JP2003183995A - Auxiliary for papermaking, and papermaking feedstock composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an auxiliary for papermaking, capable of reducing an amount of the formulated auxiliary for the papermaking when used in the production of paper under a neutral or an alkaline condition, providing the paper having good quality, and reducing a production cost and bad influence on the global environment by reducing staining by pitch, and further to provide a papermaking feedstock composition. <P>SOLUTION: This auxiliary for the papermaking contains a cationic polymer having at least 200,000 viscosity average molecular weight, and a cationic monomer in a proportion of (95:5)-(50:50) by weight. The papermaking feedstock composition is obtained by formulating the cationic polymer having at least 200,000 viscosity average molecular weight and the cationic monomer within a range of weight ratios of (95:5)-(50:50) in an aqueous slurry containing 0.5-5.0 wt.% pulp component so that the concentration of the sum of the cationic polymer and the cationic monomer based on the pulp component is 50-1,000 ppm. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel papermaking auxiliary agent and a papermaking raw material composition using the same, and more specifically, to the quality of paper obtained by producing paper in a neutral range or an alkaline range. It is possible to reduce the amount of conventional papermaking auxiliaries used to maintain or improve the quality of paper, reduce production costs, reduce stains on papermaking machines, and reduce the impact on the global environment. The present invention relates to a novel papermaking auxiliary which can be achieved, and a papermaking raw material composition using the same.

[0002]

2. Description of the Related Art In the production of paper in a neutral range or an alkaline range, compared with a method of producing a paper in an acidic range, the obtained paper undergoes less change over time, the whiteness is improved, and the papermaking machine Due to the advantage of low corrosion rate, it has recently been generally used instead of the acid papermaking method.

By the way, in the production of paper in an acidic region, usually, a sulfuric acid band is used to improve the fixability of the paper-strengthening agent and the sizing agent and the cohesiveness of pulp and pigments, and to further increase the sizing effect. Although used, the sulfuric acid band is also used for the same purpose in the production of paper in the neutral range or the alkaline range.

However, this sulfuric acid band has a sufficiently large positive charge required to exert its effect in an acidic region, while it has a small positive charge in a neutral region or an alkaline region, so that its effect is acidic. Inevitably lower than in the region (see Non-Patent Document 1).

The decrease in the effect of the sulfuric acid band means that the surface charge neutralizing ability of the pulp fiber is decreased,
As a result, the fixing rate of the paper-making auxiliary such as the paper-strengthening agent, the sizing agent, the retention agent, and the drainage agent is lowered. As a result, the yield and drainage of the papermaking raw material, the sizing degree of the paper, a decrease in paper strength occurs, the amount of the papermaking auxiliary is further increased to compensate for it, but when the papermaking auxiliary becomes excessive in this way, This causes contamination of the papermaking machine, paper breakage, etc., resulting in reduced productivity.

On the other hand, one of the important causes of contamination of papermaking machines
There is dirt on the pitch. This pitch stain is caused by fatty acids, resin acids, essential oils from wood pulp, hot-melt resins from waste paper, additives such as defoaming agents, water-proofing agents, and sizing agents used in printing inks and paper manufacturing processes. It is known.

[0007] In recent years, the amount of used paper has increased from the viewpoint of waste recycling, and foreign matter in the paper, such as pitch components derived from pulp and coating color components from coat broke, causes stains. In addition, reductions in papermaking speed, yield, paper quality, and production efficiency are problems.

The amount of the sulfuric acid band used is important for solving such a problem, but the effect of the sulfuric acid band is lowered as described above in the neutral region and the alkaline region, and as a result, , The ability to capture harmful substances that adversely affect the papermaking process is reduced. Therefore, in order to compensate for this, it is necessary to add an excessive amount of sulfuric acid band, but this sulfuric acid band forms agglomerates of aluminum hydroxide that has lost the cohesive force, and adheres to papermaking piping and flow chests to contaminate them. It causes an unfavorable situation.

In order to deal with such a problem, (1) a polymer containing a polyvalent quaternary ammonium salt was added at the time of paper making, and then an anionic sizing agent was added.
Method for improving size (see Patent Document 1), (2)
A method of improving the fixability of a rosin-based sizing agent by adding a copolymer of dimethyldi (meth) allyl ammonium salt to a papermaking raw material slurry (see Patent Document 2),
(3) A dehydration aid composed of a water-soluble cationic polymer is added to the cellulose pulp, and then this pulp is dehydrated,
The dehydrated pulp is diluted to form an aqueous cellulose suspension, a main polymer selected from cationic starch and cationic polymers is added to the suspension before the shearing step, and bentonite and colloidal silica are added after the shearing step. A method for producing paper or paperboard by adding at least one inorganic substance, dehydrating and drying (see Patent Document 3),
(4) Low molecular weight cationic organic polymer (molecular weight of less than 700,000), high molecular weight cationic or amphoteric polymer (molecular weight of more than 1 million) and anionic inorganic particles in a suspension containing cellulose fibers Has been proposed, and a papermaking method (see Patent Document 4) in which the suspension is made into paper on a wire and dehydrated is proposed.

