CN114150529A - Cationic rosin emulsion sizing agent and paper - Google Patents

Cationic rosin emulsion sizing agent and paper Download PDF

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Publication number
CN114150529A
CN114150529A CN202111032546.1A CN202111032546A CN114150529A CN 114150529 A CN114150529 A CN 114150529A CN 202111032546 A CN202111032546 A CN 202111032546A CN 114150529 A CN114150529 A CN 114150529A
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Prior art keywords
rosin
sizing agent
emulsion sizing
paper
cationic
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高木贤至
梅田拓未
须田雅彦
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Arakawa Chemical Industries Ltd
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Arakawa Chemical Industries Ltd
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/62—Rosin; Derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/66—Salts, e.g. alums

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

[ problem of the invention]Provided is a cationic rosin-based emulsion sizing agent which is excellent in emulsifiability and mechanical stability and exhibits a good sizing effect. [ means for solving the problems ]]A cationic rosin-based emulsion sizing agent comprising an emulsion of a rosin-based resin (A) and an emulsifier (B) comprising a polymer containing, as a reaction component, an epihalohydrin (B1), an alkylene polyamine (B2), and a monoamine (B3) represented by the following general formula (1) [ formula 1]]R1‑NH‑R2In the formula 1, R1、R2Independently represent a hydrogen atom, an alkyl group,Cycloalkyl, aryl or aralkyl; in addition, R1And R2Except for the case where both are hydrogen atoms.

Description

Cationic rosin emulsion sizing agent and paper
Technical Field
The present invention relates to a cationic rosin emulsion sizing agent and paper.
Background
The rosin-based emulsion sizing agent is a composition obtained by emulsifying a rosin-based resin in the presence of various emulsifiers and water, and is classified into a cationic sizing agent or an anionic sizing agent according to the ionic properties of the emulsifiers used. The paper obtained using this sizing agent shows good sizing due to the emulsion particles fixed on the pulp fibers.
Among them, as cationic rosin-based emulsion sizing agents, those obtained by dispersing rosin-based resins with an emulsifier obtained by reacting an epihalohydrin with a polyalkylpolyamine (patent document 1) and a polyamide polyamine and a water-soluble acid (patent document 2) are known. However, in such a technique, the emulsifying properties of the rosin-based resin and the emulsifier are insufficient, and the resulting sizing agent is also inferior in mechanical stability and sizing effect.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 5-98001
Patent document 2: japanese patent laid-open No. 2012 and 007284
Disclosure of Invention
Technical problem to be solved by the invention
The invention provides a cationic rosin emulsion sizing agent which has excellent emulsibility and mechanical stability and shows good sizing effect.
Means for solving the problems
The present inventors have made intensive studies on the composition of an emulsifier, and as a result, the present invention has been completed. Namely, the present invention relates to the following cationic rosin-based emulsion sizing agent and paper.
1. A cationic rosin-based emulsion sizing agent comprising an emulsion of a rosin-based resin (A) and an emulsifier (B) comprising a polymer containing an epihalohydrin (B1), an alkylene polyamine (B2) and a monoamine (B3) represented by the following general formula (1) as a reactive component,
[ formula 1]R1-NH-R2
In the formula 1, R1、R2Independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group; in addition, R1And R2All being hydrogen atomsExcept where the case may be.
2. The cationic rosin-based emulsion sizing agent according to item 1 above, wherein the component (b2) is an alkylene diamine and/or an alkylene triamine.
3. The cationic rosin-based emulsion sizing agent according to item 1 or 2, wherein the component (b3) is at least 1 selected from the group consisting of primary aliphatic amines, secondary aliphatic amines, and primary aromatic amines.
4. The cationic rosin emulsion sizing agent according to any one of items 1 to 3, wherein the component (b3) is used in an amount of 0.3 to 40% by weight based on the total 100% by weight of the components (b1), (b2) and (b3) as a solid content.
5. The cationic rosin emulsion sizing agent according to any one of items 1 to 4, wherein the content of the emulsifier (B) is 3 to 30 parts by weight based on the solid content per 100 parts by weight of the rosin resin (A).
6. The cationic rosin-based emulsion sizing agent according to any one of claims 1 to 5, wherein the cationic rosin-based emulsion sizing agent further contains a water-soluble aluminum compound (C).
