TW202248498A - Rosin sizing agent for papermaking and paper - Google Patents

Abstract

To provide a rosin-based sizing agent for papermaking, which has excellent storage stability and exhibits a good sizing effect during papermaking. The invention relates to a rosin sizing agent for papermaking and paper containing the rosin sizing agent. The rosin sizing agent for papermaking contains an anionic rosin emulsion (A), a nonionic dispersant and/or an anionic dispersant (B) (excluding a dispersant containing a (meth) acrylamide polymer), a water-soluble aluminum compound (C), and a polymer (D) having an amino group.

Description

Rosin-based sizing agent for papermaking, paper

The invention relates to a rosin-based sizing agent for papermaking and paper.

Rosin-based sizing agent for papermaking refers to a composition obtained by emulsifying rosin-based resins in the presence of various emulsifiers and water. According to the ionicity of the emulsifier used, it is classified as cationic or anionic. Slurry. Paper obtained using such a sizing agent exhibits a good sizing effect due to the emulsion particles fixed on the pulp fibers.

Among them, cationic rosin-based sizing agents are known as emulsifiers obtained by reacting epihalohydrins and polyalkylpolyamines (Patent Document 1) and polyamide polyamines and water-soluble acids (Patent Document 2) A substance obtained by dispersing a rosin-based resin. However, in general, rosin-based resins and cationic emulsifiers have different ionic properties, so emulsification is difficult, and even if an emulsion is obtained, storage stability and sizing effect tend to deteriorate.

On the other hand, as another method, a cationic rosin-based emulsion-type sizing agent in which an acrylamide-based polymer, a polyvalent metal salt, and a cationic resin is mixed with an anionic rosin emulsion is also known (Patent Document 3), However, in this case, the storage stability is adversely affected due to the electrostatic interaction between the anionic nature of the emulsion of the material and the cationic nature of the acrylamide polymer, polyvalent metal salt and/or cationic resin. [Prior Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 5-98001 [Patent Document 2] Japanese Unexamined Patent Publication No. 2012-007284 [Patent Document 3] Japanese Patent Application Laid-Open No. 3-008893

[Technical problem to be solved by the invention]

An object of the present invention is to provide a rosin-based sizing agent for papermaking that is excellent in storage stability and exhibits a good sizing effect during papermaking. [Technical means]

The inventors of the present invention completed the present invention through intensive studies. That is, the present invention relates to the following rosin-based sizing agent for papermaking and paper.

1. A rosin-based sizing agent for papermaking, characterized in that it contains an anionic rosin-based emulsion (A), a nonionic dispersant and/or an anionic dispersant (B) (excluding (meth)acrylamide polymer-like dispersants), water-soluble aluminum compounds (C) and polymers with amine groups (D).

2. The rosin-based sizing agent for papermaking as described in item 1 above, wherein the component (B) is selected from polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, and polyoxyalkylene styryl phenyl ethers. At least one of the groups.

3. The rosin-based sizing agent for papermaking according to item 1 or 2 above, wherein the component (D) contains an alkylene polyamine-epihalohydrin resin and/or a polyamide polyamine-epihalohydrin resin.

4. The rosin-based sizing agent for papermaking according to any one of items 1 to 3 above, wherein the content of the component (B) is 0.5 to 30 parts by weight of the solid content relative to 100 parts by weight of the component (A). parts by weight.

5. The rosin-based sizing agent for papermaking according to any one of items 1 to 4 above, wherein the content of component (D) is 1 to 20 parts by weight of solid content relative to 100 parts by weight of component (A). parts by weight.

6. A paper characterized by containing the rosin-based sizing agent for papermaking as described in any one of items 1 to 5 above. [Effect of the invention]

The rosin-based sizing agent for papermaking according to the present invention has excellent storage stability, and the paper obtained by using the sizing agent also shows good sizing effect.

The rosin-based sizing agent for papermaking of the present invention contains anionic rosin-based emulsion (A) (hereinafter also referred to as component (A)), a nonionic dispersant and/or anionic dispersant (B) (hereinafter also referred to as (B) component), a water-soluble aluminum compound (C) (hereinafter also referred to as (C) component), and a polymer (D) having an amine group (hereinafter also referred to as (D) component).

Component (A) is an anionic rosin-based emulsion comprising emulsification of a rosin-based resin (a1) (hereinafter also referred to as component (a1)) and an anionic emulsifier (a2) (hereinafter also referred to as component (a2)) things. Since the component (A) contains a rosin-based resin, it has a good sizing effect at the time of papermaking.

(a1) Components include, for example, gum rosin, wood rosin, tall oil rosin, pine rosin (rosin containing dihydroagathic acid), slash rosin (rosin containing acacia acid), etc. Unmodified rosin, hydrogenated rosin, α, β-unsaturated carboxylic acid modified rosin, disproportionated rosin or their esterified products (unmodified rosin ester, hydrogenated rosin ester, α, β-unsaturated carboxylic acid modified rosin ester, disproportionated rosin ester), etc. These may be used alone or in combination of two or more.

In addition, the component (a1) can also be purified by known vacuum distillation, steam distillation, extraction, recrystallization, and the like.

Also, α,β-unsaturated carboxylic acid-modified rosin (hereinafter also simply referred to as carboxylic acid-modified rosin) refers to one obtained by adding α,β-unsaturated carboxylic acid to unmodified rosin. The α,β-unsaturated carboxylic acid is not particularly limited, and examples include: α,β-unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, and fumaric acid; α,β-unsaturated dicarboxylic acids such as acrylic acid and methacrylic acid; monocarboxylic acid etc. The usage-amount of α,β-unsaturated carboxylic acid is also not specifically limited, Usually, it is about 1-30 weight part with respect to 100 weight part of unmodified rosins.

The method for producing α,β-unsaturated carboxylic acid-modified rosin is not particularly limited, and examples include: mixing unmodified rosin and α,β-unsaturated carboxylic acid in a suitable reaction vessel, heating and melting, A method of performing Diels-Alder reaction at about 190-230°C for about 1-3 hours.

The physical properties of α,β-unsaturated carboxylic acid modified rosin are not particularly limited. From the viewpoint of good sizing effect on paper, the softening point is usually around 85-140°C and the acid value is around 195-320mgKOH/g. , the ideal softening point is about 95-130°C and the acid value is about 240-295mgKOH/g.

(a2) The component is an anionic emulsifier. (a2) Components include, for example: polyoxyalkylene alkyl sulfate, polyoxyalkylene alkyl phenyl ether sulfate, higher alcohol sulfate ester salt, higher alcohol phosphate ester salt, alkyl sulfonate, alkyl Phenyl ether sulfonate, alkyl diphenyl ether sulfonate, alkylbenzene sulfonate, naphthalene sulfonate, formaldehyde condensate of naphthalene sulfonate, lignin sulfonate, alkyl sulfosuccinic acid salt, polyoxyalkylene alkyl sulfosuccinate, polyoxyalkylene phenyl ether sulfosuccinate, polyoxyalkylene alkylphenyl ether sulfosuccinate, polyoxyalkylene styryl phenyl ether sulfosuccinate Succinate, polymers containing anionic groups, aqueous alkali metal hydroxide solutions (aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, etc.), etc. These may be used alone or in combination of two or more.

In addition, in the description in the above paragraph, the oxyalkylene group includes, for example, an oxyethylene group, an oxypropylene group, an oxyprenyl group, an oxybutenyl group, and the like. In addition, the alkyl group includes, for example, n-hexyl, isohexyl, n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, n-decyl, isodecyl, n-undecyl, n-dodecyl Alkyl (lauryl), n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, etc. In addition, examples of salts include sodium salts, potassium salts, and ammonium salts.

