JPH0280690A - Production of paper - Google Patents

Abstract

PURPOSE:To provide paper in a highly improved yield of a filler in a pulp slurry and in a state capable of clarifying a white water without destroying the weave of the paper by preliminarily adding a water-soluble cationizing agent to the white water and specifying the specific conductivity of the added white water. CONSTITUTION:A pulp slurry containing a filler is diluted with (A) a white water and subsequently used to produce paper wherein (B) a water-soluble cationizing agent is preliminarily added to the component A in an amount of 0.01-3.0wt.% based on the pulp and the specific conductivity of the component A is adjusted to a value of <=1.2mS/cm. The component B is preferably added to the component A so that the zeta potential of the component A is satisfied with the equation [Z.P is the zeta potential (mV) of the white water; Ci is the varied value (mV) of the zeta potential per unit addition amount (0.1wt.%) determined depending on an inner additive auxiliary for the production of paper; Vi is the addition amount (wt.%) of the inner additive auxiliary for the production of the paper] and the inner additive auxiliary for the production of the paper is preferably added to the pulp slurry having been diluted with the white water A.

Description

Detailed Description of the Invention "Industrial Application Field" The present invention relates to a paper manufacturing method, and is particularly applicable to increasing the speed of paper machines and increasing the ash content of paper. It significantly improves the retention of fine fibers and fillers inside, and has an excellent effect of clarifying white water generated in the papermaking process and improving problems caused by dirt in the system, and is a retention aid, paper strength enhancer, etc. The present invention relates to a paper manufacturing method that enhances the effects of various internal additives for papermaking.

"Prior art" - In the papermaking process of C, fillers are added to the pulp slurry in order to improve the paper's properties such as whiteness, opacity, smoothness, writability, printability, and the feel and feel of the paper. It is added and incorporated.

Originally, pulp fibers and fillers, which are raw materials for paper manufacturing, have anionic surface charges, and in a slurry system where they simply coexist, they electrically repel each other, resulting in extremely low fixing properties. Therefore, fine substances such as pulp fine fibers and fillers pass through the paper machine wire for 1 meter and flow into the white water, polluting the white water and increasing SS, COD, and BOD loads, gradually deteriorating the water quality environment. . In addition, satisfactory paper quality cannot be obtained and there is a large economic disadvantage, so some kind of retention aid is generally used to fix these fine substances.

For example, in the so-called acid paper-making method, in which paper is made in an acidic range of pH 4 to 6, sulfuric acid is used as a retention aid to fix pulp fibers, fillers, etc.; Retention aids such as polyacrylamide are used in papermaking processes.

By the way, in recent years in the paper industry, quality requirements for paper whiteness, opacity, feel, texture, etc. have become stricter.
As the raw wood situation worsens, paper is becoming more ash-based in order to conserve pulp. Furthermore, there is a need to reduce the weight of paper and increase the speed of paper machines, and as a result, the importance of technology that effectively fixes fine substances such as fillers while ensuring paper strength is increasing. .

Therefore, improvements in retention aids are underway, including a method using colloidal silica and cationic starch (Japanese Patent Laid-Open No. 57
-51900) and a method for adjusting the zeta potential of pulp slurry (Japanese Patent Publication No. 17958/1983) have also been proposed. However, the actual situation is that it has not yet achieved a sufficient yield improvement effect or white water clarification effect, and has not been able to sufficiently respond to increased speeds of paper machines and high ash content of paper.

Although it is possible to increase the retention by adding a large amount of a retention aid to the pulp slurry, the resulting paper will have poor texture and the commercial value of the paper will decrease. Another possibility is to improve the paper strength by adding a large amount of a paper strength enhancer, but this is not practical as it deteriorates the redisintegration properties of waste paper and broken paper.

``Problems to be Solved by the Invention'' In view of the current situation, the present inventors have attempted to significantly improve the retention of fine fibers and fillers in pulp slurry without destroying the paper structure, and to reduce the white water generated from the papermaking process. (hereinafter simply referred to as white water), it improves troubles caused by dirt in the system, and also improves the effects of various internal additives for papermaking such as retention improvers and paper strength enhancers. We have conducted extensive research on ways to increase this.

