but it is desirable to add the acid salt that makes chitosan insoluble last.

By adding these, the water-soluble acid salt of chitosan becomes an insoluble acid salt of chitosan, and together with the water-soluble polymer substance, adheres to the surface of the cellulose fiber dispersed in white water, and is formed here. Since the modifier is efficiently held in the polymer matrix and the cellulose fibers are also bonded to each other, white water in which the leakage of the cellulose component into the waste water is small can be obtained. Further, other short fibers, for example, one or several kinds of synthetic fibers such as nylon, acryl, polyvinyl alcohol, polyester, polypropylene and polyethylene, and semi-synthetic fibers such as acetate can be added and mixed.

The white water thus obtained is subjected to papermaking by a usual method to obtain a cellulosic papermaking product. In addition, the cellulosic papermaking product obtained in the present invention can be subjected to secondary processing such as embossing or surface modification processing, if necessary.

[0017]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to this range. Each numerical value measured in this example was measured based on the following method.

<Thickness and Density> JIS P-8118 (1
976) Measured by "Testing method for thickness and density of paper and paperboard".

<Organic Mass in Waste Water> JIS P-8209
(1976) When carrying out hand plow according to "Handmade paper adjustment method for pulp test", 1 L of papermaking white water to be discharged is sampled from the water receiver shown in Fig. 3D of the hand plow device of item 2-2.
Biochemical oxygen consumption (BOD) of IS K-0102
Was calculated as

<Modifier retention> As for the sizing agent, 12 g of each dried sample was added to 200 ml of a 5% potassium hydroxide solution.
And boiled for about 1 hour. After filtering through 2 filter paper, concentrated sulfuric acid is added to the filtrate to adjust the pH to about 2. Ether 1
Add 00 ml for extraction, add sodium sulfate and let stand overnight. After filtering and concentrating with an evaporator, about 20 mg of this concentrate was dissolved in 5 ml of THF, and 1 g of maleic anhydride / 200 ml of THF was used as a standard solution for quantitative analysis by gel filtration. Regarding the filler, JIS P-
8128 (1976) “Test method for ash content of paper and board”
The ash content was measured according to and the yield was calculated from this. For the biodegradation promoting material, the absorbance at 280 nm of the waste water was measured, and the total protein mass was calculated by subtracting it from the added amount.

<Size Degree> JIS P-8122 (19
1976) Measured according to "Steckigt Sizing Test Method for Paper".

<Opacity> JIS P-8138 (19)
1976) "Paper opacity test method, 4.1, Method A".

<Whiteness> JIS P-8123 (196)
1 year) Measured by "Hunter whiteness test method for paper and pulp".

<Chitosan content> Using a pyrolysis gas chromatography mass spectrometer, the molecular ion peak of diazine (molecular weight 80) generated by pyrolyzing chitosan was quantified.

<Antibacterial performance> of the Textile Products Sanitary Processing Council,
It was measured by the bacterial count method in the processing effect evaluation test manual for antibacterial and deodorant processed products. Ie Staphylococcus aureus IFO
12732 is used as a test bacterium, and the culture is adjusted in advance in a normal broth medium to a concentration of 5 to 30 × 10 ⁵ cells / ml to give a test bacterium suspension. 0.2 ml of the suspension was uniformly inoculated into 0.2 g of a sample in a sterilized screw-equipped vial, and after static culture at 35 to 37 ° C. for 18 hours, 20 ml of sterile buffered saline was added to the container. After shaking vigorously by hand for 25 to 30 times with an amplitude of about 30 cm to disperse the live bacteria under test in the solution, make an appropriate dilution series with sterile buffered saline,
1 ml of the diluted solution at each stage was placed in a sterilized petri dish, and about 15 ml of a standard agar medium-pour plate was prepared in duplicate for each same diluted solution. After culturing this at 35 to 37 ° C. for 24 to 48 hours, the number of growing colonies was counted, and the number of viable bacteria in the sample was calculated by multiplying by the dilution ratio. And the judgment of the effect is
Based on the average number of bacteria of the non-added sample of chitosan and each mixed sample, the difference in increase / decrease value was determined by the following formula, and 1.6 or more was determined to have an antibacterial effect. Difference in increase / decrease value = log (B / A) -log (C / A) A: Immediately after inoculation of the test bacteria into the non-addition sample, the average number of cells dispersed and collected B: Inoculation of the non-addition sample with the test bacteria and culturing for 18 hours Average number of cells collected and dispersed and collected C: Average number of cells that were dispersed and collected after inoculating the added sample with the test strain and culturing for 18 hours

<Antifungal Performance> JIS Z-2911 (1
960) "Mold resistance test method 6-2 Textile product test method (dry method)". However, the mold must be Aspergillus niger.
er) ATCC 9642 was used.

