TW202223200A - Cationic rosin emulsion type sizing agent and paper having excellent emulsifying property and mechanical stability and showing a good sizing effect - Google Patents

Abstract

The present invention provides a cationic rosin emulsion type sizing agent, which is excellent in emulsifying property and mechanical stability and shows a good sizing effect. The cationic rosin emulsion type sizing agent of the present invention is characterized by comprising an emulsification product of a rosin-based resin (A) and an emulsifier (B), wherein the emulsifier (B) contains a polymer containing an epihalohydrin (b1), an alkylene polyamine (b2), and a monoamine (b3) represented by the following general formula (1) in the reaction components. [Formula 1] R<1>-NH-R<2> (In Formula 1, R<1> and R<2> independently represent hydrogen atoms, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. Moreover, a case where both R<1> and R<2> are hydrogen atoms is excluded.).

Description

Cationic rosin emulsion type sizing agent, paper

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

Rosin-based emulsion-type sizing agent refers to a composition obtained by emulsification of rosin-based resin in the presence of various emulsifiers and water. According to the ionicity of the emulsifier used, it is classified as cationic or anionic. slurry. The paper obtained by using such a sizing agent exhibits a good sizing effect due to the emulsion particles fixed to the pulp fibers.

Among them, as cationic rosin-based emulsion type sizing agents, emulsifiers obtained by reacting epihalohydrin with polyalkylpolyamine (Patent Document 1), polyamide polyamines and water-soluble acids (Patent Document 2) are known. A substance obtained by dispersing a rosin-based resin. However, in such a technique, the emulsifying properties of the rosin-based resin and the emulsifier are insufficient, and the obtained sizing agent is also inferior in terms of mechanical stability and sizing effect. [Prior Art Literature] [Patent Literature]

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

[Technical problem to be solved by the invention]

An object of the present invention is to provide a cationic rosin-based emulsion-type sizing agent which is excellent in emulsifiability and mechanical stability and exhibits a good sizing effect. [Technical means]

The present inventors completed the present invention by intensively studying the composition of the emulsifier. That is, the present invention relates to the following cationic rosin-based emulsion-type sizing agent and paper.

1. A cationic rosin-based emulsion-type sizing agent is characterized in that the emulsion containing a rosin-based resin (A) and an emulsifier (B), the emulsifier (B) containing an epihalohydrin (b1) in a reaction component. ), an alkylene polyamine (b2), and a polymer of a monoamine (b3) represented by the following general formula (1), [Formula 1] R ¹ -NH-R ² (in formula 1, R ¹ , R ² independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group; in addition, unless R ¹ and R ² are both hydrogen atoms).

2. The cationic rosin-based emulsion-type sizing agent according to the above item 1, wherein the component (b2) is an alkylene diamine and/or an alkylene triamine.

3. The cationic rosin-based emulsion-type sizing agent according to 1 or 2 above, wherein the component (b3) is one selected from the group consisting of aliphatic primary amines, aliphatic secondary amines, and aromatic primary amines above.

4. The cationic rosin-based emulsion-type sizing agent according to any one of the preceding paragraphs 1 to 3, wherein, in terms of solid content weight, relative to the total of the components (b1), (b2) and (b3) 100% by weight, the usage amount of the component (b3) is 0.3 to 40% by weight.

5. The cationic rosin-based emulsion-type sizing agent according to any one of the preceding paragraphs 1 to 4, wherein, based on the solid content weight, with respect to 100 parts by weight of the rosin-based resin (A), the amount of the emulsifier (B) The content is 3 to 30 parts by weight.

6. The cationic rosin-based emulsion-type sizing agent according to any one of the preceding paragraphs 1 to 5, wherein the cationic rosin-based emulsion-type sizing agent further contains a water-soluble aluminum compound (C).

7. A paper characterized by containing the cationic rosin-based emulsion type sizing agent as described in any one of the preceding items 1 to 6. [Effect of invention]

According to the cationic rosin-based emulsion-type 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 properties and mechanical stability, and the sizing agent is used The paper obtained by the agent also showed good sizing effect.

