JP2018012904A - Agent for imparting flexibility to paper and preventing occurrence of paper powder and method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an agent capable of imparting flexibility to paper and preventing the occurrence of paper powder.SOLUTION: An agent is added to aqueous slurry of pulp for imparting flexibility to paper and preventing the occurrence of paper powder in a paper-making process. The agent contains at least one of an imidazoline quaternary ammonium salt represented by formula (I) and an imidazolinium betaine represented by formula (II) (Ris H, C1-32 alkyl or alkenyl; Ris ethylene amide or ethylene ether; Ris H, C1-32 alkyl or C1-4 hydroxyalkyl; Xis a halogen anion, an alkyl sulfuric acid anion or the like).SELECTED DRAWING: None

Description

  The present invention relates to a drug and a method for imparting flexibility to papers and suppressing paper dust generation.

  In daily life, paper is used for various purposes such as bookbinding paper such as comic books and paper bags, sanitary paper such as toilet paper and tissue paper, and wrapping paper such as cardboard and colored paperboard.

  In recent years, high functionality of paper has been demanded, and sanitary paper such as toilet paper, tissue paper, paper diapers, paper towels and the like are required to have an appropriate softness for use. The flexibility of paper is thought to be manifested by complicated involvement of many factors such as fiber type, paper density, and moisture of paper. Conventionally, glycerin and fatty acids have been used as agents that give paper flexibility. Esters, paraffin emulsions, quaternary ammonium salts and the like have been used. Specifically, for example, a paper softener using a quaternary ammonium salt having an imidazoline ring is disclosed (Patent Documents 1 to 3).

  On the other hand, from the viewpoint of increasing environmental protection and resource conservation awareness and reducing paper manufacturing costs, the use of recycled paper pulp and fillers is increasing, or the weight and volume are increasing.

  However, the fibers contained in the waste paper pulp are short because the pulp fibers are cut by repeated use and regeneration treatment, and the flakes of the pulp fibers are generated and changed into a flexible property. Papers containing such waste paper pulp having a short fiber length and high flexibility are weak in entanglement between celluloses, and often suffer from a decrease in paper strength and generation of paper dust.

  Paper dust is generated in papermaking, application processing, printing processes, etc. due to, for example, fluffing of the surface of the paper or paperboard caused by friction or other causes, or cutting defects when cutting the paper with a cutter or guillotine. In some cases, fibers, fillers, coatings, etc. exist in a state of being separated from paper or weakly bonded to paper, the former being called dust and the latter being called lint.

  Since paper dust adheres to the paper cut edge or is placed on the paper surface, it is very easy to remove, causing operational troubles during papermaking and application processing, and causing pinholes in the printing process. Further, when paper dust is mixed when packing industrial products and foodstuffs with corrugated cardboard, the product is soiled, and when paper dust is generated when toilet paper or tissue paper is used, the feeling of use becomes worse.

  As a technique for reducing such paper dust generation, a method using a composition containing a phosphate ester which is an anionic compound (Patent Document 4), a sulfuric acid band or a high molecular weight cationic compound, starch paste, and inorganic particles are used. A method of adding a mixed slurry to a stock (Patent Document 5), a method using a mixture of a copolymer containing a hydrophobic monomer and a cationic monomer and a filler (Patent Document 6), polyamide-epichlorohydrin, etc. Proposed are a method of using a wet strength improver, a dry strength improver such as carboxymethylcellulose (Patent Document 7), and a method of using a paper additive containing an amide compound and a quaternary ammonium salt (Patent Document 8). Has been.

  Patent Document 9 proposes that an antistatic property is imparted by an external addition method in which a surface treatment agent containing a cationic surfactant and an organopolysiloxane as essential components is applied to the paper surface. It is suggested that paper dust can be prevented from adhering to the paper.

Japanese Patent Laid-Open No. 48-22701 JP 2004-044058 A JP 2008-223161 A Special table 2007-508465 gazette Japanese Patent Laid-Open No. 2007-092203 JP 2010-031391 A Special table 2003-502519 gazette JP 2004-308095 A Japanese Patent Laid-Open No. 11-12985

  However, in Patent Documents 1 to 3, attention is focused on imparting flexibility to papers, and studies for suppressing generation of paper dust from papers are not made. Moreover, it is hard to say that the papers obtained by the methods of Patent Documents 4 to 7 are sufficiently suppressed from generating paper dust, and improvement is still desired.