The anionic group-containing polymer includes, for example, a polymer or a salt thereof containing a polymerizable monomer having an anionic group and a polymerizable monomer having a hydrophobic group in a reaction component. Salts include sodium salts, potassium salts, and ammonium salts.

Polymerizable monomer with anionic group A monomer with a polymerizable carbon-carbon double bond and an anionic functional group. Polymerizable monomers having an anionic group include, for example: polymerizable monomers having one carboxyl group such as (meth)acrylic acid and crotonic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, Citraconic acid, citraconic anhydride, and other polymerizable monomers with two carboxyl groups; (meth)allylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, (meth)acrylic acid 2-ethanesulfonate, etc. Polymerizable monomers with sulfonic acid groups; mono[(meth)acrylate 2-hydroxyethyl]acid phosphate, mono[(meth)acrylate 2-hydroxypropyl]acid phosphate, mono[(meth)acrylate base) 3-hydroxypropyl acrylate] acid phosphate, mono[(meth)acrylate 3-chloro-2-hydroxypropyl] acid phosphate, (methyl) allyl alcohol acid phosphate, mono[ (Meth) 2-hydroxyethyl acrylate] acid phosphite and other polymerizable monomers with phosphoric acid groups. These may be used alone or in combination of two or more. Here, (meth)acrylate means methacrylate or acrylate, and (meth)allyl means methallyl or allyl (the same applies hereinafter).

In addition, as the polymerizable monomer having an anionic group, salts of the above-mentioned substances can also be used, and the salts thereof include, for example, sodium salts, potassium salts, ammonium salts, and the like.

Examples of polymerizable monomers having a hydrophobic group include styrenes, alkyl (meth)acrylates, vinyl carboxylates, and the like. These may be used alone or in combination of two or more.

Styrenes, for example: styrene, α-methylstyrene, tertiary butylstyrene, dimethylstyrene, acetyloxystyrene, hydroxystyrene, vinyltoluene, vinyl chloride toluene Wait.

Alkyl (meth)acrylates include, for example, alkyl (meth)acrylates having about 1 to 18 carbon atoms in the alkyl group. In addition, the alkyl group includes, for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, n-hexyl, isohexyl, n-heptyl , n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, n-hexadecyl, n-octadecyl, n-behenyl, cyclopentyl, cyclohexyl, etc.

Carboxylic acid vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl laurate, and the like.

Based on the weight of the solid content, the ratio of polymerizable monomers with anionic groups to polymerizable monomers with hydrophobic groups is ideally (polymerizable monomers with anionic groups) / (polymerizable monomers with hydrophobic groups) Group polymerizable monomer) = 10/90 ~ 50/50, more preferably 20/80 ~ 40/60.

In addition, the aforementioned reaction components may further contain chain transfer unsaturated monomers, hydroxyl-containing unsaturated monomers, and crosslinkable unsaturated monomers described in JP-A-2017-066579. The production conditions (contents of monomers, organic solvents, reaction temperature, reaction time, etc.) of polymers with sexual groups can also be appropriately used as described in the publication.

(a2) The physical properties of the component, for example, the weight average molecular weight (polyethylene oxide conversion value in the gel permeation chromatography (GPC) method) is usually 5,000 to 100,000, preferably 10,000 to 50,000. In addition, the solid content concentration of the component (a2) is 20 to 30% by weight, the viscosity (25°C) at a solid content concentration of 25% by weight is 10 to 500 mPa·s, and the pH (25°C) is 8 to 10.

Among these (a2) components, polyoxyalkylene styryl phenyl ether sulfosuccinate, an aqueous alkali metal hydroxide solution, an anionic group-containing polymer, or a salt thereof is preferable.

Also, as the component (a2), an aqueous alkali metal hydroxide aqueous solution may be used for emulsification of the rosin-based resin (a1) in an aqueous solution of an alkali metal salt of the rosin-based resin mixed with the rosin-based resin (a1) in advance.

The content of the component (a2) is preferably 0.5 to 10 parts by weight in terms of solid content based on 100 parts by weight of the component (a1) from the viewpoint of good emulsifying properties of the component (a1) and the component (a2). , more preferably 1 to 5 parts by weight.

The method of dispersing the component (a1) with the component (a2), that is, the method of producing the component (A), can be any one of the high-pressure emulsification method and the phase inversion emulsification method. Also, the dispersion medium is alcohol such as ethanol or isopropanol; water is ideally used from the viewpoint of reducing environmental load, but a mixed solvent of water and an organic solvent may also be used.

The organic solvent is not particularly limited as long as it is an organic solvent soluble in water, for example: methanol, ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, tertiary butanol, isobutanol , n-hexanol, n-octanol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, diacetone alcohol and other alcohols; ethers of ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc. These may be used alone or in combination of two or more. Also, when an organic solvent is contained, its content is preferably less than 10% by weight.

In the case of using the high-pressure emulsification method, the component (a1) forming the dispersed phase can be melted or dissolved in an organic solvent such as benzene or toluene, and then the component (a2) can be added thereto at the above-mentioned content while mixing and warming. Water is emulsified with a high-pressure emulsifier to obtain a dispersion as it is, or the organic solvent is evaporated to obtain a dispersion.

In addition, in the case of using the phase inversion emulsification method, after fully kneading the (a1) and (a2) components of the solid content, warm water can be slowly added dropwise while stirring, and the phase can be reversed to avoid use. In the case of organic solvents and special emulsification equipment, dispersion liquid is obtained. The solid content concentration of the dispersion liquid is not particularly limited, but is usually 10 to 50% by weight, and may be used after being diluted with water as necessary.

In addition, to the component (A), for example, paper strength enhancers such as celluloses such as carboxymethyl cellulose, polyvinyl alcohols, polyacrylamides, and water-soluble polymers such as sodium alginate, antislip agents, and preservatives may be added. , antirust agent, pH regulator, defoamer (silicone defoamer, etc.), thickener, filler, antioxidant, water-resistant agent, film-forming aid, pigment, dye, etc.

(A) The physical properties of the component. For example, when the solid content concentration is 50% by weight, the viscosity obtained by a B-type viscometer at a temperature of 25°C is usually about 10-300mPa·s, ideally about 20-50mPa·s .

Furthermore, the volume average particle diameter of (A) component is about 0.1-2 micrometers normally, Preferably it is about 0.4-0.8 micrometers. In addition, the volume average particle diameter is the value measured with the particle diameter measuring apparatus by the laser diffraction-scattering method (it is the same below).

Component (B) is a nonionic dispersant and/or anionic dispersant, which suppresses aggregation caused by electrostatic interaction between component (A) and component (C) and component (D), and has the function of making these components good The effect of dispersal. Moreover, (B) component is desirably a component different from the (a2) component used at the time of manufacture of (A) component in order to exhibit the said effect further.

In addition, component (B) does not include a dispersant containing a (meth)acrylamide-based polymer. (Meth)acrylamide refers to methacrylamide and acrylamide. In addition, (meth)acrylamide-based polymers refer to polymers containing (meth)acrylamide-based reaction components. If such a dispersant is added, the rosin-based sizing agent for papermaking tends to increase viscosity and tend to have poor storage stability.

Examples of nonionic dispersants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene styrylphenyl ethers, polyoxyalkylene alkyl esters, and polyoxyalkylene sorbitan Alkyl esters, condensates of alkylene oxide and aliphatic amines, ethylene oxide-propylene oxide polymers, etc. These may be used alone or in combination of two or more.

