JP2022045340A - Cationic rosin-based emulsion size agent, paper - Google Patents

Abstract

To provide a cationic rosin-based emulsion size agent having excellent emulsifiability and mechanical stability and showing good size effect.SOLUTION: Disclosed is a cationic rosin-based emulsion size agent containing emulsification products of a rosin-based resin (A) and an emulsifier (B) containing a polymer including epihalohydrin (b1), alkylene polyamine (b2), and monoamine (b3) represented by the general formula (1) in reactive components. [formula 1] R1-NH-R2 (In the formula 1, R1 and R2 independently show hydrogen atoms, an alkyl group, a cycloalkyl group, an aryl group, or an arylalkyl group. Here, a case where R1 and R2 are both hydrogen atoms is excluded.)SELECTED DRAWING: None

Description

The present invention relates to a cationic rosin-based emulsion sizing agent and paper.

The rosin-based emulsion sizing agent refers to a composition obtained by emulsifying a rosin-based resin in the presence of various emulsifiers and water, and is classified into a cationic or anionic sizing agent depending on the ionicity of the emulsifier used. .. The paper obtained using this shows a good sizing effect due to the emulsion particles fixed on the pulp fibers.

Among them, as the cationic rosin-based emulsion sizing agent, the rosin-based resin is dispersed with an emulsifier obtained by reacting epihalohydrin with polyalkylpolyamine (Patent Document 1), polyamide polyamine and water-soluble acids (Patent Document 2). Is known. However, with such a technique, the emulsifying property of the rosin-based resin and the emulsifier is poor, and the obtained sizing agent is also inferior in mechanical stability and sizing effect.

Japanese Unexamined Patent Publication No. 5-98001 Japanese Unexamined Patent Publication No. 2012-007284

An object of the present invention is to provide a cationic rosin-based emulsion sizing agent which is excellent in emulsifying property and mechanical stability and exhibits a good sizing effect.

The present inventors have completed the present invention by diligently studying the composition of the emulsifier. That is, the present invention relates to the following cationic rosin-based emulsion sizing agents and papers.

1. 1. An emulsion of a rosin-based resin (A) and an emulsifier (B) containing a polymer containing epihalohydrin (b1), an alkylene polyamine (b2), and a monoamine (b3) represented by the following general formula (1) as reaction components. A cationic rosin-based emulsion sizing agent containing.
[Equation 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 arylalkyl group. In the case where both R ¹ and R ² are hydrogen atoms. except.)

2. 2. (B2) The cationic rosin-based emulsion sizing agent according to item 1 above, wherein the component is an alkylene diamine and / or an alkylene triamine.

3. 3. The cationic rosin-based emulsion size according to the above item 1 or 2, wherein the component (b3) is at least one selected from the group consisting of an aliphatic primary amine, an aliphatic secondary amine and an aromatic primary amine. Agent.

4. The amount of the component (b3) used is 0.3 to 40% by weight based on 100% by weight of the total of the components (b1), (b2) and (b3) in terms of solid content weight. The cationic rosin-based emulsion sizing agent according to any one of.

5. The cationic rosin emulsion size according to any one of the above items 1 to 4, wherein the content of the emulsifier (B) is 3 to 30 parts by weight with respect to 100 parts by weight of the rosin resin (A) in terms of solid content weight. Agent.

6. The cationic rosin-based emulsion sizing agent according to any one of the above items 1 to 5, further comprising a water-soluble aluminum compound (C).

7. Paper containing the cationic rosin-based emulsion sizing agent according to any one of the above items 1 to 6.

According to the cationic rosin-based emulsion sizing agent of the present invention (hereinafter, also simply referred to as “sizing agent”), by using an emulsifier containing a specific amine, it has excellent emulsifying property and mechanical stability. The paper obtained by using the sizing agent also shows a good sizing effect.

The cationic rosin-based emulsion sizing agent of the present invention contains a rosin-based resin (A) and a emulsion of a specific emulsifier (B).

The rosin-based resin (A) (hereinafter, also referred to as resin (A)) is a component that exhibits good emulsifying property and sizing effect of a sizing agent.