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

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

The resin (A) includes, for example, gum rosin, wood rosin, tall oil rosin, Nanyang rosin (dihydroagathic acid-containing rosin), squat rosin (yinboric acid-containing rosin), and the like. Unmodified rosin; hydrogenated rosin, α,β-unsaturated carboxylic acid modified rosin, disproportionated rosin, or esters of these (unmodified rosin ester, hydrogenated rosin ester, α,β-unsaturated carboxylic acid modified rosin) rosin ester, disproportionated rosin ester), etc. These may be used alone or in combination of two or more. Among them, it is desirable to contain at least one selected from the group consisting of unmodified rosin, α,β-unsaturated carboxylic acid-modified rosin, and unmodified rosin ester, from the viewpoint that the paper exhibits a good sizing effect. More preferably, it contains α,β-unsaturated carboxylic acid-modified rosin.

In addition, resin (A) can also be purified by a known vacuum distillation method, steam distillation method, extraction method, recrystallization method, or the like.

α,β-unsaturated carboxylic acid-modified rosin (hereinafter also referred to as carboxylic acid-modified rosin) refers to a product obtained by adding α,β-unsaturated carboxylic acid to unmodified rosin. The α,β-unsaturated carboxylic acid is not particularly limited, and examples thereof 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. -Unsaturated monocarboxylic acids, etc. The usage-amount of α,β-unsaturated carboxylic acid is also not particularly limited, but is usually about 1 to 30 parts by weight relative to 100 parts by weight of unmodified rosin.

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

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

Unmodified rosin ester is the reaction product of unmodified rosin and polyol.

The polyhydric alcohol is not particularly limited, but is ideally a trihydric alcohol and/or a tetrahydric alcohol, and examples of the former include glycerin, trimethylolethane, trimethylolpropane, and 3-methylpentane-1,3, 5-triol and the like; in addition, as the latter, neopentaerythritol, diglycerol, and the like can be exemplified.

Unmodified rosin esters can be produced by various conventional methods. For example, it can be obtained by subjecting unmodified rosin and a polyhydric alcohol to an esterification reaction at usually 200 to 350° C. for 6 to 20 hours. In addition, the reaction can be carried out under any one of normal pressure, reduced pressure, and increased pressure. In addition, the ratio of the amount of the unmodified rosin and the polyol to be used is not particularly limited. Usually, the equivalent ratio of the carboxyl group of the former to the hydroxyl group of the latter [OH _(eq) /COOH _(eq) ] is about 0.2 to 1.5, preferably 0.2 to 1.5. 0.4 ~ 1.2 or so. In addition, at the time of the reaction, an esterification catalyst such as p-toluenesulfonic acid or various antioxidants may be used. In addition, the reaction can also be carried out under nitrogen flow.

The physical properties of the unmodified rosin ester are not particularly limited, but from the viewpoint that the paper exhibits a good sizing effect, the softening point is usually about 80 to 100°C, the acid value is about 0 to 25 mgKOH/g, and the hydroxyl value is 0. About ∼30 mgKOH/g, the ideal softening point is about 85 to 95° C., the acid value is about 10 to 20 mgKOH/g, and the hydroxyl value is about 0 to 10 mgKOH/g.

The emulsifier (B) used in the present invention contains, among the reaction components, epihalohydrin (b1) (hereinafter referred to as (b1) component), alkylene polyamine (b2) (hereinafter referred to as (b2) component), and a polymer of monoamine (b3) (hereinafter referred to as (b3) component) represented by the general formula (1). In addition, the alkyl group in the general formula (1) (including the alkyl group in the cycloalkyl group) may be a straight chain structure or a branched chain structure.

[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. Moreover, both R ¹ and R ² are Except in the case of hydrogen atoms.)

The component (b1) is an epihalohydrin, and examples thereof include epichlorohydrin, epibromohydrin, and the like. These may be used individually or in combination of 2 or more types.