In particular, as a result of a detailed study of the white water system of paper machines, it was found that the pulp raw material slurry obtained by conventionally adding internal additives and adjusting the zeta potential has a surface charge of - However, in reality, it is not uniformly neutralized, and for example, the zeta potential of fine substances such as fine fibers and fillers that have been washed away into white water is not supplied to the paper machine. raw materials (hereinafter referred to as inlet raw materials)
The anionic nature is strong compared to the zeta potential of the inlet material, and as the white water is recycled and reused many times, fine substances gradually accumulate in the paper machine system, resulting in an increase in the anionic nature of the surface charge of the inlet raw material. We have discovered the fact that this is the cause of decreased yield and paper strength.

Based on this knowledge, and as a result of further intensive research, it was found that the desired effects can be obtained extremely efficiently by adding a specific amount of water-soluble cationizing agent to white water in advance and specifying the specific conductivity of white water. This discovery led to the completion of the present invention.

"Means for Solving the Problems" The present invention provides a paper manufacturing method in which a pulp slurry containing a filler is diluted with white water and then paper is made. ~3.
0% by weight, and the specific conductivity of white water was 1.2n+S/
This is a paper manufacturing method characterized by adjusting the paper to below c-.

"Function" In general, in the preparation process, LKP, NKP, waste paper, etc. are appropriately blended into pulp slurry for papermaking depending on the desired product quality, and various fillers, sizing agents, retention improvers, and freeness improvers are also added. Additives, paper strength enhancers, dyes, and other internal additives for papermaking are added as needed to maintain a pulp density of approximately 2.
~5% pulp slurry sent to the inlet Bonobu (
or fan pump) is sent to the population.

On the other hand, white water generated from the papermaking process is collected in a bit called a white water tank and recycled for reuse. That is, this white water is added to the pulp slurry to which various internal additives for papermaking have been added at the inlet of the inlet feed pump.

The pulp concentration of the pulp slurry diluted by the addition of white water is approximately 0.2 to 2%. Furthermore, this pulp slurry is supplemented with additives, such as improving yield, increasing paper strength, and improving sizing properties, as necessary. For this purpose, internal additives for papermaking are added, for example, at the entrance of the screen, and prepared as an in-left raw material.

It is said that inlet raw materials need to be adjusted so that the zeta potential approaches 0 in order to increase the yield of fine substances such as fine fibers and fillers, and such adjustment is usually not done. ing. However, when measuring the zeta potential of white water that passes through the wires of a paper machine, it shows strong anionic properties.

This is because the surface charge of some fine substances passes through the paper machine wire without being neutralized and remains as a main component in white water.

In the method of the present invention, a water-soluble cationizing agent (hereinafter simply referred to as cationizing agent) is added in advance to white water that is recycled and reused as dilution water for pulp slurry, and after dilution with the cationizing agent and white water. It maximizes the effects of papermaking internal additives (hereinafter referred to as internal additives unless otherwise specified) added to the pulp slurry, and further enhances the clarification effect of white water. It has an extremely significant feature in that the specific conductivity (hereinafter referred to as S and C) of white water is specified in order to prevent staining of the water.

Furthermore, after neutralizing the surface charge of highly anionic fine substances remaining in the white water using the method of the present invention, this white water is added to the pulp slurry, resulting in the inlet raw material being mixed and diluted with the white water. The zeta potential is adjusted to neutralize the surface charge of any substances inside.

Specifically, the cationizing agent was added to white water at a rate of 0 per pulp.
．． S of white water is added within the range of 01 to 3.0% by weight.
, C, is preferably 1.2 mS/cm or less, c1.
The internal additive is added after the white water is added to the pulp slurry and diluted to a specified value of OmS/cm or less.

Incidentally, if the amount of cationizing agent added is 0.01% by weight, the desired retention effect cannot be obtained, and if it exceeds 3.0% by weight, fine fibers, fillers, etc., which are solids in white water, will be removed. It may form strong aggregates and deteriorate the paper's texture. Also,
When pulp slurry is diluted with white water in which S, C, exceeds 1.2 mS/cra, dissolved ionic substances are dissolved into alkaline substances contained in fillers, coated paper blocks, etc. in the valve slurry. As a result, it may make it difficult to clarify white water, cause stains in the papermaking process, or reduce the effectiveness of internal additives, etc., resulting in unsatisfactory effects. You must avoid it because you will not be able to obtain it.