7. A paper containing the cationic rosin emulsion sizing agent as described in any one of items 1 to 6.
Advantageous effects
According to the cationic rosin-based emulsion sizing agent (hereinafter also simply referred to as "sizing agent") of the present invention, excellent emulsifiability and mechanical stability are obtained by using an emulsifier containing a specific amine, and paper obtained by using the sizing agent also exhibits a good sizing effect.
Detailed Description
The cationic rosin-based emulsion sizing agent of the present invention contains an emulsion of a rosin-based resin (a) and a specific emulsifier (B).
The rosin-based resin (a) (hereinafter also referred to as resin (a)) is a component that exerts good emulsifying properties and sizing effects of the sizing agent.
Examples of the resin (a) include unmodified rosins such as gum rosin, wood rosin, tall oil rosin, southern pine rosin (メルクシ pine ロジン) (rosin containing dihydrokainic acid (ジヒドロアガト acid)), and slash pine rosin (rosin containing slash pine acid (コムン acid)), hydrogenated rosin, α, β -unsaturated carboxylic acid-modified rosin, disproportionated rosin, and esterified products thereof (unmodified rosin ester, hydrogenated rosin ester, α, β -unsaturated carboxylic acid-modified rosin ester, disproportionated rosin ester), and the like. These may be used alone, or 2 or more of them may be used in combination. Among them, from the viewpoint that the paper exhibits a good sizing effect, at least one selected from the group consisting of an unmodified rosin, an α, β -unsaturated carboxylic acid-modified rosin, and an unmodified rosin ester is preferably contained, and an α, β -unsaturated carboxylic acid-modified rosin is more preferably contained.
The resin (a) may be purified by a known vacuum evaporation 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 obtained by adding an α, β -unsaturated carboxylic acid to an 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; and α, β -unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid. The amount of the α, β -unsaturated carboxylic acid used is not particularly limited, and is usually about 1 to 30 parts by weight based on 100 parts by weight of the unmodified rosin.
The method for producing the α, β -unsaturated carboxylic acid-modified rosin is not particularly limited, and examples thereof include a method in which an unmodified rosin and an α, β -unsaturated carboxylic acid are mixed together in an appropriate reaction vessel, and then heated and melted to perform a diels-alder (ディールス · アルダー) reaction at about 190 ℃ to 230 ℃ for about 1 hour to 3 hours.
The physical properties of the α, β -unsaturated carboxylic acid-modified rosin are not particularly limited, and from the viewpoint of exhibiting a good sizing effect on paper, the softening point is usually about 85 to 140 ℃ and the acid value is about 195 to 320mgKOH/g, and preferably about 95 to 130 ℃ and the acid value is about 240 to 295 mgKOH/g.
The unmodified rosin ester is the reaction product of an unmodified rosin and a polyol.
The polyhydric alcohol is not particularly limited, but is preferably a trihydric alcohol and/or a tetrahydric alcohol, and examples of the former include glycerin, trimethylolethane, trimethylolpropane, and 3-methylpentane-1, 3, 5-triol; the latter includes pentaerythritol, diethylene glycol, and the like.
The unmodified rosin ester can be produced by various known methods. For example, the resin composition can be obtained by subjecting an unmodified rosin and a polyol to an esterification reaction at a temperature of usually 200 to 350 ℃ for 6 to 20 hours. Further, the reaction may be carried out under any one of normal pressure, reduced pressure and increased pressure. The ratio of the amount of the unmodified rosin to the polyol used is not particularly limited, and is usually an equivalent ratio of the carboxyl group of the unmodified rosin to the hydroxyl group of the polyol [ OH ](eq)/COOH(eq)]About 0.2 to 1.5, preferably about 0.4 to 1.2. In the reaction, an esterification catalyst such as p-toluenesulfonic acid and various antioxidants may be used. The reaction may be carried out under a nitrogen stream.
The physical properties of the unmodified rosin ester are not particularly limited, and from the viewpoint of exhibiting a good sizing effect on paper, the softening point is usually about 80 to 100 ℃, the acid value is about 0 to 25mgKOH/g, and the hydroxyl value is about 0 to 30mgKOH/g, and preferably the softening point is about 85 to 95 ℃, the acid value is about 10 to 20mgKOH/g, and the hydroxyl value is about 0 to 10 mgKOH/g.