The component (b2) is an alkylene polyamine, preferably one having at least two primary amine groups. As such a component (b2), for example, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine (pentamethylene diamine) can be mentioned. alkylene diamine), 1,6-hexanediamine (hexamethylene diamine), etc.; diethylenetriamine, dipropylenetriamine, dibutylenetriamine, etc. Alkylenetriamines; alkylenetetramines such as triethylenetetramine, tripropylenetetramine, etc.; tris(2-aminoethyl)amine, tris(2-aminopropyl)amine, etc. Tris(2-aminoalkyl)amines; alkylene pentamines such as tetraethylene pentamine and tetrapropylene pentamine; alkylene hexaamines such as pentaethylene hexaamine and the like. These may be used individually or in combination of 2 or more types. Among them, from the viewpoint that the resin (A) can be favorably emulsified by the emulsifier (B) containing the obtained polymer, alkylene diamine and alkylene triamine are preferable, and ethylene diamine is more preferable Amine, hexamethylene diamine, diethylene triamine.

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 emulsifiability is improved. In addition, the resulting sizing also exhibits excellent mechanical stability.

[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. Moreover, both R ¹ and R ² are Except in the case of hydrogen atoms.)

(b3) Component, for example: 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 (palmamine), n-stearylamine Aliphatic primary amines such as amine, isostearylamine, etc.; Dimethylamine, diethylamine, ethylmethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-2-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 (di-laurylamine), di-n-tridecylamine, di-n-tetradecylamine (dimyristylamine), di-n-hexadecylamine (dipalmitamine), di-n-stearylamine, diisostearylamine, two-hardened 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, 9-aminoanthracene, etc.; N-methylaniline, N-ethylaniline, N-propylaniline, N-isopropylaniline, N-butylaniline, N-isobutylaniline, N-methylbenzylamine, N-ethylbenzyl Aromatics of amine, N-propylbenzylamine, N-isopropylbenzylamine, N-butylbenzylamine, 1-(methylaminomethyl)naphthalene, 9-(methylamino)methylanthracene, etc. family of secondary amines, etc.

These (b3) components may be used alone or in combination of two or more. Among them, a polymer having a hydrophobic group (such as an alkyl group, a cycloalkyl group, etc. (the same applies hereinafter)) derived from the component (b3) can be obtained, and the resin ( A) From the viewpoint of good emulsification, preferably at least one selected from the group consisting of aliphatic primary amines, aliphatic secondary amines, and aromatic primary amines, and more preferably n-octylamine and 2-ethylhexylamine , Di-n-butylamine, benzylamine.

The usage amounts of (b1) component, (b2) component and (b3) component are not particularly limited. From the viewpoint of sizing performance, the molar amount of epoxy group of (b1) component and (b2) component and The ratio of the total molar amount of the amine groups of the component (b3) is preferably (the molar amount of the epoxy groups of the component (b1))/(the total molar of the amine groups of the component (b2) and (b3) amount) = about 0.8 to 1.4, more preferably 1 to 1.2.

In addition, the amount of the component (b3) used is based on the solid content weight of 100% by weight of the total of the components (b1), (b2) and (b3), from which a hydrophobicity derived from the (b3) component can be obtained. From the viewpoint of emulsification of the resin (A) well by the polymer of the volatile group and the emulsifier (B) containing the polymer, it is desirably 0.3 to 40 wt %, more desirably 1 to 20 wt %, and further Ideally, it is 5 to 15% by weight.

The manufacturing method of a polymer is not specifically limited, For example, (b2) component and (b3) component are added and mixed at room temperature, and (b1) component is added by batch or dropwise addition, and it heats and reacts.

In addition, the above-mentioned reaction conditions are not particularly limited, but 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).

In the above-mentioned production method, it is desirable to prepare a reaction liquid 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 individually or in combination of 2 or more types. In addition, when adding water, the reaction concentration is preferably about 40 to 60% by weight, more preferably about 45 to 55% by weight.