The cationizing agent used in the method of the present invention is not particularly limited, but includes, for example, cationic polyacrylamide, polyamine, polyamide/polyamine and its derivatives, polyethyleneimine and its derivatives, cationic starch, and cationic starch. Cationic organic compounds such as urea-formalin resin, cationic melamine-formalin resin, cationic vegetable gum, or water-soluble compounds such as sulfuric acid, aluminum chloride, alumina sol, basic aluminum sulfate, basic aluminum chloride, and basic polyaluminum hydroxide. Examples include inorganic compounds such as ferrous aluminum compounds and ferrous sulfate, but water-soluble aluminum compounds are particularly preferred from the viewpoint of economy, toxicity, whiteness, and the like.

Furthermore, the internal additives referred to in the present invention are not particularly limited, and may include various conventionally used anionic, nonionic, cationic, or amphoteric retention aids, paper strength enhancers, These agents are appropriately selected and used.Specifically, for example, polyacrylamide-based cationic, nonionic,
Anionic and amphoteric resins, polyethyleneimine and its K1 form, polyamines, polyamides, polyamines and their derivatives, cationic, anionic and amphoteric starches, urea formalin resin, melamine formalin resin, vegetable gum, polyvinyl alcohol, cationic latex , polyethylene oxide, polyamide resin, alkyl ketene dimer, alkenyl succinic anhydride, stearic anhydride, organic compounds such as hydrophilic polymer particles, sulfuric acid hand, alumina sol, basic aluminum sulfate, basic aluminum chloride, basic polywater One or more of water-soluble aluminum compounds such as aluminum oxide and inorganic compounds such as colloidal silica and bentonite are used in appropriate combinations.

In addition, in the method of the present invention, it is preferable to adjust the zeta potential of the white water according to the ionic strength of the internal additive added after diluting the pulp slurry with white water, and in particular, adjust the zeta potential of the white water so that the following formula is satisfied. By adjusting the type and amount of the cationizing agent added, the desired effects of the present invention can be very clearly obtained.

5(2+ΣC, Vi) ≦Z, P, ≦+5(0,8-
ΣC+Vi) rz, p, ; Zeta potential of white water (mV
) Cii unit addition amount (0
, 1% by weight) change in zeta potential (mV) v. ; Addition amount (wt%) of internal additive for papermaking J Note that the zeta potential as used in the present invention refers to a value measured by microelectrophoresis for a portion of pulp slurry or white water component that has passed through 100 meshes.

In addition, the change value C8 of the zeta potential per unit addition amount determined according to the internal additive additive is determined by adding the internal additive additive to the pulp slurry in an amount of 0.1% by weight based on the pulp, and calculating z, p before and after the addition.
The change value C1 is obtained by measuring . That is, this change value C2 is the unit addition l (0.1% by weight) of the internal additive auxiliary agent.
It can be defined as the strength of ionicity per unit, and hereinafter it will simply be written as C value and expressed as a value specific to the internal additive.

The filler used in the method of the present invention is not particularly limited, and examples include talc, kaolin, calcined kaolin, clay,
Inorganic fillers such as heavy calcium carbonate, light calcium carbonate, aluminum hydroxide, titanium dioxide, magnesium carbonate, magnesium sulfate, silica, aluminosilicate, etc., organic synthetic fillers such as polystyrene resin fine particles, urea formalin resin fine particles, micro hollow particles, etc. are selected and used as appropriate,
Filler contained in waste paper, broken paper, etc. can also be used effectively.

In addition, the pulp slurry before being diluted with white water contains various sizing agents that are the same as or different from the internal additives referred to in the present invention, paper strength enhancers, retention aids, freeness improvers, dyes, and pH adjusters. agent, pitch control agent, slime control agent,
Internal additives for paper making such as antifoaming agents can be added as appropriate depending on the use of the paper. Of course, it is also possible to apply starch, polyvinyl alcohol, various surface siping agents, pigments, etc. to the surface of the paper using various coaters such as a size press, gate roll, bill blade, etc.

The method of the present invention can be applied to various methods of making paper from valve slurry regardless of the type of pulp, and can be applied to the production of paper products of all grades and types.
In particular, extremely remarkable effects can be obtained in the so-called neutral paper-making method, in which an alkaline filler such as calcium carbonate is used as a filler and paper is made under pH conditions ranging from weakly acidic to slightly alkaline. This is a preferred embodiment of the invention.

