JP6180917B2 - Dispersant for sizing agent, sizing agent composition and paper - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a sizing agent dispersant, a sizing agent composition, and paper. More specifically, the sizing agent dispersing agent, a sizing agent composition in which a sizing agent is dispersed by the sizing agent dispersing agent, and the sizing agent. The present invention relates to a paper obtained using the composition.

  Conventionally, in the papermaking industry, a sizing agent has been used for imparting water resistance to paper and exhibiting a size effect such as water penetration and suppression of ink bleeding. As such a sizing agent, a rosin-based sizing agent is widely known because of its low cost and excellent product life.

  Specifically, rosin-based sizing agents are used from the viewpoint of workability and the like, for example, in the form of a dispersion (rosin emulsion) in which fine particles of rosin are dispersed in water with a dispersant. For example, a cationic rosin emulsion sizing agent in which a rosin-based substance is dispersed and stabilized by a polyaminopolyamide epichlorohydrin resin having a hydrophobic group has been proposed (see Patent Document 1).

JP-A-3-294596

  On the other hand, as a sizing agent, further improvement in size effect is desired.

  Accordingly, an object of the present invention is to provide a sizing agent dispersant for obtaining a sizing agent composition that exhibits an excellent sizing effect, a sizing agent composition in which a sizing agent is dispersed by the sizing agent dispersing agent, and The object is to provide a paper obtained using the sizing composition.

  In order to achieve the above object, the dispersant for sizing agent of the present invention comprises a polyaminopolyamide-epichlorohydrin resin whose molecular ends are capped by an end capping agent, and the end capping agent is a monovalent cation. It is characterized by containing an aromatic carboxylic acid and / or a monovalent araliphatic carboxylic acid.

  In the sizing agent dispersant of the present invention, the end-capping agent contains a monovalent aromatic carboxylic acid, and the aromatic carboxylic acid contains an optionally substituted benzoic acid. Is preferred.

  In the sizing agent dispersant of the present invention, it is preferable that the end capping agent further contains a monovalent aliphatic carboxylic acid.

  In the sizing agent dispersant of the present invention, the content of the aliphatic carboxylic acid is 5 with respect to 100 mol of the aromatic carboxylic acid and / or the araliphatic carboxylic acid in the end-capping agent. It is preferable that the amount is not less than mol and not more than 2000 mol.

  The sizing agent dispersant of the present invention preferably further contains at least one cationic polymer selected from the group consisting of polydiallyldimethylammonium chloride, polyethyleneimine, and polyvinylamine.

  Moreover, in the dispersing agent for sizing agents of this invention, it is preferable that content of the said cationic polymer is 5 mass parts or more and 200 mass parts or less with respect to 100 mass parts of said polyamino polyamide-epichlorohydrin resin. Is preferred.

  The sizing composition of the present invention is characterized by containing the above sizing agent dispersant and a rosin sizing agent.

  The paper of the present invention is characterized by being obtained using the above sizing agent composition.

  In the sizing agent dispersant of the present invention, the molecular terminal of the polyaminopolyamide-epichlorohydrin resin is capped with an end capping agent containing a monovalent aromatic carboxylic acid and / or a monovalent araliphatic carboxylic acid. Therefore, a sizing composition that exhibits an excellent size effect can be obtained.

  Further, since the sizing agent composition of the present invention uses the above sizing agent dispersant, it can exhibit an excellent sizing effect and can impart excellent water resistance to paper.

  Moreover, since the paper of this invention is obtained using said sizing agent composition, it is excellent in water resistance.

  The sizing agent dispersant of the present invention contains a polyaminopolyamide-epichlorohydrin resin (hereinafter also referred to as molecular end-blocking PAE) whose molecular ends are capped by an end capping agent. .

  Molecular end-capped PAE can be obtained, for example, by a reaction of a polyaminopolyamide resin, an end capping agent, and epichlorohydrin.

  More specifically, in order to obtain molecular end-capped PAE, for example, first, a polyaminopolyamide resin is synthesized.

  The polyaminopolyamide resin is not particularly limited, and can be obtained, for example, by a dehydration condensation reaction between a polyalkylenepolyamine and a dicarboxylic acid and / or a derivative thereof.

  Examples of the polyalkylene polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and diaminodipropylamine (iminobispropylamine).

  These polyalkylene polyamines can be used alone or in combination of two or more.

  As the polyalkylene polyamine, diethylenetriamine is preferable.

  Moreover, in this method, monoalkylene diamine can be used together if necessary.

  Examples of the monoalkylene diamine include ethylene diamine and hexamethylene diamine.

  These monoalkylene diamines can be used alone or in combination of two or more.

  In addition, when using together polyalkylene polyamine and monoalkylene diamine, those compounding ratios are suitably set according to the objective and use.

  Dicarboxylic acids and / or derivatives thereof include, for example, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid, and , Anhydrides of these dicarboxylic acids, and esterified products of dicarboxylic acids.

  These dicarboxylic acids and / or derivatives thereof can be used alone or in combination of two or more.

  The dicarboxylic acid and / or derivative thereof is preferably dicarboxylic acid (non-derivative), more preferably adipic acid.

  The blending ratio of the polyalkylene polyamine and the dicarboxylic acid and / or derivative thereof is, for example, 20 moles or more, preferably 40 moles or more, for example, 80 moles or more with respect to 100 moles in total. It is less than mol, preferably less than 60 mol. Moreover, dicarboxylic acid and / or its derivative (s) are 20 mol or more, for example, Preferably it is 40 mol or more, for example, 80 mol or less, Preferably, it is 60 mol or less.

  When the blending ratio of the polyalkylene polyamine and the dicarboxylic acid and / or derivative thereof is within the above range, the sizing agent can be dispersed well and a polyamino polyamide resin having a viscosity excellent in workability can be obtained.

  The reaction conditions of the polyalkylene polyamine and the dicarboxylic acid and / or derivative thereof are such that the reaction temperature is, for example, 110 ° C. or higher, preferably 140 ° C. or higher, for example, 250 ° C. or lower, preferably 200 ° C. It is as follows. The reaction time is, for example, 0.5 hours or more, preferably 2 hours or more, for example, 12 hours or less, preferably 6 hours or less.

  Thereby, a polyamino polyamide resin can be obtained.

  The number average molecular weight (calculated value) of the obtained polyaminopolyamide resin is, for example, 200 or more, preferably 500 or more, for example, 10,000 or less, preferably 5000 or less.

  The number average molecular weight (calculated value) of the polyaminopolyamide resin can be calculated from the amount of raw material charged.

  Next, in this method, the primary amino group at the molecular end of the polyaminopolyamide resin is reacted with the end capping agent to cap the molecular end of the polyaminopolyamide resin.

  The end-capping agent contains a monovalent aromatic carboxylic acid and / or a monovalent araliphatic carboxylic acid.

  Examples of the monovalent aromatic carboxylic acid include aromatic carboxylic acids having an aromatic ring having 6 to 20 carbon atoms, and more specifically, benzoic acid (carbon number of aromatic ring: 6), naphthalene. Aromatic monocarboxylic acids such as carboxylic acid (carbon number of aromatic ring: 10) and anthracene carboxylic acid (carbon number of aromatic ring: 14) are listed. These monovalent aromatic carboxylic acids can be used alone or in combination of two or more.