Examples of the resin (A) include unmodified rosins such as gum rosin, wood rosin, tall oil rosin, merkusi pine rosin (rosin containing dihydroagatoic acid) and wetland pine rosin (rosin containing comic acid), hydride rosin, α and β. -Unsaturated carboxylic acid-modified rosin, unmodified rosin, or esterified products thereof (unmodified rosin ester, α, β-unsaturated carboxylic acid-modified rosin ester, unmodified rosin ester) and the like can be mentioned. These may be used alone or in combination of two or more. Above all, from the viewpoint that paper exhibits a good size effect, it is preferable to contain at least one selected from the group consisting of unmodified rosin, α, β-unsaturated carboxylic acid-modified rosin and unmodified rosin ester, and α, β. -It is more preferable to contain unsaturated carboxylic acid-modified rosin.

Further, the resin (A) may be purified by a known vacuum distillation method, steam distillation method, extraction method, recrystallization method or the like.

The α, β-unsaturated carboxylic acid-modified rosin (hereinafter, also simply referred to as carboxylic acid-modified rosin) is an unmodified rosin to which α, β-unsaturated carboxylic acid is added. The α, β-unsaturated carboxylic acid is not particularly limited, and is, for example, α, β-unsaturated dicarboxylic acid such as maleic acid, maleic anhydride, fumaric acid; α, β-unmodified such as acrylic acid and methacrylic acid. Saturated monocarboxylic acid and the like can be mentioned. The amount of the α, β-unsaturated carboxylic acid used is also not particularly limited, and is usually about 1 to 30 parts by weight with respect to 100 parts by weight of the unmodified rosin.

The method for producing the α, β-unsaturated carboxylic acid-modified rosin is not particularly limited, but for example, the unmodified rosin and the α, β-unsaturated carboxylic acid are collectively mixed in a suitable reaction vessel, and then heated and melted. A method of reacting with a Diels-Alder reaction at about 190 to 230 ° C. for about 1 to 3 hours can be mentioned.

The physical properties of the α, β-unsaturated carboxylic acid-modified rosin are not particularly limited, but usually the softening point is about 85 to 140 ° C. and the acid value is about 195 to 320 mgKOH / g because the paper shows a good size effect. The softening point is preferably about 95 to 130 ° C. and the acid value is about 240 to 295 mgKOH / g.

Unmodified rosin ester is a reaction product of unmodified rosin and a polyhydric alcohol.

The polyhydric alcohol is not particularly limited, but a trihydric alcohol and / or a tetrahydric alcohol is preferable, and examples of the former include glycerin, trimethylolethane, trimethylolpropane and 3-methylpentane-1,3,5-triol. Etc., and examples of the latter include pentaerythritol and diglycerin.

The unmodified rosin ester can be produced by various known methods. For example, it is obtained by subjecting unmodified rosin and a polyhydric alcohol to an esterification reaction at 200 to 350 ° C. for 6 to 20 hours. Further, the reaction may be carried out under normal pressure, reduced pressure or pressurized pressure. Further, the ratio of the amount of the unmodified rosin to the polyhydric alcohol used is not particularly limited, but usually, the equivalent ratio [OH _(eq) / COOH _(eq) ] of the former carboxyl group to the latter hydroxy group is 0. It is about 2 to 1.5, preferably about 0.4 to 1.2. Further, in the reaction, an esterification catalyst such as p-toluenesulfonic acid or various antioxidants may be used. Moreover, the reaction may be carried out under a nitrogen stream.

The physical properties of the unmodified rosin ester are not particularly limited, but usually, the softening point is about 80 to 100 ° C., the acid value is about 0 to 25 mgKOH / g, and the hydroxyl value is 0 to 30 mgKOH because the paper shows a good size effect. It is about / g, preferably a softening point of about 85 to 95 ° C., an acid value of about 10 to 20 mgKOH / g, and a hydroxyl value of about 0 to 10 mgKOH / g.

The emulsifier (B) used in the present invention is represented by epihalohydrin (b1) (hereinafter referred to as (b1) component), an alkylene polyamine (b2) (hereinafter referred to as (b2) component), and a general formula (1). It contains a polymer containing a monoamine (b3) (hereinafter referred to as (b3) component) as a reaction component. The alkyl group (including the alkyl group in the cycloalkyl group) in the general formula (1) may have a linear structure or a branched structure.