"Example" The present invention will be described in more detail with reference to Examples below, but it is of course not limited to these.

Note that parts and % in the examples indicate parts by weight and % by weight, respectively, unless otherwise specified.

Example I C,S,F, 75 parts of LBKP of 450 cC and C,S
, F, 470 cc of light calcium carbonate (trade name: TNC-
Ci0, manufactured by Toyo Denka Co., Ltd.) and 10 parts of talc were added, 0.5 parts of sulfuric acid bandate, and cationic starch (product name: ON
L-400, manufactured by Tamago National Co., Ltd.) 0.5 part and alkyl ketene dimer (trade name: Sizevine-902)
0.1 part (manufactured by Arayo Kagaku Co., Ltd.) was added with thorough stirring.

This pulp slurry is diluted by mixing white water to which sulfuric acid is added in advance so that the amount of addition to the pulp fiber content is 0.5%.Finally, anionic polyacrylamide (product name: Percoll 155 , manufactured by Allied Colloid Co., Ltd.) was added to prepare an inlet raw material. In addition, the C value of Percoll 155 is -6
It was mV.

The obtained inleft raw material is made into paper using a long paper machine to produce paper of 6 m2
0 g/rdO paper was obtained. Paper pH was 7.6. Also, white water concentration (%), white water specific conductivity (mS/
cm), zeta potential of white water (mν), COD of white water
(ppH+), total raw material yield (%), ash yield (%)
), stains, and paper texture were measured or evaluated using the following methods, and the results are shown in Table 1.

[Specific conductivity of white water]

The sample was filtered through a 100 mesowire and the La5e
r Measured using Zee Model 500 (manufactured by PEM KEM).

[Zeta potential of white water]

The sample was passed through a 100 mesh wire, and the components passing through the wire were analyzed by microelectrophoresis using La5er.
Measured using Zee Model 500.

[Yield of all raw materials]

The concentration (%) of the inlet raw material and the concentration B (%) of white water were measured and calculated from the following formula.

8 [Ash content retention] Ash content a (%) in inleft raw material and ash content b (%) in white water
%) was measured and calculated from the following formula.

[Texture of base paper] The resulting paper was visually evaluated using the following evaluation criteria.

◎ ・・・・・・・・・ ○ ・・・・・・・・・ △
・・・・・・・・・ × [Excellent] [Good]
[Slightly inferior] [Poor] [Stain evaluation test] The inlet raw material was filtered with a 100 mesh wire, and the filtrate 1001 was poured onto a stainless steel plate at a flow rate of 100 m/min for 10 days while circulating.

After washing with water, the degree of staining was visually evaluated using the following evaluation criteria.

■ ・・・・・・・・・ ○ ・・・・・・・・・ △
・・・・・・・・・ × (Excellent) [Good] [
Slightly dirty] [A lot of dirt] Example 2 Inlet raw material was prepared and paper was made in the same manner as in Example 1, except that sulfuric acid hand was not added to the pulp slurry before dilution with white water. . Note that the papermaking pH was 7.7. Further, the results of measurement or evaluation in the same manner as in Example 1 are shown in Table 1.

Example 3 An inlet raw material was prepared and paper was made in the same manner as in Example 2, except that the amount of sulfate added to the white water in advance was 1.5% based on the pulp fiber content. In addition,
Papermaking pH was 7.5. In addition, the results of measurement or evaluation in the same manner as in Example 1 are shown in Table 1.

Example 4 In Example 2, the sulfuric acid band added to the white water in advance was replaced with a polyamine-based polymer (trade name: Acura Tsuku 35, manufactured by Mitsui Cyanamid Co., Ltd.), and the amount added was also 0.15% based on the pulp fiber content. Except for this, an inlet raw material was prepared and paper was made in the same manner as in Example 2. In addition, the papermaking pH is 8
．． It was 0. In addition, the results of measurements and evaluations in the same manner as in Example 1 are shown in Table-■.

Example 5 In Example 2, the sulfuric acid band added to white water in advance was replaced with basic polyaluminum hydroxide (trade name: Paho 2).
An inlet raw material was prepared and paper was made in the same manner as in Example 2, except that the amount added was 0.5% based on the bulb fiber content.

Note that the papermaking pH was 7.9. In addition, the results of measurement or evaluation in the same manner as in Example 1 are shown in Table 1.