  Examples of the monovalent araliphatic carboxylic acid include a monovalent fragrance having an aromatic ring having 6 to 20 carbon atoms and an aliphatic hydrocarbon group having 1 to 20 carbon atoms bonded to the aromatic ring. More specifically, phenylacetic acid (carbon number of aromatic ring: 6, carbon number of aliphatic hydrocarbon group: 1), phenylpropionic acid (carbon number of aromatic ring: 6, aliphatic Examples include aromatic aliphatic monocarboxylic acids such as hydrocarbon group carbon number: 2) and phenyldecanoic acid (aromatic ring carbon number: 6, aliphatic hydrocarbon group carbon number: 10). These monovalent araliphatic carboxylic acids can be used alone or in combination of two or more.

  Further, the monovalent aromatic carboxylic acid and / or the monovalent araliphatic carboxylic acid may have a substituent.

  Examples of the substituent include an alkyl group and a halogen atom. Examples of the alkyl group include linear or branched alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. . Examples of the halogen atom include bromine, chlorine, fluorine, iodine and the like.

  In addition, when multiple substituents are substituted, each substituent may be the same as or different from each other. In addition, the substitution position of each substituent is not particularly limited, and can be an appropriate position.

  The monovalent aromatic carboxylic acid and / or the monovalent araliphatic carboxylic acid is preferably a monovalent aromatic carboxylic acid, more preferably a benzoic acid optionally having a substituent, More preferably, benzoic acid which does not have a substituent is mentioned.

  By using these, it is possible to ensure excellent dispersibility and improve storage stability.

  The end-capping agent preferably further contains a monovalent aliphatic carboxylic acid from the viewpoint of improving storage stability.

  Examples of the monovalent aliphatic carboxylic acid include aliphatic carboxylic acids having a hydrocarbon group having 6 to 22 carbon atoms, and more specifically, lauric acid (carbon number of hydrocarbon group: 11). ), Stearic acid (carbon number of hydrocarbon group: 17), oleic acid (carbon number of hydrocarbon group: 17), behenic acid (carbon number of hydrocarbon group: 21), and the like.

  These monovalent aliphatic carboxylic acids can be used alone or in combination of two or more.

  Moreover, monovalent aliphatic carboxylic acid may have said substituent.

  In addition, when multiple substituents are substituted, each substituent may be the same as or different from each other. In addition, the substitution position of each substituent is not particularly limited, and can be an appropriate position.

  As monovalent aliphatic carboxylic acid, Preferably, a stearic acid and lauric acid are mentioned, More preferably, a stearic acid is mentioned.

  That is, the end capping agent is particularly preferably a combination of benzoic acid having no substituent and stearic acid.

  When the end capping agent contains a monovalent aromatic carboxylic acid and / or a monovalent araliphatic carboxylic acid and a monovalent aliphatic carboxylic acid, the content thereof is a monovalent aromatic carboxylic acid. And / or the monovalent aliphatic carboxylic acid content is, for example, 5 mol or more, preferably 10 mol or more, for example, 2000 mol or less, with respect to 100 mol of the monovalent araliphatic carboxylic acid. Preferably, it is 1000 mol or less.

  If the content of the monovalent aromatic carboxylic acid and / or the monovalent araliphatic carboxylic acid and the monovalent aliphatic carboxylic acid is in the above range, more excellent storage stability can be ensured. .

  The mixing ratio of the end capping agent is, for example, 1.0 mol or more, preferably 2.0 mol or more with respect to 100 mol of the polyalkylene polyamine which is a raw material component of the polyaminopolyamide resin. , 60 mol or less, preferably 40 mol or less.

  Further, the end capping agent is, for example, 2.0 mol or more, preferably 4.0 mol or more, for example, 70 mol or less, preferably 100 mol, based on 100 mol of the primary amino group at the molecular end of the polyaminopolyamide resin. Is 50 mol or less.

  As for the reaction conditions between the polyaminopolyamide resin and the end-capping agent, the reaction temperature is, for example, 110 ° C. or more, preferably 140 ° C. or more, for example, 250 ° C. or less, preferably 200 ° C. or less. The reaction time is, for example, 0.5 hours or more, preferably 2 hours or more, for example, 12 hours or less, preferably 6 hours or less. As a result, a polyaminopolyamide resin whose molecular ends are sealed (hereinafter sometimes referred to as molecular end-blocked PA) is obtained.

  Next, in this method, if necessary, the obtained molecular end-capped PA is diluted with water to obtain an aqueous solution or aqueous dispersion of the molecular end-capped PA.

  The solid content concentration of the molecular end-capped PA is, for example, 10% by mass or more, preferably 20% by mass or more, for example, 60% by mass or less, preferably 40% by mass or less.

  Thereafter, in this method, epichlorohydrin is subjected to an addition reaction with respect to the secondary amino group in the middle portion (that is, the non-terminal portion) in the molecular chain of the molecular end-capped PA.

  The blending ratio of the molecular end-blocking PA and epichlorohydrin is, for example, 50 mol or more, preferably 80 mol of epichlorohydrin with respect to 100 mol of the polyalkylenepolyamine which is a raw material component of the polyaminopolyamide resin. For example, it is 200 mol or less, preferably 140 mol or less.

  As for the reaction conditions between the molecular end-capped PA and epichlorohydrin, the reaction temperature is, for example, 30 ° C. or higher, preferably 40 ° C. or higher, for example, 80 ° C. or lower, preferably 70 ° C. or lower. The reaction time is, for example, 0.5 hours or more, preferably 1.0 hours or more, for example, 10 hours or less, preferably 6 hours or less. Thereby, molecular end-capped PAE can be obtained.

  Further, in this method, if necessary, the molecular end-capped PAE can be heated to cause a crosslinking reaction (crosslinking reaction of epichlorohydrin).

  As for the reaction conditions in the crosslinking reaction, the reaction temperature is, for example, 40 ° C. or higher, preferably 50 ° C. or higher, for example, 90 ° C. or lower, preferably 80 ° C. or lower. The reaction time is, for example, 0.5 hours or more, preferably 1 hour or more, for example, 10 hours or less, preferably 6 hours or less.

  Moreover, in said crosslinking reaction, a crosslinking agent can be mix | blended as needed.

  Examples of the crosslinking agent include ethylene glycol diglycidyl ether, 1,6-hexanediol glycidyl ether, bisphenol A diglycidyl ether, toluene diisocyanate, hexamethylene diisocyanate, and the like.

  These crosslinking agents can be used alone or in combination of two or more.

  The blending ratio of the crosslinking agent is appropriately set depending on the purpose and application.

  By crosslinking in this manner, the size effect can be expressed more efficiently.

  Further, in this method, the quaternary cation density is improved, thereby fixing the sizing agent (described later) to the pulp fiber without depending on the papermaking pH. The tertiary amino group can be quaternized.

  In the quaternization treatment, for example, a quaternizing agent is added together with the epichlorohydrin, and the reaction is performed under the above conditions.

