KR20060133679A - Paper whose content of flurescence whitening agents is diminished and manufacturing method thereof - Google Patents

Abstract

A paper with a reduced content of a fluorescent whitening agent and a manufacturing method thereof are provided to separate a remaining content of a fluorescent whitening agent from a paper and remove the remaining content by green technology using enzymes. In a method for manufacturing a paper with a reduced content of a fluorescent whitening agent, an endosperm layer is separated from raw material pulp in a pulper and/or a beater while carrying out hydrolysis for an endosperm layer containing a fluorescent whitening agent by adding enzymes such as amylase, cellulase, xylanase, and mixture thereof to the raw material pump, wherein the raw material pulp is treated with the endosperm layer. Impurities are removed from the beaten raw material pulp through a cleaner and/or a screen, so that perfect pulp stuff is screened from the raw material pulp. The pulp stuff is compressed, dried and wound on a winder.

Description

Paper making with reduced content of fluorescent brightener and its manufacturing method {PAPER WHOSE CONTENT OF FLURESCENCE WHITENING AGENTS IS DIMINISHED AND MANUFACTURING METHOD THEREOF}

Figure 1a is a view showing the correlation between the amount of internal brightening brightener and the amount of fluorescence emission.

Figure 1b is a view showing the correlation between the amount of fluorescent brightener for surface treatment and the amount of fluorescent emission.

2 is a view showing the amount of fluorescence emitted from a sheet of paper according to Experimental Example 2. FIG.

3 is a view showing a fluorescent brightener content according to Experimental Example 2.

4 is a view showing the amount of fluorescence emitted from a sheet of paper according to Experimental Example 3. FIG.

5 is a view showing a fluorescent brightener content according to Experimental Example 3.

6 is a view comparing the amount of fluorescence emitted from a sheet of paper according to Experimental Example 4. FIG.

7 is a view showing a fluorescent brightener content according to Experimental Example 4.

FIG. 8 is a graph comparing the separation rate of the optical brightener obtained through Experimental Examples 1 to 4 and the COD of the filtrate.

9 is a view showing the amount of fluorescence emitted from a sheet of paper according to Experimental Example 6. FIG.

10 is a view showing a fluorescent brightener content according to Experimental Example 6.

FIG. 11 is a graph comparing the separation rate of the optical brightener obtained through Experimental Example 5 and Experimental Example 8 and the COD of the filtrate.

The present invention relates to a method for reducing the content of fluorescent substances in sanitary paper, and particularly, among the fluorescence whitening agents (FWA) contained in the raw material and remaining in the waste paper through surface treatment. The present invention relates to a method for separating and removing more than%.

The use of sanitary paper and toilet paper and napkins is continuously increasing to improve the economic and cultural level of Korea. At present, the consumption of toilet paper per capita in Korea has increased rapidly, and this trend is expected to continue in the future.

As raw materials for the production of toilet paper, bleached kraft pulp, which is a natural pulp, and recycled waste papers based on CPO (computer printout) and white ledger are used. Natural pulp is used only for the manufacture of premium premium cosmetic tissues, so most commonly used toilet paper is made of recycled materials. Printing papers such as CPO and white leisure, which are the main raw materials of sanitary paper, require very high whiteness and strength. Therefore, the producers of this paper use more fluorescent materials to meet these characteristics, and the demand for printing paper is increasing.

Fluorescent whitening agent is one of the most widely used additives for the production of printing paper, which is an important quality standard for whiteness, and is embedded in pulp or chest or escaped to the surface with starch or polyvinyl alcohol in size press.

Fluorescent brighteners generally used are mostly diaminostilbene disulfonic acid compounds. Fluorescent brighteners of this type make to water-soluble nitro-toluene sulfonic acid via toluene or nitrotoluene. After oxidizing with air, the two molecules condense into dinitro stilbene disulfonic acid, which in turn becomes diaminostilbene disulfonic acid. The above reaction scheme is represented by the formula (1).

As such, the fluorescent dyes contained in the inside, the surface, and the coating layer of the paper may cause the fluorescent dyes to remain in the paper produced again when these papers are recycled. It is known that the risk of this residual fluorescent substance to the human body is generally bad. In particular, since hygienic paper is used in contact with the skin, skin side effects and carcinogenic potential are constantly being raised, and the Ministry of Health and Welfare regulates the addition of fluorescent brighteners in the case of food packaging paper.