In addition, pH adjusters, antifoaming agents, antioxidants, antiseptics, chelating agents, cationic surfactants other than the aforementioned polymers, anionic surfactants, and nonionic surfactants may be further added to the obtained polymer. surfactants, etc.

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.

In addition, the viscosity of an aqueous solution with 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 hydrophobic group derived from the monoamine of the component (b3) is introduced into the polymer, the emulsifier (B) containing the polymer is rich in emulsification with the resin (A). That is, a cationic rosin-based emulsion-type sizing agent with low viscosity and small particle size can be obtained by dispersing the resin (A) and the emulsifier (B) with good compatibility. In addition, the sizing agent also has excellent mechanical stability and sizing effect.

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

The method of dispersing the resin (A) using the emulsifier (B), that is, the method of producing the sizing agent, can be either a high pressure emulsification method or a phase inversion emulsification method. In addition, the dispersion medium is an alcohol such as ethanol and isopropanol; from the viewpoint of reducing the environmental load, it is preferable to use water, 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 a water-soluble organic solvent, and examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, tertiary butanol, and isobutanol. , n-hexanol, n-octanol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, diacetone alcohol and other alcohols; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc. . These may be used individually or in combination of 2 or more types. In addition, when an organic solvent is contained, its content is desirably less than 10 weight%.

In the case of using the high-pressure emulsification method, the resin (A) forming the dispersed phase can be melted or dissolved in an organic solvent such as benzene, toluene, etc., and then the emulsifier (B) is added thereto at the aforementioned usage ratio. After mixing warm water and emulsification using a high-pressure emulsifier, a dispersion liquid is directly obtained, or the organic solvent is distilled off to obtain a dispersion liquid.

In addition, in the case of using the phase inversion emulsification method, after sufficiently kneading the resin (A) as the solid content and the emulsifier (B), warm water is slowly added dropwise while stirring to invert the phases, whereby the A dispersion is obtained without using an organic solvent and a special emulsifying device. The solid content concentration of the dispersion liquid is not particularly limited, but is usually 10 to 50% by weight, and it may be used after diluting with water if necessary.

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

As the aluminum compound (C), it is desirable to use at least one polymer selected from, for example, aluminum sulfate, aluminum hydroxide, aluminum chloride, basic aluminum sulfate, basic aluminum chloride, aluminum sulfate sulfate, and the like. Among these, aluminum sulfate is desirable from the viewpoint of cost.

The content of the aluminum compound is desirably 1 to 100 parts by weight relative to 100 parts by weight of the component (A) in terms of solid content from the viewpoint of showing a favorable sizing effect when the obtained sizing agent is used to make paper. 20 parts by weight, more preferably 5 to 15 parts by weight.

In addition, the sizing agent of the present invention can be added with celluloses such as carboxymethyl cellulose; paper strength enhancers such as polyvinyl alcohols, polyacrylamides, water-soluble polymers such as sodium alginate, etc. , anti-slip agent, preservative, rust inhibitor, pH adjuster, defoamer (silicone defoamer, etc.), tackifier, filler, antioxidant, water repellant, film-forming aid, pigment, dye, etc. .

In addition, other physical properties are not particularly limited. When the solid content concentration of the sizing agent is 35% by weight, the viscosity obtained by using a B-type viscometer at a temperature of 25°C is usually about 10 to 200 mPa･s, preferably 10 to 100 mPa ･s around.

Moreover, the volume average particle diameter of a sizing agent is about 0.1-2 micrometers normally, Preferably it is about 0.4-1.5 micrometers. In addition, the volume average particle diameter is a value measured by a particle diameter measuring apparatus by a laser diffraction-scattering method.

The paper of the present invention can be obtained using the sizing agent of the present invention. The method of sizing includes internal sizing, surface sizing, and combinations thereof.