[Equation 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 arylalkyl group. In the case where both R ¹ and R ² are hydrogen atoms. except.)

The component (b1) is epichlorohydrin, and examples thereof include epichlorohydrin and epibromohydrin. These may be used alone or in combination of two or more.

The component (b2) is an alkylene polyamine, preferably one having at least two primary amino groups. Examples of such the component (b2) include ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,5-pentanediamine (pentamethylenediamine), and 1,6. -Alkylene diamines such as hexanediamine (hexamethylenediamine); alkylene triamines such as diethylenetriamine, dipropylenetriamine and dibutylenetriamine; alkylenetetraamines such as triethylenetetramine and tripropylenetetramine; tris (2-aminoethyl) amines and triss. Tris (2-aminoalkyl) amines such as (2-aminopropyl) amines; alkylenepentamines such as tetraethylenepentamine and tetrapropylenepentamine; alkylenehexamines such as pentaethylenehexamine and the like can be mentioned. These may be used alone or in combination of two or more. Among them, alkylenediamine and alkylenetriamine are preferable, and ethylenediamine, hexamethylenediamine and diethylenetriamine are more preferable, because the emulsifier (B) containing the obtained polymer can emulsify the resin (A) satisfactorily.

The component (b3) is a monoamine represented by the general formula (1). By using the component (b3), the hydrophobicity of the polymer is increased, and the emulsifier (B) containing the polymer is easily compatible with the resin (A), so that the emulsifying property is improved. The resulting sizing agent also exhibits excellent mechanical stability.

[Equation 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 arylalkyl group. In the case where both R ¹ and R ² are hydrogen atoms. except.)

Examples of the component (b3) include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, s-butylamine, t-butylamine, n-pentylamine, n-hexylamine and isohexylamine. , N-Heptylamine, n-octylamine, 2-ethylhexylamine, n-decylamine, n-undecylamine, n-dodecylamine (laurylamine), n-tridecylamine, n-tetradecylamine (myristylamine) , N-Hexadecylamine (palmitylamine), n-stearylamine, isostearylamine and other aliphatic primary amines;
Dimethylamine, diethylamine, ethylmethylamine, din-propylamine, diisopropylamine, din-butylamine, diisobutylamine, dis-butylamine, dit-butylamine, N-methylbutylamine, N-ethylbutylamine, din-pentyl Amine, din-hexylamine, din-heptylamine, din-octylamine, di2-ethylhexylamine, din-decylamine, din-undecylamine, din-dodecylamine (dilaurylamine), di Adipose group such as n-tridecylamine, din-tetradecylamine (dimyristylamine), din-hexadecylamine (dipalmitylamine), din-stearylamine, diisostearylamine, di-cured beef fat amine, etc. Secondary amine;
Alicyclics such as cyclobutylamine, cyclopentylamine, cyclopentylmethylamine, 1-cyclopentylethylamine, 2-cyclopentylethylamine, cyclohexylamine, cyclohexylmethylamine, 1-cyclohexylethylamine, 2-cyclohexylethylamine, cycloheptylamine, cyclooctylamine, etc. Primary amine;
Alicyclic secondary amines such as N-methylcyclopentylamine, N-ethylcyclopentylamine, N-propylcyclopentylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, N-propylcyclohexylamine, N-isopropylcyclohexylamine and the like. ;
Aniline, o-toluidine, m-toluidine, p-toluidine, phenylmethylamine (benzylamine), 1-phenylethylamine, 2-phenylethylamine, 1-phenylpropylamine, 2-phenylpropylamine, 3-phenylpropylamine, 4-phenyl Aromas such as butylamine, 1-naphthylamine, 2-naphthylamine, 2-methylnaphthylamine, 1- (aminomethylnaphthalene), 2- (aminomethyl) naphthalene, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene and the like. Primary amine;
N-Methylaniline, N-ethylaniline, N-propylaniline, N-isopropylaniline, N-butylaniline, N-isobutylaniline, N-methylbenzylamine, N-ethylbenzylamine, N-propylbenzylamine, N- Examples thereof include aromatic secondary amines such as isopropylbenzylamine, N-butylbenzylamine, 1- (methylaminomethyl) naphthalene, and 9- (methylamino) methylanthracene.