In addition, in the description in the above paragraph, the oxyalkylene group includes, for example, an oxyethylene group, an oxypropylene group, an oxyprenyl group, an oxybutenyl group, and the like. In addition, the alkyl group includes, for example, n-hexyl, isohexyl, n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, n-decyl, isodecyl, n-undecyl, n-dodecyl Alkyl (lauryl), n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, etc.

Anionic dispersants include, for example, polyoxyalkylene alkyl sulfates, polyoxyalkylene alkyl phenyl ether sulfates, higher alcohol sulfate ester salts, higher alcohol phosphate ester salts, alkyl sulfonates, alkyl Phenyl ether sulfonate, alkyl diphenyl ether sulfonate, alkylbenzene sulfonate, naphthalene sulfonate, formaldehyde condensate of naphthalene sulfonate, lignin sulfonate, alkyl sulfosuccinic acid salt, polyoxyalkylene alkyl sulfosuccinate, polyoxyalkylene phenyl ether sulfosuccinate, polyoxyalkylene alkylphenyl ether sulfosuccinate, polyoxyalkylene styryl phenyl ether sulfosuccinate succinate etc. These may be used alone or in combination of two or more.

Among them, from the viewpoint of suppressing the aggregation caused by the electrostatic interaction between (A), (C) and (D), the (B) component is ideally a nonionic dispersant, more preferably a polyoxyalkylene dispersant. At least one selected from the group consisting of alkyl ethers, polyoxyalkylene alkylphenyl ethers, and polyoxyalkylene styrylphenyl ethers.

The content of the component (B) is preferably 0.5 based on the weight of the solid content relative to 100 parts by weight of the component (A) from the viewpoint that the paper obtained by using a rosin-based sizing agent for papermaking exhibits a good sizing effect. -30 parts by weight, preferably 1-10 parts by weight.

(C) The component is a water-soluble aluminum compound. In the component (C), the aluminum atom is positively charged in the acidic papermaking system or the neutral papermaking system. Therefore, if a rosin-based sizing agent for papermaking containing component (C) is added, the aluminum atoms will bond to the hydroxyl groups in the pulp fibers, and the sizing agent will be easily fixed on the pulp fibers, and the resulting paper will show a good sizing effect . (C) Components include, for example, aluminum sulfate, aluminum hydroxide, aluminum chloride, basic aluminum sulfate, basic aluminum chloride, aluminum silicate, and polymers thereof. In addition, (C) component can also use a hydrate. These may be used alone or in combination of two or more. Among them, aluminum sulfate is ideal in terms of cost.

The content of the component (C) is preferably 0.5 to 30 parts by weight based on the weight of the solid content relative to 100 parts by weight of the component (A) from the viewpoint that the rosin-based sizing agent for papermaking exhibits excellent storage stability. , preferably 5 to 10 parts by weight.

(D) The component is a polymer with an amine group. Since it is a component that makes the rosin-based sizing agent for papermaking show excellent storage stability and is easy to fix on pulp fibers, it is used to make rosin-based sizing agents for papermaking. The composition of the paper obtained by the sizing agent exerts a good sizing effect. In addition, the amino group here refers to a primary amino group, a secondary amino group, and a tertiary amino group.

(D) Components include, for example: alkylene polyamine-epihalohydrin resins, acid salts of polyamide polyamines, polyamide polyamine-epihalohydrin resins, (meth)acrylamides with amino groups Amine polymers, etc. These may be used alone or in combination of two or more.

〔About alkylene polyamine-epihalohydrin resin〕 Alkylene polyamine-epihalohydrin resin is a polymer containing alkylene polyamine and epihalohydrin in the reaction components.

Alkylene polyamines are compounds with an alkylene structure and two or more amine groups, such as: ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butanediamine Alkylenediamines such as amine (tetramethylenediamine), 1,5-pentamethylenediamine (pentamethylenediamine), 1,6-hexanediamine (hexamethylenediamine); Alkylenetriamines such as ethylenetriamine, dipropylenetriamine, and dibutylenetriamine; alkylenetetramines such as triethylenetetramine and tripropylenetetramine; tris(2-aminoethyl )amine, tris(2-aminoalkyl)amine such as tris(2-aminopropyl)amine; alkylenepentamine such as tetraethylenepentamine and tetrapropylenepentamine; pentaethylenehexaamine Amines and other alkylene hexamines, etc. These may be used alone or in combination of two or more. Among them, ethylenediamine and 1,6-hexanediamine are ideal.

Examples of epihalohydrin include epichlorohydrin, epibromohydrin, and the like. These may be used alone or in combination of two or more.

Moreover, the monoamine represented by the following general formula (1) may also be contained in the said reaction component. [Formula 1] R ¹ -NH-R ² (In Formula 1, R ¹ and R ² independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. In addition, R ¹ and R ² are both Except in the case of hydrogen atoms.)

Examples of monoamines represented by the general formula (1) include: Methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, secondary butylamine, tertiary butylamine, n-pentylamine, n-hexylamine, isohexylamine, n-heptylamine, n-octylamine, 2- Ethylhexylamine, n-decylamine, n-undecylamine, n-dodecylamine (laurylamine), n-tridecylamine, n-tetradecylamine (myristylamine), n-hexadecylamine (palmitamine), n-stearyl Aliphatic primary amines such as amine and isostearylamine; Dimethylamine, diethylamine, ethylmethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-second-butylamine, di-tertiary-butylamine, N-methylbutylamine, N-ethylbutylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-2-ethylhexylamine, di-n-decylamine, di-n-undecylamine, di-n-dodecylamine (Dilaurylamine), Ditridecylamine, Ditetradecylamine (Dimyristylamine), Dihexadecylamine (Dipalmitylamine), Di-n-Stearylamine, Diisostearylamine, Dihardened Tallow Aliphatic secondary amines such as amines; Cyclobutylamine, cyclopentylamine, cyclopentylmethylamine, 1-cyclopentylethylamine, 2-cyclopentylethylamine, cyclohexylamine, cyclohexylmethylamine, 1-cyclohexylethylamine, 2-cyclohexyl Alicyclic primary amines such as ethylamine, cycloheptylamine, and cyclooctylamine; N-methylcyclopentylamine, N-ethylcyclopentylamine, N-propylcyclopentylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, N-propylcyclohexylamine, N- Alicyclic secondary amines such as isopropylcyclohexylamine; Aniline, o-toluidine, m-toluidine, p-toluidine, phenylmethylamine (benzylamine), 1-phenylethylamine, 2-phenylethylamine, 1-phenylpropylamine, 2-phenylpropylamine, 3 -Phenylpropylamine, 4-phenylbutylamine, 1-naphthylamine, 2-naphthylamine, 2-methylnaphthylamine, 1-(aminomethylnaphthalene), 2-(aminomethyl)naphthalene, 1 -Aromatic primary amines such as aminoanthracene, 2-aminoanthracene, and 9-aminoanthracene; N-methylaniline, N-ethylaniline, N-propylaniline, N-isopropylaniline, N-butylaniline, N-isobutylaniline, N-methylbenzylamine, N-ethylbenzylamine Amine, N-propylbenzylamine, N-isopropylbenzylamine, N-butylbenzylamine, 1-(methylaminomethyl)naphthalene, 9-(methylamino)methylanthracene and other aromatics Secondary amines, etc.

These monoamines may be used alone or in combination of two or more.

The amount of epihalohydrin, alkylene polyamine and monoamine represented by general formula (1) is not particularly limited. In terms of the ratio of the total molar amount of the amine groups of the monoamine represented, the ideal system is (the molar amount of the epoxy group of the epihalohydrin)/(the amine of the monoamine represented by the alkylene polyamine and the general formula (1) Based on the total molar amount) = about 0.8 to 1.4, ideally 1 to 1.2. (Also, when only any one of the alkylene polyamine or the monoamine represented by the general formula (1) is used, it is desirable to set it within the same range.)

