WO2014123087A1

WO2014123087A1 - Method for manufacturing composite filler for manufacturing paper, and method for manufacturing filler-containing paper

Info

Publication number: WO2014123087A1
Application number: PCT/JP2014/052453
Authority: WO
Inventors: 和寛久米田; 茂樹信国; 義之三谷
Original assignee: 星光Pmc株式会社
Priority date: 2013-02-05
Filing date: 2014-02-03
Publication date: 2014-08-14
Also published as: CN103966895A; JP2016102265A

Abstract

A composite filler for paper manufacture is prepared in which calcium carbonate is aggregated using an acrylamide copolymer, the composite filler being appropriately treated so that: prior to mixing with a pulp slurry, the 50%-volume average particle diameter is 60-300 μm, as measured by the laser diffraction method; particles measuring 5 μm or less are 1 % or less in terms of volume ratio; and the visible light transmittance is increased in the DFR filtrate of a slurry obtained by adding the composite filler in an amount of 30 wt%, in terms of solid content, relative to the solid weight of an LBKP pulp. The composite filler is blended with the pulp slurry and is made into paper. The present invention makes it possible to provide a filler for manufacturing paper in which a decrease in paper strength during manufacture of paper having a high ash content is prevented and a deterioration of optical characteristics is impeded, and to provide a filler-containing paper in which said filler is used.

Description

Method for producing composite filler for papermaking, and method for producing filler-added paper

The present invention relates to a filler used for papermaking and a filler-added paper. More specifically, the present invention relates to a composite filler prepared by mixing calcium carbonate and an acrylamide copolymer in order to obtain excellent paper strength, and a filler-added paper made by adding the filler to a pulp slurry.

In recent years, due to the expansion of global paper demand, it has become more difficult to stably supply wood as a raw material, and a paper manufacturing technology that satisfies the conventional quality with a smaller amount of pulp is desired. Since the price of pulp is more expensive than the filler, reducing the pulp and increasing the blending ratio of the filler is an important issue in the paper industry as a cost reduction measure. However, as the amount of pulp in the paper decreases and the filler content increases, a decrease in paper strength (paper strength) becomes a problem. In order to increase paper strength, a method of internally adding a paper strength enhancer such as starch or polyacrylamide is widely used. However, even if the amount of these chemicals is increased more than usual, the paper strength may be increased. Since the effect reaches its peak, the efficiency is low and it is not practical from the viewpoint of cost. In addition, there is a problem that the paper texture is deteriorated and the operation becomes unstable.

As a method for avoiding such a problem and suppressing a decrease in paper strength, a method of modifying the filler by adding various additives has been proposed (see, for example, Patent Documents 1 to 7).

Patent Document 1 discloses a method of treating calcium carbonate with an amphoteric acrylamide copolymer to prevent deterioration of optical properties and paper strength.

Patent Document 2 discloses a method in which calcium carbonate is treated with anionic xanthan gum, guar gum or the like to prevent a decrease in paper strength.

Patent Document 3 discloses a method in which calcium carbonate is treated with cationized starch or cationized guar gum to prevent the yield of filler and the decrease in paper strength.

Patent Document 4 discloses a method of preventing a decrease in opacity and paper strength by treating a filler such as calcium carbonate with an acrylic latex.

Patent Document 5 discloses a method of treating a filler such as calcium carbonate with alginic acid to prevent the yield of the filler and the decrease in paper strength.

Patent Document 6 discloses a method for efficiently improving paper strength by coating a filler with a composite acrylamide copolymer comprising an anionic polysaccharide and a cationic or amphoteric acrylamide copolymer. Yes.

Patent Document 7 discloses a method for producing a composite filler and a filler-added paper having a high bulk, whiteness, opacity, paper strength, and filler yield by treating calcium carbonate with an amphoteric acrylamide copolymer.

JP 59-26595 A JP-T 09-505063 Japanese Patent Laid-Open No. 10-60794 JP 2004-100119 A JP 2011-106075 A Japanese Patent No. 4406882 JP 2004-018323 A

However, the composite filler obtained by the above treatment was not uniform and appropriate in agglomerated form, and the behavior after addition to the pulp slurry was not taken into consideration. For this reason, there are many problems such as a case where an appropriate agglomeration form cannot be maintained with respect to the shearing force in the pulp slurry, and a sufficient paper strength cannot be obtained or the paper machine is soiled.

Thus, it cannot be said that the effect obtained by the conventional method is sufficient, and a more effective method is desired.

The present invention is a method for producing a composite filler for papermaking that can provide a filler-added paper with less deterioration of optical properties and better paper strength than before, and excellent paper strength and optical properties by using such a composite filler. It is an object of the present invention to provide a method for producing a filler-added paper having the following.