These (b3) components may be used alone or in combination of two or more. Among them, a polymer having a hydrophobic group derived from the component (b3) (for example, an alkyl group, a cycloalkyl group, etc. (same below)) can be obtained, and the emulsifier (B) containing the polymer makes the resin (A) good. At least one selected from the group consisting of aliphatic primary amines, aliphatic secondary amines and aromatic primary amines is preferable because it can be emulsified into n-octylamine, 2-ethylhexylamine, and din. -Butylamine and benzylamine are more preferable.

The amount of the component (b1), the component (b2) and the component (b3) used is not particularly limited, but from the viewpoint of size performance, the molar amount of the epoxy group of the component (b1) and the component (b2) and (b2) and ( b3) The ratio of the total molar amount of the amino groups of the component, (the molar amount of the epoxy group of the (b1) component) / (the total molar amount of the amino groups of the (b2) component and the (b3) component) = 0.8 to About 1.4 is preferable, and 1 to 1.2 is more preferable.

As for the amount of the component (b3) used, the hydrophobic group derived from the component (b3) is used with respect to 100% by weight of the total of the component (b1), the component (b2) and the component (b3) in terms of solid content weight. 0.3 to 40% by weight is preferable, and 1 to 20% by weight is more preferable, and 5 to 5 to 20% by weight, from the viewpoint that the polymer having the polymer can be obtained and the resin (A) can be satisfactorily emulsified by the emulsifier (B) containing the polymer. 15% by weight is more preferable.

The method for producing the polymer is not particularly limited, but for example, the component (b2) and the component (b3) are first charged and mixed at room temperature, and the component (b1) is added in portions or drops and heated for reaction. Let me.

The reaction conditions are not particularly limited, and the temperature is about 50 to 100 ° C. (preferably about 60 to 90 ° C.), and the time is about 1 to 12 hours (preferably about 2 to 8 hours). be.

In the above-mentioned production method, it is preferable to prepare a reaction solution to which water is added from the viewpoint of reaction control. Examples of water include pure water, ion-exchanged water, tap water, industrial water and the like. These may be used alone or in combination of two or more. When water is added, the reaction concentration is preferably about 40 to 60% by weight, more preferably about 45 to 55% by weight.

Further, the obtained polymer further includes a pH adjuster, an antifoaming agent, an antioxidant, a preservative, a chelating agent, a cationic surfactant other than the polymer, an anionic surfactant, and a nonionic surfactant. Agents and the like may be added.

The physical properties of the polymer are not particularly limited, but for example, the solid content concentration is usually about 20 to 50% by weight, preferably about 30 to 45% by weight.

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

Since the polymer has a hydrophobic group derived from the monoamine component (b3) introduced therein, the emulsifier (B) containing the polymer is highly emulsifying with the resin (A). That is, the resin (A) and the emulsifier (B) are well blended and dispersed to obtain a cationic rosin-based emulsion sizing agent having a low viscosity and a small particle size. Further, the sizing agent is excellent in mechanical stability and sizing effect.

The content of the emulsifier (B) in the sizing agent of the present invention is not particularly limited, but from the viewpoint of good emulsifying property between the resin (A) and the emulsifier (B), 100 parts by weight of the resin (A) is used. The solid content weight is preferably 3 to 30 parts by weight, more preferably 5 to 25 parts by weight.

As a method of dispersing the resin (A) with the emulsifier (B), that is, a method of producing a sizing agent, either a high-pressure emulsification method or an inverted emulsification method can be adopted. As the dispersion medium, alcohol such as ethanol and isopropanol; water is preferably used from the viewpoint of reducing the environmental load, but a mixed solvent of water and an organic solvent may be used.

The organic solvent is not particularly limited as long as it is soluble in water, and for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, and isobutyl alcohol. , N-hexyl alcohol, n-octyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, diacetone alcohol and other alcohols; ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and other ethers. Can be mentioned. These may be used alone or in combination of two or more. When an organic solvent is contained, the content thereof is preferably less than 10% by weight.