  Further, in the paper additive of Patent Document 8, a tertiary amine type polyamine amide compound having an imidazoline ring or an acid neutralized salt thereof, and a specific tetra type quaternary quaternary such as a dilong chain acylalkylene monohydroxyalkylene type. Only when an ammonium salt is used in combination, the effect of suppressing the generation of paper dust is manifested. For this reason, each of the polyamine amide compound or its acid neutralized salt and the tetra-type quaternary ammonium salt alone has no effect of suppressing the generation of paper dust, and the effect of suppressing the generation of paper dust is not sufficient.

  Moreover, the method of patent document 9 is based on prevention of paper dust adhesion to paper by the external addition method, and does not suppress the generation of paper dust from paper.

  This invention is made | formed in view of said situation, and makes it a subject to provide the chemical | medical agent and method which can provide a softness | flexibility to papers and can suppress paper dust generation | occurrence | production. .

  The agent of the present invention is an agent capable of imparting flexibility to papers and suppressing the generation of paper dust in the papermaking process by being added to an aqueous pulp slurry, and represented by the following general formula (I): It is characterized by containing one or more of imidazoline type quaternary ammonium salts and imidazolinium type betaines represented by the following general formula (II).

(In the above general formula (I),
R ₁ represents any one of hydrogen, an alkyl group having _{1 to} 32 carbon atoms, or an alkenyl group,
R ₂ represents CH ₂ CH ₂ NHCOR ₄ (R ₄ represents hydrogen, an alkyl group having 1 to 32 carbon atoms or an alkenyl group), CH ₂ CH ₂ OR ₅ (R ₅ represents hydrogen, carbon, Any one of the acyl groups represented by formulas 1 to 33).
R ₃ represents any one of hydrogen, an alkyl group having 1 to 32 carbon atoms, and a hydroxyalkyl group having 1 to 4 carbon atoms,
X ⁻ represents any one of a halogen anion, an alkyl sulfate anion, a sulfonate anion, a phosphate anion, and an alkyl carbonate anion. )

(In the above general formula (II),
R ₆ represents any one of hydrogen, an alkyl group having 1 to 32 carbon atoms, or an alkenyl group,
R ₇ represents an alkylene group having 1 to 4 carbon atoms,
R ₈ represents CH ₂ CH ₂ NHCOR ₉ (R ₉ represents any one of hydrogen, an alkyl group having 1 to 32 carbon atoms or an alkenyl group), CH ₂ CH ₂ OR ₁₀ (R ₁₀ represents hydrogen, carbon, Represents an acyl group having 1 to 33 or an alkyl carboxylate having 1 to 4 carbon atoms in the alkyl group). )
This drug further contains a nonionic surfactant, and is a total of the imidazoline type quaternary ammonium salt represented by the general formula (I) and the imidazolinium type betaine represented by the general formula (II). And the mass ratio of the nonionic surfactant is preferably 25:75 to 99: 1.

In this drug, the imidazoline type quaternary ammonium salt represented by the general formula (I) is such that R ₁ is an alkyl group or alkenyl group having 11 to 21 carbon atoms, R ₂ is CH ₂ CH ₂ NHCOR ₄ (R ₄ is Preferably, the alkyl group or alkenyl group having 11 to 21 carbon atoms) and R ₃ is an alkyl group having 1 to 21 carbon atoms.

  The method of the present invention is a method of imparting flexibility to papers and suppressing the generation of paper dust in the papermaking process, wherein the imidazoline-type first represented by the above general formula (I) is added to an aqueous pulp slurry. And a step of adding a quaternary ammonium salt, a drug containing one or more of imidazolinium type betaines represented by the general formula (II).

  In the method of the present invention, the amount of the drug added is preferably 0.01 to 2% by mass with respect to the pulp.

  By adding the agent of the present invention in the paper making process and making paper, it is possible to obtain paper having excellent flexibility and generation of paper dust suppressed. For this reason, it is possible to reduce troubles caused by the generation of paper dust during papermaking, application processing, printing process and use.

  By adding the agent of the present invention to an aqueous pulp slurry, it is possible to impart flexibility to papers and to suppress the generation of paper dust in the papermaking process.

  Specifically, the agent of the present invention contains one or more of imidazoline type quaternary ammonium salt and imidazolinium type betaine.