As a method for removing the fluorescent brightener, there is a method of adding a liquid containing a triazin UVA compound in the process of treating the fluorescent brightener, as proposed in Japanese Patent Laid-Open No. 2003-502517.

However, since it contains chemicals such as ammonium group (-NH ₂ ), sulfone group (-SO ₃ ), it is accompanied by toxic and odor, and is not environmentally friendly, there is a problem that handling is difficult in the field.

In order to solve the above problems, the present invention is to propose a method for reducing the amount of fluorescent brightener as much as possible through an environmentally friendly method for producing recycled paper.

In order to achieve the above object, a method of preparing paper with reduced content of a fluorescent brightener according to a feature of the present invention is

(a) adding an enzyme to the raw pulp treated with a starch layer containing a fluorescent brightener to dissociate the starch layer in pulper and / or a beaker while hydrolyzing the starch layer; And / or removing foreign matter by passing through the screen and selecting a stock from the dissociated raw pulp, and (c) a papermaking step of compressing and drying the selected stock to wind it into a winder.

Another feature of the present invention is paper making with reduced content of the optical brightener prepared by the above method.

In general, in the case of dyes, the absorbed light energy is used as thermal energy such as vibration of molecules, and thus is not re-emitted in the form of light. However, fluorescent brighteners have a much stronger molecular structure than dyes, making it difficult to consume the light energy absorbed by the vibrations of the molecules. Therefore, the energy of the absorbed light energy cannot be released through the vibrations. Has the property of returning to the state. In addition, the fluorescent brightener emits light as soon as it reaches the excited state of the light and does not return to the ground state and remains in the excited state for a relatively long time.

Fluorescent whitening agent is based on stilbene. Since stilbene is an unsaturated hydrocarbon in which a double bond exists between carbon and carbon, the fluorescent brightener has a compound represented by Formula 2 or an isomer thereof.

Generally, trans type fluorescent brighteners show fluorescence ability, but cis type fluorescent brighteners cannot have the performance. In particular, trans-fluorescent brighteners may also be converted to cis-type by sudden exposure to ultraviolet rays or rapid dilution. However, the conversion of isomers does not occur once the transfluorescent brightener is fixed to the fiber.

At this time, the fluorescent brightener is divided into three types, such as disulpho, tetrasulpho, and hexasulpho, depending on the number of sulfone groups to be introduced.

Fluorescent whitening agent has 4,4'-diaminostilbene-2,2'-disulfonic acid (4,4'-diaminostilbene-2,2'-disulfonic acid) as basic structure and introduces the same substituents The number of sulfone groups will be determined.

The type of fluorescent brightener varies depending on the substituents of R1 and R2 in Formula 2, and Table 1 shows the types of substituents depending on the type of fluorescent brightener. Regardless of the type of fluorescent brightener, a constant substituent is always attached to the position of R1, but the type of fluorescent brightener is changed as a substituent having a different number of sulfone groups is introduced at the position of R2.

Fluorescent brighteners can be broadly divided into internal additives directly added to pulp slurry, surface treatments applied to starch solution during surface sizing treatment, and coatings applied to coating solution during coating.

Disulpho FWA (Disulpho FWA) is mainly used for internal additives because of its good directivity to fibers, but it is also used for papers that have good compatibility with cationic additives and are added during coating and require relatively good optical properties.

Tetrasulpho FWA (Tetrasulpho FWA) is less direct to the fiber than the disulpho type, but is widely used for internal additives and surface sizing. Tetrasulpho FWA is widely used for papers that require relatively low optical properties because it is relatively inexpensive compared to other types of fluorescent brighteners and has higher stability than disulpho type.

Hexasulpho FWA (Hexasulpho FWA) is used for papers that have high solubility and resistance to acids and require significantly higher optical properties.

In general, in the application of fluorescent brighteners, the ratio of the amount of fluorescent brighteners used in the internal treatment and the surface treatment is about 1: 4, so that a larger amount of the optical brightener is used in the surface treatment.

On the other hand, since the optical brightener has a sulfone group (-SO ₃ Na), it shows anionicity when dissolved in water. As the optical brightener is adsorbed on the fiber, the anionicity of the optical brightener increases the zeta potential of the fiber to a negative value and the high cation demand is increased as the content of the optical brightener in the aqueous solution increases. By using these properties, adsorption of fluorescent brighteners can be quantitatively and qualitatively analyzed.