However, in the above methods (1) and (2), since the rosin-based sizing agent is efficiently fixed on the pulp surface by mainly adjusting the surface charge of the pulp, the fixing agent to be used is used. Has a high cation density, for example, it is necessary to use a copolymer having a dimethyldi (meth) allyl ammonium salt unit of 50 mol% or more. When fixing, the fixing effect of the sizing agent is high, but it is difficult to reduce the cationic demand of the slurry, so various components (heavy calcium carbonate, kaolin,
Talc, clay, titanium oxide, silica, zinc oxide, aluminum hydroxide, clay, lake, synthetic plastic pigments and other fillers and pulp) yield rate improvement, suppression of size reduction due to aging, and by these effects It becomes difficult to reduce the blending ratio of the sizing agent, the sulfuric acid band, the retention agent, the paper strengthening agent, and the filler (hereinafter, these are referred to as papermaking auxiliary agents), and as a result, large flocs are generated in the slurry, resulting in the paper It has a drawback that the formation is deteriorated.

Further, in the methods (3) and (4), the cation requirement of the suspension can be reduced more than in the methods (1) and (2).
In the method of (3), the number of steps for producing the suspension is large and complicated, and the work efficiency is unavoidable, and at least one of bentonite and colloidal silica must be used, and (4) The method (1) has the limitation that anionic inorganic particles must be used. These are used to supplement the point that cannot be controlled only by the function of the retention agent with other materials, but when this is done, an excess state of the papermaking auxiliary agent easily occurs in the slurry, and therefore,
The paper machine is contaminated and the manufacturing cost is high. Moreover, the obtained paper is liable to cause deterioration of texture, and it cannot be said that the paper quality is sufficiently satisfactory.

[0012]

[Non-Patent Document 1] Paper and Paper Cooperative Journal, Volume 56, No. 8, No. 5
8-65 pages

[Patent Document 1] Japanese Patent Application Laid-Open No. 54-96104 (claims and others)

[Patent Document 2] Japanese Unexamined Patent Publication No. 9-188994 (claims and others)

[Patent Document 3] Japanese Patent Application Laid-Open No. 5-239800 (claims and others)

[Patent Document 4] Japanese Patent Laid-Open No. 9-31885 (claims and others)

[0013]

Under these circumstances, the present invention can reduce the amount of the papermaking auxiliary compounded when used in the production of paper in the neutral or alkaline range. A paper-making auxiliary and a paper-making raw material composition capable of providing high-quality paper and reducing production cost and reduction of adverse effects on the global environment, in addition to being able to provide high-quality paper. It was made for the purpose of providing.

[0014]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies as to a papermaking auxiliary agent and a papermaking raw material composition used for papermaking particularly in a neutral range or an alkaline range, and as a result, a pulp component having a predetermined concentration is contained. By mixing a cationic polymer having a molecular weight of a certain value or more and a cationic monomer in a specific ratio to an aqueous slurry so as to have a predetermined concentration, a conventional combination in which the quality of the resulting paper is not deteriorated is used. It has been found that the amount of the papermaking auxiliary used can be reduced and the pitch stain can be reduced, and the present invention has been completed based on this finding.

That is, the present invention comprises a cationic polymer having a viscosity average molecular weight of at least 200,000 and a cationic monomer in a mass ratio of 95: 5 to 50:50, and a papermaking aid, and pulp. A cationic polymer and a cationic monomer having a viscosity average molecular weight of at least 200,000 are added to an aqueous slurry containing the components in a concentration of 0.5 to 5.0% by mass in a mass ratio of 95:
It is intended to provide a papermaking raw material composition characterized in that it is contained in the range of 5 to 50:50, and the concentration of the total amount of both components with respect to the pulp component is in the range of 50 to 1000 ppm.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The papermaking aid of the present invention contains a cationic polymer and a cationic monomer. As this cationic polymer, one having a viscosity average molecular weight of 200,000 or more is used. The viscosity average molecular weight as referred to herein is a polyvinyl alcohol-equivalent viscosity average molecular weight measured by an intrinsic viscosity method. This viscosity average molecular weight is 20
When the one having a size smaller than 0000 is used, the crosslinking action between pulp fibers is not sufficiently exerted, so that the yield improving effect cannot be obtained, and the effect of reducing the blending ratio of the papermaking auxiliary agent is not exerted. Can't achieve the purpose. The viscosity average molecular weight of the cationic polymer is preferably 1,000,000 or more, and more preferably 15,000, from the viewpoints of the yield improving effect and the effect of reducing the amount of papermaking auxiliary used.
It is 00 or more. Further, the upper limit of the viscosity average molecular weight is not particularly limited, but it is about 20,000,000 in consideration of production efficiency and handleability. In particular, the viscosity average molecular weight is 150,000 to 500 from the viewpoints of the yield improvement effect, the effect of reducing the amount of papermaking auxiliary used, and the handling property.
The range of 0000 is preferable.