The emulsifier (B) used in the present invention comprises a polymer containing, in the reaction components, an epihalohydrin (B1) (hereinafter referred to as (B1) component), an alkylene polyamine (B2) (hereinafter referred to as (B2) component), and a monoamine (B3) represented by the general formula (1) (hereinafter referred to as (B3) component). The alkyl group in the general formula (1) (including the alkyl group in the cycloalkyl group) may have a straight chain structure or a branched structure.
[ formula 1]R1-NH-R2
(in formula 1, R1、R2Independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. In addition, R1And R2Except for the case where both are hydrogen atoms. )
(b1) The component (B) is an epihalohydrin, and examples thereof include epichlorohydrin and epibromohydrin. These may be used alone, or 2 or more of them may be used in combination.
(b2) The component (A) is an alkylene polyamine, preferably an alkylene polyamine having at least 2 primary amino groups. Examples of the component (b2) include alkylenediamines such as ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine (pentamethylenediamine), and 1, 6-hexylenediamine (hexamethylenediamine); alkylene triamines such as diethylene triamine, dipropylene triamine and dibutylene triamine; alkylene tetraamines such as triethylene tetraamine and tripropylene tetraamine; tri (2-aminoalkyl) amines such as tri (2-aminoethyl) amine and tri (2-aminopropyl) amine; alkylenepentamines such as tetraethylenepentamine and tetrapropylenepentamine; and alkylenehexamines such as pentaethylenehexamine. These may be used alone, or 2 or more of them may be used in combination. Among them, alkylene diamines and alkylene triamines are preferable, and ethylene diamine, hexamethylene diamine, and diethylene triamine are more preferable, from the viewpoint that the resin (a) can be well emulsified by the emulsifier (B) containing the obtained polymer.
(b3) The component (A) is a monoamine represented by the general formula (1). By using the component (B3), the hydrophobicity of the polymer increases, and the emulsifier (B) containing the polymer is easily compatible with the resin (a) well (み as shown in な), and thus the emulsifiability is improved. In addition, the sizing agent obtained also shows excellent mechanical stability.
[ formula 1]R1-NH-R2
(in formula 1, R1、R2Independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. In addition, R1And R2Except for the case where both are hydrogen atoms. )
Examples of the component (b3) include:
aliphatic primary amines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-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 (palmitylamine), n-stearylamine, and isostearylamine;
aliphatic secondary amines such as dimethylamine, diethylamine, ethylmethylamine, di-N-propylamine, diisopropylamine, di-N-butylamine, diisobutylamine, di-sec-butylamine, di-tert-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), di-N-tridecylamine, di-N-tetradecylamine (dimyristylamine), di-N-hexadecylamine (dipalmitylamine), di-N-stearylamine, diisostearylamine, and diprosolidine;
alicyclic primary amines such as cyclobutylamine, cyclopentylamine, cyclopentylmethylamine, 1-cyclopentylethylamine, 2-cyclopentylethylamine, cyclohexylamine, cyclohexylmethylamine, 1-cyclohexylethylamine, 2-cyclohexylethylamine, cycloheptylamine, and cyclooctylamine;
alicyclic secondary amines such as N-methylcyclopentylamine, N-ethylcyclopentylamine, N-propylcyclopentylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, N-propylcyclohexylamine, and N-isopropylcyclohexylamine;
primary aromatic amines such as aniline, o-toluidine, m-toluidine, p-toluidine, phenylmethylamine (benzylamine), 1-phenylethylamine, 2-phenylethylamine, 1-phenylpropylamine, 2-phenylpropylamine, 3-phenylpropylamine, 4-phenylbutylamine, 1-naphthylamine, 2-methylnaphthylamine, 1- (aminomethylnaphthalene), 2- (aminomethyl) naphthalene, 1-aminoanthracene, 2-aminoanthracene, and 9-aminoanthracene;
and aromatic secondary amines such as N-methylaniline, N-ethylaniline, N-propylaniline, N-isopropylaniline, N-butylaniline, N-isobutylaniline, N-methylbenzylamine, N-ethylbenzylamine, N-propylbenzylamine, N-isopropylbenzylamine, N-butylbenzylamine, 1- (methylaminomethyl) naphthalene, and 9- (methylamino) methylanthracene.