  Examples of the quaternizing agent include dimethyl sulfate, dimethyl carbonate, methyl chloride, allyl chloride, benzyl chloride, propylene oxide, butylene oxide, styrene oxide, epibromohydrin, ethylene chlorohydrin, 3-chloro-1,2 -Propanediol, 3-chloro-2-hydroxypropyltrimethylammonium chloride, glycidyltrimethylammonium chloride, glycidol, butyl glycidyl ether, allyl glycidyl ether, glycidyl methacrylate and the like.

  These quaternizing agents can be used alone or in combination of two or more.

  Preferred examples of the quaternizing agent include 3-chloro-2-hydroxypropyltrimethylammonium chloride and glycidyltrimethylammonium chloride.

  The blending ratio of the quaternizing agent is, for example, more than 0 mole, preferably 5 moles or more, for example, 100 moles or less, preferably 100 moles relative to 100 moles of the polyalkylenepolyamine which is a raw material component of the polyaminopolyamide resin. Is 50 mol or less.

  If the blending ratio of the quaternizing agent is within the above range, the quaternization treatment can be carried out efficiently and efficiently.

  In this method, the pH of the reaction solution can be adjusted to about 2 to 6 by adding an acid as necessary. The acid is not particularly limited, and examples thereof include inorganic acids such as sulfuric acid and hydrochloric acid, and organic acids such as formic acid and acetic acid.

  In such a method, the molecular end-capped PAE is obtained, for example, as an aqueous solution or an aqueous dispersion, and the solid content concentration thereof is, for example, 5% by mass or more, preferably 10% by mass or more. It is not more than mass%, preferably not more than 30 mass%.

  Further, the viscosity (25 ° C.) at 28% by mass of the obtained aqueous solution or dispersion of molecular end-capped PAE is, for example, 50 mPa · s or more, preferably 100 mPa · s or more, for example, 500 mPa · s. Hereinafter, it is preferably 300 mPa · s or less.

  When the viscosity is in the above range, excellent dispersibility can be obtained, and gelation can be suppressed.

  The viscosity can be measured according to JISZ8803.

  Moreover, the cation degree (pH 7) of the molecular end-capped PAE is, for example, 1.0 meq / g or more, and preferably 2.0 meq / g or more.

  When the cation degree is in the above range, the fixability of a sizing agent (described later) to pulp fibers can be improved, and a more excellent size effect can be exhibited.

  The cation degree can be measured with a particle charge meter or the like.

  In the above description, a polyaminopolyamide resin was synthesized by reacting a polyalkylenepolyamine with a dicarboxylic acid and / or a derivative thereof, and then the molecular ends of the polyaminopolyamide resin were capped with an end capping agent. For example, the raw material component (polyalkylene polyamine, dicarboxylic acid and / or derivative thereof) and an end-capping agent may be reacted in advance before the synthesis of the polyaminopolyamide resin. The end capping agent may be reacted simultaneously with the polyamine and the dicarboxylic acid and / or derivative thereof.

  In the above description, the molecular end-capped PAE was synthesized by capping the molecular terminal of the polyaminopolyamide resin with an end-capping agent and then adding epichlorohydrin to the reaction. For example, first, polyaminopolyamide was synthesized. Epichlorohydrin can be subjected to addition reaction with the resin, and then the molecular end of the resulting polyaminopolyamide-epichlorohydrin resin can be capped with an end capping agent. Furthermore, for example, a polyaminopolyamide resin, epichlorohydrin, and an end capping agent can be reacted simultaneously.

  Such a dispersant for sizing agent is capped with an end capping agent in which the molecular terminal of the polyaminopolyamide-epichlorohydrin resin contains a monovalent aromatic carboxylic acid and / or a monovalent araliphatic carboxylic acid. Therefore, a sizing composition that exhibits an excellent size effect can be obtained.

  The sizing agent dispersant preferably contains a cationic polymer in addition to the molecular end-capped PAE from the viewpoint of better expressing the size effect, and particularly preferably, the sizing agent dispersant is It consists of the above-mentioned molecular end-capped PAE and a cationic polymer.

  Specific examples of the cationic polymer include polydiallyldimethylammonium chloride, polyethyleneimine, polyvinylamine, alkyleneimine-modified polyanod polyamide resin, diethylamine epichlorohydrin resin, methacryloyloxyethyltrimethylammonium chloride homopolymer, polyamino Polyamide-epichlorohydrin resin (polyaminopolyamide-epichlorohydrin resin whose molecular ends are not capped), cationic starch and the like can be mentioned.

  These cationic polymers can be used alone or in combination of two or more.

  Preferred examples of the cationic polymer include polydiallyldimethylammonium chloride, polyethyleneimine, and polyvinylamine. More preferred are polydiallyldimethylammonium chloride and polyethyleneimine. More preferred are polydiallyldimethylammonium chloride. It is done.

  By using these as the cationic polymer, it is possible to obtain a sizing agent composition that exhibits a more excellent size effect.

  The number average molecular weight of the cationic polymer is, for example, 500 or more, preferably 1000 or more, for example, 1,000,000 or less, preferably 600,000 or less.

  When the number average molecular weight of the cationic polymer is within the above range, an excellent cation density can be maintained and an excessive increase in viscosity can be suppressed.

  The number average molecular weight can be determined by size exclusion chromatography.

  Moreover, when the dispersing agent for sizing agents contains a cationic polymer, the content thereof is, for example, 5 parts by mass or more, preferably 10 parts by mass or more with respect to 100 parts by mass of the molecular end-capped PAE. , 200 parts by mass or less, preferably 180 parts by mass or less.

  When the content of the cationic polymer is within the above range, an excellent cation density can be maintained, an excessive increase in viscosity can be suppressed, and excellent dispersibility can be ensured.

  The cationic polymer may be prepared, for example, by mixing with the above-described molecular end-capped PAE in advance and preparing as a sizing agent dispersant. For example, when the sizing agent dispersing agent is used, It may be added simultaneously with molecular end-capping PAE.

  The sizing agent dispersing agent described above is a single agent independent of the paper used to disperse the sizing agent, and the state contained in the paper is excluded.

  Such a sizing agent dispersant is suitably used in the preparation of a sizing composition containing a rosin sizing agent.

  More specifically, the sizing composition contains, for example, the above sizing agent dispersant and a rosin sizing agent, preferably the above sizing agent dispersing agent and rosin sizing agent. It consists of.

  Examples of the rosin sizing agent include rosin resins such as rosins and rosin derivatives.

  The rosins are tall rosin, gum rosin, and wood rosin, and are a concept including a disproportionated rosin, a polymerized rosin, a hydrogenated rosin, other chemically modified rosins, or purified products thereof.

  The rosin derivatives include rosin esters, unsaturated carboxylic acid-modified rosins, unsaturated carboxylic acid-modified rosin esters, or rosin-modified phenols, carboxylic acid groups of rosins modified with rosins and unsaturated carboxylic acids. And rosin alcohols that have been reduced.

  Rosin esters can be obtained, for example, by reacting the above rosins with a polyhydric alcohol by a known esterification method.