<Deodorizing Performance> The sample was pre-dried at 70 ° C. for 1 hour and then exposed to the standard atmosphere, and 10 g of the sample was placed in a 3 L Tedlar bag and trimethylamine 100 was added thereto.
ppm, hydrogen sulfide 100 ppm, ammonia 100 pp
The treatment was performed for 1 hour in an atmosphere in which the concentration of m was enclosed, and the change in the gas concentration after the treatment was measured and calculated by the following formula. Deodorization rate (%) = [(initial gas concentration-residual gas concentration) /
(Initial gas concentration)] × 100

<Biodegradability> A sample was embedded in a soil 8 cm from the ground, and the condition after 1 month was visually judged.

Example 1 Pulp of Canadian Standard Freeness (hereinafter referred to as CSF) of 360 ml (softwood bleached kraft pulp (hereinafter referred to as N-BKP) /
Hardwood bleached kraft pulp (L-BKP) = 50/50
(Weight ratio)) 900 g was suspended in 90 kg of water, and 9 g of an anionic rosin sizing agent (trade name "Size Pine E" manufactured by Arakawa Chemical Industry Co., Ltd.) was added and uniformly dispersed therein. To this solution, 4.5 g of a polyacrylamide-based water-soluble polymer substance (trade name "Polystron 191" manufactured by Arakawa Chemical Industry Co., Ltd.) was added, stirred well, and then uniformly divided into 9 containers to prepare solution 1 ~ Solution 9 was obtained. this house,
For solution 1, 2 g of aluminum sulfate was added to make white water 1, and for solutions 2 to 5, the average molecular weight was 8.0.
A chitosan acetate aqueous solution prepared by dissolving 10% by weight of chitosan having a degree of deacetylation of 82% (hereinafter referred to as chitosan A) in an amount of 10% by weight, 5% by weight of acetic acid and 85% by weight of water in proportions shown in Table 1, respectively. 2 g of aluminum sulphate after each addition
Each of them was added to prepare white water 2 to white water 5 in which chitosan was sufficiently insolubilized. Further, for solutions 6 to 9, chitosan having an average molecular weight of 45,000 and a deacetylation degree of 80% (hereinafter,
Chitosan B) (5% by weight), 2.5% by weight of acetic acid, and 92.5% by weight of water are dissolved in the aqueous solution of chitosan acetate at a rate shown in Table 1, and then 2 g of aluminum sulfate is added. Each of them was added to obtain white water 6 to white water 9 in which chitosan was sufficiently insolubilized. Next, these white water 1 to white water 9 were paper-made using a TAPPI standard sheet machine so that the basis weight was about 50 g / m ² , and 5 kg / c
Dehydration at m ² pressure for 5 minutes, drying at 100 ° C. for 5 minutes, 2
The humidity was adjusted for 24 hours under the condition of 0 ° C. × 65% RH to obtain a cellulosic papermaking product (Sample 1 to Sample 9). Table 1 shows the measurement results of the amount of organic substances in the wastewater and various physical properties at the time of each of these papermaking processes.
Shown in.

[0030]

[Table 1]

As is clear from Table 1, Samples 2 to 2 of the present invention
Sample 9 has less organic mass in the waste water than sample 1 without addition of chitosan acetic acid solution, regardless of the average molecular weight and degree of deacetylation of chitosan, can reduce leakage of cellulose components, and increase the amount of chitosan added. And, the effect is improved. Further, since the yield of the sizing agent which is a modifier is also improved, it is understood that the sizing degree which is an effect of the modifier also has an excellent result.