The production method of the alkylene polyamine-epihalohydrin resin is not particularly limited, for example: first add the epihalohydrin, and if necessary, add the monoamine represented by the general formula (1) and mix at room temperature. Alkylene polyamines are added batchwise or dropwise, and reacted by heating.

In addition, the above-mentioned reaction conditions are not particularly limited, and the temperature is about 50-100°C (ideally about 60-90°C), and the time is about 1-12 hours (ideally about 2-8 hours).

In the above production method, from the viewpoint of reaction control, it is desirable to use a reaction liquid in which water is added. As water, pure water, ion-exchanged water, tap water, industrial water etc. are mentioned, for example. These may be used alone or in combination of two or more. In addition, when water is added, the reaction concentration is preferably about 40 to 60% by weight, more preferably about 45 to 55% by weight.

Further, in the obtained alkylene polyamine-epihalohydrin resin, pH regulators, defoamers, antioxidants, preservatives, chelating agents, cationic emulsifiers, anionic emulsifiers, Nonionic emulsifiers, etc.

The physical properties of the alkylene polyamine-epihalohydrin resin are not particularly limited. For example, the solid content concentration is usually about 20 to 50% by weight, preferably about 30 to 45% by weight.

The viscosity of an aqueous solution having a solid content concentration of 40% by weight of the alkylene polyamine-epihalohydrin resin at a temperature of 25° C. is usually about 10 to 500 mPa·s, preferably 50 to 300 mPa·s.

〔About acid salt of polyamide polyamine〕 Acid salts of polyamide polyamines are salts formed by adding inorganic acids and/or organic acids to polyamide polyamines.

Polyamide polyamine is a condensate of aliphatic dibasic acid and/or its derivatives and alkylene polyamine.

Aliphatic dibasic acids, for example: saturated aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid; Aconic acid, citraconic acid and other unsaturated aliphatic dibasic acids, etc. In addition, the derivatives thereof include, for example, acid anhydrides of the aforementioned aliphatic dibasic acids; esters with saturated aliphatic alcohols such as methanol and ethanol; and the like. These may be used alone or in combination of two or more. Among them, saturated aliphatic dibasic acids are preferable, and adipic acid and sebacic acid are more preferable.

Examples of alkylene polyamines include those described in the above paragraphs.

The amount of aliphatic dibasic acid and/or its derivatives and alkylene polyamine used, usually in molar ratio, (alkylene polyamine)/(aliphatic dibasic acid and/or its derivative)= About 0.8 to 1.5, ideally about 0.9 to 1.2.

The condensation reaction of aliphatic dibasic acid and/or its derivatives with alkylene polyamine is not particularly limited, for example, in the presence or absence of catalysts such as sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, at a reaction temperature of 110 It is carried out under the conditions of about 250°C and a reaction time of about 2 to 24 hours. In addition, the obtained condensate is preferably diluted with water or an organic solvent. The solid content concentration after dilution is about 20 to 80% by weight.

As water, pure water, ion-exchanged water, tap water, industrial water etc. are mentioned, for example. These may be used alone or in combination of two or more.

Examples of organic solvents include alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone and methyl ethyl ketone; and dimethylsulfoxide, toluene, and hexane. These may be used alone or in combination of two or more. Among them, methanol, ethanol, and isopropanol are preferable from the viewpoint of easily dissolving polyamide polyamine.

The physical properties of the obtained polyamide polyamine, for example, the viscosity of an aqueous solution with a solid content concentration of 50% by weight at a temperature of 25°C is ideally about 200 to 1000 mPa·s.

Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like. Moreover, examples of organic acids include acetic acid, propionic acid, succinic acid, malic acid, maleic acid, citric acid and the like. These may be used alone or in combination of two or more.

The amount of inorganic acid and/or organic acid used is preferably 30-75%, more preferably 40-60%, based on the proton equivalent ratio relative to the amine group in the polyamide polyamine. Also, the equivalent ratio refers to the protons from inorganic acids and/or organic acids, assuming that all the protons from inorganic acids and/or organic acids are consumed in order to neutralize all the amine groups contained in the polyamide polyamine. The ratio (%) of the number of protons (moles) of the acid to the total number of amine groups (moles) in the polyamide polyamine.

The salt of polyamide polyamine can be obtained, for example, by directly adding an inorganic acid and/or an organic acid to polyamide polyamine and stirring. In addition, the above-mentioned water may also be added at this time.

The physical properties of the acid salt of polyamide polyamine, for example, the viscosity of an aqueous solution with a solid content concentration of 50% by weight at a temperature of 25°C is ideally about 200 to 1000 mPa·s.

〔About polyamide polyamine-epihalohydrin resin〕 Polyamide polyamine-epihalohydrin resin is a polymer containing polyamide polyamine and epihalohydrin in the reaction components.

The definition, raw materials, production methods and physical properties of polyamide polyamine are as described in the above paragraphs.

As epihalohydrin, the epihalohydrin described in the said paragraph is mentioned, for example.

The amount of epihalohydrin used, from the point of view of suppressing the production of halohydrin, the ideal ratio of polyamide polyamine and epihalohydrin used is (epoxy equivalent of epihalohydrin)/(polyamide polyamine Secondary amine equivalent) = about 0.8 to 2.0, preferably about 0.9 to 1.6, more preferably about 0.9 to 1.3.

The method for producing polyamide polyamine-epihalohydrin resin includes, for example, adding epihalohydrin to polyamide polyamine to perform an addition reaction and then subjecting it to a crosslinking reaction.

The method of adding epihalohydrin is preferably dropwise addition from the viewpoint of inhibiting gelation during the addition reaction with polyamide polyamine, and the dropping time is preferably 0.5 to 5 hours.

The conditions of the addition reaction are not particularly limited, but from the viewpoint of preferentially advancing the reaction, the ideal temperature is, for example, about 5 to 40°C. In addition, the reaction time is preferably about 0.5 to 24 hours, more preferably about 2 to 24 hours. In addition, the reaction temperature can also be appropriately set by heating or cooling. In addition, the concentration of the reaction solution in the addition reaction is not particularly limited, but is preferably about 30 to 70% by weight.

Next, the liquid after the addition reaction is subjected to a crosslinking reaction, but in order to control the viscosity of the resulting polyamide polyamine-epihalohydrin resin, it is desirable to add water after the addition reaction is completed. When adding water, the concentration of the reaction solution is preferably about 20 to 40% by weight.

The conditions of the cross-linking reaction, for example, the ideal temperature is about 40-80°C, more preferably about 40-70°C. In addition, the reaction time is preferably about 2 to 10 hours, more preferably about 2 to 6 hours. In addition, the reaction time can also be managed by measuring the viscosity of the reaction solution with a B-type viscometer.

In addition, in the above-mentioned crosslinking reaction, an amine may be added on the way.

The amine is not particularly limited, and examples thereof include alkanol primary amines such as monoethanolamine and monoisopropanolamine; diethanolamine, diisopropanolamine, di-2-hydroxybutylamine, N-methylethanolamine, N-ethyl Alkanol secondary amines such as ethanolamine and N-benzyl ethanolamine; alkanol tertiary amines such as triethanolamine and tripropanolamine; saturated aliphatic primary amines such as methylamine, ethylamine and n-propylamine; dimethylamine and diethylamine , di-n-propylamine and other saturated aliphatic secondary amines; trimethylamine, triethylamine, tri-n-propylamine and other saturated aliphatic tertiary amines, etc. These may be used alone or in combination of two or more. In addition, the amount of the amine used is preferably 10 parts by weight or less based on the weight of the solid content relative to 100 parts by weight of the polyamide polyamine.