The cationic polymer is preferably a homopolymer or a copolymer containing a cationic monomer having a quaternary ammonium salt residue as a constituent unit. Examples of the cationic monomer having a quaternary ammonium salt residue constituting such a cationic polymer include 2-
(Meth) acryloyloxyethyltrimethylammonium chloride, 2- (meth) acryloyloxyethyldimethylbenzylammonium chloride, 2- (meth)
Acryloyloxyethyltriethylammonium chloride, 2- (meth) acryloyloxyethyldiethylbenzylammonium chloride, 3- (meth) acrylamidopropyltrimethylammonium chloride, 3-
(Meth) acrylamidopropyltriethylammonium chloride, 3- (meth) acrylamidopropyldimethylbenzylammonium chloride, diallyldimethylammonium chloride, diallyldiethylammonium chloride, 2- (meth) acryloyloxyethyltrimethylammonium sulfate, 2- (meth) acrylamidoethyl Trimethylammonium chloride, 2-
(Meth) acryloyloxyethyltriethylammonium bromide, 3- (meth) acryloyloxypropyl dimethylethylammonium chloride, 3-methacryloyloxy-2-hydroxypropyltrimethylammonium chloride, 3-methacryloyloxy-2-hydroxypropylmethyldiethylammonium chloride, 3-methacryloyloxy-2-hydroxypropyltrimethylammonium chloride, 2- (meth) acryloylaminoethyltrimethylammonium chloride, 3- (meth) acryloylamino-2-hydroxypropyltrimethylammonium chloride, 2- (meth) acryloylaminoethyltrimethyl Examples thereof include ammonium chloride. Among these, a homopolymer or a copolymer using diallyldimethylammonium chloride is preferable because it is easy to adjust the cation amount and the molecular weight to desired values.

The cationic polymer may be a copolymer of the above-mentioned cationic monomer and a monomer copolymerizable therewith, for example, an ethylenically unsaturated compound. Examples of the ethylenically unsaturated compound constituting this copolymer include ethylenically unsaturated monocarboxylic acids and dicarboxylic acids, (meth) acrylic acid alkyl esters, aromatic vinyl compounds, unsaturated amide compounds and unsaturated nitrile compounds. And so on. Examples of such things are:
(Meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, 2-Methylbutyl (meth) acrylate, ter (meth) acrylate
t-butyl, 2-ethylhexyl (meth) acrylate,
Octyl (meth) acrylate, hexyl (meth) acrylate, 2-hydroxyhexyl (meth) acrylate, styrene, α-methylstyrene, (meth) acrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, (meth ) Acrylonitrile and the like can be mentioned. Among them, (meth) acrylamide, particularly acrylamide, is preferable because it is easily available and can be easily polymerized. The term (meth) acrylic means acrylic or methacrylic.

When the cationic polymer is a copolymer, the content of the cationic monomer unit having a quaternary ammonium salt residue in the cationic polymer is 5 mol% or more and 4
A range of less than 0 mol% is preferred. When the content of the cationic monomer unit is less than 5 mol%, it is difficult to obtain a desired cation amount, and when the content is 40 mol% or more, it is difficult to improve the yield of pulp and filler, and the amount of the conventional papermaking auxiliary used is It is also difficult to reduce the amount used.

Further, the cationic polymer preferably has a cation amount in the range of 1.3 to 5.3 meq / g. The term “cation amount” as used herein means the equivalent amount of the cationic monomer contained in 1 g of the cationic polymer, and is determined by the colloid titration method using 2.5 mol / m ² potassium polyvinyl sulfate. If the amount of cations is less than 1.3 meq / g, the negative charge of the papermaking raw material slurry, especially the surface charge of the pulp cannot be sufficiently neutralized, which may cause deterioration of papermaking physical properties such as drainage and retention. Become. If it is larger than 5.3 meq / g, the yield may be low. Considering drainage, retention and size, etc., the preferable amount of cation is in the range of 2.2 to 4.5 meq / g.