The present invention relates to the following contents.
<1> A method for producing a composite filler for papermaking, wherein calcium carbonate is treated so as to satisfy the following condition (3) using an acrylamide copolymer satisfying the following conditions (1) and (2).
(1) The acrylamide copolymer is amphoteric, the molar ratio of ionic monomer / nonionic monomer is 5/95 to 40/60, and (number of moles of cationic monomer × cationic group of cationic monomer) Ratio) / (number of moles of anionic monomer × number of anionic groups of anionic monomer) is 50/50 to 90/10
(2) The weight average molecular weight of the acrylamide copolymer is 2 million to 7 million (3) The 50% volume average particle diameter of the composite filler is 60 μm to 300 μm, and the particles of 5 μm or less are 1% or less by volume. And, when the DFR measurement is performed, the pulp slurry containing 30% by weight of the composite filler in the dilution condition in which the filtrate light transmittance of the pulp slurry containing 30% by weight of the untreated filler with respect to the pulp solid becomes 50%. The filtrate light transmittance is 60% or more. <2> The method for producing a composite filler for papermaking according to <1>, wherein the 50% volume average particle diameter before aggregation of the calcium carbonate is 10 μm or less.
<3> The method for producing a composite filler for papermaking according to the above <1> or <2>, wherein the ratio of the ionic monomer / the nonionic monomer is 10/90 to 25/75.
The ratio of <4> (number of moles of the cationic monomer × number of cationic groups of the cationic monomer) / (number of moles of the anionic monomer × number of anionic groups of the anionic monomer) is 50/50. The method for producing a composite filler for papermaking as described in any one of the above items <1> to <3>, which is 80/20.
<5> The method for producing a composite filler for papermaking according to any one of the above <1> to <4>, wherein the molecular weight of the acrylamide copolymer is 2.5 million to 5 million in terms of weight average molecular weight by GPC-MALS method .
<6> The method for producing a composite filler for papermaking according to any one of <1> to <5>, wherein the 50% volume average particle size of the composite filler is 100 μm to 200 μm.
<7> The treatment amount of the acrylamide copolymer is any one of the above items <1> to <6>, which is in the range of 0.1 to 3.0% by weight in terms of solids with respect to the solid weight of the calcium carbonate. The manufacturing method of the composite filler for paper manufacture as described in one.
<8> A method for producing a filler-added paper, wherein the paper-made composite filler obtained by the production method according to any one of <1> to <7> is added to a pulp slurry.
<9> The method for producing a filler-added paper according to <8>, wherein the ash content in the filler-added paper is 10% or more.
<10> The method for producing a filler-added paper according to <8>, wherein the ash content in the paper of the filler-added paper is 20% or more and 50% or less.

When the composite filler obtained according to the present invention is used, it is possible to obtain a filler-added paper that is less deteriorated in optical properties and has better paper strength than the conventional one.

The present inventors apply a uniform and appropriate agglomeration treatment to an inorganic filler with an acrylamide copolymer to form a composite filler with very few unagglomerated filler particles, whereby paper is made after mixing into a pulp slurry. The composite filler was successfully redispersed under the conditions where the shearing force was applied until then, and at this time, the composite filler with little release of filler fine particles was successfully obtained. It has been found that a paper made by mixing a composite filler having such a function with a pulp slurry can achieve both high paper strength and optical properties (whiteness and opacity), and has completed the present invention. In particular, in high ash paper, where paper strength is difficult to generate, the use of composite fillers has the effect of increasing the contact area between pulp fibers, which is thought to improve paper strength. The reason why the paper strength and optical characteristics are improved is not clear, but can be considered as follows.
When the acrylamide copolymer serves as a binder, calcium carbonate is aggregated, and a composite filler having a 50% volume average particle diameter of 60 μm to 300 μm is obtained. The binding strength as a binder is such that it is peeled off by the shearing force of the mixer, and can be appropriately redispersed by the share of the papermaking system. In addition, the acrylamide copolymer functions as a dispersant or compatibilizer, so that the optical properties are less likely to deteriorate due to the uniform dispersion of the small particle size composite filler during papermaking. It is considered that the paper strength is improved by the strength (elasticity) of the object itself. Thus, it is considered that paper strength and optical characteristics are improved by performing an appropriate aggregation treatment.

As the calcium carbonate used in the present invention, both heavy calcium carbonate (ground calcium carbonate) and light calcium carbonate (precipitated calcium carbonate) can be used. Specific examples of such calcium carbonate include heavy calcium carbonate such as Softon 1000, Softon 1500, Softon 3200 (all manufactured by Shiroishi Calcium Industry), and Tama Pearl TP-121 (Okutama Industry). Examples include light calcium carbonate. As long as the effects of the invention are not impaired, fillers such as clay, talc, silica, aluminosilicate, titanium oxide, zinc oxide, white carbon, aluminum hydroxide and zeolite, and organic fillers may be used in combination.

The particle diameter before aggregation of calcium carbonate is preferably 10 μm or less in terms of 50% volume average particle diameter. If it is larger than this, there will be a problem that the filler particles will easily fall off the paper, which may cause trouble.

The calcium carbonate slurry may be subjected to a dispersion treatment for the purpose of facilitating transport at a high concentration, but if the effect of the present invention is not impaired, the presence or absence of such treatment on the calcium carbonate prior to the aggregation treatment is determined. It doesn't matter. Further, auxiliary agents such as a sizing agent, a water-resistant agent, a sulfuric acid band, an ultraviolet absorber, an anti-fading agent, and a dye may be added.

In the method for producing the composite filler, an acrylamide copolymer satisfying the following conditions (1) and (2) is used so that the calcium carbonate particles can be uniformly and appropriately aggregated.
(1) The acrylamide copolymer is amphoteric, the molar ratio of ionic monomer / nonionic monomer is 5/95 to 40/60, and (number of moles of cationic monomer × cationic group of cationic monomer) Ratio) / (number of moles of anionic monomer × number of anionic groups of anionic monomer) is 50/50 to 90/10
(2) The weight average molecular weight of the acrylamide copolymer is 2 million to 7 million.

Examples of the nonionic monomer constituting the acrylamide copolymer include acrylamide, methacrylamide, dimethylacrylamide, and methylenebisacrylamide, and any of powder and aqueous solution may be used for polymerization.

Examples of the ionic monomer constituting the acrylamide copolymer include a cationic monomer and an anionic monomer.