In addition, in the above-mentioned production method, the above-mentioned amine, pH adjuster, water, etc. may be added after obtaining the polyamide polyamine-epihalohydrin resin. Water includes the water described in the above paragraphs. These may also be added after completion of the crosslinking reaction, simultaneously with cooling, or after cooling.

The pH adjuster is not particularly limited, and examples thereof include inorganic acids such as sulfuric acid, nitric acid, and phosphoric acid; organic acids such as formic acid and acetic acid; inorganic bases such as sodium hydroxide and potassium hydroxide; methylamine, ethylamine, diethylamine, triethylamine, and the like; Organic bases such as amines; ammonia solution, etc. These may be used alone or in combination of two or more. Also, the pH is not particularly limited, but it is preferably about 2.5 to 4 from the viewpoint of suppressing thickening of the polyamide polyamine-epihalohydrin resin during standing.

Various known additives such as defoamers, antioxidants, preservatives, and chelating agents can be further added to the obtained polyamide polyamine-epihalohydrin resin.

The physical properties of the polyamide polyamine-epihalohydrin resin are not particularly limited. For example, the solid content concentration is usually about 5 to 40% by weight, preferably about 10 to 30% by weight.

In addition, from the viewpoint of storage stability, the viscosity of an aqueous solution having a solid content concentration of 25% by weight of polyamide polyamine-epihalohydrin resin at a temperature of 25° C. is usually about 10 to 500 mPa·s.

[About (meth)acrylamide-based polymers having amino groups] The (meth)acrylamide-based polymer having an amine group is a polymer containing (meth)acrylamide and a polymerizable monomer having an amine group as reaction components.

(Meth)acrylamide includes methacrylamide and acrylamide. These may be used alone or in combination of two or more.

The amount of (meth)acrylamide used is desirably 60-99 mol%, more preferably 70-99 mol%, taking all the constituent monomers as 100 mol%. Here, "all constituent monomers" refers to all monomers used in the production of the (meth)acrylamide-based polymer having an amine group.

As the polymerizable monomer with amine groups, various known components can be used, for example: polymerizable monomers with secondary amine groups, polymerizable monomers with tertiary amine groups, and combinations of these polymerizable monomers. Quaternary ammonium salt, etc. These may be used alone or in combination of two or more.

The polymerizable monomer having a secondary amino group includes, for example, diallylamine and the like.

Polymerizable monomers with tertiary amino groups, for example: N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, etc. Tertiary amino (meth)acrylates; N,N-dimethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, etc. (Meth)acrylamide with tertiary amino groups, etc. These may be used alone or in combination of two or more.

The quaternary ammonium salts of these monomers refer to substances obtained by reacting the above-mentioned polymerizable monomers having secondary amine groups or polymerizable monomers having tertiary amine groups with a quaternizing agent, etc., quaternary ammonium salts, It may be an inorganic acid salt such as hydrochloride or sulfate, or may be an organic acid salt such as acetate. Moreover, examples of the quaternization agent include methyl chloride, benzyl chloride, dimethyl sulfate, epichlorohydrin, and the like. These may be used alone or in combination of two or more. Among them, polymerizable monomers with tertiary amine groups and/or their quaternary ammonium salts are ideal, and (meth)acrylates with tertiary amine groups and/or four of the (meth)acrylates are more ideal. Grade ammonium salt, more ideally N,N-dimethylaminoethyl (meth)acrylate, quaternary ammonium salt of N,N-dimethylaminoethyl (meth)acrylate, especially acrylic acid N,N-Dimethylaminoethyl acrylate, N,N-Dimethylaminoethyl acrylate, benzyl chloride, N,N-dimethylaminoethyl methacrylate, benzyl chloride. Moreover, "(meth)acrylate" means methacrylate or acrylate.

The amount of the polymerizable monomer having an amino group is preferably 0.5-10 mol%, more preferably 0.5-7 mol%, taking the total of all constituent monomers as 100 mol%.

The above-mentioned reaction components may further contain a polymerizable monomer having a carboxyl group, a polymerizable monomer having a sulfonic acid group, a cross-linking monomer, and other monomers.

Examples of polymerizable monomers having a carboxyl group include (meth)acrylic acid, itaconic acid, itaconic anhydride, fumaric acid, and maleic acid. In addition, the polymerizable monomer having a carboxyl group can be used in the form of salts such as alkali metal salts such as sodium and potassium, and ammonium salts. These may be used alone or in combination of two or more.

The amount of the polymerizable monomer having a carboxyl group is preferably 5 mol % or less, more preferably 3 mol % or less, with the total of all constituent monomers being 100 mol %.

Examples of polymerizable monomers having sulfonic acid groups include polymerizable monomers having sulfonic acid groups such as vinylsulfonic acid and methallylsulfonic acid. In addition, the polymerizable monomer having a sulfonic acid group can be used in the form of salts such as alkali metal salts such as sodium and potassium, and ammonium salts. These may be used alone or in combination of two or more.

The amount of the polymerizable monomer having a sulfonic acid group is preferably 5 mol % or less, more preferably 3 mol % or less, taking the total of all constituent monomers as 100 mol %.

Cross-linking monomers, for example: N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-tris N-alkyl (meth)acrylamide such as butyl (meth)acrylamide; N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide N,N-dialkyl(meth)acrylamide such as amide, N,N-diisopropyl(meth)acrylamide; N,N'-methylenebis(meth)acrylamide , N,N'-ethylenebis(meth)acrylamide and other N,N'-alkylenebis(meth)acrylamide; triallyl isocyanurate, trimellitic acid tris Allyl ester, triallylamine, triallyl (meth)acrylamide and other cross-linking monomers with triallyl; 1,3,5-triacryl-1,3,5 - Triazine, 1,3,5-triacryloylhexahydro-1,3,5-triazine, etc. Triazines having a (meth)acryloyl group, etc. These may be used alone or in combination of two or more.

The amount of the cross-linking monomer used is preferably 5 mol % or less, more preferably 2 mol % or less, taking the total of all constituent monomers as 100 mol %.

Other monomers are not particularly limited, and examples thereof include polymerizable monomers having an aromatic ring such as styrene, α-methylstyrene, and vinyl toluene; methyl (meth)acrylate, ethyl (meth)acrylate, Alkyl (meth)acrylates such as n-propyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, etc.; vinyl acetate , vinyl propionate and other carboxylic acid vinyl esters; acrylonitrile and other nitriles; 2-mercaptoethanol, n-dodecyl mercaptan and other mercaptans; ethanol, isopropanol, n-pentanol and other alcohols; α-methylstyrene Aromatic compounds such as dimers, ethylbenzene, cumene, and cumene; carbon tetrachloride, etc. These may be used alone or in combination of two or more. Also, the total of all constituent monomers is taken as 100 mol%, and the usage-amount of other monomers is less than 5 mol%.

In the manufacture of polymers, organic acids such as citric acid, succinic acid, and oxalic acid; acid; sodium hydroxide, potassium hydroxide, calcium hydroxide and other inorganic bases; defoamers, antioxidants and other additives. These may be used alone or in combination of two or more, and the content is preferably 15 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of all the constituent monomers.

The (meth)acrylamide-based polymer having an amine group can be obtained by polymerizing a monomer including (meth)acrylamide and a polymerizable monomer having an amine group in a solvent.

The above-mentioned polymerization method is not particularly limited, and examples thereof include a method of only using drop polymerization, or a method of combining simultaneous polymerization (adding the monomer mixture at one time) and drop polymerization, and the like.