In order to quantitatively evaluate the adsorption of the fluorescent brightener, the amount of unadsorbed fluorescent brightener present in the pulp supernatant is measured. The pulp supernatant was filtered using a filter after a fluorescent whitening agent was added to the same amount of pulp as in the case of manufacturing a sheet of paper. The filtered pulp supernatant is measured for cation demand using a particle charge detector (PCD). After filtering the pulp supernatant to which the fluorescent brightener was not added, the amount of the titrant (poly-DADMAC) consumed by the unadsorbed fluorescent brightener was measured. In addition, by measuring the charge density of the fluorescent brightener measured at the same pH condition as the pulp, the content of the unadsorbed fluorescent brightener is calculated, and the adsorption amount of the fluorescent brightener is measured.

On the other hand, the following analytical methods were applied to quantify the amount of fluorescent brightener present in the paper or on the surface and pulp supernatant. For the qualitative analysis of the fluorescent material, the presence of the fluorescent material was evaluated by using an UV lamp.

Fluorescent brighteners absorb ultraviolet light having a wavelength of 240-380 nm and emit blue visible light having a wavelength of 400-500 nm. Using this property, the amount of fluorescent brightener is quantified using an image restoration microscopy (IRM) that emits ultraviolet rays of a specific wavelength.

The image reconstruction microscope uses a mercury arc lamp as a light source, and uses a filter and a fiber optic to supply a light source having a constant wavelength and stable energy intensity to obtain a high resolution image.

When the image and fluorescence emission of the paper to which the fluorescent brightener is added are measured, light blue fluorescence starts to occur as the fluorescent brightener is added.

Figure 1a is a view showing the correlation between the content of the internal brightening brightener and the amount of fluorescence emission, Figure 1b is a view showing the correlation between the amount of fluorescent brightener for surface treatment and the amount of fluorescent emission (fluorescence in Figures 1a and 1b) All brighteners use T-FWA). The value of the fluorescent emission amount used at this time was made into the average value.

As shown in Figure 1a and Figure 1b it can be seen that the area showing the fluorescence is widening as the amount of addition increases. In addition, the mean value of the amount of fluorescent brightener and the amount of fluorescent emission shows a correlation between the exponential function.

Equation 1 shows the correlation between the fluorescent brightener content and the average value of the fluorescent emission. At this time, M is the average value of the fluorescence emission, y represents the content of T-FWA contained in the paper.

y = y ₀ + a × exp (b × M)

In this case, the values of y _0, a, b in the case of using the internal brightening brightener and in the case of using the surface brightening brightener are shown in Table 2 below.

On the other hand, a significant amount of fluorescent brightener is added to art paper or printing paper that requires excellent optical properties, and more than the internal brightening brightener is used for the surface sizing fluorescent brightener.

In general, the optical brightener is located on the film formed on the surface of the paper together with the starch, so that the optical brightener can be removed simultaneously by hydrolyzing the starch layer.

Therefore, in the present invention, three kinds of enzymes were used to remove the starch layer present on the paper surface. Amylase to elute starch by hydrolyzing α-D- (1-4) glucosidic bond of starch, cellulase / fibrezyme and fiber used for treatment of virgin fiber and secondary processed fiber Cellulase, hemicellulase and xylase complex enzymes (hereinafter referred to as "xylase complex enzymes") used to improve properties were used.

First, prior to explaining the experimental example of the present invention, looking at the papermaking process generally includes a dissociation step, paper stock selection step, grass paper step.

First, in the beating, the pulp is dissociated in water using a machine (pulper). At this time, the raw pulp may be subjected to a sizing treatment of mixing the colloidal material having water resistance, or a filler or a dye may be further added.

Next, the papermaking process is completed by passing the beaten raw pulp through a cleaner and / or screen to remove foreign substances, selecting a stock from the beaten raw pulp, compressing and drying the selected stock, and drying the wound. do.

Therefore, in the following experimental example, the experiment was carried out to add the enzyme in the dissociation step, and the stock selection step, the papermaking step, etc. are easily understood by those skilled in the art to which the present invention belongs, so the description thereof will be omitted.

Example 1

In order to form a paper, first, a paper sized with a fluorescent brightener and starch oxide was prepared. After using the hardwoods to prepare a sheet of paper with a basis weight of 100 g / ㎡ was surface sizing. At this time, the fluorescent brightener (T-FWA) was added 1.0% to the starch. The surface-sized paper was dissociated at 50,000 rev. At 3.0% concentration using a dissociator to prepare a stock.