These (b3) components may be used alone or in combination of 2 or more. Among them, from the viewpoint of obtaining a polymer having a hydrophobic group (for example, an alkyl group, a cycloalkyl group, and the like (the same applies hereinafter)) derived from the component (B3) and well emulsifying the resin (a) with an emulsifier (B) containing the polymer, 1 or more selected from the group consisting of an aliphatic primary amine, an aliphatic secondary amine, and an aromatic primary amine is preferable, and n-octylamine, 2-ethylhexylamine, di-n-butylamine, and benzylamine are more preferable.
The amount of the component (b1), the component (b2), and the component (b3) to be used is not particularly limited, but from the viewpoint of sizing performance, the ratio of the molar amount of epoxy groups in the component (b1) to the total molar amount of amino groups in the components (b2) and (b3) is preferably about 0.8 to 1.4, more preferably 1 to 1.2, in terms of the molar amount of epoxy groups in the component (b 1)/((total molar amount of amino groups in the components (b2) and (b 3)).
The amount of the component (B3) used is preferably 0.3 to 40% by weight, more preferably 1 to 20% by weight, and still more preferably 5 to 15% by weight, based on the solid content, from the viewpoint that a polymer having a hydrophobic group derived from the component (B3) can be obtained and the resin (a) can be well emulsified by the emulsifier (B) containing the polymer, relative to 100% by weight of the total amount of the components (B1), (B2), and (B3).
The method for producing the polymer is not particularly limited, and for example, the component (b2) and the component (b3) are added and mixed at room temperature, and the component (b1) is added in portions or dropwise and reacted by heating.
The reaction conditions are not particularly limited, and the temperature is about 50 ℃ to 100 ℃ (preferably about 60 ℃ to 90 ℃), and the time is about 1 hour to 12 hours (preferably about 2 hours to 8 hours).
In the above production method, it is preferable to prepare a reaction solution to which water is added from the viewpoint of reaction control. Examples of the water include pure water, ion-exchanged water, tap water, and industrial water. These may be used alone, or 2 or more of them may be used in combination. When water is added, the reaction concentration is preferably about 40 to 60% by weight, more preferably about 45 to 55% by weight.
Further, a pH adjuster, an antifoaming agent, an antioxidant, a preservative, a chelating agent, a cationic surfactant other than the above-mentioned polymers, an anionic surfactant, a nonionic surfactant, and the like may be further added to the obtained polymer.
The physical properties of the polymer are not particularly limited, and the solid content concentration is usually about 20 to 50 wt%, and preferably about 30 to 45 wt%, for example.
The viscosity of an aqueous solution having a solid content concentration of 40% by weight of the polymer at 25 ℃ is usually about 10 to 500 mPas, preferably 50 to 300 mPas.
Since the polymer has hydrophobic groups derived from monoamines in the component (B3), the emulsifier (B) containing the polymer is rich in emulsifiability with the resin (a). That is, the resin (a) and the emulsifier (B) are well compatible and dispersed, whereby a cationic rosin-based emulsion sizing agent having a low viscosity and a small particle size can be obtained. Further, 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, and is preferably 3 to 30 parts by weight, more preferably 5 to 25 parts by weight, based on the solid content, relative to 100 parts by weight of the resin (a) from the viewpoint of good emulsifiability of the resin (a) and the emulsifier (B).
As a method for dispersing the resin (a) with the emulsifier (B), that is, a method for producing a sizing agent, any of a high-pressure emulsification method and a phase inversion emulsification method can be used. Examples of the dispersion medium include alcohols such as ethanol and isopropyl alcohol; from the viewpoint of reducing the environmental load, it is advantageous 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 water-soluble, and examples thereof include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, n-hexanol, n-octanol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and diacetone alcohol; and ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. These may be used alone, or 2 or more of them may be used in combination. When the organic solvent is contained, the content is preferably less than 10% by weight.