The dropping polymerization method is a method in which a monomer mixture is added dropwise to a reaction system in which a solvent such as water has been added in advance, and only methods using this polymerization method include, for example, the following (1) to (3). Moreover, dropwise addition may be continuous dropwise addition, and dropwise addition may be continued after stopping in the middle of dropwise addition and polymerizing for a certain period of time. (1) The method of dropwise adding the monomer mixture of all monomer components (2) The method of preparing two or more kinds of monomer mixtures and adding them dropwise at the same time (3) The method of preparing two or more kinds of monomer mixtures and adding them sequentially

Moreover, the method of combining the simultaneous polymerization method and the dropwise polymerization method includes, for example, the following (4) to (7). (4) A method in which each monomer mixture is separately and simultaneously polymerized and then mixed with each polymer (5) The method of adding the remaining monomer mixture dropwise after simultaneous polymerization of more than one monomer mixture (6) A method in which one or more monomer mixtures are simultaneously polymerized and the remaining monomer mixture is added dropwise to polymerize (7) A method in which one or more monomer mixtures are dropwise polymerized, and the remaining monomer mixture is added at one time and then polymerized simultaneously

As a solvent, water, an organic solvent, etc. are mentioned, These may be used individually or in combination of 2 or more types. The organic solvent is not particularly limited, and examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, tertiary butanol, isobutanol, n-hexanol, n-octanol, ethylene glycol, Alcohols such as propylene glycol, diethylene glycol, triethylene glycol, and diacetone alcohol; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Among them, water is desirably used.

The polymerization initiator is not particularly limited, and examples thereof include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate; 2,2'-azobis(2-amidinopropane) hydrochloride, 2,2' -Azo compounds such as azobis[2(2-imidazolin-2-yl)propane]hydrochloride; hydrogen peroxide, etc. These may be used alone or in combination of two or more. Among these, ammonium persulfate, potassium persulfate, and 2,2'-azobis(2-amidinopropane) hydrochloride are preferable from the viewpoint of sufficiently advancing solution polymerization. Moreover, the addition method of a polymerization initiator is not specifically limited either, One time addition, batch addition, continuous dripping, etc. can be selected suitably. Also, the content of the polymerization initiator is not particularly limited, and is usually about 0.001 to 5 parts by weight, preferably about 0.01 to 1 part by weight, based on 100 parts by weight of all the constituent monomers.

The polymerization conditions are not particularly limited, for example, the temperature is about 50 to 100° C., and the time is about 1 to 8 hours.

The physical properties of the obtained (meth)acrylamide polymer having amine groups, for example, the weight average molecular weight is usually 500,000-7 million, ideally 1 million-6 million. The "weight-average molecular weight" here refers to a value obtained by gel permeation chromatography (GPC).

In addition, the viscosity of the (meth)acrylamide polymer having amine groups is usually 500-150,000 mPa·s, ideally 1,500-100,000 mPa·s. The "viscosity" here refers to the value measured with a B-type viscometer by using a solution with a solid content concentration of 15% by weight and pre-adjusting the solution to a temperature of 25°C.

Among them, from the viewpoint that the paper obtained by using a rosin-based sizing agent for papermaking exhibits a good sizing effect, it is desirable to contain an alkylene polyamine-epihalohydrin resin and/or a polyamide polyamine-epihalohydrin resin. resin.

The content of the component (D) is preferably 1 to 20 parts by weight based on the weight of the solid content relative to 100 parts by weight of the component (A) from the viewpoint that the rosin-based sizing agent for papermaking exhibits excellent storage stability. , preferably 5 to 10 parts by weight.

The rosin-based sizing agent for papermaking of this invention is obtained by mixing (A) component, (B) component, (C) component, and (D) component. The mixing of these components may be performed in one batch or in batches, and may be performed simultaneously with heating or cooling as necessary. In addition, the temperature at the time of mixing is preferably 20 to 40° C., and the time is preferably 30 to 180 minutes. Among them, from the viewpoint that the obtained rosin-based sizing agent for papermaking exhibits excellent storage stability and the paper obtained by using the sizing agent also exhibits a good sizing effect, it is desirable to combine (A) component and ( The production method of adding (C) component after mixing component B) and then adding (D) component and mixing.

In addition, paper strengthening agents such as cellulose such as carboxymethyl cellulose, polyvinyl alcohols, and water-soluble polymers such as sodium alginate, antislip agents, and preservatives may be added to the rosin-based sizing agent for papermaking of the present invention. , antirust agent, pH regulator, defoamer (silicone defoamer, etc.), thickener, filler, antioxidant, water-resistant agent, film-forming aid, pigment, dye, etc.

The physical properties of the rosin-based sizing agent for papermaking of the present invention, for example, when the solid content concentration is 35% by weight, the viscosity measured by a B-type viscometer at a temperature of 25°C is usually about 10 to 100 mPa·s, ideally 20 ~50mPa·s or so.

In addition, the volume average particle size of the rosin-based sizing agent for papermaking is usually about 0.1 to 2 μm, preferably about 0.4 to 1 μm.

Furthermore, the zeta potential of the rosin-based sizing agent for papermaking is usually about 5 to 50 mV, preferably about 15 to 30 mV. The zeta potential here refers to the value measured with a commercially available zeta potentiometer.

The paper of the present invention can be obtained by using the rosin-based sizing agent for papermaking of the present invention. The sizing method includes internal sizing, surface sizing and combinations thereof.

In internal sizing, the rosin-based sizing agent for papermaking of the present invention is added to pulp slurry, and papermaking is performed in an acidic region or even a neutral region. In addition, the usage-amount of the rosin-based sizing agent for papermaking of this invention is not specifically limited, Usually, it is the range of about 0.05-3 weight% with respect to the dry weight of pulp. In addition, the type of pulp is not particularly limited, and examples include chemical pulp such as hardwood pulp (LBKP) and softwood pulp (NBKP); groundwood pulp (GP), refined pulp (RGP), and thermomechanical pulp (TMP). ) and other mechanical pulp; corrugated cardboard waste paper and other waste paper pulp. In addition, when sizing internally, the fixing agent is ideally aluminum sulfate and/or aluminum hydroxide. In addition, the pH of the pulp slurry can be adjusted by sulfuric acid, sodium hydroxide, and the like. In addition, other sizing agents, such as epichlorohydrin modified styrene-dimethylaminoethyl methacrylate polymer, alkenyl succinic anhydride, alkyl ketene dimer, fatty acid- Modified epichlorohydrin of polyalkyl polyamine condensate, etc. In addition, other paper strength enhancers, such as starches such as cationized starch, polyacrylamide paper strength enhancers, and epichlorohydrin-modified styrene-dimethylaminoethyl methacrylate polymers can be used in combination. Polymer, Mannich modified polyacrylamide, acrylamide-dimethylaminoethyl methacrylate polymer, Hoffmann decomposition polyacrylamide, dialkyl diallyl Polymers of ammonium chloride and sulfur dioxide, etc. In addition, fillers such as talc, clay, kaolin, titanium dioxide, and calcium carbonate can be added to the pulp slurry.

In surface sizing, the rosin-based sizing agent for papermaking of the present invention is diluted to a solid content concentration of about 0.01 to 2% by weight to form a sizing liquid, which is coated on the base paper by various known methods. The coating method is not particularly limited, and examples thereof include a size press method, a gate roll coating method, a bar coating method, a calendar method, and a spray coating method. In addition, the size press method includes, for example, a twin-roll size press coating method and a bar metering size press coating method. In addition, the coating amount (solid content) of the sizing liquid is not particularly limited, but it is usually about 0.001 to 2 g/m ² , preferably about 0.005 to 0.5 g/m ² . In addition, the base paper is not particularly limited, and for example, uncoated paper made of wood cellulose fibers can be used. In addition, the pulp constituting the base paper includes the above-mentioned pulps. In addition, the base paper may be a base paper obtained by making paper using one selected from the group consisting of the above-mentioned fixing agent, a sizing agent other than the rosin-based sizing agent for papermaking of the present invention, a paper strength enhancer, and a filler; It may be a base paper obtained by coating the sizing agent and/or paper strengthening agent on the surface.