<Comparative Example 1> (1) In the same production method as in Example 1, the operation was performed without adding any polyacrylamide-based water-soluble polymer substance,
Cellulosic papermaking products (Sample 10 to Sample 18) were obtained. (2) In the same manufacturing method as in Example 1, 2 g each of sodium hydroxide as an alkali was used instead of aluminum sulfate as an acid salt that insolubilizes chitosan without adding any polyacrylamide-based water-soluble polymer substance. Addition was performed to obtain a cellulosic papermaking product (Sample 19 to Sample 27). Table 2 shows the measurement results of the amount of organic substances in the waste water and various physical properties at the time of each paper making of Sample 10 to Sample 27 obtained in (1) to (2) above.

[0033]

[Table 2]

From Table 2, Samples 11 to 18 containing no polyacrylamide-based water-soluble polymer are those of Example 1
Compared with Samples 2 to 9 of the present invention shown in 1., the organic mass in waste water, the yield of the sizing agent as a modifier, and the size effect are all inferior, and the polyacrylamide-based water-soluble polymer substance, chitosan Since the sample 10 containing neither of the water-soluble acid salts described above is further inferior, it can be seen from Tables 1 and 2 that the water-soluble polymeric substance, the water-soluble acid salt of chitosan, and chitosan are insoluble. The addition of an acid salt to prevent leakage of the cellulose component in the wastewater and improve the yield of the modifier,
It is clear that it has contributed.

Samples 20 to 20 containing insoluble chitosan by adding sodium hydroxide as an alkali instead of aluminum sulfate which is an acid salt insolubilizing chitosan and does not contain a water-soluble polymer of polyacrylamide type Compared with the samples 2 to 9 of the present invention shown in Example 1, sample 27 was inferior in all of the organic mass in the waste water, the yield of the sizing agent as a modifier, and the size effect, and the water solubility of chitosan. Since the sample 19 containing no acid salt is further inferior, it can be seen from Tables 1 and 2 that the addition of the water-soluble polymer substance, the water-soluble acid salt of chitosan, and the acid salt that makes chitosan insoluble, which is a feature of the present invention. The method according to, is more conventional than the method by adding a water-soluble acid salt of chitosan and alkali,
It is clear that it is excellent in the leakage of the cellulose component in the waste water and the improvement in the yield of the modifier.

Example 2 Pulp with CSF of 360 ml (N-BKP / L-BKP = 50/50 (weight ratio)) 4
After suspending 00 g in 40 kg of water and adding 40 g of talc (filler) as a modifier and stirring for 15 minutes, anionic rosin sizing agent (trade name "Size Pine E" Arakawa Chemical Industries, Ltd.) was further used as a modifier. (Manufactured by K.K.) was added and uniformly dispersed. To this solution, 2 g of a polyacrylamide-based water-soluble polymer substance (trade name "Polystron 117" manufactured by Arakawa Chemical Industry Co., Ltd.) and 8 g of aluminum sulfate were added, and the mixture was stirred well and then evenly divided into 4 containers. Solution 28 ~
A solution 31 was obtained. Of these, the solution 28 was used as white water 28 as it was, and the solutions 29 to 31 were added with an aqueous solution of chitosan acetate containing 10% by weight of chitosan A, 5% by weight of acetic acid, and 85% by weight of water. White water 29 to white water 31 in which chitosan was sufficiently insolubilized was added. Next, the white water 28 to white water 31 was made into paper by using a TAPPI standard sheet machine so that the basis weight was about 50 g / m ² , and the paper was made 5 k.
Dehydration for 5 minutes at a pressure of g / cm ² , drying at 100 ° C. for 5 minutes, and humidity conditioning under conditions of 20 ° C. × 65% RH for 24 hours,
Cellulosic papermaking bodies (Sample 28 to Sample 31) were obtained. Table 3 shows the measurement results of the amount of organic substances in the waste water and various physical properties at the time of each paper making.

[0037]

[Table 3]

From the results of Table 3, since the organic mass in the wastewater of Samples 29 to 31 of the present invention is lower than that of Sample 28 to which the chitosan acetic acid solution is not added, the leakage of the cellulose component in the wastewater is suppressed. It is suppressed, and the yield of the modifier is excellent, and as a result, it is clear that whiteness and opacity are also high.