Examples of the cationic monomer include a vinyl monomer having a tertiary amino group or a quaternary ammonium salt.

Examples of vinyl monomers having a tertiary amino group include dialkylaminoalkyl (meth) such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meth) acrylate. Inorganic acids such as acrylates, dialkylaminoalkyl (meth) acrylamides such as dimethylaminopropyl (meth) acrylamide and diethylaminopropyl (meth) acrylamide, hydrochlorides of vinyl monomers having the above tertiary amino groups, and sulfates Examples thereof include salts, and organic acid salts such as formate and acetate of vinyl monomers having the above tertiary amino group.

Also, examples of the vinyl monomer having a quaternary ammonium salt include vinyl monomers obtained by reacting the above-described vinyl monomer having a tertiary amino group with a quaternizing agent. Examples of the quaternizing agent include alkyl halides such as methyl chloride and methyl bromide, aralkyl halides such as benzyl chloride and benzyl bromide, dimethyl sulfate, diethyl sulfate, epichlorohydrin, and 3-chloro-2-hydroxypropyl. Examples thereof include trimethylammonium chloride and glycidyltrialkylammonium chloride. These vinyl monomers having a tertiary amino group or a quaternary ammonium salt may be used alone or in combination of two or more.

Examples of the anionic monomers include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated tricarboxylic acids, unsaturated tetracarboxylic acids, unsaturated sulfonic acids, unsaturated phosphonic acids, and salts thereof. It can be used alone or in combination of two or more.

Among these, examples of the unsaturated monocarboxylic acid and salts thereof include acrylic acid, methacrylic acid, 2-acrylamide-N-glycolic acid, and alkali metals such as sodium and potassium salts, ammonium salts, and the like.

Examples of unsaturated dicarboxylic acids and salts thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid and alkali metal salts such as sodium and potassium salts thereof, ammonium salts, and the like.

Examples of unsaturated tricarboxylic acids and their salts include alkalis such as aconitic acid, 3-butene-1,2,3-tricarboxylic acid, 4-pentene-1,2,4-tricarboxylic acid and their sodium and potassium salts Examples thereof include metal salts or ammonium salts.

Examples of unsaturated tetracarboxylic acids and their salts include 1-pentene-1,1,4,4-tetracarboxylic acid, 4-pentene-1,2,3,4-tetracarboxylic acid, 3-hexene- Examples thereof include 1,1,6,6-tetracarboxylic acid and alkali metal salts such as sodium and potassium salts thereof or ammonium salts.

Examples of unsaturated sulfonic acids include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and alkali metal salts or ammonium salts thereof such as sodium and potassium. Can be mentioned.

Examples of the unsaturated phosphonic acid include vinylphosphonic acid, α-phenylvinylphosphonic acid and alkali metal salts such as sodium and potassium salts, ammonium salts, and the like.

Among the above anionic vinyl monomers, unsaturated monocarboxylic acid and unsaturated dicarboxylic acid, specifically acrylic acid, itaconic acid, 2-acrylamide-N-glycolic acid, And its salts are particularly preferred.

From the viewpoint of the cohesiveness of calcium carbonate and the paper strength effect, the ratio of ionic monomer / nonionic monomer needs to be 5/95 to 40/60 (mol%) as the composition of the acrylamide copolymer. The ratio is preferably 10/90 to 25/75. For the same reason, the ratio of (number of moles of cationic monomer × number of cationic groups of cationic monomer) / (number of moles of anionic monomer × number of anionic groups of anionic monomer) is 50 / 50˜ Those satisfying the condition of 90/10 (mol%) can provide a good effect, more preferably 50/50 to 80/20.

Acrylamide copolymer can be obtained by polymerization by a known method. An acrylamide copolymer can also be obtained by dividing the monomer for polymerization or by dropping the monomer for polymerization.

The molecular weight of the acrylamide copolymer having a weight average molecular weight in the range of 2 million to 7 million as measured by the GPC-MALS method shows a good effect, and is preferably 2.5 million to 5 million. When it is lower than 2 million, the effect of improving the paper strength is insufficient, and when it is higher than 7 million, over-aggregation of the filler causes deterioration of paper strength, or the viscosity of the aqueous solution becomes high and handling is inconvenient.
Throughout the present application, the symbol “˜” indicating a range is merely used for convenience and conciseness, and does not limit the scope of the present invention. Accordingly, the symbol “˜” should be considered as specifically disclosing the subrange and individual numerical values within that range. For example, the description of the range of the weight average molecular weight “2 million to 7 million” includes a partial range, specifically, 2.5 million to 3 million, 2.5 million to 4 million, 2.5 million to 5 million, and the range. It should be regarded as disclosing the number of individual members, specifically 2 million, 2.5 million, 3 million, 4 million, 5 million.

The weight average molecular weight of the acrylamide copolymer is measured by GPC-MALS method in which a multi-angle light scattering detector is connected to GPC. The measurement conditions are as follows.
GPC main unit: LC1100 series manufactured by Agilent Technologies Inc. Column: SHODEX SB806M HQ manufactured by Showa Denko KK
Eluent: N / 10 phosphate buffer (pH 3) containing N / 10 sodium nitrate
Flow rate: 1.0 ml / min Detector 1: Multi-angle light scattering detector DAWN manufactured by Wyatt Technology
Detector 2: Suggested refractive index detector RI-101 manufactured by Showa Denko KK

As long as the effects of the invention are not impaired, in addition to the above acrylamide copolymer, polyvinylamine, polyethyleneimine, polyallylamine, polydiallylamine, polydiallyldimethylammonium chloride, polyacrylate, polyethylene oxide, polyvinyl alcohol , Polymer compounds such as cationized starch and amphoteric starch can be used in combination.