In internal sizing, the sizing agent of the present invention is added to the pulp slurry, and paper is produced in an acidic region or even a neutral region. In addition, the usage-amount of the sizing agent of this invention is not specifically limited, It is the range of about 0.05 to 3 weight% normally with respect to the dry weight of a pulp. In addition, the type of pulp is not particularly limited, and examples thereof include chemical pulps such as hardwood pulp (LBKP) and softwood pulp (NBKP); ground wood pulp (GP), refined pulp (RGP), and thermomechanical pulp (TMP). and other mechanical pulp; corrugated cardboard waste paper and other waste paper pulp, etc. In addition, when sizing is added, the fixative is preferably aluminum sulfate and/or aluminum hydroxide. In addition, the pH of the pulp slurry can be adjusted by sulfuric acid, sodium hydroxide, or the like. In addition, other neutral sizing agents such as epichlorohydrin modified products of styrene-dimethylaminoethyl methacrylate copolymer, alkenyl succinic anhydride, alkyl ketene dimer, fatty acid can be used together -Epichlorohydrin modifications of polyalkylpolyamine condensates, etc. In addition, other paper strength enhancers, such as starches such as cationized starch, can be used in combination; polypropylene amide-based paper strength enhancers, epichlorohydrin modified products of polyamide polyamine resins, and epichlorohydrin of dicyandiamide resins Alcohol modification, epichlorohydrin modification of styrene-dimethylaminoethyl methacrylate copolymer, Mannich modification of polypropyleneamide, acrylamide-dimethyl Amino ethyl methacrylate copolymer, Hofmann decomposition product of polypropylene amide, copolymer of dialkyl diallyl 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 the surface sizing, the sizing agent of the present invention is diluted to a solid content concentration of about 0.01 to 2 wt % to form a sizing solution, which is applied to base paper by various conventional methods. The coating method is not particularly limited, and examples thereof include a squeezing method, a gate roll method, a bar coating method, a calendering method, a spraying method, and the like. In addition, as a squeezing method, for example, a twin roll squeezing coating method and a bar-type metering squeezing coating method can be mentioned. In addition, the coating amount (solid content) of the sizing solution 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 . In addition, the base paper is also not particularly limited, and for example, uncoated paper using wood cellulose fibers as a raw material can be used. In addition, the pulp constituting the base paper includes the above-mentioned pulp. In addition, the base paper may be a base paper obtained by making paper using one selected from the group consisting of the aforementioned fixing agent, neutral sizing agent, paper strength enhancer, and filler, and the neutral sizing may be coated on the surface. The base paper obtained from the agent and/or the paper strength enhancer.

The paper of the present invention can be used in various products depending on the basis weight. For example, the finished paper of low basis weight to medium basis weight of about ^20-150g /m2 can be used as recording paper such as form paper, PPC paper, thermal recording base paper and pressure-sensitive recording base paper; coated paper, cast-coated paper, etc. , Coated paper such as high-quality coated paper; packaging paper such as kraft paper, pure white roll paper, etc.; Western paper such as note paper, book paper, printing paper, newspaper paper, etc. In addition, the finished paper with a high basis weight of 150 g/m ² or more can be used as, for example, cardboard such as manila cardboard, white cardboard, grey cardboard, backing cardboard, core paper, and the like. [Example]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. In addition, unless otherwise specified, "%" is based on weight.

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

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 added, and the reaction was carried out at 200° C. while stirring under a nitrogen stream for 2 hours, thereby obtaining maleic acid-modified rosin (A-1).

Production Example B (Production of Fumaric Acid-Modified Rosin (A-3)) 20 g of fumaric acid was added, and the same method as in Production Example A was carried out 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-made gum rosin and 55.6 g of glycerin were added, and 10 g of NOCRAC 300 (manufactured by Ouchi Shinshin Chemical Industry Co., Ltd.) as an antioxidant and p-toluenesulfonic acid as a catalyst were added. 0.1 g of acid was reacted at 270° C. for 15 hours with stirring under a nitrogen stream to obtain a rosin ester (A-4).