In the case of the high-pressure emulsification method, the resin (a) forming the dispersed phase may be melted or dissolved in an organic solvent such as benzene or toluene, and then warm water may be mixed while adding the emulsifier (B) thereto at the above-mentioned use ratio, and the mixture may be emulsified in a high-pressure emulsifier to obtain a dispersion as it is, or the dispersion may be obtained by evaporating the organic solvent.
In the case of the phase inversion emulsification method, after the resin (a) as a solid component and the emulsifier (B) are sufficiently kneaded, warm water is slowly added dropwise while stirring, and a dispersion can be obtained by reversing the process without using an organic solvent or a special emulsification apparatus. The solid content concentration of the dispersion is not particularly limited, but is usually 10 to 50% by weight, and if necessary, it may be diluted with water and used.
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 the cationic rosin-based emulsion sizing agent is obtained.
As the aluminum compound (C), for example, at least one selected from aluminum sulfate, aluminum hydroxide, aluminum chloride, basic aluminum sulfate, basic aluminum chloride, aluminum silicate sulfate, and polymers thereof is preferably used. Among these, aluminum sulfate is preferable from the viewpoint of cost.
The content of the aluminum compound is preferably 1 to 20 parts by weight, more preferably 5 to 15 parts by weight, based on 100 parts by weight of the (a) component, in terms of solid content, from the viewpoint of exhibiting a good sizing effect when the obtained sizing agent is used to produce paper.
The sizing agent of the present invention may further contain, for example, cellulose such as carboxymethyl cellulose, paper strength agents such as water-soluble polymers such as polyvinyl alcohols, polyacrylamides and sodium alginate, anti-slip agents, corrosion inhibitors, rust inhibitors, pH adjusters, defoaming agents (silicone defoaming agents and the like), thickeners, fillers, antioxidants, water resistance agents, film forming aids, pigments, dyes and the like.
Further, other physical properties are not particularly limited, and the viscosity of the sizing agent measured by a B-type viscometer at a temperature of 25 ℃ at a solid content concentration of 35% by weight is usually about 10 mPas to 200 mPas, and preferably about 10 mPas to 100 mPas.
Further, the volume average particle diameter 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 apparatus by a laser diffraction/scattering method.
The paper of the invention can be obtained using the sizing agent of the invention. As the sizing method, internal sizing and surface sizing and a combination thereof are cited.
In the internal sizing, the sizing agent of the present invention is added to a pulp slurry, and papermaking is performed in an acidic region or a neutral region. The amount of the sizing agent of the present invention to be used is not particularly limited, and is usually in the range of about 0.05 to 3 wt% based on the dry weight of the pulp. Further, the kind of pulp is not particularly limited, and examples thereof include chemical pulps such as hardwood pulp (LBKP) and softwood pulp (NBKP); mechanical pulp such as ground wood pulp (GP), refined pulp (RGP), thermomechanical pulp (TMP), etc.; an old corrugated cardboard (segment ボール ancient input), and other wastepaper pulp. In addition, at the time of internal sizing, as a fixing agent, aluminum sulfate and/or aluminum hydroxide is preferable. Further, the pH of the pulp slurry may be adjusted by sulfuric acid, sodium hydroxide, and the like. As other neutral sizing agents, for example, epichlorohydrin-modified products of styrene-dimethylaminoethyl methacrylate copolymers, epichlorohydrin-modified products of alkenyl succinic anhydrides, alkyl ketene dimers, fatty acid-polyalkyl polyamine condensates, and the like can be used in combination. Further, as other paper strength enhancers, for example, starches such as cationized starch, polyacrylamide type paper strength enhancers, epichlorohydrin-modified polyamide polyamine resins, epichlorohydrin-modified dicyandiamide resins, epichlorohydrin-modified styrene-dimethylaminoethyl methacrylate copolymers, mannich-modified polyacrylamides (マンニッヒ modified products), acrylamide-dimethylaminoethyl methacrylate copolymers, hofmann-decomposed polyacrylamides (ホフマン decomposed products), copolymers of dialkyldiallylammonium chloride and sulfur dioxide, and the like can be used in combination. Further, fillers such as talc, clay, kaolin, titanium dioxide, and calcium carbonate may be added to the pulp slurry.