In the method for producing a composite filler of the present invention, it is necessary to perform uniform and appropriate treatment of the filler. Specifically, the above acrylamide copolymer is used so as to satisfy the following condition (3). To treat calcium carbonate.
(3) The 50% volume average particle diameter of the composite filler is 60 μm to 300 μm, and the particles having a volume ratio of 5 μm or less are 1% or less in volume ratio, and when the DFR measurement is performed, the untreated filler to the pulp solid In a dilution condition where the filtrate light transmittance of the pulp slurry containing 30% by weight is 50%, the filtrate light transmittance of the pulp slurry containing 30% by weight of the composite filler is 60% or more.

When the 50% volume average particle diameter of the composite filler measured by the laser diffraction method is in the range of 60 μm to 300 μm, a good paper strength improvement effect can be obtained. More preferably, it is 100 μm to 200 μm. When the thickness is smaller than 60 μm, a sufficient paper strength improvement effect cannot be obtained. When the thickness is larger than 300 μm, there is a possibility that defects derived from aggregates may occur on the paper surface after paper making. In this case, the opacity is lowered, which is not preferable. There is also a concern that the paper machine is likely to get dirty.

In addition, regarding the particle size distribution of the composite filler, it is preferable that particles having a size of 5 μm or less be 1% or less by volume ratio. This is because if there are many unagglomerated fine particles in the slurry of the composite filler after the filler treatment, a sufficient paper strength improvement effect cannot be obtained.

The 50% volume average particle diameter and the volume ratio of particles of 5 μm or less can be measured using a laser diffraction / scattering particle size distribution measuring machine (Nikkiso Co., Ltd. Microtrac MT3300EXII).

Furthermore, when the visible light (wavelength: 620 nm) transmittance of the filtrate by DFR of the slurry in which 30% by weight of the composite filler is added to the solid weight of the LBKP pulp is 60% or more, the shear in the pulp slurry The stability of the composite filler with respect to force is increased, and good paper strength is obtained. When the visible light transmittance is less than 60%, it is determined that the cohesive force is weak or the coagulation is non-uniform, and the coagulation is loosened due to re-dispersion due to the shear and many fine particles are generated. When there are many fine particles, the paper strength is greatly reduced, making it difficult to solve this problem.

(Measurement method of DFR)
The above-mentioned DFR refers to a Drainage Freeness Retention measuring device (DFR-05, hereinafter referred to as “DFR”) manufactured by Mutech. As a feature of DFR, it is possible to apply a shearing force to a sample, and evaluation can be performed under conditions close to those of an actual paper machine. A shear force is applied to the pulp slurry to which the composite filler has been added using a DFR apparatus, and the light transmittance of the filtrate is measured with a spectrophotometer. When the light transmittance of the filtrate is high, it is presumed that the composite filler maintains an appropriate agglomerated form even under a condition where shearing force is applied, which leads to a high yield to the pulp slurry. Thus, the optimal particle size range and composition of the acrylamide copolymer can be grasped by observing the filler yield after the shearing force is applied.

In the production of the composite filler, the mixing method, processing method, or processing conditions are appropriately selected and adjusted so that the obtained composite filler satisfies the above condition (3).

The method of mixing the acrylamide copolymer with calcium carbonate is not particularly limited, but can be agglomerated efficiently by mixing by multistage addition or dropwise addition rather than batch mixing. This is preferable in terms of uniform fixing to calcium.

As the filler processing method, a method of mixing a calcium carbonate slurry using water as a solvent and an aqueous solution of an acrylamide copolymer is the simplest. As a mixing method, a known method capable of uniformly mixing is used. Mixing can be performed in a reaction vessel or tank capable of stirring by a stirrer, an agitator, bubbling or the like. Alternatively, it can be prepared by adding an aqueous solution of an acrylamide copolymer on the transfer line of the calcium carbonate slurry. In such a case, it is preferable to ensure a sufficient flow rate and a length until mixing with the flow path, that is, the pulp slurry, for performing a uniform and appropriate treatment so as to satisfy the above condition (3), If necessary, an in-line mixer may be used. After adding the acrylamide copolymer to the calcium carbonate slurry, if the shear force is too strong, there is a risk that unaggregated particles will increase and sufficient paper strength may not be obtained. It is preferable to perform the adjustment.

The treatment amount of the acrylamide copolymer is preferably in the range of 0.1 to 3.0% by weight in terms of solids with respect to the solid weight of calcium carbonate, more preferably 0.5 to 2 in terms of improving paper strength. 0.0% by weight. If the amount is less than 0.1% by weight, the aggregation of the inorganic filler is insufficient and the effect of improving the paper strength is small. If the amount exceeds 3.0% by weight, the effect of improving the paper strength is peaked, and the ion balance is largely biased. There is a possibility that the fine particles of 5 μm or less increase and the paper strength is lowered.

The filler-added paper can be obtained by adding a composite filler to the pulp slurry and making paper. It is preferable to use a composite filler of 10 to 100% by weight in solid conversion with respect to the pulp solid content, and more preferably 20 to 70% by weight. The pulp slurry used in the present invention contains pulp, and has a form in which the pulp is made into a slurry by being dispersed with an aqueous solvent. The pulp slurry may be an acidic pulp slurry using aluminum sulfate, a neutral system using a small amount of aluminum sulfate, or an alkaline pulp slurry using no aluminum sulfate.