In the process of dissociating the prepared stock, amylase was added at a concentration of 0.01 to 1.0% at a temperature of pH 6.0 to 8.0 and 40 to 80 ° C, and the reaction was performed for about 30 minutes to 3 hours. At this time, a heating mantle was used to apply a constant temperature and a constant speed was stirred with a stirrer.

After the amylase treatment in order to remove the activity of the enzyme through a selection step and the papermaking step was quickly produced a paper sheet (basic weight 80 g / ㎡).

Example 2

The disintegrated stock was obtained under the same conditions and methods as in Example 1. At this time, in the process of dissociating the prepared stock, the cellulase was added at a concentration of 0.01 to 1.0% at a temperature of pH 4.0 to 8.0 and 40 to 80 ° C., and the reaction was performed for about 30 minutes to 3 hours. Hereinafter, the method for obtaining a sheet of paper is the same as that of Example 1, and a description thereof will be omitted.

Example 3

The disintegrated stock was obtained under the same conditions and methods as in Example 1. At this time, in the process of dissociating the prepared stock, the xylase complex enzyme was added at a concentration of 0.01 to 1.0% at a temperature of pH 4.0 to 7.0 and 40 to 80 ° C., and the reaction was performed for about 30 minutes to 3 hours. Hereinafter, the method for obtaining a sheet of paper is the same as that of Example 1, and a description thereof will be omitted.

Example 4

Instead of the surface sized paper in Example 1, a printing paper having a basis weight of 100 g / m 2 was prepared. At this time, the fluorescent brightener (T-FWA) was added 1.0% to starch starch as in Example 1. Printing paper was prepared by dissociating 50,000 rev. At 3.0% concentration using a dissociator.

In the process of dissociating the prepared stock, amylase was added at a concentration of 0.01 to 1.0% at a temperature of pH 6.0 to 8.0 and 40 to 80 ° C, and the reaction was performed for about 30 minutes to 3 hours. At this time, a heating mantle was used to apply a constant temperature and a constant speed was stirred with a stirrer.

After the amylase treatment in order to remove the activity of the enzyme through a selection step and the papermaking step was quickly produced a paper sheet (basic weight 80 g / ㎡).

Example 5

The disintegrated stock was obtained under the same conditions and methods as in Example 4. At this time, in the process of dissociating the prepared stock, the cellulase was added at a concentration of 0.01 to 1.0% at a temperature of pH 4.0 to 8.0 and 25 to 60 ° C., and the reaction was performed for about 30 minutes to 3 hours. Hereinafter, the method for obtaining a sheet of paper is the same as that of Example 1, and a description thereof will be omitted.

Example 6

The disintegrated stock was obtained under the same conditions and methods as in Example 4. At this time, in the process of dissociating the prepared stock, the xylase complex enzyme was added at a concentration of 0.01 to 1.0% at a temperature of pH 4.0 to 7.0 and 40 to 80 ° C., and the reaction was performed for about 30 minutes to 3 hours. Hereinafter, the method for obtaining a sheet of paper is the same as that of Example 1, and a description thereof will be omitted.

The following experiments were carried out using the sheet paper prepared in the above examples, the surface-sized paper and the printing paper used as raw materials.

Experimental Example 1

Images were obtained by using an image reconstruction microscope (IRM) to evaluate the fluorescent brightener content of the surface-sized paper having a basis weight of 100 g / m 2 used as raw materials in Examples 1 to 3, and the average fluorescence emission was determined by image analysis. Measured. In addition, the stock to which the enzyme was reacted was filtered through a filter, and the COD (chemical oxygen demand) of the filtrate was measured. The amount of fluorescence brightener measured by substituting the amount of fluorescence emission measured in this manner into Equation 1 is obtained.

Experimental Example 2

The amount of fluorescent brightener was determined using the same method as Experimental Example 1, using the same method as Experimental Example 1, using the surface-sized paper prepared in Example 1 as a raw material pulp and adding amylase.

At this time, the separation rate of the fluorescent brightener was calculated through the following equation (2). That is, before dissociation, the amount of fluorescence emission of FWA on paper was measured and substituted in Equation 1 to obtain the content of fluorescent brightener, and the content of fluorescent brightener of dissociated and enzymatically treated paper was calculated in the same manner.

% Separation = (A-B) / A * 100

(A: amount of FWA contained in paper before dissociation, B: amount of FWA remaining on paper after physicochemical treatment)

First, Figure 2 compares the fluorescence emission measured by the amount of fluorescence brightener contained in the paper before the dissociation for Experimental Example 1 and Experimental Example 2 and the fluorescence emission of the paper produced by enzyme treatment with amylase Drawing. As shown in Fig. 2, the amount of fluorescence emission was measured to be smaller than that of the paper before the dissociated paper produced by the enzyme treatment with amylase.