The paper of the present invention can be used in various products according to basis weight. For example, paper with a low to medium basis weight of about ²⁰ to 150g/m2 can be used as form paper, PPC paper, heat-sensitive recording base paper and pressure-sensitive recording base paper, etc.; coated paper, cast coated paper, Coated paper such as high-quality coated paper; packaging paper such as kraft paper and pure white roll paper; western paper such as notebook paper, book paper, printing paper, newspaper paper, etc. In addition, paper with a high basis weight above 150g/ ^m2 can be used as Manila cardboard, white cardboard, gray cardboard, backing cardboard, core paper, etc., for example. [Example]

Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited. In addition, "%" is based on weight unless otherwise specified.

(viscosity) The viscosity of the sample kept at 25°C was measured using a Brookfield rotational viscometer (product name "VISCOMETER TVK-10", manufactured by Toki Sangyo Co., Ltd.).

(volume average particle size) The volume average particle diameter of the emulsion was measured by a laser diffraction/scattering method with a particle diameter measuring device (device name "LASER DIFFRACTION PARTICLE SIZE ANALYZER SALD-7500nano", manufactured by Shimadzu Corporation).

(Zeta potential) For samples in which ion-exchanged water was added to the rosin-based sizing agent for papermaking so that the solid content concentration was 1%, a commercially available Zeta potentiometer (trade name: "LAZER ZEE METER MODEL501", PEN KEM Inc. company) to measure Zeta potential (Zp, unit: mV).

〔Manufacture of anionic rosin emulsion〕

Manufacturing Example A In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction pipe, and a cooler, 500 g of a melt of gum rosin produced in China at about 160°C and 20 g of maleic acid were added, and they were reacted at 200°C while stirring under a nitrogen stream. hours, thus obtaining maleic acid modified rosin.

Manufacturing Example B Add fumaric acid 20g, carry out with the same method among the manufacture example A, obtain fumaric acid modified rosin.

Manufacturing Example C In the same reaction vessel as in Production Example A, 663.2 g of Chinese gum rosin and 55.6 g of glycerin were added, and 10 g of NOCRAC300 (manufactured by Ouchi Shinshin Chemical Co., Ltd.) as an antioxidant and p-toluenesulfonic acid as a catalyst were added. 0.1 g was reacted at 270° C. for 15 hours while stirring under a nitrogen stream, thereby obtaining rosin glyceride.

Manufacturing Example D In the same reaction vessel as in Production Example A, add 30.5 g (5 mole %) of n-butyl acrylate, 33.8 g (5 mole %) of n-butyl methacrylate, 142.8 g (30 mole %) of methyl methacrylate mol%), styrene 59.5g (12 mol%), α-methylstyrene 73.1g (13 mol%), methacrylic acid 153.5g (30 mol%) and sodium methallyl sulfonate 37.6g (5 mol%), 1563.6g of water, 8.6g of n-dodecyl mercaptan as a chain transfer agent (0.9 mol% relative to the total mole of the polymerization components), stirring while bubbling with nitrogen , heated up to 80°C. Next, 25.2 g of ammonium persulfate (APS) was added, and the temperature was raised to 90° C., followed by stirring for 100 minutes, and then 10.1 g of ammonium persulfate (APS) was added, followed by further stirring for 60 minutes. 118.9 g of a 48% sodium hydroxide aqueous solution was added to neutralize unreacted methacrylic acid, water was added so that the solid content concentration became 25%, and cooling was performed to obtain a saponified product (StMAA) of a styrene-methacrylic acid polymer.

Manufacturing Example 1 In the same reaction vessel as in Production Example A, 100 g of maleic acid-modified rosin was added, and heated and melted at about 160°C. Next, sodium polyoxyethylene styryl phenyl ether sulfosuccinate (trade name: "HITENOL F-13", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) was slowly added dropwise under stirring (weight of solid content: 5.0 g), Make a W/O emulsion, then add hot water to make a stable O/W emulsion. Then, an anionic rosin-based emulsion (A-1) was obtained by cooling this emulsion to room temperature. The volume average particle diameters of (A-1) are shown in Table 1 (the same applies hereinafter).

Production examples 2 to 12 It was changed to the composition shown in Table 1, and it carried out by the method similar to manufacture example 1, and obtained the anionic rosin type emulsion (A-2) - (A-12), respectively.

※1：乳化劑之使用量係以固體成分重量計之值。 〔Table 1〕

※1: The amount of emulsifier used is based on the weight of solid content.

The abbreviations shown in Table 1 represent the following compounds and the like. ＜(a1) Ingredients＞ ・MnRo: Maleic acid-modified rosin in Production Example A ・FuRo: Fumaric Acid Modified Rosin in Production Example B ・RoEs: Rosin Glyceride in Production Example C ＜(a2) Ingredients＞ ・F-13: Sodium polyoxyethylene styryl phenyl ether sulfosuccinate, trade name: "HITENOL F-13", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd. ・NaOH: Sodium hydroxide aqueous solution (solid content concentration: 48%) ・StMAA: Saponified product of styrene-methacrylic acid polymer in Production Example D

〔Manufacture of polymers with amine groups〕

Production Example E (production of alkylenepolyamine-epihalohydrin resin (D-1)) Add 452.4g (75.4%) of epichlorohydrin, 30.0g (5.0%) of 2-ethylhexylamine, and 157.9g of water to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a reflux condenser, and a nitrogen gas introduction tube. After stirring at room temperature for 30 minutes, 168.0 g (solid content weight: 117.6 g) (19.6%) of an aqueous solution of ethylenediamine with a solid content concentration of 70% was added dropwise over 30 minutes. After heating up to 80 degreeC, it was made to react for 6 hours. To stop the reaction, 28.1 g of concentrated sulfuric acid (solid content concentration: 62.5%) was added, and then 592.7 g of water was added to obtain an aqueous solution of an alkylenepolyamine-epihalohydrin resin (D-1) with a solid content concentration of 40%.

Production example F (production of polyamide polyamine-epihalohydrin resin (D-2)) In the same reaction vessel as in Production Example E, add 730 g (5 moles) of adipic acid and 619 g (6 moles) of diethylenetriamine, and raise the temperature while removing the generated water to the outside of the system. After reacting at 200° C. for 5 hours, 1200 g of water was gradually added to obtain a polyamide polyamine having a solid content concentration of 50%. Next, 400 g of the above-mentioned polyamide polyamine and 91 g of water were added to an apparatus equipped with a thermometer, a cooler, and a stirrer, and the temperature of the liquid was adjusted to 15° C. while stirring. After adding 110 g of epichlorohydrin dropwise over 120 minutes, the temperature was raised to 32° C., and an addition reaction was performed for 5 hours. After adding 475 g of water, the temperature was raised to 60° C., and a crosslinking reaction was performed for 3 hours. Next, 155 g of water and 20 g of concentrated sulfuric acid (solid content concentration: 62.5%) were added and cooled to obtain an aqueous solution of polyamide polyamine-epihalohydrin resin (D-2) with a solid content concentration of 25% and a viscosity of 200 mPa·s.