Comparative Example 1 An inlet raw material was prepared and paper was made in the same manner as in Example 1, except that sulfate was not added to the white water in advance. Note that the papermaking pH was 7.8. In addition, Example 1
Table 1 shows the results of measurements and evaluations in the same manner as above.

Comparative Example 2 An inlet raw material was prepared and paper was made in the same manner as in Example 2, except that sulfate was not added to the white water in advance. Note that the papermaking pH was 8.0. In addition, Example 1
Table 1 shows the results of measurements and evaluations in the same manner as above.

Comparative Example 3 In Example 2, sulfate was not added to the white water in advance,
An inlet raw material was prepared and paper was made in the same manner as in Example 2, except that the amount of anionic polyacrylamide added at the end was increased to 0.1 part. Note that the papermaking pH is 8.
It was 0. In addition, the results of measurement or evaluation in the same manner as in Example 1 are shown in Table 1.

Comparative Example 4 An inlet raw material was prepared and paper was made in the same manner as in Example 2, except that the amount of sulfate added to the white water was 5% based on the pulp fiber content.

Note that the paper making ptr was 7.0. In addition, the results of measurement or evaluation in the same manner as in Example 1 are shown in Table 1.

Example 6 20 parts of heavy calcium carbonate (trade name: Softon 1200, manufactured by Bihoku Funka Kogyo Co., Ltd.) was added to a pulp slurry dispersed in the same formulation as in Example 1, and cationic starch (trade name:
0NL-400, manufactured by Oji National Co., Ltd.) and 0.5 part of alkyl ketene dimer (product name: Size Pine-902)
, manufactured by Kanyo Kagaku Co., Ltd.) was added with thorough stirring.

The pulp slurry was diluted by mixing white water to which sulfuric acid was added in advance so that the amount added to the pulp fiber content was 0.5%, and finally, cationic polyacrylamide ( An inleft raw material was prepared by adding 0.02 part of Percoll 47° (trade name, manufactured by Allied Colloids). Note that the C value of Percoll 47 was +11 mV.

The obtained inlet raw material is made into paper using a Fourdrinier paper machine to produce paper of 6 m2
0 g/rrrO paper was obtained. The papermaking pH was 7.8. In addition, the results of measurement or evaluation in the same manner as in Example 1 are shown in Table 1.

Example 7 Same as Example 6, except that the sulfuric acid band added to the white water in advance was replaced with a polyamine-based polymer (trade name: Niaculac 35, manufactured by Mitsui Cyanamid Co., Ltd.), and the amount added was also 0.10% based on the pulp fiber content. The inleft raw material was prepared and paper was made. Note that the papermaking pH was 8.0. In addition, the results of measurement or evaluation in the same manner as in Example 1 are shown in Table 1.

Comparative Example 5 An inlet raw material was prepared and paper was made in the same manner as in Example 6, except that sulfate was not added to the white water in advance. Note that the papermaking pH was 8.0. In addition, Example 1
Table 1 shows the results of measurements and evaluations in the same manner as above.

Example 8 16 parts of light calcium carbonate (trade name: TNC-Ci0, manufactured by Toyo Denka Co., Ltd.) and 4 parts of talc were added to a valve slurry dispersed with the same composition as in Example 1, and cationic starch (
Product name: ONL-400, manufactured by Oji National) 0
．． 5 parts of alkenyl succinic anhydride (trade name: FIBRAN) previously emulsified with cationic starch.
81. 0.1 part of Oji National Co., Ltd.) and 0.02 part of cationic polyacrylamide (trade name: Hydrocol 858, manufactured by Allied Colloid Co., Ltd.) were added with thorough stirring. This valve slurry is diluted by mixing white water to which sulfuric acid is added in advance so that the amount added to the pulp fiber content is 0.5%, and finally bentonite (trade name: diorganosorb O, allied colloid An inlet raw material was prepared by adding 0.2 part of (manufactured by Seiko Co., Ltd.).

Note that the organosorb OOC value was -2 mV.

The obtained inlet raw material is made into paper using a Fourdrinier paper machine to produce paper of 6 m2
A paper of 0 g/rrr was obtained. The papermaking pH was 7.8.

In addition, the results of measurements and evaluations in the same manner as in Example 1 are shown in the table.
Shown in 2.