<Comparative Example 2> (1) In the same production method as in Example 2, a cellulosic papermaking product (Samples 32 to 35) was prepared by adding no water-soluble polyacrylamide-based polymer to the liquid. Got (2) In the same production method as in Example 2, a cellulosic papermaking product (Sample 36 to Sample 3) was prepared by the operation of adding no aluminum sulfate, which is an acid salt insolubilizing chitosan, to the liquid.
9) was obtained. (3) In the same production method as in Example 2, a cellulosic papermaking product (Sample 40) was prepared by adding no polyacrylamide water-soluble polymer substance and aluminum sulfate, which is an acid salt insolubilizing chitosan, to the liquid. ~ Sample 43) was obtained. (4) In the same production method as in Example 2, sodium hydrate, which is an alkali, is used in place of aluminum sulfate, which is an acid salt that insolubilizes chitosan, without adding a polyacrylamide-based water-soluble polymer substance to the liquid. By adding 2 g each, a cellulosic papermaking product (Sample 44 to Sample 4)
7) was obtained. Table 4 shows the measurement results of the amount of organic substances and various physical properties in the waste water at the time of each paper making of Sample 32 to Sample 47 obtained in (1) to (4) above.

[0040]

[Table 4]

As shown in Table 4, Samples 33 to 35 containing no polyacrylamide water-soluble polymer have a higher organic mass in waste water than Samples 29 to 31 of the present invention shown in Example 2. The yield of the filler is inferior, and as a result, the whiteness and opacity, which are the effects of the modifier, are low. Similarly, Samples 35 to 39 that do not contain aluminum sulfate that is an acid salt that insolubilizes chitosan, and Sample 41 that does not contain a water-soluble polymeric substance of polyacrylamide and aluminum sulfate that is an acid salt that insolubilizes chitosan.
Also with respect to the sample 43, a large effect was not obtained, and the sample 32, the sample 36, and the water-soluble acid salt of chitosan were not added.
It is clear that sample 40 is ineffective. From this result, it is understood that the present invention can be achieved only by adding the water-soluble acid salt of chitosan, the water-soluble polymer substance, and the acid salt insolubilizing chitosan, in addition to the modifier.

Further, it was obtained by adding sodium hydroxide, which is an alkali, in place of aluminum sulfate, which is an acid salt for insolubilizing chitosan, without adding any polyacrylamide-based water-soluble polymer substance, and insolubilizing chitosan. Sample 4
5 to Sample 47, the organic mass in the waste water and the yield of the modifier were improved with the increase of the added amount of chitosan, but when compared with Samples 29 to 31 of the present invention shown in Example 2,
It is clear that it is still inferior.

<Application Example 1> Samples 28 and 31 obtained in Example 2 and samples 35, 39 and 4 obtained in Comparative Example 2
3, for sample 47, chitosan content, antibacterial test,
Antifungal test, deodorant test and biodegradability test were conducted. The results are shown in Table 5.

[0044]

[Table 5]

From these results, it can be seen that the sample 31 of the present invention has not only antibacterial performance, antifungal performance and deodorant performance but also decomposition in soil as compared with the sample 28 in which the water-soluble acid salt of chitosan is not added. It can be seen that the performance is also excellent. Further, sample 35 containing no polyacrylamide water-soluble polymer, sample 39 containing no aluminum sulfate, which is an acid salt that insolubilizes chitosan, polyacrylamide water-soluble polymer and chitosan. Similarly to Sample 31 of the present invention, Sample 43 in which aluminum sulfate, which is an acid salt that insolubilizes C., is added to the water-soluble acid salt of chitosan with respect to the cellulose fiber by 0.4 in terms of chitosan.
The chitosan content is inferior to sample 31 of the present invention, despite the addition in%. From this, it can be seen that the sample 31 of the present invention supports the effect of reducing the organic mass in the wastewater, and has a high chitosan content, and thus has high antibacterial performance, antifungal performance, deodorizing performance, and biodegradation performance. .
In addition, the sample 47 in which sodium hydroxide, which is an alkali, was added instead of the aluminum sulfate that is an acid salt that insolubilizes chitosan, also has a lower chitosan content as compared with the sample 31 of the present invention, and this is equivalent to the organic mass in wastewater. It is clear that this proves that the improvement effect is inferior.