The method for polymerizing the cationic polymer is not particularly limited, and any method such as a solution polymerization method, an emulsion polymerization method and a solid polymerization method can be used. As the polymerization initiator used at this time, a water-soluble azo compound or a peroxide such as hydrogen peroxide, 2,2′-azobis (2-amidinopropane) dihydrochloride, a water-soluble inorganic oxide, or a water-soluble reduction agent is used. There are combinations of agents with water-soluble inorganic oxides and organic peroxides. Examples of the water-soluble inorganic oxide include potassium persulfate and ammonium persulfate.
Further, as an example of the water-soluble reducing agent, a reducing agent used as a water-soluble normal radical redox polymerization catalyst component,
For example, ethylenediaminetetraacetic acid or its sodium salt or potassium salt, or a complex compound of these with a heavy metal such as iron, copper or chromium, sulfinic acid or its sodium salt or potassium salt, L-ascorbic acid or its sodium salt or potassium salt, Examples thereof include calcium salts, ferrous pyrophosphate, ferrous sulfate, ferrous ammonium sulfate, sodium sulfite, acidic sodium sulfite, and sodium formaldehyde sulfoxylate.

On the other hand, examples of the water-soluble organic peroxide include cumene hydroperoxide, p-cymene hydroperoxide, tert-butylisopropylbenzene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, decalin hydroperoxide, tert- Examples thereof include hydroperoxides such as amyl hydroperoxide, tert-butyl hydroperoxide, and isopropyl hydroperoxide.

Further, as the emulsifier in this emulsion polymerization, an anionic surfactant or a combination thereof with a nonionic surfactant is usually used. The anionic surfactant and nonionic surfactant can be arbitrarily selected from those used in ordinary emulsion polymerization. Examples of such anionic surfactants include alkylbenzene sulfonates, alkyl sulfonates, alkyl sulfate ester salts, fatty acid metal salts, polyoxyalkyl ether sulfate ester salts, polyoxyethylene carboxylic acid ester sulfate ester salts, Examples thereof include polyoxyethylene alkyl phenyl ether sulfate ester salt and succinic acid dialkyl ester sulfonate.

Examples of nonionic surfactants include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether glycerin borate ester. A compound having a polyoxyethylene chain in the molecule, such as polyoxyethylene alkyl ether phosphate, and having surface-active ability, and the polyoxyethylene chain of the compound is replaced by a copolymer of oxyethylene and oxypropylene. Compounds, sorbitan fatty acid ester, glycerin fatty acid ester, pentaerythritol fatty acid ester and the like.

The cationic monomer used together with the cationic polymer in the papermaking aid of the present invention is used mainly for penetrating into the pulp fiber and adjusting the cationic demand of the papermaking raw material slurry. It is preferable to select from among the cationic monomers constituting the constitutional unit therein. This cationic monomer may be used alone or in combination of two or more. The cationic monomer is preferably dimethyldiallylammonium chloride, acryloyloxyethyltrimethylammonium chloride, methacryloxyethyltrimethylammonium chloride, or the like, from the viewpoint of penetrability into the pulp fiber and controllability of the cationic demand, and particularly dimethyldiallyl. Ammonium chloride is preferred.

In the papermaking aid of the present invention, the mixing ratio of the cationic polymer and the cationic monomer is selected in the range of 95: 5 to 50:50 by mass ratio.
When the blending ratio of the cationic monomer is less than the above range, it is difficult to reduce the blending effect, particularly the required amount of cation, and when it is more than the above range, it becomes difficult to lower the zeta potential, and as a result, freezing and The size is reduced. The ratio of the cationic polymer and the cationic monomer is preferably 85:15 to 65:35 from the viewpoints of reduction of the cation requirement, drainage and size.

Next, the papermaking raw material composition of the present invention comprises an aqueous slurry containing a pulp component and the above-mentioned papermaking auxiliary compounded therein so that the concentration with respect to the pulp component is in the range of 50 to 1000 ppm. is there. If this concentration is less than the above range, sufficient drainage, retention, sizing cannot be obtained, and sizing agent, retention agent, paper strengthening agent, pitch control agent, deposit control agent, which is optionally blended in the aqueous slurry, It becomes difficult to reduce the blending amount of the paper strengthening agent, the filler, the slime control agent and the like. On the other hand, if the amount is more than the above range, the cation will be excessive in the slurry, and the effects of other additives will not be sufficiently exhibited. From the standpoints of the effect of the compounded agent, the decrease of the compounded amount of the additive agent, drainage, retention and sizing degree, the preferred amount of the papermaking auxiliary compounded is 50 to 30 with respect to the pulp component.
It is within the range of 0 ppm.

In the papermaking raw material composition of the present invention, an aqueous slurry containing a pulp component is used. Examples of the pulp contained in this aqueous slurry include virgin pulp, deinked waste paper pulp, and coat broke.
You may use these individually or in combination of 2 or more types. When two or more pulps are combined, the mixing ratio is not particularly limited and is appropriately selected according to the type of paper to be obtained. Here, the virgin pulp refers to pulp that does not include used paper (recycled paper) or coat broke. In the present invention, the concentration of the pulp contained in this aqueous slurry is selected in the range of 0.5 to 5.0% by mass.