The fluorescence brightener content obtained by substituting the fluorescence emission measured as described above in Equation 1 is shown in FIG. 3. The smaller the value of the fluorescence emission amount, the smaller the content of the fluorescence brightener. That is, it can be seen that as the enzyme treatment process by amylase proceeds, the content of fluorescent brightener is also reduced.

At this time, before dissociation in Equation 2, the amount of FWA contained in the paper and the amount of FWA remaining in the paper produced by adding amylase were substituted to obtain a separation rate. About 57% of the whitening agent was separated off.

Experimental Example 3

The surface-treated paper prepared in Example 1 was used as a raw material pulp, and the amount of fluorescent whitening agent was determined using the same method as that of Experimental Example 1, using the paper produced by adding cellulase.

4 is a view comparing the fluorescence emission measured by the amount of fluorescence brightener contained in the paper before the dissociation for Experimental Example 1 and Experimental Example 3 and the amount of fluorescence emission of the paper produced by enzyme treatment with cellulase . As shown in FIG. 4, the amount of fluorescence emission was measured to be smaller than that of the paper before dissociation of the prepared paper including the enzymatic treatment with cellulase.

The fluorescence brightener content obtained by substituting the fluorescence emission measured as described above in Equation 1 is shown in FIG. 5, and as in Experimental Example 1, it can be seen that the fluorescence brightener content decreases as the enzyme treatment process proceeds with the cellulase. .

At this time, before dissociation in Equation 2, the amount of FWA contained in the paper and the amount of FWA remaining in the paper produced by adding cellulase were substituted, and the separation rate was obtained. Cellulase hydrolyzed the starch layer remaining on the fiber surface. About 53% of the brightener was separated off.

Experimental Example 4

The surface-treated paper prepared in Example 1 was used as a raw material pulp, and the amount of fluorescent whitening agent was determined using the same method as Experimental Example 1 by adding xylanase complex enzyme.

Figure 6 shows the fluorescence emission amount measured by the amount of fluorescence brightener contained in the paper before the dissociation for Experimental Example 1 and Experimental Example 4 and the amount of fluorescence emission of the paper produced by enzymatic treatment with xylanase complex enzyme It is a figure compared.

As in the case of addition of amylase and cellulase, the amount of fluorescence emission was measured to be smaller than that of the paper before dissociation of the prepared paper, including the enzymatic treatment with xylanase complex enzyme.

The fluorescence brightener content obtained by substituting the fluorescence emission measured as described above in Equation 1 is shown in FIG. 7. It can be seen that the fluorescence brightener content decreases as the enzymatic treatment with the xylanase complex enzyme proceeds.

Similarly, when the separation rate of the fluorescence brightener was obtained through Equation 2, about 54% of the fluorescence brightener was separated and removed by the hydrolysis of the starch layer remaining on the surface of the xylanase complex enzyme.

FIG. 8 is a graph comparing the separation rate of the fluorescent brightener and the COD (chemical oxygen demand) of the filtrate when three kinds of enzymes obtained through Experimental Examples 1 to 4 were added.

As shown in FIG. 8, amylase showed the highest separation rate of fluorescence brightener among amylase, cellulase, and xylase complex enzyme, and the COD of the filtrate also showed the highest value.

That is, since the separated optical brightener is mixed in the filtrate, it can be seen that the chemical oxygen demand is further increased.

Experimental Example 5

Instead of the surface-sized paper in Experimental Example 1, Experimental Example 5 used an image reconstruction microscope (IRM) to evaluate the fluorescence brightener content of the printing paper having a basis weight of 100 g / m 2 used as raw materials in Examples 4 to 6. Images were acquired and the average fluorescence emission was measured through image analysis. In addition, the stock to which the enzyme was reacted was filtered through a filter, and the COD (chemical oxygen demand) of the filtrate was measured. The amount of fluorescence brightener measured by substituting the amount of fluorescence emission measured in this manner into Equation 1 is obtained.

Experimental Example 6

The amount of fluorescent brightener was determined using the same method as Experimental Example 1, which was prepared by adding amylase to the printing paper in Example 4 as a raw material pulp.