<Example 3, Comparative Example 3> (1) Pulp having CSF of 360 ml (N-BKP / l-B)
KP-50 / 50 (weight ratio) 200 g was suspended in 20 kg of water, and Bacillus (Bacil) was added to this as a modifier.
lus) -derived cellulase (degradation promoter: enzyme activity 0.04 CMC-U / ml) and 10 ml of Bacillus
Chitosanase derived from Bacillus pumilus (degradation promoter: enzyme activity 20,000u
/ G, product name "MEIJI CHITOSANASE
5 mg of “BP” manufactured by Meiji Seika Co., Ltd. was added and uniformly dispersed. To this solution, 2 g of carboxymethyl cellulose, which is a water-soluble polymer substance, was added and stirred well, and then, Example 1
40 g of chitosan lactate aqueous solution containing 2 g of chitosan A
Then, 2 g of magnesium sulfate, which is an acid salt insolubilizing chitosan, was added to prepare white water in which chitosan was sufficiently insolubilized. Next, using a TAPPI standard sheet machine, paper was made to have a basis weight of about 50 g / m ² , and 5 kg
/ Cm ² pressure for 5 minutes dehydration, 100 ℃ 5 minutes dry, 20 ℃ × 65% RH conditions for 24 hours,
A cellulosic papermaking product (Sample 48) was obtained. (2) In the same manufacturing method as in (1), a cellulose-based paper product (Sample 49) was obtained by the operation of adding no lactate salt of chitosan A to the liquid. (3) In the same production method as in (1), 2 g of cationized starch, which is a cationic polymer other than chitosan, was added to the liquid instead of the lactate salt of chitosan A. ) Got. (4) In the same production method as in (1), carboxymethylcellulose, which is a water-soluble polymer, is not added to the liquid at all, and sodium hydroxide, which is an alkali, is used instead of magnesium sulfate, which is an acid salt that insolubilizes chitosan. By the operation of adding 2 g, a cellulosic papermaking product (Sample 51) was obtained. Table 6 shows the measurement results of the amounts of organic substances and various physical properties in the wastewater at the time of each paper making of the samples 48 to 51 obtained in (1) to (4).

[0047]

[Table 6]

From these results, it is understood that the sample 48 of the present invention has a lower organic mass in the waste water than the samples 49 to 51 of the comparative examples, and thus contributes to the prevention of leakage of the cellulose component in the waste water. . In addition, since the activity of the enzyme that is a modifier is low in the wastewater, it is clear that there is no leakage of the modifier into the wastewater and that the yield of the modifier is excellent. There is no decrease in the enzyme activity expression rate in the papermaking product.

On the other hand, a sample 49 containing no water-soluble acid salt of chitosan and a sample 50 containing cationized starch with a cationic polysaccharide similar to chitosan in place of the water-soluble acid salt of chitosan were used in the papermaking product. Although there is no reduction in the enzyme activity expression rate, it is found that the organic mass in the waste water is reduced and the yield improving effect of the modifier is inferior. Further, in the sample 51 to which an alkali was added instead of the salt that insolubilizes chitosan, although the organic mass in the wastewater was reduced and the yield improvement effect of the modifier was observed, the enzyme activity expression rate in the papermaking body was significantly increased. It is inferior and it is clear that the modifier is modified by the addition of alkali.

[0050]

INDUSTRIAL APPLICABILITY The method of the present invention has a great effect of reducing the leakage of the cellulose component in the waste water generated in the papermaking process and improving the yield of the modifier in the papermaking stage. The cellulosic paper product obtained by the method has excellent antibacterial properties, antifungal properties, and deodorant properties, and is completely decomposed by soil microorganisms,
Greatly effective in the field of application for the prevention of environmental pollution.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location D21H 21/36 23/04 D21H 3/22 ZAB 3/68 5/22 D (56) References Kai 63-92799 (JP, A)

Claims (1)

[Claims] 1. A water suspension containing cellulose fibers and a modifier is added with a water-soluble acid salt of chitosan, a water-soluble polymeric substance, and an acid salt that makes chitosan insoluble, and stirred to prepare white water. A method for producing a cellulosic papermaking product, which comprises performing papermaking.