In order to adjust the cation requirement of the papermaking raw material composition of the present invention, it is necessary to review not only the blending ratio of the above-mentioned papermaking raw materials but also the blending ratio of the conventional papermaking auxiliary used together. For example, the cationic demand of the aqueous slurry before blending the papermaking aid of the present invention is measured, and the blending ratio of the conventional papermaking aid used in combination with the papermaking aid of the present invention is adjusted according to the result, The cation requirement is adjusted so that the paper with the highest productivity and paper quality can be obtained.

In this case, if the cation requirement is adjusted so as to be reduced, the retention and drainage are improved. This is because the negative charge in the slurry is neutralized, the charge repulsion between pulp fibers is reduced, the cohesiveness is improved, and at the same time, the anion trash is easily adsorbed on the pulp fiber surface.
Then, the effects of the papermaking aids such as the sulfuric acid band, the retention agent, and the paper-strengthening agent, which have been reduced in effect due to the influence of anion trash, are improved.

Further, by reducing the amount of the conventional papermaking auxiliary and mixing the papermaking auxiliary of the present invention, the properties of the slurry composition, for example, large flocs are generated even if the cationic demand of the papermaking raw material composition is almost the same as the initial amount. And paper quality such as yield rate, size effect, and formation can be improved.
Furthermore, in the cation-excessive slurry composition, the cation-excess state is improved by adjusting the blending ratio of the conventional papermaking auxiliary agent and the papermaking auxiliary agent of the present invention. , Productivity, etc. can be improved.

In the papermaking raw material composition of the present invention, the amount of the filler and the conventional papermaking auxiliary used can be reduced.
For example, when the amount of the papermaking aid of the present invention is 1.5% by mass of the total pulp component solids, the reduction rate of the conventional papermaking aid is about 15 to 70% for the paper strength enhancer and about 5 for the retention agent. ~ 35
%, Sulfuric acid band about 25 to 100%, size about 10 to 5
It is about 0%.

The sizing agent can improve the paper quality by reducing the amount used. Examples of the sizing agent used when producing paper in the neutral range or the alkaline range include AKD sizing agent, ASA sizing agent, and neutral rosin sizing agent. In the presence of a sulfuric acid band, the AKD sizing agent is unlikely to exert its sizing effect, so the amount added tends to increase.
When the amount of D size agent is increased, the paper strength tends to decrease.

However, the amount of the sulfuric acid band used can be reduced by blending the papermaking auxiliary of the present invention in the aqueous slurry, so that the environment in which the sizing effect of the AKD sizing agent is easily exhibited. Furthermore, by blending the papermaking auxiliary of the present invention, the anion trash in the aqueous slurry is efficiently neutralized, so that the fixing rate of the AKD sizing agent is improved. By improving the fixing rate, it is possible to reduce the amount of AKD sizing agent used, and obtain a paper with improved paper quality, especially paper strength.

Further, the neutral rosin sizing agent needs to be added in a larger amount than the AKD sizing agent and the ASA sizing agent, so that the papermaking machine is likely to be soiled. Therefore, reduction of the amount of the neutral rosin sizing agent has been studied, but reduction of the neutral rosin sizing agent not only lowers the sizing degree but also tends to cause deterioration of the sizing degree with time. In the papermaking raw material composition containing the papermaking auxiliary agent of the present invention, it is possible to reduce the amount of the neutral rosin used, and also to prevent stains on the papermaking machine, improve the sizing degree, and prevent deterioration of the sizing degree over time. You can

Furthermore, the amount of filler used (when calcium carbonate is used) is increased by using the papermaking auxiliary of the present invention.
Since it can be reduced by about 5 to 15%, the total cost of the wet end can be reduced. As a result, it is possible to reduce the production cost, reduce the stain on the papermaking machine, and reduce the adverse effect on the global environment.

When the papermaking aid of the present invention is blended in an aqueous slurry, the cationic polymer in the papermaking aid of the present invention is prepared by emulsion polymerization, that is, in an aqueous medium containing a polymerization initiator and an emulsifier, for example, If an ethylenically unsaturated compound and a cationic monomer are mixed at a predetermined ratio and prepared by a method of polymerizing at a temperature usually in the range of 30 to 80 ° C, an emulsion in which desired copolymer fine particles are uniformly dispersed can be obtained. And this emulsion is
It is advantageous because it can be directly blended in the aqueous slurry.

[0038]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The physical properties of the paper in each example were determined according to the following methods.