In 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, and the sizing solution is applied to 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 rolling method, and a spray coating method. Further, examples of the size press method include a two-roll size press coating method and a metering size press coating method. The amount of the sizing liquid (solid content) is not particularly limited, but is usually 0.001g/m2～2g/m2About 0.005g/m is preferable2～0.5g/m2Left and right. Further, the base paper is not particularly limited, and for example, uncoated paper using wood cellulose fibers as a raw material can be used. The pulp constituting the base paper is exemplified by the above pulp. Further, the base paper may be one obtained by papermaking using 1 type selected from the group consisting of the above-mentioned fixing agent, neutral sizing agent, paper strength agent and filler; further, the base paper may be one obtained by coating the surface with the neutral sizing agent and/or the paper strength agent.
The paper of the present invention can be used for various products according to basis weight (basis weight). For example, 20g/m2～150g/m2The left and right low-medium weight paper can be used as recording paper such as form paper (フォーム for use), PPC paper, thermosensitive recording paper and pressure sensitive recording paper; coated paper such as coated paper, cast coated paper, high-quality coated paper and the like; packaging paper such as kraft paper and white roll paper; western papers such as notebook papers, book papers, printing papers, and newspaper papers. Furthermore, 150g/m2The high basis weight paper can be used as paper boards such as manila board (マ ニ ラ ボール), white board, gray board (チ ッ プ ボール), liner (ライナー), and medium paper (medium).
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In addition, "%" is based on weight unless otherwise specified.
(viscosity)
The viscosities of the emulsifier and the sizing agent incubated at 25 ℃ were measured using a Brookfield (ブルックフィールド) rotational VISCOMETER (product name "VISCOMETER TVK-10", manufactured by Tokyo industries, Ltd.).
Production example A (production of maleic acid-modified rosin (A-1))
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube and a cooler, 500g of a melt of gum rosin produced in China at about 160 ℃ and 20g of maleic acid were added, and the mixture was reacted at 200 ℃ for 2 hours while stirring under a nitrogen stream, thereby obtaining maleic acid-modified rosin (A-1).
Production example B (production of fumaric acid-modified rosin (A-3))
20g of fumaric acid was added thereto, and the mixture was processed in the same manner as in production example A to obtain fumaric acid-modified rosin (A-3).
Production example C (production of rosin ester (A-4))
In a reaction vessel similar to that of production example A, 663.2g of Chinese gum rosin and 55.6g of glycerin were added, ノクラック 300 g (manufactured by Dainioxin chemical industry Co., Ltd.) of 10g as an antioxidant and 0.1g of p-toluenesulfonic acid as a catalyst were added, and the mixture was reacted at 270 ℃ for 15 hours while stirring under a nitrogen stream to obtain a rosin ester (A-4).
Production example 1
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a reflux condenser and a nitrogen inlet, 452.4g (75.4 wt%) of epichlorohydrin, 30.0g (5.0 wt%) of 2-ethylhexylamine and 157.9g of water were added and stirred at room temperature for 30 minutes, and then 168.0g (19.6 wt%) of ethylenediamine was added dropwise over 30 minutes. After the temperature was raised to 80 ℃, the reaction was allowed to proceed for 6 hours. To stop the reaction, 28.1g of an aqueous sulfuric acid solution having a solid content concentration of 62.5% was added, and 592.7g of water was further added to the solution, thereby obtaining an aqueous solution of the polymer (B-1) having a solid content 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, and comparative production examples 1 to 4
According to the compositions shown in Table 1, aqueous solutions of the polymers (B-2) to (B-20) and aqueous solutions of the polymers (D-1) to (D-4) were obtained in a manner similar to that in production example 1, respectively, at a solid content concentration of 40%.
[ Table 1]
Figure BDA0003245739050000111
The abbreviations shown in table 1 represent the following compounds.
(b1) Composition (I)
ECH: epichlorohydrin
(b2) Composition (I)
EDA: ethylene diamine
HMDA: hexamethylene diamine
DETA: diethylenetriamine
(b3) Composition (I)
2 EHA: 2-ethylhexylamine
n-OA: n-octylamine
BnA: benzylamine
DBA: di-n-butylamine
Comparative production example 5
730g (5 mol) of adipic acid and 619g (6 mol) of diethylenetriamine were added to the same reaction vessel as in production example 1, and the temperature was raised while removing the water produced, and after reaction at 120 to 200 ℃ for 5 hours, 1200g of water was gradually added to obtain a polyamide polyamine having a solid content of 50%.