Manufacturing Example 1 In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a reflux cooler, and a nitrogen introduction tube, 452.4 g (75.4 wt %) of epichlorohydrin, 30.0 g (5.0 wt %) of 2-ethylhexylamine, and 157.9 g of water were added g and stirred at room temperature for 30 minutes, then 168.0 g (19.6% by weight) of ethylenediamine 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 a sulfuric acid aqueous solution with a solid concentration of 62.5% was added, and then 592.7 g of water was added to obtain an aqueous solution of the polymer (B-1) with a solid concentration of 40%. The viscosity of the aqueous solution of the polymer (B-1) is shown in Table 1 (the same applies hereinafter).

Production Examples 2 to 20, Comparative Production Examples 1 to 4 According to the compositions shown in Table 1, the same method as in Production Example 1 was carried out to obtain aqueous solutions of polymers (B-2) to (B-20) with a solid content concentration of 40% and polymers (D-1) to (D-4) aqueous solution.

[Table 1]

The abbreviations shown in Table 1 mean the following compounds. (b1) Ingredients ・ECH: Epichlorohydrin (b2) Ingredients ・EDA: Ethylenediamine ・HMDA: Hexamethylenediamine ・DETA: Diethylenetriamine (b3) Ingredients ・2EHA: 2-ethylhexylamine ・n-OA: n-Octylamine ・BnA: Benzylamine ・DBA: Di-n-butylamine

Comparative Production Example 5 In the same reaction vessel as in Production Example 1, 730 g (5 moles) of adipic acid and 619 g (6 moles) of diethylenetriamine were added, and the temperature was raised while removing the generated water to the outside of the system. After reacting at 200°C for 5 hours, 1200 g of water was slowly 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 it was adjusted while stirring so that the liquid temperature became 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 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 polymer (D-5) having a solid content concentration of 25% and a viscosity of 200 mPa·s.

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

Example 1 In the same reaction vessel as in Production Example 1, 100 g of maleic acid-modified rosin (A-1) was added, and it was heated and melted at about 160°C. Next, an aqueous solution of the emulsifier (B-1) (solid content weight: 10.0 g) was slowly added dropwise with stirring to prepare a W/O emulsion, and hot water was added to prepare a stable O/W emulsion. Then, by cooling this emulsion to room temperature, a cationic rosin-based emulsion-type sizing agent having a solid content concentration of 35% was obtained. The physical properties are shown in Table 2 (the same applies hereinafter).

Examples 2 to 26, 29 to 33, and Comparative Examples 1 to 5 Using the rosin-based resin and emulsifier shown in Table 2, the same method as in Example 1 was performed to obtain a cationic rosin-based emulsion-type sizing agent with a solid content concentration of 35%, respectively. In addition, in the comparative example 1 and the comparative example 5, since the residue of the rosin-type resin was produced|generated in the emulsification process, the following evaluation was not performed.

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

(volume average particle size) Use laser diffraction. The scattering method was measured by a particle size measuring apparatus (apparatus name "LASER DIFFRACTION PARTICLE SIZE ANALYZER SALD-7500nano", manufactured by SHIMADZU). The results are shown in Table 2 (the same applies hereinafter).

(mechanical stability) 50 g of each sizing agent was weighed into a container of a Maron-type stability tester (manufactured by Shinsei Sangyo Co., Ltd.), and vigorously stirred for 5 minutes at a temperature of 25° C., a load of 10 kg, and a rotation speed of 1000 r.p.m. After that, the generated aggregates were collected by filtration with a 350-mesh wire mesh, and the values were calculated according to the formula 2, and were evaluated according to the following criteria. (Formula 2) Mechanical stability (%) = (absolute dry weight of aggregates/absolute dry weight of sizing agent) × 100 (Evaluation Criteria) ◎: The value obtained from the formula 2 is less than 0.5% 〇: The value obtained from the formula 2 is 0.5% or more and less than 1.0% △: The value obtained from the formula 2 is 1.0% or more and less than 5.0% ×: The value obtained from Equation 2 is 5.0% or more