  Examples of polyhydric alcohols include dihydric alcohols such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylene glycol, tetramethylene glycol, 1,3-butanediol, and 1,6-hexanediol, such as glycerin, triethylene glycol, and the like. Trihydric alcohols such as methylolpropane, trimethylolethane and triethylolethane, for example, tetrahydric alcohols such as pentaerythritol and dipentaerythritol, such as triethanolamine, tripropanolamine, triisopropanolamine, N-isobutyldiethanolamine, N -Amino alcohols such as normal butyl diethanolamine. These polyhydric alcohols can be used alone or in combination of two or more.

  The mixing ratio of rosins and polyhydric alcohols is such that the molar ratio (OH / COOH) of the hydroxyl groups of the polyhydric alcohol to the carboxyl groups of the rosins is 0.2 to 1.2. In the reaction between rosins and polyhydric alcohols, the reaction temperature is, for example, 150 to 300 ° C., and the reaction time is, for example, 2 to 30 hours. In this reaction, a known catalyst can be blended at an appropriate ratio as necessary.

  Unsaturated carboxylic acid-modified rosins can be obtained, for example, by reacting the above rosins with α, β-unsaturated carboxylic acids by a known method.

  Examples of the α, β-unsaturated carboxylic acids include α, β-unsaturated carboxylic acids and acid anhydrides thereof. Specifically, for example, fumaric acid, maleic acid, maleic anhydride, Itaconic acid, citraconic acid, citraconic anhydride, acrylic acid, methacrylic acid and the like can be mentioned. These α, β-unsaturated carboxylic acids can be used alone or in combination of two or more.

  The blending ratio of rosins and α, β-unsaturated carboxylic acids is, for example, 1 mol or less for α, β-unsaturated carboxylic acids with respect to 1 mol of rosins. In the reaction between rosins and α, β-unsaturated carboxylic acids, the reaction temperature is, for example, 150 to 300 ° C., and the reaction time is, for example, 1 to 24 hours. In this reaction, a known catalyst can be blended at an appropriate ratio as necessary.

  Unsaturated carboxylic acid-modified rosin esters can be obtained, for example, by reacting the above-mentioned rosins with the above-mentioned polyhydric alcohols and the above-mentioned α, β-unsaturated carboxylic acids sequentially or simultaneously. .

  When sequentially reacting the above components, first, rosins and polyhydric alcohol are reacted, and then α, β-unsaturated carboxylic acids are reacted, or first, rosins and α, β-unsaturated. A carboxylic acid is reacted, and then a polyhydric alcohol is reacted. The reaction conditions in the esterification reaction between rosins and polyhydric alcohols and the modification reaction between rosins and α, β-unsaturated carboxylic acids can be the same as described above.

  Examples of the rosin derivative further include an amide compound of rosin and an amine salt of rosin.

  The amide compound of rosin can be obtained, for example, by reacting the above rosins with an amidating agent.

  Examples of the amidating agent include primary and / or secondary polyamine compounds, polyoxazoline compounds, and polyisocyanate compounds.

  The primary and / or secondary polyamine compound is a compound containing two or more primary and / or secondary amino groups in one molecule, and rosin is formed by a condensation reaction with a carboxyl group contained in rosins. Can be amidated. Specific examples of such polyamine compounds include ethylenediamine, N-ethylaminoethylamine, 1,2-propanediamine, 1,3-propanediamine, N-methyl-1,3-propanediamine, and bis (3 -Aminopropyl) ether, 1,2-bis (3-aminopropoxy) ethane, 1,3-bis (3-aminopropoxy) -2,2-dimethylpropane, 1,4-diaminobutane, laurylaminopropyl Chain diamines such as amines, for example, cyclic diamines such as 2-aminomethylpiperidine, 4-aminomethylpiperidine, 1,3-di (4-piperidyl) -propane, homopiperazine, such as diethylenetriamine, triethylenetetramine , Iminobispropylamine, methyliminobispropylamine, etc. Riamin such news, etc. These hydrohalic acid salts.

  These primary and / or secondary polyamine compounds can be used alone or in combination of two or more.

  The polyoxazoline compound is a compound containing two or more polyoxazoline rings in one molecule, and rosin can be amidated by addition reaction with a carboxyl group contained in rosins. Examples of such polyoxazoline compounds include 2,2 '-(1,3-phenylene) -bis (2-oxazoline).

  These polyoxazoline compounds can be used alone or in combination of two or more.

  The polyisocyanate compound is a compound containing two or more isocyanate groups in one molecule, and rosin can be amidated by addition condensation decarboxylation reaction with a carboxyl group contained in rosins. Examples of such polyisocyanate compounds include aromatic diisocyanates (for example, tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof). Mixture), 1,5-naphthalene diisocyanate, diphenylmethane diisocyanate (4,4′-, 2,4′- or 2,2′-diphenylmethane diisocyanate or mixtures thereof), 4,4′-toluidine diisocyanate, etc.) Araliphatic diisocyanates (eg, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixtures thereof), tetramethyl xylylene diisocyanate (1,3- or 1,4-tet Methyl xylylene diisocyanate or mixtures thereof), aliphatic diisocyanates (eg, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, etc.) Alicyclic diisocyanates (for example, cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorodiisocyanate), methylene bis (cyclohexyl isocyanate), norbornane diisocyanate, bis (isocyanatomethyl) cyclohexane, etc. Examples thereof include diisocyanates and derivatives thereof (for example, multimers, polyol adducts, and the like).

  These polyisocyanate compounds can be used alone or in combination of two or more.

  These amidating agents can be used alone or in combination of two or more.

  The mixing ratio of rosins and amidating agents is the molar ratio (OH / activity) of active groups (primary and / or secondary amino groups, polyoxazoline rings, isocyanate groups) of amidating agents to carboxyl groups of rosins. Group) is, for example, 0.2 to 1.2. In the reaction between rosins and polyhydric alcohols, the reaction temperature is, for example, 120 to 300 ° C., and the reaction time is, for example, 2 to 30 hours. In this reaction, a known catalyst can be blended at an appropriate ratio as necessary.

  The amine salt of rosin can be obtained by neutralizing a carboxyl group contained in rosins with a tertiary amine compound.

  Examples of the tertiary amine compound include tri-C1-4 alkylamines such as trimethylamine and triethylamine, and heterocyclic amines such as morpholine.

  These tertiary amine compounds can be used alone or in combination of two or more.

  These rosin sizing agents can be used alone or in combination of two or more.

  And a sizing agent composition can be obtained as a rosin emulsion by carrying out water dispersion of the rosin type sizing agent (rosin type resin) using said dispersing agent for sizing agents.

  More specifically, the sizing agent composition is produced, for example, by a solvent-type emulsification method, a solventless emulsification method, a phase inversion emulsification method, or other known emulsification methods.

  Although the emulsification method is not particularly limited, for example, it can conform to the method described in paragraph numbers [0024] to [0025] of JP-A-2008-303269.