Next, 400g of the above polyamide polyamine and 91g of water were added to a device equipped with a thermometer, a cooler and a stirrer, and the mixture was stirred to adjust the liquid temperature to 15 ℃. After 110g of epichlorohydrin was added dropwise over 120 minutes, the temperature was raised to 32 ℃ to allow addition reaction to proceed for 5 hours. After adding 475g of water, the temperature was raised to 60 ℃ to cause a crosslinking reaction for 3 hours. Then, 155g of water and 20g 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 mPas.
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
100g of maleic acid-modified rosin (A-1) was added to the same reaction vessel as in production example 1, and heated and melted at about 160 ℃. Then, an aqueous solution (10.0 g in solid content weight) of the emulsifier (B-1) was slowly dropped under stirring to prepare a W/O emulsion, and then hot water was added thereto to prepare a stable O/W emulsion. 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 properties are shown in table 2 (the same applies hereinafter).
Examples 2 to 26, examples 29 to 33, and comparative examples 1 to 5
The procedure of example 1 was repeated using the rosin-based resin and the emulsifier shown in table 2 to obtain a cationic rosin-based emulsion sizing agent having a solid content of 35%. In comparative examples 1 and 5, the residue of the rosin-based resin was generated during the emulsification process, and therefore the following evaluations were not performed.
Example 27 and example 28
The procedure of example 1 was repeated using the rosin-based resin and the emulsifier shown in table 2 to obtain a cationic rosin-based emulsion sizing agent having a solid content of 35%. Then, 10g of the water-soluble aluminum compound shown in Table 2 (based on 100g of the solid content of the resin (A)) was mixed with each of the obtained sizing agents, and the mixture was stirred at room temperature for 30 minutes.
(volume average particle diameter)
The measurement was carried out by a LASER DIFFRACTION/scattering method using a PARTICLE SIZE measuring apparatus (apparatus name "LASER DIFFRACTION PARTICLE SIZE ANALYZER SALD-7500 nano", manufactured by SHIMADZU). The results are shown in Table 2 (the same applies hereinafter).
(mechanical stability)
50g of each sizing agent was weighed into a container of a Maron type (マーロン type) stability tester (manufactured by Xinxing industry Co., Ltd.), strongly stirred at 25 ℃ for 5 minutes under a load of 10kg and a rotation speed of 1000 r.p.m., and then the resulting aggregate was collected by filtration through a 350 mesh wire gauze, and the value was calculated according to formula 2 and evaluated according to the following criteria.
(formula 2) mechanical stability (%) (oven dry weight of aggregate/oven dry weight of sizing agent) × 100
(evaluation criteria)
Very good: the value obtained by formula 2 is less than 0.5%
Good: the value obtained by the formula 2 is 0.5% or more and less than 1.0%
And (delta): the value obtained by the formula 2 is 1.0% or more and less than 5.0%
X: the value obtained by the formula 2 is 5.0% or more
< evaluation of papermaking >
To broadleaf wood bleached kraft pulp (hereinafter referred to as L-BKP), tap water was added so that the solid content concentration of the pulp became 2.0%, and the pulp was pulped with a beater until the canadian standard freeness (c.s.f) became 300 mL. Then, the obtained pulp slurry was further diluted with tap water to adjust the solid content concentration to 1.0%. To this pulp slurry, 16.0% (same as below on an absolute dry weight basis) of a filler (a mixture of calcium carbonate and talc), 1.5% of aluminum sulfate, and 0.3% of a commercially available cationic modified starch were added, based on the solid content of the pulp, to prepare a pulp slurry having a pH of 5.0. Further, the pH of the papermaking system was adjusted with an aqueous sulfuric acid solution.
Next, to the pulp slurry, each sizing agent was added in an amount of 0.3% (in terms of solid content) relative to the solid content of the pulp, and papermaking was performed using a paper Machine (Tappi Standard Sheet Machine (hereinafter, the same shall apply) to obtain wet paper. The wet paper was dewatered by a roll press (conditions: linear pressure 5.5kg/cm, conveying speed 2 m/min) and dried at 90 ℃ for 6 minutes using a rotary dryer. The obtained dried paper was subjected to humidity conditioning in a constant temperature and humidity environment (temperature 23 ℃ C., humidity 50%) for 24 hours, thereby obtaining a quantitative 80g/m2To form a paper (test paper).