The above-mentioned pulp may be any commonly used pulp, such as bleached kraft pulp and sulfite pulp, or bleached unbleached chemical pulp, groundwood pulp, mechanical pulp, thermomechanical pulp, or the like. Examples include bleached high-yield pulp, and used paper pulp such as used newspaper, magazine used paper, cardboard used paper, and deinked used paper, and one or more of these can be used. Various additives other than pulp can be used in the pulp slurry as necessary.

Various additives can be added to the pulp slurry. As additives, fillers other than the composite filler of the present invention, sizing agent, dry paper strength agent, wet paper strength agent, paper thickness improver, yield, drainage improvement An agent etc. can be mentioned. For example, the types of sizing agent include rosin sizing agent, AKD sizing agent, ASA sizing agent and the like, and the use of 0.02 to 0.5% is preferable. As the dry paper strength agent, amphoteric starch, cationized starch, Examples thereof include acrylamide copolymers, Hoffman PAM, anion-mannic PAM, and the like, and the use of 0.05 to 2% is preferable. A known system is used as the yield and drainage improver, and examples thereof include a single polymer, a twins system, a composite system, and a hydrocoal system. Various additives are appropriately selected and used according to the physical properties required for each paper type.

The paper may be any of acid papermaking, neutral papermaking, and alkaline papermaking, but neutral papermaking or alkaline papermaking is preferred.

Examples of the filler-added paper obtained by the present invention include information paper, printing paper, printing coating base paper, wrapping paper, building material base paper, wallpaper base paper, and the like.

(Ash content in paper)
The ash content in the filler-added paper is preferably 10% or more, and more preferably 20% or more. If it is less than 10%, the advantage of the effect of the present invention may not be exhibited. As long as the paper strength level has practical strength, there is no particular upper limit, but it is preferable to add about 50%.

Hereinafter, the present invention will be specifically described with reference to production examples and comparative production examples, examples and comparative examples, but the present invention is not limited to the following examples. In addition, the percentage in description shows weight%.

(Production example 1 of acrylamide copolymer used for the treatment of calcium carbonate)
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, nitrogen gas inlet tube, 40.55 g of water, 159.93 g of 50% acrylamide aqueous solution, 1.97 g of dimethylaminoethyl methacrylate, monomer, itacone 8.13 g of acid, 0.50 g of N, N-dimethylacrylamide and 0.99 g of sodium methallylsulfonate were charged. Next, the temperature was raised to 60 ° C. in a nitrogen gas atmosphere, 0.18 g of ammonium persulfate was added as a polymerization initiator, polymerization was started, and the reaction temperature was raised to 90 ° C. Thereafter, 161.64 g of water, 26.86 g of 30% aqueous sulfuric acid solution, 159.93 g of 50% aqueous acrylamide solution, 25.55 g of dimethylaminoethyl methacrylate, 1.63 g of itaconic acid, 0.50 g of N, N-dimethylacrylamide, and methallylsulfone. A monomer mixture consisting of 0.99 g of sodium acid was added, 0.65 g of ammonium persulfate was further added, and when reacted for 2 hours, 51.00 g of water was added, the solid content was 20.2%, and the weight average molecular weight was 3.3 million. Of amphoteric polyacrylamide was obtained.

(Production Example 2)
As shown in Table 1, the same procedure as in Production Example 1 was performed except that the monomer ratio was changed so that the weight average molecular weight of the acrylamide copolymer used for the treatment of calcium carbonate was 6.9 million.

(Production Example 3)
As shown in Table 1, the same procedure as in Production Example 1 was performed except that the monomer ratio was changed so that the weight average molecular weight of the acrylamide copolymer used for the treatment of calcium carbonate was 2.1 million.

(Production Examples 4 to 9)
The same operation as in Production Example 1 was carried out except that the ratio of the monomer of the acrylamide copolymer used for the treatment of calcium carbonate was changed as shown in Table 1.

(Production Example 10)
The same procedure as in Production Example 1 was carried out except that the acrylamide copolymer used for the treatment of calcium carbonate was synthesized by substituting a part of dimethylaminoethyl methacrylate with a quaternary compound with benzyl chloride as shown in Table 1. It was.

(Production Example 11)
The same operation as in Production Example 1 was carried out except that the acrylamide copolymer used for the treatment of calcium carbonate was synthesized by substituting a part of dimethylaminoethyl methacrylate with dimethylaminopropylacrylamide as shown in Table 1.

(Production Example 12)
The same procedure as in Example 1 was performed except that the acrylamide copolymer used for the treatment of calcium carbonate was synthesized by substituting a part of itaconic acid with 2-acrylamide-N-glycolic acid as shown in Table 1. It was.

(Comparative Production Example 13)
As shown in Table 2, the same procedure as in Production Example 1 was performed except that the monomer ratio was changed so that the weight average molecular weight of the acrylamide copolymer used for the treatment of calcium carbonate was 9 million.

(Comparative Production Example 14)
As shown in Table 2, the same procedure as in Production Example 1 was performed except that the monomer ratio was changed so that the weight average molecular weight of the acrylamide copolymer used for the treatment of calcium carbonate was 1,400,000.

(Comparative Production Examples 15 to 18)
The same operation as in Production Example 1 was carried out except that the monomer ratio was changed as shown in Table 2 for the acrylamide copolymer used for the treatment of calcium carbonate.