  Specifically, for example, in the solvent-type emulsification method, first, a rosin-based sizing agent such as a chlorine-based hydrocarbon solvent such as methylene chloride, an aromatic solvent such as toluene or xylene, methyl ketone, methyl isobutyl ketone, etc. A rosin sizing agent solution is obtained by dissolving it in an organic solvent such as a ketone solvent or other solvent capable of dissolving rosin sizing agent. Then, separately, a dispersion in which a sizing agent dispersant and water are mixed and dissolved is prepared, and the dispersion and the rosin sizing agent solution are premixed to obtain an aqueous emulsion of coarse particles (preliminary emulsion). ) Is prepared. Then, after finely emulsifying the obtained aqueous emulsion using various mixers, colloid mills, high-pressure emulsifiers, high-pressure discharge emulsifiers, high-shear emulsifiers, etc., while heating at normal pressure or reduced pressure, Remove the organic solvent.

  In the solventless emulsification method, for example, a molten rosin-based sizing agent and a dispersion are preliminarily mixed at normal pressure or under pressure to prepare an aqueous emulsion of coarse particles. Similarly emulsify.

  In the phase inversion emulsification method, after the rosin sizing agent is heated and melted at normal pressure or under pressure, the dispersion is gradually added while stirring to obtain a water-in-oil emulsion. Invert to oil emulsion. In addition, this method can be employed by either a solvent method or a solventless method.

  Further, in this method, other dispersants (dispersants excluding the above sizing agent dispersant) can be used as necessary.

  Specific examples of other dispersants include cationic dispersants, nonionic dispersants, amphoteric dispersants, and synthetic polymer dispersants.

  Examples of the cationic dispersant include alkyl trimethyl ammonium chloride, alkyl trimethyl ammonium bromide, benzalkonium chloride, benzalkonium bromide, alkyl pyridinium chloride and the like.

  Nonionic dispersants include, for example, polyoxyethylene alkyl (or alkenyl) ethers such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene styryl phenyl ether and other polyoxyethylene styryl phenyl ether. Sorbitan higher fatty acid esters such as ethylene alkylphenyl ethers, sorbitan monolaurate, sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene monolaurate, polyoxyethylene Polyoxyethylene higher fatty acid esters such as monooleate, oleic acid monoglyceride, stearic acid monoglyceride Serine higher fatty acid esters, polyoxyethylene-polyoxypropylene block copolymers.

  Examples of the amphoteric dispersant include carboxybetaine, imidazoline betaine, sulfobetaine, aminocarboxylic acid, sulfation of a product condensate of ethylene oxide and / or propylene oxide and alkylamine or diamine, or a sulfonated adduct. .

  Synthetic polymer dispersants include, for example, styrene, α-methylstyrene, vinyl toluene, (meth) acrylic acid, maleic acid, (meth) acrylic acid esters, acrylic amide, vinyl acetate, styrene sulfonic acid, isoprene sulfone. Water dispersion in which a polymer obtained by polymerizing two or more polymerizable monomers such as acid, vinyl sulfonic acid, allyl sulfonic acid and 2- (meth) acrylamide-2-methylpropane sulfonic acid is dispersed or solubilized in water And water-dispersible or water-soluble polymers obtained by copolymerization reaction of styrenic polymers and styrenes with aminoalkyl esters of acrylic acid or methacrylic acid, and the like.

  These other dispersants (dispersants excluding the sizing agent dispersant) can be used alone or in combination of two or more.

  Further, the blending ratio with other dispersants (dispersants excluding the sizing agent dispersant) is not particularly limited, and is appropriately set according to the purpose and application.

  In the sizing composition thus obtained (rosin emulsion), the solid content concentration of the rosin sizing agent is, for example, 30% by mass or more, preferably 35% by mass or more, for example, 55% by mass or less, Preferably, it is 50 mass% or less. Moreover, the solid content concentration of the dispersing agent for sizing agents is, for example, 5% by mass or more, preferably 10% by mass or more, for example, 40% by mass or less, preferably 30% by mass or less.

  The blending ratio of the rosin sizing agent to the sizing agent dispersing agent is such that the solid content of the sizing agent dispersing agent is, for example, 3 parts by mass or more, preferably 5 to 100 parts by mass of the rosin sizing agent. For example, 20 parts by mass or less, preferably 15 parts by mass or less.

  Moreover, the average particle diameter of the sizing composition (rosin emulsion) obtained is, for example, 0.3 μm or more, preferably 0.4 μm or more, for example, 2.0 μm or less, preferably 1.5 μm or less. is there.

  The average particle size can be measured with a particle size distribution meter or the like.

  When the average particle diameter is in the above range, excellent foamability, cation density and storage stability can be obtained.

  Moreover, an additive can be mix | blended with a sizing agent composition as needed.

  Examples of the additive include inorganic flocculants such as aluminum sulfate, polyaluminum chloride, and basic aluminum chloride.

  These additives can be used alone or in combination of two or more.

  As an additive, Preferably, an inorganic flocculant, More preferably, an aluminum sulfate is mentioned.

  The blending ratio of the additive is, for example, more than 0 parts by mass, preferably 5 parts by mass or more, for example, 50 parts by mass or less, preferably 100 parts by mass of the total solid content of the sizing agent composition. 30 parts by mass or less.

  If the blending ratio of the additive is in the above range, the size effect can be improved with good cost.

  Such an additive may be prepared, for example, as a sizing composition by previously mixing with the above sizing agent dispersant and rosin-based sizing agent. The sizing agent dispersant and the rosin sizing agent may be added simultaneously.

  Note that the sizing composition described above is a single drug independent of paper, and the state contained in the paper is excluded.

  And since such a sizing agent dispersant is used for such a sizing agent composition, an excellent sizing effect can be exhibited, and excellent water resistance can be imparted to paper.

  Therefore, the above sizing agent composition is suitably used in the production of paper.

  The method for producing the paper is not particularly limited, and a known method can be adopted.

  More specifically, for example, paper can be obtained by adding the sizing agent composition to a pulp slurry and making paper. In addition, for example, by applying the above sizing composition to paper obtained by papermaking from pulp slurry (untreated paper) and drying, paper treated with the sizing composition can be obtained.

  Such paper is excellent in water resistance because it is obtained using the sizing composition.

Next, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited by the following Example. “Part” and “%” are based on mass unless otherwise specified. Moreover, the numerical value of the Example shown below can be substituted for the numerical value (namely, upper limit value or lower limit value) described in embodiment.
<Dispersant for sizing agent>
Example 1
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen gas inlet tube was charged with 344 parts (3.34 mol) of diethylenetriamine and 370 parts (2.53 mol) of adipic acid. After changing to a nitrogen atmosphere, the temperature was gradually raised, and a dehydration condensation reaction was performed at 150 to 160 ° C. for 3 hours to obtain a polyaminopolyamide resin. The number average molecular weight (calculated value) of the polyaminopolyamide resin was 523.

  Subsequently, 80 parts (0.65 mol) of benzoic acid was added, subjected to a dehydration condensation reaction at 160 to 170 ° C. for 4 hours, diluted with warm water to obtain a 30% benzoic acid-introduced polyaminopolyamide (molecularly end-capped PA) aqueous solution. Obtained.

  Subsequently, 2490 parts of 30% benzoic acid-introduced polyaminopolyamide aqueous solution was charged into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water separator, and a nitrogen gas introduction tube, and epichloromethane was stirred at 40 ° C. with stirring. Hydrin 432 parts (4.67 mol) was added dropwise over 30 minutes and left for 30 minutes.