Figure 9 shows the amount of fluorescence emission measured by the amount of fluorescent brightener contained in the printing paper before dissociation for Experimental Example 5 and Experimental Example 6 and the amylase enzyme treatment using the printing paper as a raw material. It is a figure which compared the fluorescent emission amount of papermaking. As shown in FIG. 9, the amount of fluorescence emission was measured to be smaller than that of the paper before dissociation of the prepared sheet including the enzyme treatment with amylase.

The fluorescence brightener content obtained by substituting the fluorescence emission measured as described above in Equation 1 is shown in FIG. As the enzyme treatment proceeds, it can be seen that the content of the fluorescent brightener is reduced.

Experimental Example 7

The amount of fluorescent brightener was determined using the same method as Experimental Example 1, using the same method as Experimental Example 1, which was prepared by adding cellulase to the printing paper as a raw material pulp.

Experimental Example 8

The amount of fluorescent whitening agent was determined using the same method as Experimental Example 1, using the same method as Experimental Example 1, which was prepared by adding the xylase complex enzyme to the printing paper as a raw material pulp.

Using the results of Experimental Example 7 and Experimental Example 8, the fluorescent whitening agent separation rate and the COD of the filtrate obtained by enzymatic treatment of cellulase and xylanase complex enzyme, respectively, were used as printing paper as raw materials. Shown together.

As shown in FIG. 11, about 60% of the fluorescent brightener was isolated in the case of amylase, and about 30% in the case of the cellulase and xylanase complex enzyme. In addition, when the amylase was added, the COD of the filtrate also showed the highest value.

As can be seen from the above experimental examples, when enzyme is added in the process of making a sheet paper using the surface-sized paper and the printing paper as raw materials, in most cases, 50% or more of the fluorescent brightener contained in the first paper. This was removed and separated.

In particular, the addition of amylase as an enzyme can be seen that the separation rate of the optical brightener is the most excellent.

Although the preferred experimental examples of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

The present invention relates to a paper making with reduced amount of fluorescent brightener and a method for producing the same, according to the present invention, it is possible to provide a paper making the removal of at least about 50% of the fluorescent brightener contained in the pulp material in an environmentally friendly manner. Can be.

Claims (12)

(a) adding an enzyme to the raw pulp treated with a starch layer containing a fluorescent brightener to dissociate it in the pulper and / or the beaker while hydrolyzing the starch layer; (b) passing the dissociated raw pulp through a cleaner and / or screen to remove debris and selecting a stock from the dissociated raw pulp; And (c) a papermaking step of compressing and drying the selected stock and winding it to a winder; A method for producing paper with a reduced content of fluorescent brightener. The method of claim 1, The fluorescent brightener is a compound represented by the following formula (2) or a method for producing paper, characterized in that an isomer thereof. [Formula 2]

In Chemical Formula 2, R1 is

Is, R2 is

,

or

being. The method of claim 1, Said enzyme is selected from the group consisting of cellulase, hemi cellulase, amylase, xylanase and mixtures thereof. The method of claim 1, A sizing step of mixing the colloidal material having water resistance to the raw material pulp between steps (a) and (b); And / or A method of making paper with a reduced content of fluorescent brightener, further comprising the step of adding a filler or dye. The method of claim 1, The raw material pulp is a paper manufacturing method of the surface-sized paper or printing paper. The method of claim 3, The amylase has an optimum pH of 6.0 to 8.0, and is treated with 0.01 to 1.0 parts by weight based on 100 parts by weight of the paper. The method of claim 3, The amylase is a method for producing paper, characterized in that the treatment for 30 minutes to 3 hours at a temperature of 40 to 80 ℃. The method of claim 3, The cellulase has an optimum pH of 4.0 to 8.0, the method of producing paper, characterized in that the treatment is 0.01 to 1.0 parts by weight based on 100 parts by weight of the paper. The method of claim 3, The cellulase is a manufacturing method of paper making, characterized in that the treatment for 30 minutes to 3 hours at a temperature of 40 to 80 ℃.

The method of claim 3, The mixture selected from the cellulase, hemi cellulase, amylase, and xylase among the xylase has an optimum pH of 4.0 to 7.0, and is treated with 0.01 to 1.0 parts by weight with respect to 100 parts by weight of the paper. . The method of claim 3, The cellulase, hemi cellulase, amylase, the mixture selected including xylanase of xylanase is a method of producing paper, characterized in that the treatment for 30 minutes to 3 hours at a temperature of 40 to 80 ℃. Papermaking produced by any one of the preceding claims.

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