(1) 500 ml of filtered-water / turbidity-pulp-containing aqueous slurry was stirred at 1200 rpm, and various chemicals were added thereto at intervals of 10 seconds in the following order. Paper-strengthening agent, sulfuric acid band, cationic monomer, cationic polymer, sizing agent, filler, retention agent (In the comparative examples, the above components or components may not be added). The papermaking raw material composition thus prepared was transferred to a cylindrical container of acrylic resin having an inner diameter of 50 mm and covered with 100 mesh, and the time until the amount of drainage was 300 ml was measured using a graduated cylinder. Further, the formazine turbidity of the filtrate was measured according to JIS K0101.

(2) Retention, cationic demand, zeta potential pulp-containing aqueous slurry (500 ml) was placed in a brid type dynamic jar (40 mesh), and various chemicals were added in the same order as in (1) with stirring to obtain a prescribed amount. When the time came, 100 ml of filtered water was collected from the prepared hole while stirring, suction-filtered with filter paper, dried at 110 ° C. for 60 minutes, and the mass after drying was measured to determine the yield (OPR). Also, collect 150 ml of filtered water and
Cation demand was measured by le Charge Detector PCD03. Further, the zeta potential of the filtered water was measured.

(3) Sizing degree The papermaking raw material composition was placed in a square container so that the basis weight was 70 to 75 g / m ^2, and the mixture was stirred in a square paper machine [manufactured by Tozai Seiki Co., Ltd.]. The slurry composition was added, and the mixture was stirred up and down twice with constant force using a stirring bar, and finally gently stirred.
Then open the drain valve of the paper machine, and mesh (# 40)
A filter paper and one stainless steel plate were placed on the mat (250 mm × 250 mm) formed above, and dehydrated with a roller. Peel the mat from the mesh, sandwich it with filter paper and stainless steel plate, and load two sheets each with a press machine at a load of 0.515.
N / mm ² , pressing was performed once under the condition of 5 minutes, and further pressing was performed once under the condition of the above load for 2 minutes. Then, it was dried for 3 minutes with a drum type dryer (drum surface temperature 95 ° C.), and was conditioned overnight (20 ° C., humidity 55%) to obtain a paper for evaluation. Using this paper, the Stoeckigt sizing degree was measured according to JIS P8122.

(4) Texture The paper prepared in (3) above is used for MK Systems (M / K
The formation index was measured using a 3-D sheet analyzer manufactured by SYSTEMS). The larger the obtained index value, the better the formation.

(5) Tensile Strength (Tear Length) The tensile strength of the paper prepared in (3) above was measured according to JIS P8113. (6) Opacity / Whiteness The paper produced in (3) above is manufactured by Nippon Denshoku Industries Co., Ltd. as "SPEC.
TRO COLOR METER MODEL PF-1
Opacity and whiteness were measured using "0".

(7) Pitch adhesion amount (mg) 250 ml of the papermaking raw material composition and the foamed plastic (A) (12 cm × 3 cm × 1 cm) whose mass was measured in advance were put in a glass bottle and shaken for 2 hours, and then the plastic was removed. The product was taken out, washed with 100 ml of ion-exchanged water, and then dried, and the mass of the plastic (B) was measured, and the adhered amount (mg) was obtained by the following calculation formula. (B)-(A) = Adhesion amount

(8) Pitch adhesion amount reduction ratio Pitch adhesion amount (B) (mg), dimethyldiallylammonium chloride and cationic polymer were prepared using a papermaking raw material composition in which dimethyldiallylammonium chloride and a cationic polymer were not blended. The reduction rate (%) was calculated from the pitch adhesion amount (A) (mg) obtained by using the papermaking raw material composition to be blended by the following formula. Pitch adhesion amount (A) / Pitch adhesion amount (B) x 100

(9) Specific burst strength (-) Based on JIS P 8131, the specific burst strength was determined. (10) Cobb Water Absorption (g / m ² ) The Cobb Water Absorption was determined based on JIS P 8140. The contact time between the test piece and water was 60 seconds.

Example 1 Hardwood kraft pulp (LBKP) In a pulp-containing aqueous slurry having a concentration of 0.7% by mass, a paper-strengthening agent was 0.75% by mass with respect to kraft pulp, and a sulfuric acid band was 0.1% by mass with respect to pulp. 7 mass%, dimethyldiallylammonium chloride to the above pulp at 10 ppm, acrylamide-dimethyldiallylammonium chloride copolymer (viscosity average molecular weight 2500000, cation amount 2.3 meq /
190 g of the cationic polymer of g) to the pulp
pm, neutral rosin sizing agent 0.25 to the pulp
10% by mass of calcium carbonate and talc with respect to the pulp, and 4% of retention agent with respect to the pulp.
30 ppm was added in this order with stirring, then
The papermaking raw material composition was prepared by adjusting the pH to be in the range of 7.5 to 7.7. Table 2 shows the physical properties of the papermaking raw material composition and the properties of the paper obtained by making paper from the papermaking raw material composition.