  Then, warm water was added to dilute to 28%, followed by a crosslinking reaction at 60 ° C. for 3 hours. When the viscosity reached 50 mPa · s (60 ° C.) or more, the pH was adjusted to 3 or less with 10% sulfuric acid, and the solid content concentration A molecular end-capped PAE (emulsifying dispersant) having 28.0%, a viscosity of 150 mPa · s (25 ° C.), and a cationic degree of 2.1 meq / g (pH 7) was obtained.

  The viscosity was measured according to JIS Z 8803, and the cation degree was measured by a particle charge meter (model number: PCD-04, manufactured by BTG).

Example 2
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen gas inlet tube was charged with 344 parts (3.34 mol) of diethylenetriamine and 407 parts (2.79 mol) of adipic acid. After changing to a nitrogen atmosphere, the temperature was gradually raised, and a dehydration condensation reaction was carried out at 150 to 160 ° C. for 3 hours.

  Subsequently, 40 parts (0.33 mol) of benzoic acid and 18.5 parts (0.07 mol) of stearic acid were added, subjected to a dehydration condensation reaction at 160-170 ° C. for 4 hours, diluted with warm water, and 30% benzoic acid. An acid / stearic acid-introduced polyaminopolyamide (molecular end-capped PA) aqueous solution was obtained.

  Subsequently, 2531 parts of the 30% benzoic acid / stearic acid-introduced polyaminopolyamide aqueous solution obtained above was charged into a four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen gas introduction tube. At 40 ° C. with stirring, 129 parts (0.68 mol) of 80% glycidyltrimethylammonium chloride solution was added and reacted for 60 minutes.

  Subsequently, 309 parts (3.34 mol) of epichlorohydrin was added dropwise over 30 minutes, and then left for 30 minutes.

  Then, warm water was added to dilute to 28%, and a 60 ° C. cross-linking reaction was performed. When the viscosity reached 50 mPa · s (60 ° C.) or higher, the pH was adjusted to 3 or lower with 10% sulfuric acid, and the solid content concentration was 28.6%. A molecular end-capped PAE (emulsifying dispersant) having a viscosity of 260 mPa · s (25 ° C.) and a cationic degree of 2.5 meq / g (pH 7) was obtained.

Example 3
The blending amount of diethylenetriamine is 344 parts (3.34 mol), the blending amount of adipic acid is 360 parts (2.46 mol), the blending amount of benzoic acid is 8 parts (0.07 mol), and lauric acid is used instead of stearic acid. A 30% aqueous benzoic acid / lauric acid-introduced polyaminopolyamide (molecularly end-capped PA) aqueous solution was obtained in the same manner as in Example 2 except that the part (0.65 mol) was used.

  Subsequently, Examples were prepared except that 2659 parts of the 30% benzoic acid / lauric acid-introduced polyaminopolyamide aqueous solution obtained above were charged and the blending amount of the 80% glycidyltrimethylammonium chloride solution was 317 parts (1.68 mol). In the same manner as in No. 2, molecular end-capped PAE (emulsifying dispersant) having a solid content concentration of 28.3%, a viscosity of 170 mPa · s (25 ° C.), and a cation degree of 2.7 meq / g (pH 7) was obtained.

Example 4
344 parts (3.34 mol) of diethyleneamine, 360 parts (2.46 mol) of adipic acid, 80 parts (0.65 mol) of benzoic acid, 13 parts of lauric acid A 30% benzoic acid / lauric acid-introduced polyaminopolyamide (molecular end-capped PA) aqueous solution was obtained in the same manner as in Example 3 except that the amount was changed to (0.07 mol).

  Subsequently, 2505 parts of the 30% benzoic acid / lauric acid-introduced polyaminopolyamide aqueous solution obtained above were charged, and in the same manner as in Example 3, the solid content concentration was 28.0% and the viscosity was 100 mPa · s (25 ° C.). A molecular end-capped PAE (emulsifying dispersant) having a cationic degree of 2.7 meq / g (pH 7) was obtained.

Example 5
344 parts (3.34 mol) of diethyleneamine, 436 parts (2.99 mol) of adipic acid, 16 parts (0.13 mol) of benzoic acid, 19 parts of stearic acid A 30% benzoic acid / stearic acid-introduced polyaminopolyamide aqueous solution was obtained in the same manner as in Example 2 except that the amount was changed to (0.09 mol).

  Subsequently, 2535 parts of the 30% benzoic acid / stearic acid-introduced polyaminopolyamide aqueous solution obtained above were charged, the amount of epichlorohydrin was 309 parts (3.34 mol), and the 80% glycidyltrimethylammonium chloride solution was added. Instead, a solid concentration of 28.3% and a viscosity of 200 mPa · s were obtained in the same manner as in Example 2 except that 160 parts (0.68 mol) of a 65% 3-chloro-2-hydroxypropyltrimethylammonium chloride solution was used. A molecular end-capped PAE (emulsifying dispersant) having a cation degree of 2.8 meq / g (pH 7) was obtained (25 ° C.).

Example 6
344 parts (3.34 mol) of diethyleneamine, 365 parts (2.50 mol) of adipic acid, 4 parts (0.03 mol) of benzoic acid, 185 parts of lauric acid A 30% benzoic acid / lauric acid-introduced polyaminopolyamide aqueous solution was obtained in the same manner as in Example 4 except for changing to (0.65 mol).

  Subsequently, 2659 parts of the 30% benzoic acid / lauric acid-introduced polyaminopolyamide aqueous solution obtained above was charged, and in the same manner as in Example 4, the solid content concentration was 28.3% and the viscosity was 145 mPa · s (25 ° C.). A molecular end-capped PAE (emulsifying dispersant) having a cationic degree of 2.6 meq / g (pH 7) was obtained.

Example 7
344 parts (3.34 mol) of diethyleneamine, 365 parts (2.50 mol) of adipic acid, 80 parts (0.65 mol) of benzoic acid, 7 parts of lauric acid A 30% benzoic acid / lauric acid-introduced polyaminopolyamide aqueous solution was obtained in the same manner as in Example 4 except that the amount was changed to (0.03 mol).

  Subsequently, 2498 parts of the 30% benzoic acid / lauric acid-introduced polyaminopolyamide aqueous solution obtained above were charged, and in the same manner as in Example 4, the solid content concentration was 28.0% and the viscosity was 150 mPa · s (25 ° C.). A molecular end-capped PAE (emulsifying dispersant) having a cationic degree of 2.7 meq / g (pH 7) was obtained.

Comparative Example 1
Example 3 except that the amount of diethylenetriamine was changed to 344 parts (3.34 mol), the amount of adipic acid was changed to 370 parts (2.53 mol), and the amount of stearic acid was changed to 185 parts (0.65 mol). A 30% stearic acid-introduced polyaminopolyamide aqueous solution was obtained in the same manner.

  Subsequently, 2842 parts of the 30% stearic acid-introduced polyaminopolyamide aqueous solution obtained above was charged, and a molecular end having a solid content concentration of 28.5% and a viscosity of 180 mPa · s (25 ° C.) in the same manner as in Example 4. A sealed PAE (emulsifying dispersant) was obtained.

  Table 1 shows the formulation of Examples 1 to 7 and Comparative Example 1.