Comparative Example 6 An inlet raw material was prepared and paper was made in the same manner as in Example 8, except that sulfate was not added to the white water in advance. Note that the papermaking pH was 8.0. In addition, Example 1
Table 2 shows the results of measurements and evaluations in the same manner as above.

Example 9 16 parts of light calcium carbonate (trade name: TNC-Ci0, manufactured by Toyo Denka Co., Ltd.) and 4 parts of talc were added to a pulp slurry dispersed in the same formulation as in Example 1, and cationic starch (trade name: BMB) was added. , manufactured by Nissan Eka Nobel Co., Ltd.) 0.8 parts and alkyl ketene dimer (product name: Size Pine -
902, manufactured by Kanyo Kagaku Co., Ltd.) was added with thorough stirring. This pulp slurry is diluted by mixing white water to which sulfuric acid is added in advance so that the amount of addition to the pulp fiber content is 0.5%, and finally colloidal silicic acid (product name: BMA, An inlet raw material was prepared by adding 0.2 part of Nissan Eka Nobel Co., Ltd.).

In addition, the C4 voltage of HMA was -3.5 mV.

The obtained inleft raw material is made into paper using a long paper machine to produce paper of 6 m2
A paper of 0 g/rd was obtained. The papermaking pH was 7.8. In addition, the results of measurements and evaluations in the same manner as in Example 1 are shown in Table 2.
It was shown to.

Comparative Example 7 An inlet raw material was prepared and paper was made in the same manner as in Example 9, except that sulfate was not added to the white water in advance. Note that the papermaking pH was 8.0. In addition, Example 1
Table 2 shows the results of measurements and evaluations in the same manner as above.

Example 10 A pulp slurry containing 100 parts of pulp consisting of 75 parts of LBKP and 25 parts of coated paper was mixed with 2 parts of talc.
0 part was added, and 0.1 part of a rosin sizing agent and 2.0 parts of aluminum sulfate were added with thorough stirring. This pulp slurry is diluted by mixing white water to which a polyamine polymer (trade name: 7 Kyurasoku 35, manufactured by Mitsui Cyanamid Co., Ltd.) has been added in advance so that the amount added to the pulp fiber content is 0.1%. Finally, 0.02 part of cationic polyacrylamide (trade name: Dehydrer C, manufactured by Misawa Ceramic Chemical Co., Ltd.) was added to prepare an inleft raw material. In addition, the C value of the divider is +1
It was 0 mV.

The obtained inleft raw material is made into paper using a long paper machine to produce paper of 6 m2
A paper of 0 g/m was obtained. Papermaking pH was 5.2. Further, the results of measurement or evaluation in the same manner as in Example 1 are shown in Table 2.

Comparative Example 8 An inlet raw material was prepared and paper was made in the same manner as in Example 10, except that the polyamine polymer was not added to the white water in advance. Papermaking pH was 5.2. Further, the results of measurement or evaluation in the same manner as in Example 1 are shown in Table 2.

"Effects" As is clear from the results in Tables 1 and 2, the method of the present invention can significantly improve the retention of fine fibers and fillers without destroying the paper structure, and is also effective in clarifying white water. It was also excellent in improving troubles caused by strain during the papermaking process.

Table-1

Claims (1)

Scope of Claims: (1) A paper manufacturing method in which a pulp slurry containing a filler is diluted with white water and then paper is made, in which a water-soluble cationizing agent is added to the white water in advance in an amount of 0.01 to 3.0 per pulp. 1. A method for producing paper, characterized in that the specific conductivity of white water is adjusted to 1.2 mS/cm or less. (2) The production of paper according to claim (1), wherein a cationizing agent is added so that the zeta potential of white water satisfies the following formula, and an internal additive aid for paper making is added to the pulp slurry after diluting with white water. Method. −5(2+ΣC_iV_i)≦Z. P. ≦+5 (0.8
-ΣC_iV_i) "Z.P.; Zeta potential of white water (
mV) C_i; Unit addition amount (0
．． (3) The water-soluble cationizing agent is an aluminum compound.
The method for producing paper according to 1) or (2). (4) Claim (1) wherein the filler is mainly calcium carbonate.
), (2) or (3). (5) The method for producing paper according to claim (2), (3) or (4), wherein the papermaking internal additive is an organic or inorganic retention aid.