Examples 2 to 6 and Comparative Examples 1 to 3 In the same manner as in Example 1, a papermaking raw material composition having the composition shown in Table 1 was prepared. Table 2 shows the physical properties of each composition and the physical properties of the paper obtained by making each composition.

[0049]

[Table 1]

(Note) DMDAAC: dimethyldiallylammonium chloride AM-DMDAAC: acrylamide-dimethyldiallylammonium chloride copolymer

[0051]

[Table 2]

In Examples 1 to 6 of the present invention, compared with Comparative Examples 1 to 3, the paper quality, particularly the sizing degree and the sizing degree are less deteriorated with time, the texture and the breaking length are good, and the opacity is high. It turns out to be expensive.

Comparative Example 4 A papermaking raw material slurry was prepared in the same manner as in Example 2, except that dimethyldiallylammonium chloride oligomer (viscosity average molecular weight 20000) was used in place of dimethyldiallylammonium chloride (monomer). did. Table 2 shows the physical properties of this product and papers produced from this product.

Example 7 Dimethyldiallylammonium chloride was added to kraft pulp in Comparative Example 2 so that the paper obtained in Comparative Example 2 had physical properties similar to those of the sizing, drainage, retention and texture. A sizing agent, a retention agent, a sulfuric acid band, and a paper when 10 ppm of a cationic polymer of acrylamide-dimethyldiallylammonium chloride copolymer (viscosity average molecular weight 2500000, cation amount 2.3 meq / g) was blended with kraft pulp at 190 ppm The amounts of the strength enhancer, calcium carbonate and talc were determined. The results are shown in Table 3.

[0055]

[Table 3]

Example 8 As a pulp component, a mixture of deinked waste paper pulp and coat broke (the blending ratio of deinked waste paper pulp and coat broke is 9: 1 by mass), a pulp-containing aqueous solution having a concentration of 0.7% by mass In the slurry, a paper-strengthening agent is 0.75% by mass with respect to the pulp, a sulfuric acid band is 0.35% by mass with respect to the pulp, and dimethyldiallylammonium chloride is 24 with respect to the pulp.
ppm, acrylamide-dimethidyl diallylammonium chloride copolymer (viscosity average molecular weight 250,000
0, a cationic amount of 2.3 meq / g) of the cationic polymer to the pulp, 176 ppm, a neutral rosin sizing agent to the pulp of 0.085% by mass, and a retention agent to the pulp of 200 ppm with stirring in this order. ,afterwards,
The papermaking raw material composition was prepared by adjusting the pH to be in the range of 7.5 to 7.7. Table 4 shows the physical properties of this papermaking raw material composition and the properties of the paper obtained by making paper from this papermaking raw material composition.
Shown in.

Example 9 In Example 8, the addition ratio of each additive component was 1.0% by weight of the paper-strengthening agent to pulp, 0.5% by weight of sulfuric acid band to the pulp, and neutral rosin sizing agent. 0.1% by weight to pulp and retention agent to pulp at 250 p
A papermaking raw material composition was prepared in the same manner as in Example 8 except that pm was changed. Table 4 shows the physical properties of this composition and the physical properties of the paper obtained by making paper from this composition.

Comparative Example 4 Dimethyldiallylammonium chloride, acrylamide-dimethidyldiallylammonium chloride copolymer (viscosity average molecular weight 2500000, cation 2.3m)
A papermaking raw material composition was prepared in the same manner as in Example 9 except that the cationic polymer (eq / g) was not added. Table 4 shows the physical properties of this composition and the physical properties of the paper obtained by making paper from this composition.

Example 10 A papermaking raw material slurry was prepared in the same manner as in Example 8 except that the mass ratio of deinked waste paper pulp and coat broke was 7: 3. .
Table 4 shows the physical properties of this papermaking raw material composition and the properties of the paper obtained by making paper from this papermaking raw material composition.

Example 11 In Example 10, the addition ratio of each additive component was as follows.
1.0% by weight of paper strengthening agent to pulp, 0.5% by weight of sulfuric acid band to pulp, 0.1% by weight of neutral rosin sizing agent to pulp, 250% of retention agent to pulp.
A papermaking raw material composition was prepared in the same manner as in Example 8 except that the content was changed to ppm. Table 4 shows the physical properties of this composition and the physical properties of the paper obtained by making paper from this composition.

Comparative Example 5 In Example 11, dimethyldiallylammonium chloride, acrylamide-dimethidyldiallylammonium chloride copolymer (viscosity average molecular weight 250,000) was used.
A papermaking raw material composition was prepared in the same manner as in Example 9 except that a cationic polymer having a cation content of 0, and a cation amount of 2.3 meq / g) was not mixed. Table 4 shows the physical properties of this composition and the physical properties of the paper obtained by making paper from this composition.