<Rosin sizing agent>
Production Example 1 (Production of unsaturated carboxylic acid-modified rosin)
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen gas inlet tube was charged with 1000 parts of tall oil rosin (acid number 170) under nitrogen gas introduction, and the temperature was raised to 165 ° C. Thereafter, 100 parts of maleic anhydride was added. And after heating up to 200 degreeC, it was made to react for 2 hours and the unsaturated carboxylic acid modified rosin was obtained.

  The obtained unsaturated carboxylic acid-modified rosin had an acid value of 235 and a softening point of 118 ° C. (ring and ball method).

Production Example 2 (Production of rosin resin mixture)
Into the same four-necked flask as in Production Example 1 above, 887 parts of tall oil rosin (acid number 170) was charged under introduction of nitrogen gas, and the temperature was raised to 180 ° C., after which 83 parts of glycerin was added, and 6 minutes at 250 ° C. The esterification reaction was performed for a time to obtain rosin esters having an acid value of 35 or less and a softening point of 85 ° C.

  Thereafter, 50 parts of the obtained rosin esters and 50 parts of the unsaturated carboxylic acid-modified rosin of Production Example 1 were mixed to obtain a mixture of rosin resins.

Production Example 3 (Production of Unsaturated Carboxylic Acid-Modified Rosin Esters)
To a four-necked flask similar to Production Example 1 above, 9002 parts of tall oil rosin (acid number 170) was charged under nitrogen gas introduction, the temperature was raised to 160 ° C., and then 726 parts of propylene glycol and maleic anhydride at 155 ° C. 1098 copies were loaded. Then, the temperature was raised to 200 ° C. over 2 hours, and the reaction was carried out while maintaining at 260 ° C. for 5 hours, followed by cooling and unsaturated carboxylic acid-modified rosin ester having an acid value of 127 and a softening point of 90 ° C. (ring and ball method). Class 10470 parts were obtained.
<Sizing agent composition>
Example 8
200 parts of unsaturated carboxylic acid-modified rosin obtained in Production Example 1 is dissolved in 200 parts of toluene, and 64 parts of molecular end-capped PAE (emulsifying dispersant) of Example 1 and 281 parts of ion-exchanged water are added. The mixture was mixed with a homomixer at 40 ° C. to obtain a crude emulsion.

The crude emulsion was then passed twice through a piston type high pressure emulsifier (300 kg / cm ² ) to obtain a fine emulsion. Thereafter, toluene was distilled off by distillation under reduced pressure.

  Next, 125.3 parts of a 30% aluminum sulfate (sulfuric acid band) solution was added to the obtained emulsion, and then diluted with water to obtain a sizing composition.

  The obtained sizing composition had a solid content concentration of 35.1% and an average particle size of 0.80 μm.

Examples 9-14
As shown in Table 2, Example 8 was used except that instead of the molecular end-capped PAE (emulsified dispersant) of Example 1, the molecular end-capped PAE (Emulsified dispersant) of Examples 2 to 7 was used. A sizing composition was obtained in the same manner. Table 2 shows the solid content concentration and average particle diameter of the obtained sizing agent composition.

Comparative Example 2
The solid content concentration was the same as in Example 8, except that the molecular end-capped PAE (emulsifying dispersant) of Comparative Example 1 was used instead of the molecular end-capped PAE (emulsifying dispersant) of Example 1. A sizing composition having 35.3% and an average particle size of 0.54 μm was obtained. Table 2 shows the solid content concentration and average particle diameter of the obtained sizing agent composition.

Example 15
200 parts of unsaturated carboxylic acid-modified rosin obtained in Production Example 1 is dissolved in 200 parts of toluene, 25.7 parts of molecular end-capped PAE (emulsifying dispersant) of Example 2 and 40% polydiallyldimethylammonium chloride. 27.0 parts of a solution (manufactured by SNF: FL-4440) (number average molecular weight 300,000) and 292.3 parts of ion-exchanged water were added and mixed with a homomixer at 40 ° C. to obtain a crude emulsion. It was.

The crude emulsion was then passed twice through a piston type high pressure emulsifier (300 kg / cm ² ) to obtain a fine emulsion. Thereafter, toluene was distilled off by distillation under reduced pressure.

  Next, 125.3 parts of a 30% aluminum sulfate (sulfate band) solution was added to the obtained emulsion, and then diluted with water to obtain a sizing composition.

  The obtained sizing composition had a solid content concentration of 35.1% and an average particle size of 0.83 μm.

Example 16
The blending amount of molecular end-capped PAE (emulsifying dispersant) in Example 2 is 38.6 parts, the blending amount of 40% polydiallyldimethylammonium chloride solution is 18 parts, and the blending amount of ion-exchanged water is 288.4 parts. A sizing agent composition having a solid content concentration of 35.6% and an average particle size of 0.72 μm was obtained in the same manner as in Example 15 except for the change.

Example 17
The blending amount of molecular end-capped PAE (emulsifying dispersant) of Example 2 was 57.9 parts, the blending amount of 40% polydiallyldimethylammonium chloride solution was 4.5 parts, and the blending amount of ion-exchanged water was 282.6. A sizing composition having a solid content concentration of 35.1% and an average particle diameter of 0.58 μm was obtained in the same manner as in Example 15 except that the composition was changed to parts.

Example 18
The blending amount of molecular end-capped PAE (emulsifying dispersant) of Example 2 was 22.5 parts, the blending amount of 40% polydiallyldimethylammonium chloride solution was 29.3 parts, and the blending amount of ion-exchanged water was 293.3. A sizing composition having a solid content concentration of 35.2% and an average particle size of 1.28 μm was obtained in the same manner as in Example 15 except that the composition was changed to parts.

Example 19
The blending amount of molecular end-capped PAE (emulsifying dispersant) of Example 2 was 61.1 parts, the blending amount of 40% polydiallyldimethylammonium chloride solution was 2.3 parts, and the blending amount of ion-exchanged water was 281.7. A sizing composition having a solid content concentration of 35.4% and an average particle size of 0.55 μm was obtained in the same manner as in Example 15 except that the composition was changed to parts.

Example 20
The blending amount of the molecular end-capped PAE (emulsifying dispersant) in Example 2 was 41.8 parts, and instead of the 40% polydiallyldimethylammonium chloride solution, 20% polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd .: Epomin SP-006) ) (Number average molecular weight 600) 31.5 parts, and the amount of ion-exchanged water was changed to 271.7 parts by the same method as in Example 15 except that the solid content concentration was 35.0%. A sizing agent composition having an average particle size of 0.66 μm was obtained.

Example 21
The compounding amount of the molecular end-capped PAE (emulsifying dispersant) of Example 2 was 41.8 parts, and instead of the 40% polydiallyldimethylammonium chloride solution, 20% polyvinylamine (manufactured by Daianitrix Co., Ltd .: PVAm-0570B) (Number average molecular weight 100,000) 31.5 parts were used, and the solid content concentration was 35.4% in the same manner as in Example 15 except that the amount of ion-exchanged water was changed to 271.7 parts. A sizing agent composition having an average particle size of 0.63 μm was obtained.