Next, the stock sizing degree (ステキヒトサイズ degrees) of each test paper was measured in accordance with JIS P8122. The larger the value of Stockigt sizing degree, the better.
[ Table 2]
Figure BDA0003245739050000151
*1: the amount of the emulsifier used is represented by a value based on 100g of the rosin-based resin by weight of the solid content.
*2: the amount of the water-soluble aluminum compound used is represented by a value based on 100g of the rosin-based resin by weight of the solid content.
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 preparation C
< emulsifiers >
Refer to table 1.
< Water-soluble aluminum Compound >
C-1: aluminum sulfate 16 hydrate (manufactured by Fuji フイルム Wako pure chemical industries, Ltd.)
C-2: polyaluminum chloride (キシダ chemical Co., Ltd.)

Claims (7)

1. A cationic rosin-based emulsion sizing agent comprising an emulsion of a rosin-based resin (A) and an emulsifier (B) comprising a polymer containing an epihalohydrin (B1), an alkylene polyamine (B2) and a monoamine (B3) represented by the following general formula (1) as a reactive component,
[ formula 1]R1-NH-R2
In the formula 1, R1、R2Independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group; in addition, R1And R2All being hydrogen atomsExcept where the case may be.
2. The cationic rosin-based emulsion sizing agent according to claim 1, wherein the component (b2) is an alkylene diamine and/or an alkylene triamine.
3. The cationic rosin-based emulsion sizing agent according to claim 1 or 2, wherein the component (b3) is at least 1 selected from the group consisting of primary aliphatic amines, secondary aliphatic amines, and primary aromatic amines.
4. The cationic rosin emulsion sizing agent according to any one of claims 1 to 3, wherein the amount of the component (b3) used is 0.3 to 40% by weight based on the total 100% by weight of the components (b1), (b2) and (b3) in terms of solid content.
5. The cationic rosin emulsion sizing agent according to any one of claims 1 to 4, wherein the content of the emulsifier (B) is 3 to 30 parts by weight based on 100 parts by weight of the rosin resin (A) based on the solid content.
6. The cationic rosin-based emulsion sizing agent according to any one of claims 1 to 5, wherein the cationic rosin-based emulsion sizing agent further contains a water-soluble aluminum compound (C).
7. A paper containing the cationic rosin-based emulsion sizing agent according to any one of claims 1 to 6.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102261014A (en) * 2010-05-28 2011-11-30 荒川化学工业株式会社 Rosin emulsion sizing agent and paper obtained by using the sizing agnet
CN105386366A (en) * 2014-08-21 2016-03-09 荒川化学工业株式会社 Rosin emulsion sizing agent and paper
CN106868938A (en) * 2015-09-28 2017-06-20 荒川化学工业株式会社 Colophony type emulsion sizing agent and the paper obtained using the sizing agent
CN110067152A (en) * 2018-01-22 2019-07-30 荒川化学工业株式会社 The manufacturing method and coating paper of paper grade (stock) surface emulsion sizing agent, paper grade (stock) surface emulsion sizing agent

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102261014A (en) * 2010-05-28 2011-11-30 荒川化学工业株式会社 Rosin emulsion sizing agent and paper obtained by using the sizing agnet
CN105386366A (en) * 2014-08-21 2016-03-09 荒川化学工业株式会社 Rosin emulsion sizing agent and paper
CN106868938A (en) * 2015-09-28 2017-06-20 荒川化学工业株式会社 Colophony type emulsion sizing agent and the paper obtained using the sizing agent
TW201728690A (en) * 2015-09-28 2017-08-16 荒川化學工業股份有限公司 Rosin-based emulsion sizing agent and paper obtained by using the sizing agent
CN110067152A (en) * 2018-01-22 2019-07-30 荒川化学工业株式会社 The manufacturing method and coating paper of paper grade (stock) surface emulsion sizing agent, paper grade (stock) surface emulsion sizing agent

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