In the case of the high-pressure emulsification method, the resin (A) forming the dispersed phase is melted or dissolved in an organic solvent such as benzene or toluene, and then the emulsifier (B) is added thereto at the above-mentioned usage ratio and at the same time, warm water is used. Can be obtained as it is or by distilling off an organic solvent after mixing and emulsifying using a high-pressure emulsifier.

In the case of the reverse emulsification method, after the solid resin (A) and the emulsifier (B) are sufficiently kneaded, warm water is gradually added dropwise with stirring, and the phase is inverted to form an organic solvent and special emulsification. The dispersion can be obtained without using an apparatus. The solid content concentration of the dispersion is not particularly limited, but is usually 10 to 50% by weight, and can be diluted with water and used if necessary.

The sizing agent of the present invention may further contain a water-soluble aluminum compound (C) (hereinafter referred to as aluminum compound (C)). The aluminum compound (C) may be added when the resin (A) is dispersed with the emulsifier (B), or may be added after obtaining a cationic rosin-based emulsion sizing agent.

As the aluminum compound (C), for example, it is preferable to use at least one selected from aluminum sulfate, aluminum hydroxide, aluminum chloride, basic aluminum sulfate, basic aluminum chloride, aluminum silicate sulphate and polymers thereof. .. Among these, aluminum sulfate is preferable from the viewpoint of cost.

The content of the aluminum compound is 1 to 20 weight by weight with respect to 100 parts by weight of the component (A) in terms of solid content weight from the viewpoint of showing a good size effect when the obtained sizing agent is used to make paper. Parts are preferable, and 5 to 15 parts by weight are more preferable.

In addition, the sizing agent of the present invention includes, for example, a paper strength enhancer such as celluloses such as carboxymethyl cellulose, polyvinyl alcohols, polyacrylamides, and water-soluble polymers such as sodium alginate, antifoaming agents, preservatives, and antiseptic agents. Rust agents, pH adjusters, defoaming agents (silicone-based defoaming agents, etc.), thickeners, fillers, antioxidants, water resistant agents, film-forming aids, pigments, dyes and the like can be added.

The other physical properties are not particularly limited, and the viscosity of the sizing agent at a solid content concentration of 35% by weight and a temperature of 25 ° C. on a B-type viscometer is usually about 10 to 200 mPa · s, preferably 10 to 100 mPa · s. It is about s.

Further, the volume average particle size of the sizing agent is usually about 0.1 to 2 μm, preferably about 0.4 to 1.5 μm. The volume average particle diameter is a value measured by a particle diameter measuring device by a laser diffraction / scattering method.

The paper of the present invention is obtained by using the sizing agent of the present invention. Examples of the sizing method include internal sizing and surface sizing, and a combination thereof.

In the internal sizing, the sizing agent of the present invention is added to the pulp slurry, and the paper is made in the acidic region or the neutral region. The amount of the sizing agent used in the present invention is not particularly limited, but is usually in the range of about 0.05 to 3% by weight with respect to the dry weight of the pulp. The type of pulp is not particularly limited, and chemical pulp such as broadleaf pulp (LBKP) and coniferous pulp (NBKP), machine pulp such as crushed wood pulp (GP), refiner ground pulp (RGP), and thermomechanical pulp (TMP). , Waste paper pulp such as used cardboard, and the like. Further, in the case of internal sizing, aluminum sulfate and / or aluminum hydroxide is preferable as the fixing agent. Further, the pH of the pulp slurry can be adjusted with sulfuric acid, sodium hydroxide or the like. Other neutral sizing agents include, for example, epichlorohydrin modified products of styrene-dimethylaminoethyl methacrylate copolymer, alkenyl succinic anhydride, alkyl ketene dimer, and epichlorohydrin of fatty acid-polyalkyl polyamine condensate. A modified product or the like can be used in combination. In addition, as other paper strength enhancers, for example, starches such as cationized starch, polyacrylamide-based paper strength enhancer, epichlorohydrin modified product of polyamide polyamine resin, epichlorohydrin modified product of dicyandiamide resin, etc. Epichlorohydrin modified product of styrene-dimethylaminoethyl methacrylate copolymer, Mannig modified product of polyacrylamide, acrylamide-dimethylaminoethyl methacrylate copolymer, Hoffman decomposition product of polyacrylamide, dialkyldialylammonium chloride and sulfur dioxide A copolymer or the like can be used in combination. Further, fillers such as talc, clay, kaolin, titanium dioxide and calcium carbonate can be added to the pulp slurry.