Example 22
Instead of the unsaturated carboxylic acid-modified rosin obtained in Production Example 1, the mixture of the rosin resin obtained in Production Example 2 was used, and instead of aluminum sulfate, 125.3 parts of 30% polyaluminum chloride solution was used. A sizing composition having a solid content concentration of 35.3% and an average particle size of 0.81 μm was obtained in the same manner as in Example 15.

Example 23
The unsaturated carboxylic acid-modified rosin ester obtained in Production Example 3 was used in place of the unsaturated carboxylic acid-modified rosin obtained in Production Example 1, and 30% polyaluminum chloride solution 125.3 was used in place of aluminum sulfate. A sizing composition having a solid content concentration of 35.2% and an average particle size of 0.75 μm was obtained in the same manner as in Example 15 except that the parts were used.

Comparative Example 3
The solid content concentration was the same as in Example 16 except that the molecular end-capped PAE (emulsifying dispersant) of Comparative Example 1 was used instead of the molecular end-capped PAE (emulsifying dispersant) of Example 2. A sizing agent composition having 35.1% and an average particle size of 0.65 μm was obtained.
<Evaluation>
(1) Papermaking evaluation 1 (Cobb water absorption)
Using 100% corrugated paper, a 3% pulp slurry was prepared at 40 ° C.

  Next, in this pulp slurry, 0.5% (ultra dry mass basis) of aluminum sulfate (sulfuric acid band) and 0.2% of pulp (ultra dry mass basis) of each sizing composition are sequentially added. After the addition, the pulp slurry was diluted to 1%. The pH of the obtained pulp slurry was 7.0.

Next, the pulp slurry is stirred uniformly and then dehydrated for 1 minute under a pressure of 5 kg / cm ² with a target weight of 80 ± 1 g / cm ² using a TAPPI standard sheet machine (manufactured by Kumagai Riki Kogyo Co., Ltd.). Then, it was dried at 105 ° C. for 3 minutes with a drum dryer.

  The obtained paper was conditioned for 24 hours under the conditions of 23 ° C. and 50% relative humidity, and then measured for Cobb water absorption (JIS P 8140). The results are shown in Table 2.

  In addition, the measuring method of the Cobb water absorption will be described below.

That is, first, a piece of paper is sandwiched between rings and a specified amount of water is poured into the ring. After a certain time (usually 2 minutes), the water in the ring is removed, and excess water on the paper surface is wiped off, and then the mass is measured. In addition, the amount of water absorbed in the paper in a certain time is measured, and the smaller the numerical value, the better the size effect.
(2) Papermaking evaluation 2 (Stick human sizing degree)
A 3% pulp slurry was prepared at 40 ° C. using a mixed sheet of 70% hardwood pulp (LBKP) and 30% softwood pulp (NBKP).

  Then, in this pulp slurry, calcium carbonate (obtained by Okutama Kogyo Co., Ltd .; TP-121) of 10% (ultra dry mass basis) of the pulp, aluminum sulfate (sulfate band) of 1.0% of the pulp (absolute mass basis) ), 0.5% (based on absolute dry mass) cationic starch (manufactured by Nippon Food Processing Co., Ltd .; Neotec 40T), and 0.02% (based on absolute dry mass) polyacrylamide-based retention agent (based on absolute dry mass) Hymolock NR-12MLH (manufactured by Hymo Co., Ltd.) and each sizing agent composition of 0.4% to pulp (based on absolute dry mass) were sequentially added, and the slurry was diluted to 1%. The pH of the obtained pulp slurry was 7.5.

Next, the pulp slurry is stirred uniformly, and then dehydrated for 1 minute under a pressure of 5 kg / cm ² with a target of 64 ± 1 g / cm ² using a TAPPI standard sheet machine (manufactured by Kumagai Riki Kogyo Co., Ltd.). Then, it was dried at 105 ° C. for 3 minutes with a drum dryer.

  The obtained paper was conditioned for 24 hours under the conditions of 23 ° C. and 50% relative humidity, and then measured for a degree of sizing (JIS P 8122).

  In addition, the measuring method of a steech human sizing degree is described below.

That is, first, a 5 cm square paper test piece is prepared, and a ferric chloride solution is applied to the paper surface with a brush and simultaneously floated on the ammonium thiocyanate solution. As soon as the specimen is floated, the stopwatch is activated and the number of seconds until ammonium thiocyanate and ferric chloride come into contact is measured. In addition, the Steecht sizing degree is a measurement of the time taken for the water soaked from the back of the paper to reach the front, and the larger the value, the better the size effect.
(3) Storage stability (centrifugation test (Fallout))
44 g of each sizing composition was weighed and centrifuged at 4000 rpm for 30 minutes using a 50 cc centrifuge tube. Thereafter, the supernatant was removed (decantation), and the resin settled at the bottom was dissolved in acetone and transferred to a pre-weighed cup.

  Thereafter, acetone was removed on a hot plate, dried at 100 ° C. for 1 hour, and the mass was measured.

  And the centrifugal sedimentation rate was calculated | required by the following formula. The results are shown in Table 2.

Centrifugal sedimentation rate (%) = (mass of precipitated resin (g) × 100/44 × solid content concentration of sample (%)) × 100
The lower the centrifugal sedimentation rate, the better the storage stability.

  The details of the abbreviations in the table are as follows.

pDADMAC: polydiallyldimethylammonium chloride, FL-4440 manufactured by SNF
PEI: Polyethyleneimine, manufactured by Nippon Shokubai Co., Ltd., Epomin SP-006
PVAm: Polyvinylamine, manufactured by Diamond Nitrix, PVAm-0570B
Alum: Aluminum sulfate, manufactured by Asada Chemical Co., Ltd. PAC: Polyaluminum chloride, manufactured by Taki Chemical Co., Ltd .: PAC-250A

Claims (8)

A polyaminopolyamide-epichlorohydrin resin whose molecular ends are capped by an end capping agent,
The sizing agent dispersant is characterized in that the end capping agent contains a monovalent aromatic carboxylic acid and / or a monovalent araliphatic carboxylic acid. The end capping agent comprises a monovalent aromatic carboxylic acid;
The dispersing agent for sizing agents according to claim 1, wherein the aromatic carboxylic acid contains benzoic acid which may have a substituent.   The dispersing agent for sizing agents according to claim 1 or 2, wherein the end-capping agent further contains a monovalent aliphatic carboxylic acid. In the end capping agent,
The dispersion for a sizing agent according to claim 3, wherein the content of the aliphatic carboxylic acid is 5 mol or more and 2000 mol or less with respect to 100 mol of the aromatic carboxylic acid and / or the araliphatic carboxylic acid. Agent.   Furthermore, the dispersing agent for sizing agents as described in any one of Claims 1-4 containing the at least 1 sort (s) of cationic polymer selected from the group which consists of polydiallyldimethylammonium chloride, polyethyleneimine, and polyvinylamine.   The dispersing agent for sizing agents according to claim 5, wherein the content of the cationic polymer is 5 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the polyaminopolyamide-epichlorohydrin resin. Dispersant for sizing agent according to any one of claims 1 to 6,
A sizing composition comprising a rosin-based sizing agent. Characterized in that it contains a sizing composition according to claim 7, paper.