(Comparative Production Example 19)
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube was charged with 281.1 g of water, 113.72 g of 50% aqueous acrylamide solution, and 49.75 g of 65% diallyldimethylammonium chloride aqueous solution, 30 The pH was adjusted to 3.0 with a 1% aqueous sulfuric acid solution. Next, the temperature was raised to 60 ° C. in a nitrogen gas atmosphere, 1.07 g of ammonium persulfate was added as a polymerization initiator, the temperature was raised to 90 ° C., and the temperature was kept. After 1 hour and 2 hours from the start of polymerization, 0.18 g of ammonium persulfate was additionally added, and after 5 hours from the start of the reaction, the polymerization was stopped and cooled.

(Comparative Production Example 20)
Based on the synthesis method in Comparative Production Example 19, an acrylamide copolymer having the composition (AAm / IA) shown in Table 2 was obtained.

(Comparative Production Example 21)
A cationized starch having a degree of cation substitution (DS) of 0.03 was cooked at a concentration of 3%, diluted to a concentration of 1.5%, and then subjected to calcium carbonate treatment.

(Comparative Production Example 22)
Composition of Table 2 (AAm / DPA / DMBz / IA / SAS / MBAA) obtained based on 10 g of 1.5% aqueous solution of sodium carboxymethylcellulose (Daicel Chemical Industries, Ltd. 1250) and the synthesis method in Comparative Production Example 19 90 g of a 1.5% aqueous solution of acrylamide copolymer was mixed and stirred to obtain 100 g of a mixed aqueous solution of sodium carboxymethylcellulose and an acrylamide copolymer.

(Comparative Production Example 23)
Based on the synthesis method in Comparative Production Example 19, an acrylamide copolymer having the composition (AAm / DAC) shown in Table 2 was obtained.

(Comparative Production Example 24)
In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 140 g of water, 6.2 g of 2-sulfoethyl methacrylate sodium salt, 100 g of nbutyl acrylate, 100 g of styrene, 6 g of acrylic acid Then, 17.7 g of a mixed monomer solution of 1.03 g of ammonium persulfate was charged, and 150 g of water was added to start stirring. Next, the temperature was raised to 60 ° C. in a nitrogen gas atmosphere, 1.0 g of 10% ammonium persulfate was added as a polymerization initiator, and the temperature was raised to 80 ° C. The remaining 335.5 g of the mixed monomer solution was added dropwise over 2 hours, and 1 hour after the completion of the addition, 1.0 g of 10% ammonium persulfate was additionally added. After further aging for 2 hours, the polymerization was stopped, and after cooling, the pH was adjusted to 7.0 with aqueous ammonia.

Abbreviations in Table 1 and Table 2 are as follows.
AAM: Acrylamide IA: Itaconic acid SMAS: Sodium methallyl sulfonate DMAA: N, N-dimethylacrylamide DM: Dimethylaminoethyl methacrylate DMBz: Quaternized product of dimethylaminoethyl methacrylate with benzyl chloride DPA: Dimethylaminopropylacrylamide AGA: 2 -Acrylamide-N-glycolic acid DADMAC: diallyldimethylammonium chloride CMC: sodium carboxymethylcellulose SAS: sodium allylsulfonate MBAA: methylenebisacrylamide DAC: quaternized product of N, N-dimethylaminoethyl acrylate with methyl chloride ST: styrene BA : N-butyl acrylate AA: Acrylic acid

(Preparation of filler slurry)
100 g of calcium carbonate was added to 900 g of water, and a dispersion treatment was performed at 2000 rpm for 1 minute using a homomixer to prepare a filler slurry having a concentration of 10%.

(Preparation of composite filler)
(Examples 1 to 15, Comparative Examples 1 to 12)
Acrylamide copolymer shown in the above production example or comparative production example while weighing 100 g of 10% calcium carbonate slurry in a 300 mL beaker and stirring at 300 rpm with a stirrer equipped with a propeller-type stirring blade. 10 g of a 1% aqueous solution of the product was added over 1 minute. After completion of the addition, the mixture was stirred for 3 minutes to obtain a composite filler slurry. Immediately after the preparation, the average particle size and the volume ratio of 5 μm or less were measured.

(Example 16)
The same method as described above was performed except that the addition amount of the acrylamide copolymer aqueous solution having a concentration of 1% was changed to 5 g.

(Measurement method of DFR)
<Method for preparing pulp slurry for DFR measurement>
For measurement, 400 mL of Canadian Standard Freeness (CSF) beaten by a Niagara beater, LBKP pulp slurry (concentration 0.8%) adjusted to conductivity 100 (mS / m) and pH 7.5 was used. All the preparations used fresh water, and the temperature of the pulp slurry was adjusted to 40 ° C.

<Preparation of filtrate using DFR>
A mutex Drainage Freeness Retention measuring device (DFR-05) was used to evaluate the stability of the composite filler against the shearing force in the pulp slurry. Retention mode was used for the preparation of the filtrate.

<Light transmittance of DFR filtrate using untreated calcium carbonate>
1 kg of pulp slurry is set in a DFR apparatus, 30% of untreated calcium carbonate (concentration 10%) is added in solid conversion to the pulp solid, stirred for 10 seconds at 600 rpm, and further 10 seconds at 1000 rpm. After stirring at 800 rpm for 10 seconds, filtration was started and 100 mL of the first filtrate that passed through a 150 mesh wire was collected. Immediately after collecting the filtrate, it was diluted with ion-exchanged water, and the dilution factor at which the light transmittance was 50% was determined. The light transmittance was determined by measuring the visible light transmittance at a wavelength of 620.0 nm using a spectrophotometer (Hitachi ratio beam spectrophotometer U-1000 type). The light transmittance was measured immediately before the turbidity component settled immediately after preparation of the liquid.