In the surface sizing, the sizing agent 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 means. The coating method is not particularly limited, and examples thereof include a size press method, a gate roll method, a bar coater method, a calendar method, and a spray method. In addition, examples of the size press method include a two-roll size press coating method and a rod metering size press coating method. The coating amount (solid content) of the size liquid is not particularly limited, but is usually about 0.001 to 2 g / m ² , preferably about 0.005 to 0.5 g / m ² . Further, the base paper is not particularly limited, and for example, uncoated paper made from wood cellulose fiber can be used. Further, examples of the pulp constituting the base paper include those described above. Further, the base paper may be paper-made using one selected from the group consisting of the fixing agent, the neutral sizing agent, the paper strength agent and the filler, and the neutral sizing agent and / or the paper. The surface may be coated with a force agent.

The paper of the present invention is provided in various products according to the basis weight. For example, low to medium basis weight adult paper of about 20 to 150 g / m ² is, for example, recording paper such as foam paper, PPC paper, heat-sensitive recording base paper and pressure-sensitive recording base paper; art paper, cast-coated paper, and high-quality coated paper. Coated paper such as kraft paper, wrapping paper such as pure white roll paper; Western paper such as notebook paper, book paper, printing paper, newspaper paper and the like. Further, the adult paper having a high basis weight of 150 g / m ² or more can be used as, for example, a paperboard for Manila balls, white balls, chip balls, liners, cores and the like.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, "%" is based on weight.

(viscosity)
Using a Brookfield rotational viscometer (product name: "VISCOMETER TVK-10", manufactured by Toki Sangyo Co., Ltd.), the viscosities of emulsifiers and sizing agents kept at 25 ° C. were measured.

Production Example A (Production of maleic acid-modified rosin (A-1))
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube and a cooler, 500 g of a melt of Chinese gum rosin at about 160 ° C. and 20 g of maleic acid were charged, and the reaction was carried out at 200 ° C. for 2 hours while stirring under a nitrogen stream. The maleic acid-modified rosin (A-1) was obtained.

Production Example a (Production of fumaric acid-modified rosin (A-3))
In Production Example A, 20 g of fumaric acid was charged and carried out in the same manner to obtain fumaric acid-modified rosin (A-3).

Production Example C (Production of rosin ester (A-4))
In the same reaction vessel as in Production Example A, 663.2 g of Chinese gum rosin and 55.6 g of glycerin were charged, 10 g of Nocrack 300 (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) as an antioxidant, and paratoluene as a catalyst. Rosin ester (A-4) was obtained by adding 0.1 g of sulfonic acid and reacting at 270 ° C. for 15 hours with stirring under a nitrogen stream.

Production Example 1
452.4 g (75.4 wt%) of epichlorohydrin, 30.0 g (5.0) of 2-ethylhexylamine in a reaction vessel equipped with a stirrer, thermometer, dropping funnel, reflux condenser and nitrogen gas introduction tube. After charging 157.9 g of water (% by weight) and stirring at room temperature for 30 minutes, 168.0 g (19.6% by weight) of ethylenediamine was added dropwise over 30 minutes. After raising the temperature to 80 ° C., the reaction was carried out for 6 hours. In order to stop the reaction, 28.1 g of a sulfuric acid aqueous solution having a solid content concentration of 62.5% was added, and then 592.7 g of water was further added to obtain an aqueous solution of the polymer (B-1) having a solid content concentration of 40%. rice field. The viscosities of the aqueous solution of the polymer (B-1) are shown in Table 1 (the same applies hereinafter).