<Papermaking evaluation> Tap water was added to hardwood bleached kraft pulp (hereinafter referred to as L-BKP) so that the solid content concentration of the pulp was 2.0%, and the pulp was beaten to a Canadian standard freeness (CSF) of 300 ml with a beater. Next, the obtained pulp slurry was further diluted with tap water, and the solid content concentration was adjusted to 1.0%. In the pulp slurry, relative to the pulp solids, 16.0% (on an absolute dry weight basis, the same as below) of filler (a mixture of calcium carbonate and talc), 1.5% of aluminum sulfate and 0.3% of commercially available cationic modification were added starch, adjusted to a pulp slurry with a pH of 5.0. In addition, the pH of the papermaking system was adjusted using an aqueous sulfuric acid solution. Next, each sizing agent was added to the pulp slurry at 0.3% (in terms of solid content) with respect to the pulp solid content, and papermaking was carried out using a paper machine (Tappi Standard Sheet Machine (circle), the same applies hereinafter) to obtain a wet Paper. The wet paper was dehydrated with a roll press (conditions: linear pressure 5.5 kg/cm, conveyance speed 2 m/min), and was dried at 90° C. for 6 minutes using a rotary dryer. The resulting dry paper was conditioned for 24 hours in a constant temperature and humidity (temperature 23°C, humidity 50%) environment to obtain a finished paper (test paper) with a basis weight of 80 g/m ² . Next, with respect to each test paper, the Stockigt sizing degree was measured according to JIS-P8122. The higher the value of Stockigt sizing, the better.

*1：乳化劑之使用量係以固體成分重量計相對於松香系樹脂100g的值表示。 *2：水溶性鋁化合物之使用量係以固體成分重量計相對於松香系樹脂100g的值表示。 [Table 2]

*1: The usage-amount of an emulsifier is shown as the value with respect to 100 g of rosin-type resin by solid content weight. *2: The usage-amount of a water-soluble aluminum compound shows the value with respect to 100 g of rosin-type resin by solid content weight.

The symbols shown in Table 2 represent the following compounds. ＜Rosin-based 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＞ ・Refer to Table 1. ＜Water-soluble aluminum compound＞ ・C-1: Aluminum sulfate. 16 hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ・C-2: Polyaluminum chloride (manufactured by Kishida Chemical Co., Ltd.)

Claims (7)

A cationic rosin-based emulsion-type sizing agent, characterized in that it contains an emulsion of a rosin-based resin (A) and an emulsifier (B), wherein the emulsifier (B) contains epihalohydrin (b1), A polymer of an alkylene polyamine (b2) and a monoamine (b3) represented by the following general formula (1), [Formula 1] R ¹ -NH-R ² (in formula 1, R ¹ and R ² are independent Denotes a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group; in addition, unless R ¹ and R ² are both hydrogen atoms). The cationic rosin-based emulsion-type sizing agent according to claim 1, wherein the component (b2) is an alkylene diamine and/or an alkylene triamine. The cationic rosin-based emulsion-type sizing agent according to claim 1 or 2, wherein the component (b3) is at least one selected from the group consisting of aliphatic primary amines, aliphatic secondary amines, and aromatic primary amines . The cationic rosin-based emulsion-type sizing agent according to any one of claims 1 to 3, wherein the solid content weight is based on the total of 100 components (b1), (b2), and (b3) components. % by weight, the usage amount of the component (b3) is 0.3 to 40% by weight. The cationic rosin-based emulsion-type sizing agent according to any one of claims 1 to 4, wherein the content of the emulsifier (B) is based on the solid content weight relative to 100 parts by weight of the rosin-based resin (A) 3 to 30 parts by weight. The cationic rosin-based emulsion-type sizing agent according to any one of claims 1 to 5, wherein the cationic rosin-based emulsion-type sizing agent further contains a water-soluble aluminum compound (C). A paper characterized by containing the cationic rosin-based emulsion-type sizing agent according to any one of claims 1 to 6.