<Calculation method of the dilution ratio at which the light transmittance is 50%>
The filtrate obtained under DFR conditions using untreated calcium carbonate was measured as a stock solution, and solutions diluted by 10, 20, 30, 50, and 100 times, and the dilution rate at which the light transmittance was 50% was estimated. . In Comparative Example 13 in which Softon 3200 (manufactured by Shiroishi Calcium Industry) was used as the calcium carbonate, the dilution factor at which the light transmittance was 50% was 15 times, so Examples 1 to 12, 16 using the same calcium carbonate were used. In Comparative Examples 1 to 12, the dilution rate was set to 15 times. Hereinafter, in Examples 13 to 15, the dilution ratio was similarly determined using Comparative Examples 14 to 16.

<Light transmittance of DFR filtrate using composite filler>
1 kg of pulp slurry was set in a DFR apparatus, 30% of the composite filler 1 shown in Example 1 (concentration 10%) was added to the pulp solid in solid conversion, stirred for 10 seconds at 600 rpm, and further 1000 rpm. After stirring at 800 rpm for 10 seconds, filtration was started and 100 mL of the first filtrate that passed through a 150 mesh wire was collected. Immediately after collecting the filtrate, dilute with ion-exchanged water at the dilution factor obtained above (dilution factor at which light transmittance is 50% in DFR filtrate using untreated calcium carbonate) and measure the light transmittance. did.
(Examples 2 to 16, Comparative Examples 1 to 16)

Various fillers were treated using the acrylamide copolymer or the cationized starch shown in the production examples in Tables 1 and 2 and the comparative production examples to prepare composite fillers. Tables 3 and 4 show physical property values (50% volume average particle diameter, 5 μm or less volume ratio, DFR filtrate light transmittance) of the composite filler.

(Application Example 1)
(Method for producing filler-added paper)
Canadian Standard Freeness (CSF) 400 mL, conductivity 100 (mS / m), and a slurry of 2.4% LBKP pulp adjusted to pH 7.5 was stirred, and cationized starch (CATO304 manufactured by NSC Japan) 1.0% in terms of solids with respect to pulp solids, 0.2% in terms of solids with respect to pulp solids (DS4412 manufactured by Seiko PMC Co., Ltd.), alkyl ketene dimer sizing agent ( Seiko PMC Co., Ltd. AD1604) was sequentially added at 0.1% in terms of solids to the pulp solids.
After further stirring for 1 minute, the pulp concentration was diluted to 0.8% with water adjusted to pH 7.5 and conductivity 100 (mS / m), and then composite filler 1 shown in Example 1 (concentration 10%). Was added so that it might become 40% in solid conversion with respect to pulp solid content.
Add a cationic retention agent (RD7142 from Seiko PMC Co., Ltd.) to pulp solids in an amount of 0.015% in terms of solids, stir for 1 minute, and then make paper with a noble and wood sheet machine, wet paper Got.
The wet paper was press-dehydrated and dried at 100 ° C. for 100 seconds with a drum dryer to obtain paper having a basis weight of 80 g / m ² .
The obtained paper was conditioned for 24 hours under constant temperature and humidity conditions of a temperature of 23 ° C. and a humidity of 50%, and various measurements were performed. The paper quality was measured by the method described later. Paper strength effect was judged from internal strength, and optical characteristics were judged from opacity.

(Physical property measurement method)
Basis weight: Conforms to JIS P8124.
Ash content in paper: Conforms to JIS P8251 Ash test method (525 ° C combustion method).
Opacity: Conforms to JIS P8149 opacity test method.
Internal strength: JAPAN TAPPI Paper Pulp Test Method No.18-2
Paper and paperboard: Internal bond strength test method Part 2 Conforms to internal bond tester method.

(Application Examples 2 to 12)
The same operation as in Application Example 1 was performed except that the filler was changed to the composite fillers of Examples 2 to 12 in Table 4.

(Application Example 13)
The same operation as in Application Example 1 was performed except that the composite filler of Example 13 using heavy calcium carbonate (Softon 1500, particle size 3.6 μm manufactured by Shiroishi Calcium Industry Co., Ltd.) was used.

(Application Example 14)
The same operation as in Application Example 1 was performed except that the composite filler of Example 14 using heavy calcium carbonate (Softon 1000 manufactured by Shiraishi Calcium Industry Co., Ltd., particle size 5.7 μm) was used.

(Application Example 15)
The same operation as in Application Example 1 was performed except that the composite filler of Example 15 using light calcium carbonate (Tama Pearl TP-121 manufactured by Okutama Kogyo Co., Ltd., particle size 2.4 μm) was used.

(Application Example 16)
The same operation as in Application Example 1 was performed except that the composite filler 16 of Example 16 was used and the internal paper strength agent was not added.

(Application Comparative Examples 1 to 12)
The same operation as in Application Example 1 was performed except that the filler was changed to the composite fillers of Comparative Examples 1 to 12 in Table 4.

(Application Comparative Example 13)
The same operation as in Application Example 1 was performed except that untreated heavy calcium carbonate (Softon 3200 manufactured by Shiroishi Calcium Industry Co., Ltd.) was used as the filler.

(Application Comparative Example 14)
The same operation as in Application Example 1 was performed except that untreated heavy calcium carbonate (Softon 1500, manufactured by Shiroishi Calcium Industry Co., Ltd.) was used as the filler.

(Application Comparative Example 15)
The same operation as in Application Example 1 was performed except that untreated heavy calcium carbonate (Softon 1000 manufactured by Shiroishi Calcium Industry Co., Ltd.) was used as the filler.