Production Examples 2 to 20, Comparative Production Examples 1 to 4
The composition shown in Table 1 was carried out in the same manner as in Production Example 1, and the aqueous solutions of the polymers (B-2) to (B-20) having a solid content concentration of 40% and the polymers (D-1) to (D-) were used. The aqueous solution of 4) was obtained respectively.

The abbreviations shown in Table 1 mean the following compounds.
(B1) component ・ ECH: epichlorohydrin (b2) component ・ EDA: ethylenediamine ・ HMDA: hexamethylenediamine ・ DETA: diethylenetriamine (b3) component ・ 2EHA: 2-ethylhexylamine ・ n-OA: n-octylamine ・BnA: benzylamine, DBA: din-butylamine

Comparative manufacturing example 5
In the same reaction vessel as in Production Example 1, 730 g (5 mol) of adipic acid and 619 g (6 mol) of diethylenetriamine were charged, the temperature was raised while removing the generated water from the system, and the reaction was carried out at 120 to 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 charged into an apparatus equipped with a thermometer, a cooler and a stirrer, and the liquid temperature was adjusted while stirring so as to be 15 ° C. After 110 g of epichlorohydrin was added dropwise over 120 minutes, the temperature was raised to 32 ° C. and an addition reaction was carried out for 5 hours. After further adding 475 g of water, the temperature was raised to 60 ° C. and a crosslinking reaction was carried out for 3 hours. Then, 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 a polymer (D-5) having a solid content concentration of 25% and a viscosity of 200 mPa · s.

The aqueous solutions of the polymers (B-1) to (B-20) and the aqueous solutions of the polymers (D-1) to (D-5) were used as they were as emulsifiers.

Example 1
100 g of maleic acid-modified rosin (A-1) was charged in the same reaction vessel as in Production Example 1 and melted by heating at about 160 ° C. Then, under stirring, an aqueous solution of the emulsifier (B-1) (solid content weight 10.0 g) is gradually added dropwise to form a W / O form emulsion, and hot water is further added to form a stable O / W type emulsion. And said. Then, the emulsion was cooled to room temperature to obtain a cationic rosin-based emulsion sizing agent having a solid content concentration of 35%. The physical characteristics are shown in Table 2 (the same applies hereinafter).

Examples 2 to 26, 29 to 33, Comparative Examples 1 to 5
Using the rosin-based resin and emulsifier shown in Table 2, the same method as in Example 1 was carried out to obtain a cationic rosin-based emulsion sizing agent having a solid content concentration of 35%. In Comparative Examples 1 and 5, since a residue of the rosin-based resin was generated during emulsification, it was not subjected to the following evaluation.

Examples 27, 28
Using the rosin-based resin and emulsifier shown in Table 2, the same method as in Example 1 was carried out to obtain a cationic rosin-based emulsion sizing agent having a solid content concentration of 35%. Next, 10 g of the water-soluble aluminum compound shown in Table 2 (solid content weight with respect to 100 g of the resin (A)) was mixed with the obtained sizing agent, and the mixture was stirred at room temperature for 30 minutes.

(Volume average particle size)
The measurement was performed with a particle size measuring device (device name "LASER DIFFRACTION PARTICLE SIZE ANALYZER SALD-7500no", manufactured by SHIMADZU) by a laser diffraction / scattering method. The results are shown in Table 2 (the same applies hereinafter).

(Mechanical stability)
50 g of each size agent was weighed in a container of a Marlon type stability tester (manufactured by Shinsei Sangyo Co., Ltd.), and the temperature was 25 ° C., the load was 10 kg, and the rotation speed was 1000 r. p. m. After vigorous stirring for 5 minutes, the agglomerates formed were collected by filtration through a 350 mesh wire mesh, values were calculated according to Equation 2, and evaluated according to the following criteria.
(Equation 2) Mechanical stability (%) = (absolute dry weight of aggregate / absolute dry weight of sizing agent) x 100
(Evaluation criteria)
⊚: The value obtained by the formula 2 is less than 0.5% 〇: The value obtained by the formula 2 is 0.5% or more and less than 1.0% Δ: The value obtained by the formula 2 is 1.0% or more. Less than 5.0% ×: The value obtained by Equation 2 is 5.0% or more.