Example 12 As a pulp component, 60 ppm of dimethyldiallylammonium chloride was added to an pulp-containing aqueous slurry having a concentration of 0.6% by mass of coat broth with respect to the pulp, and an acrylamide-dimethidyldiallylammonium chloride copolymer (viscosity average molecular weight) was used. 15,000,000, cation amount 3.8
After adding 440 ppm of the cationic polymer (meq / g) to the pulp while stirring, the pH was adjusted to 7.7-
The papermaking raw material composition was prepared by adjusting so as to fall within the range of 8.2. Table 4 shows the physical properties of this papermaking raw material composition and the properties of the paper obtained by making paper from this papermaking raw material composition.

Comparative Example 6 In Example 12, dimethyldiallylammonium chloride and acrylamide-dimethidyldiallylammonium chloride copolymer (viscosity average molecular weight 150,000) were used.
0, the cation amount was 3.8 meq / g), and the other components were all prepared in the same manner as in Example 12 except that the cationic polymer was not blended.
A papermaking raw material composition was prepared in the same manner as in. Table 4 shows the physical properties of this composition and the physical properties of the paper obtained by making paper from this composition.

Example 13 As pulp components, in a pulp-containing aqueous slurry having a concentration of 0.7% by mass of corrugated cardboard, 0.2% by mass of a paper-strengthening agent with respect to pulp and 1.5% by mass of a sulfuric acid band with respect to pulp. %, 36 ppm of dimethyldiallylammonium chloride with respect to the pulp, acrylamide-dimethidyldiallylammonium chloride copolymer emulsion (solid content 3
0 mass%, a viscosity average molecular weight of 3500000, a cation amount of 4.3 meq / g) of a cationic polymer to the pulp is 880 ppm, and a rosin-based sizing agent is 0.1 to the pulp.
After adding 18% by mass in this order with stirring, pH
The papermaking raw material composition was prepared by adjusting so as to be in the range of 6.0 to 6.5. Table 5 shows the physical properties of this papermaking raw material composition and the properties of the paper obtained by making paper from this papermaking raw material composition.

Example 14 In Example 13, the paper strengthening agent was added to the pulp in an amount of 0.3.
Wt%, a sulfuric acid band was changed to 2.0 wt% with respect to the pulp, and a neutral rosin sizing agent was changed to 0.2 wt% with respect to the pulp, and a papermaking raw material composition was prepared in the same manner as in Example 13. . Table 5 shows the physical properties of this composition and the physical properties of the paper obtained by making paper from this composition.

Comparative Example 7 In Example 14, dimethyldiallylammonium chloride, acrylamide-dimethidyldiallylammonium chloride copolymer emulsion (solid content 30% by mass, viscosity average molecular weight 3500000, cation amount 4.3) was obtained.
A papermaking raw material composition was prepared in the same manner as in Example 14 except that the cationic polymer (meq / g) was not added. Table 5 shows the physical properties of this composition and the properties of the paper obtained by making paper from this composition.

[0067]

[Table 4]

[0068]

[Table 5]

[0069]

By using the papermaking auxiliary agent of the present invention and the papermaking raw material composition containing the same, a sizing agent, a pitch control agent, which have been conventionally used in the production of paper,
It is possible to reduce the amount of various additives such as retention agents, paper strength agents, slime control agents and preservatives, as well as reduce pitch stains and the amount of chemicals used. It is possible to reduce costs, reduce paper machine stains, and reduce the impact on the global environment.

Continued front page    F-term (reference) 4L055 AG35 AG65 AG72 AG89 AH09                       AH50 BD10 EA03 EA32 FA06                       FA09 FA10 FA13 FA17 FA20                       FA22

Claims (4)

[Claims] 1. A viscosity average molecular weight of at least 200,000.
5. A papermaking auxiliary comprising the cationic polymer and the cationic monomer in a mass ratio of 95: 5 to 50:50. 2. The cationic polymer is a copolymer of a quaternary ammonium salt residue-containing cationic monomer and acrylamide, and the content of the cationic monomer unit is in the range of 5 mol% to less than 40 mol%. Claim 1
The papermaking auxiliary described. 3. An aqueous slurry containing a pulp component in a concentration of 0.5 to 5.0% by mass, a cationic polymer having a viscosity average molecular weight of at least 200,000 and a cationic monomer in a mass ratio of 95: 5 to 50:50. , And the concentration of the total amount of both is 5
A papermaking raw material composition, which is blended in a range of 0 to 1000 ppm. 4. The cationic polymer is a copolymer of a quaternary ammonium salt residue-containing cationic monomer and acrylamide, and the content of the cationic monomer unit is in the range of 5 mol% to less than 40 mol%. 4. The papermaking raw material composition according to claim 3.