Production example G (production of (meth)acrylamide-based polymer (D-3) having an amino group) In the same reaction vessel as in Production Example E, 24.9 g (6.0 mol%) of dimethylaminoethyl methacrylate, 346.9 g (92.1 mol%) of 50% acrylamide aqueous solution, and 3.7 g of acrylic acid ( 1.9 mol%), water 284.9g, isopropanol 356.4g, n-dodecyl mercaptan 2.1g (0.4 mol% relative to the total mole of the polymerization components), using concentrated sulfuric acid (solid content concentration: 62.5 %) adjusted to pH 4. Stirring the mixed liquid, the temperature was raised to 60° C. under a nitrogen gas atmosphere. 6.1 g of a 5% ammonium persulfate (APS) aqueous solution was added as a polymerization initiator, the temperature was raised to 78° C., and after holding for 1.5 hours, 1.9 g of a 5% ammonium persulfate (APS) aqueous solution was further added. After further stirring for 1 hour, 200 g of water was added, and isopropanol was evaporated to obtain a (meth)acrylamide polymer (D-3) having an amino group.

Comparative production example (production of anionic (meth)acrylamide polymer (E-2)) In the same reaction vessel as in Production Example E, add 25.0 g (18.3 mol%) of itaconic acid, 8.0 g (4.1 mol %) of 2-ethylhexyl acrylate, 10.0 g (5.7 mol%) of cyclohexyl methacrylate mol%), sodium methallylsulfonate 2.5g (1.5 mol%), acrylamide 52.50g (70.3 mol%), water 220g, isopropanol 250g and 2-mercaptoethanol 0.5g, one side The temperature of the mixed solution was raised to 50°C while bubbling nitrogen gas with stirring. Next, 2.2 g of ammonium persulfate (APS) was added, the temperature was raised to 80° C., and the mixture was stirred for 180 minutes. Water vapor was blown in to evaporate isopropanol, water was added to make the solid content concentration 25%, and cooling was performed to obtain an anionic (meth)acrylamide-based polymer (E-2).

Example 1 Add 287.9 g (solid content: 144.0 g) of anionic rosin-based emulsion (A-1), 72.0 g of water, and polyoxyethylene ten 72.0 g (solid content: 7.2 g) of dialkyl ether (trade name: "NOIGEN XL-80", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) was stirred at 23° C. for 30 minutes. Next, 33.2 g of aluminum sulfate 16 hydrate (solid content: 6.6 g) was added, and after stirring for 30 minutes, 36.0 g (solid content: 14.4 g) of the alkylenepolyamine-epihalohydrin resin of Production Example E was added, Stirring was carried out for 30 minutes to obtain a rosin-based sizing agent for papermaking. The volume average particle diameter and Zeta potential of the obtained rosin-based sizing agent for papermaking are shown in Table 2 (the same applies hereinafter).

Embodiment 2～27, comparative example 1～5 It was changed to the composition shown in Table 2, and it carried out by the method similar to Example 1, and obtained the rosin type sizing agent for papermaking, respectively. In addition, since the sizing agents in Comparative Examples 1 and 2 solidified, the following evaluations were not performed.

＜Storage stability＞ Put 220g of rosin-based sizing agent for papermaking that has been filtered through a 350-mesh metal mesh and let it stand in a thermostat at a temperature of 40°C for 1 week, and filter the resulting condensate through a pre-dried and weighed 350-mesh metal mesh. The amount of filter residue was calculated by Equation 2, and evaluated according to the following criteria. (Formula 2) Filtration residue amount (ppm) = {[(total weight of aggregate after drying and metal mesh) - (weight of pre-dried metal mesh)]/(solid content of rosin-based sizing agent for papermaking Weight)}×1000000

(evaluation standard) 〇: Filtration residue is less than 300ppm △: Filtration residue amount is more than 300ppm and less than 1000ppm ×: Filtration residue amount is 1000ppm or more

<Papermaking Evaluation> Tap water was added to hardwood bleached kraft pulp (hereinafter referred to as L-BKP) so that the pulp had a solid content concentration of 2.0%, and it was beaten with a beater until the Canadian Standard Freeness (CSF) was 300 mL. Then, the obtained pulp slurry was further diluted with tap water, and the solid content concentration was adjusted to 1.0%. In the pulp slurry, 16.0% (dry weight basis, the same below) of filler (mixture of calcium carbonate and talc), 1.5% of aluminum sulfate and 0.3% of commercially available cationic modified Starch, prepared as a pulp slurry with a pH of 5.0. In addition, the pH of the papermaking system was adjusted with an aqueous sulfuric acid solution. Next, to this pulp slurry, each rosin-based sizing agent for papermaking was added at 0.3% (solid content conversion) based on the solid content of the pulp, and a paper machine (Tappi Standard Sheet Machine (round), the same below) was used to carry out Paper was made to obtain wet paper. The wet paper was dehydrated with a roll press (conditions: linear pressure 5.5 kg/cm, conveying speed 2 m/min), and dried at 90° C. for 6 minutes using a rotary dryer. The obtained dried paper was conditioned for 24 hours in a constant temperature and humidity environment (temperature 23°C, humidity 50%) to obtain finished paper (test paper) with a basis weight of 80 g/m ² . Next, for each test paper, the Stockigt sizing degree was measured in accordance with JIS-P8122. The larger the value of Stockigt sizing, the better.

※2：各成分之使用量係以固體成分重量計之值。 〔Table 2〕

※2: The usage amount of each ingredient is based on the weight of solid ingredients.

The symbols shown in Table 2 represent the following compounds. ＜Anionic rosin-based emulsion＞ ・A-1～A-12: Refer to Table 1. ＜Dispersant＞ ・B-1: Polyoxyethylene lauryl ether, trade name: "NOIGEN XL-80", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd. ・B-2: Polyoxyethylene styryl phenyl ether, trade name: "NOIGEN EA-167", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd. ・B-3: Sodium naphthalenesulfonate formaldehyde condensate, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd. ・B-4: Sodium lignosulfonate, manufactured by Kishida Chemical Co., Ltd. ・E-1: Lauryltrimethylammonium chloride, trade name: "CATIOGEN TML", manufactured by Daiichi Pharmaceutical Co., Ltd. ・E-2: Anionic (meth)acrylamide-based polymer in a comparative production example ＜Water-soluble aluminum compound＞ ・C-1: Aluminum sulfate 16 hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ・C-2: Aluminum chloride hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ＜Polymers with amine groups＞ ・D-1: Alkylene polyamine-epihalohydrin resin of Production Example E ・D-2: Polyamide polyamine-epihalohydrin resin of Production Example F ・D-3: Amino group-containing (meth)acrylamide polymer of Production Example G

Claims (6)

A rosin-based sizing agent for papermaking, which is characterized by containing anionic rosin-based emulsion (A), nonionic dispersant and/or anionic dispersant (B) (excluding (meth)acrylamide polymerized dispersant), water-soluble aluminum compound (C) and polymer with amine groups (D). The rosin-based sizing agent for papermaking as described in Claim 1, wherein the component (B) is selected from polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, and polyoxyalkylene styryl phenyl ethers. At least one of the group. The rosin-based sizing agent for papermaking according to claim 1 or 2, wherein the component (D) contains an alkylene polyamine-epihalohydrin resin and/or a polyamide polyamine-epihalohydrin resin. The rosin-based sizing agent for papermaking according to any one of claims 1 to 3, wherein the content of component (B) is 0.5 to 30 wt. share. The rosin-based sizing agent for papermaking according to any one of claims 1 to 4, wherein the content of component (D) is 1 to 20 wt. share. A paper characterized by containing the rosin-based sizing agent for papermaking as described in any one of Claims 1 to 5.