<Papermaking evaluation>
Add tap water in an amount that makes the solid content concentration of the pulp 2.0% to hardwood bleached kraft pulp (hereinafter referred to as L-BKP), and use a beater to obtain Canadian Standard Freeness (CSF). It was beaten until it became 300 ml. Then, the obtained pulp slurry was further diluted with tap water to adjust the solid content concentration to 1.0%. In this pulp slurry, 16.0% (absolute dry weight standard, the same applies hereinafter) filler (mixture of calcium carbonate and talc), 1.5% aluminum sulfate, and 0.3% based on the pulp solid content. A commercially available cation-modified starch was added to prepare a pulp slurry having a pH of 5.0. The pH of the papermaking system was adjusted with an aqueous sulfuric acid solution.
Next, each sizing agent was added to the pulp slurry so as to be 0.3% (solid content equivalent) with respect to the pulp solid content, and a paper machine (Tappi Standard Sheet Machine (round shape), the same applies hereinafter) was used. Paper was made and wet paper was obtained. The wet paper was dehydrated with a roll press machine (conditions: linear pressure 5.5 kg / cm, feeding speed 2 m / min), and dried at 90 ° C. for 6 minutes using a rotary dryer. The obtained dried paper was humidity-controlled for 24 hours in a constant temperature and humidity (temperature 23 ° C., humidity 50%) environment to obtain an adult paper (test paper) having a basis weight of 80 g / m ² .
Then, for each test sheet, the degree of sutehito size was measured according to JIS-P8122. The larger the value, the better the degree of nice human size.

＊１：乳化剤の使用量は、固形分重量で、ロジン系樹脂１００ｇに対する値で示す。
＊２：水溶性アルミニウム化合物の使用量は、固形分重量で、ロジン系樹脂１００ｇに対する値で示す。

* 1: The amount of the emulsifier used is the weight of the solid content and is shown as a value with respect to 100 g of the rosin-based resin.
* 2: The amount of the water-soluble aluminum compound used is the weight of the solid content and is shown as a value with respect to 100 g of the rosin-based resin.

The symbols shown in Table 2 indicate the following compounds.
<Rosin resin>
-A-1: Maleic acid-modified rosin of Production Example A-A-2: Chinese gum rosin-A-3: Fumaric acid-modified rosin of Production Example B-A-4: Rosin ester of Production Example C <Emulsifier>
-See Table 1.
<Water-soluble aluminum compound>
・ C-1: Aluminum sulfate ・ 16 hydrate (manufactured by Wako Pure Chemical Industries, Ltd.)
・ C-2: Polyaluminum chloride (manufactured by Kishida Chemical Co., Ltd.)

Claims (7)

An emulsion of a rosin-based resin (A) and an emulsifier (B) containing a polymer containing epihalohydrin (b1), an alkylene polyamine (b2), and a monoamine (b3) represented by the following general formula (1) as reaction components. A cationic rosin-based emulsion sizing agent containing.
[Equation 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 arylalkyl group. In the case where both R ¹ and R ² are hydrogen atoms. except.) (B2) The cationic rosin-based emulsion sizing agent according to claim 1, wherein the component is an alkylene diamine and / or an alkylene triamine. The cationic rosin-based emulsion according to claim 1 or 2, wherein the component (b3) is at least one selected from the group consisting of an aliphatic primary amine, an aliphatic secondary amine and an aromatic primary amine. Sizing agent. Claims 1 to 40, wherein the amount of the component (b3) used is 0.3 to 40% by weight based on the total solid content weight of 100% by weight of the components (b1), (b2) and (b3). The cationic rosin-based emulsion sizing agent according to any one of 3. The cationic rosin-based emulsion according to any one of claims 1 to 4, wherein the content of the emulsifier (B) is 3 to 30 parts by weight with respect to 100 parts by weight of the rosin-based resin (A) in terms of solid content weight. Sizing agent. The cationic rosin-based emulsion sizing agent according to any one of claims 1 to 5, further comprising a water-soluble aluminum compound (C). A paper containing the cationic rosin-based emulsion sizing agent according to any one of claims 1 to 6.