(Application Comparative Example 16)
The same operation as in Application Example 1 was performed except that untreated light calcium carbonate (Tama Pearl TP-121 manufactured by Okutama Kogyo Co., Ltd.) was used as the filler.

(Application Comparative Example 17)
The same operation as in Application Example 1 was performed except that untreated light calcium carbonate (Tama Pearl TP-121 manufactured by Okutama Kogyo Co., Ltd.) was used as the filler and the addition rate of the filler was changed to 30%.

From Tables 5 and 6, the application examples 1 to 12 and the application comparison example 13, or the application example 13 and the application comparison example 14, or the application example 14 and the application comparison example 15, or the application example 15 and the application comparison. From the results of Example 16, it can be seen that the paper using the composite filler of the present invention has higher paper strength than the paper using the untreated filler.

From the results of Application Examples 1 to 3 and Application Comparison Examples 1 and 2, the paper using the composite filler used in Application Examples 1 to 3 has high paper strength, and the molecular weight of the acrylamide copolymer is appropriate. Otherwise, it can be seen that the particle diameter of the filler after the treatment is out of the proper range, and the effect of improving the paper strength cannot be obtained sufficiently.

From the results of the application examples 1 to 12 and the application comparison examples 3 to 8, it can be seen that the paper using the composite filler used in the application examples 1 to 12 has high paper strength. When the monomer composition constituting the acrylamide copolymer is not appropriate or the particle size of the filler after treatment is out of the proper range, the light transmittance of the DFR measurement filtrate is less than 60%, and the effect of improving paper strength is achieved. Not enough.

From the results of the application examples 1 to 12 and the application comparison examples 9 to 12, it can be seen that the paper using the composite filler used in the application examples 1 to 12 has high paper strength. In Comparative Examples 9 to 12, which are known methods (prior art), the particle size of the filler is not sufficient, or the volume ratio of the filler of 5 μ or less is greater than 1%, or the filtrate light transmittance of DFR is greater than 1%. Since it is less than 60%, the effect of improving paper strength cannot be obtained sufficiently.

From the results of Application Example 15 and Application Comparison Example 16, it can be seen that the paper strength is improved by using the composite filler. Here, when composite filler is used, there are cases where the ash content in paper decreases and the opacity deteriorates, but it is at a high level when compared with an untreated filler with low ash content in paper (Application Comparative Example 17). It can be seen that improvement is possible by increasing the amount of filler.

From the results of Application Example 16 and Application Comparative Example 13, when the same amount of acrylamide copolymer is used, the effect of improving paper strength is excellent by treating calcium carbonate to make a composite filler rather than adding it internally to the pulp. I understand that.

From the above, when the composite filler according to the present invention is used, it is possible to obtain a filler-added paper having paper strength and optical characteristics superior to those of the prior art.

According to the present invention, a high paper strength can be obtained efficiently even with a high ash content filler paper. The amount of pulp and chemicals can be reduced, and low cost and resource reduction can be achieved.

Claims

Using an acrylamide copolymer satisfying the following conditions (1) and (2),
The manufacturing method of the composite filler for paper manufacture characterized by processing calcium carbonate so that the conditions of following (3) may be satisfy | filled.
(1) The acrylamide copolymer is amphoteric, the molar ratio of ionic monomer / nonionic monomer is 5/95 to 40/60, and (number of moles of cationic monomer × cationic group of cationic monomer) Ratio) / (number of moles of anionic monomer × number of anionic groups of anionic monomer) is 50/50 to 90/10
(2) The weight average molecular weight of the acrylamide copolymer is 2 million to 7 million (3) The 50% volume average particle diameter of the composite filler is 60 μm to 300 μm, and the particles of 5 μm or less are 1% or less by volume. And, when the DFR measurement is performed, the pulp slurry containing 30% by weight of the composite filler in the dilution condition in which the filtrate light transmittance of the pulp slurry containing 30% by weight of the untreated filler with respect to the pulp solid becomes 50%. Filtrate light transmittance of 60% or more
The method for producing a composite filler for papermaking according to claim 1, wherein the 50% volume average particle diameter before aggregation of the calcium carbonate is 10 µm or less.
The method for producing a composite filler for papermaking according to claim 1 or 2, wherein the ratio of the ionic monomer / the nonionic monomer is 10/90 to 25/75.
The ratio of (number of moles of the cationic monomer × number of cationic groups of the cationic monomer) / (number of moles of the anionic monomer × number of anionic groups of the anionic monomer) is 50/50 to 80 / The method for producing a composite filler for papermaking according to any one of claims 1 to 3, wherein the number is 20.
The method for producing a composite filler for papermaking according to any one of claims 1 to 4, wherein the molecular weight of the acrylamide copolymer is 2.5 million to 5 million in terms of weight average molecular weight by GPC-MALS method.
The method for producing a composite filler for papermaking according to any one of claims 1 to 5, wherein the composite filler has a 50% volume average particle size of 100 µm to 200 µm.
7. The processing amount of the acrylamide copolymer is in a range of 0.1 to 3.0% by weight in terms of solid with respect to the solid weight of the calcium carbonate. The manufacturing method of the composite filler for paper manufacture as described in a term.
A method for producing a filler-added paper, wherein the paper-made composite filler obtained by the production method according to any one of claims 1 to 7 is added to a pulp slurry.
The method for producing a filler-added paper according to claim 8, wherein the ash content in the paper of the filler-added paper is 10% or more.
The method for producing a filler-added paper according to claim 8, wherein the ash content in the paper of the filler-added paper is 20% or more and 50% or less.