  The imidazoline type quaternary ammonium salt contained in the drug of the present invention is represented by the above general formula (I).

In the general formula (I), R ₁ is any one of hydrogen, an alkyl group having 1 to 32 carbon atoms, or an alkenyl group.

In the general formula (I), R ₂ represents CH ₂ CH ₂ NHCOR ₄ (R ₄ represents hydrogen, an alkyl group having 1 to 32 carbon atoms or an alkenyl group), CH ₂ CH ₂ OR _5. (R ₅ represents any one of hydrogen and an acyl group having 1 to 33 carbon atoms).

In the general formula (I), R ₃ is any one of hydrogen, an alkyl group having 1 to 32 carbon atoms, and a hydroxyalkyl group having 1 to 4 carbon atoms.

In the general formula (I), X < ^- > is any one of a halogen anion, an alkyl sulfate anion, a sulfonate anion, a phosphate anion, and an alkyl carbonate anion.

In such imidazoline type quaternary ammonium salt, R ₁ in the general formula (I) is an alkyl group or alkenyl group having 11 to 21 carbon atoms, and R ₂ is CH ₂ CH ₂ NHCOR ₄ (R ₄ is an alkyl group or alkenyl group having 11 to 21 carbon atoms, and R ₃ is preferably an alkyl group having 1 to 21 carbon atoms. In this case, it is possible to reliably obtain papers that are excellent in flexibility and in which the generation of paper dust is suppressed.

In general formula synthesis of imidazoline quaternary ammonium salts represented by formula (I) are known conventionally, for example, compounds wherein _{R 2} is _CH 2 _CH 2 NHCOR _4, the reaction of diethylene triamine with fatty acids Then, after diamidation, an imidazoline compound is synthesized by intramolecular cyclization reaction (condensation reaction), and this imidazoline compound and a quaternizing agent can be reacted. When diethylenetriamine and formic acid react, a compound in which R ₁ is hydrogen can be obtained, and when a fatty acid having 2 or more carbon atoms reacts, a compound in which R ₁ is an alkyl group or an alkenyl group can be obtained. A compound in which R ₂ is CH ₂ CH ₂ OR ₅ is amidated by reacting N- (2-aminoethyl) -2-aminoethanol with a fatty acid, and then an intramolecular cyclization reaction (condensation reaction). Thus, an imidazoline compound can be synthesized and obtained by reacting the imidazoline compound with a quaternizing agent. When N- (2-aminoethyl) -2-aminoethanol reacts with an equimolar amount of fatty acid, a compound in which R ₅ is hydrogen can be obtained, and when double moles of fatty acid react, a compound in which R ₅ is an acyl group Can be obtained.

  Here, as a fatty acid, a C1-C33 saturated fatty acid and unsaturated fatty acid can be used.

  Specifically, as saturated fatty acids, acetic acid, propionic acid, butanoic acid (butyric acid), pentanoic acid, hexanoic acid (caproic acid), heptanoic acid, octanoic acid (caprylic acid), nonanoic acid, decanoic acid (capric acid) , Undecanoic acid, dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (paltimic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid (Arachidic acid), henicosanoic acid, docosanoic acid (behenic acid), tricosanoic acid, tetracosanoic acid (lignoceric acid), pentacosanoic acid, hexacosanoic acid (serotic acid), heptacosanoic acid, octacosanoic acid (montanic acid), nonacosanoic acid, triacontane Acid (melicinic acid), hentriacontanoic acid Dotriacontanoic acid, tritriacontanoic acid and unsaturated fatty acids include butenoic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid (milli Streanic acid), pentadecenoic acid, hexadecenoic acid (palmitoleic acid), heptadecenoic acid, octadecenoic acid (oleic acid), nonadedecenoic acid, icosenoic acid, henicosenoic acid, docosenoic acid (erucic acid), tricosenoic acid, tetracosenoic acid (nervonic acid), Pentacosenoic acid, hexacosenoic acid, heptacosenoic acid, octacosenoic acid, nonacosenic acid, triacontenoic acid, hentriacontenoic acid, dotriacontenoic acid, tritriacontenoic acid, octadecadienoic acid (linoleic acid), eicosadienoic acid, docosadienoic acid, saturated fat And a mixture of unsaturated fatty acids can be exemplified tallow fatty acid, palm oil fatty acid, coconut oil fatty acid. Among these, a saturated fatty acid having 11 to 21 carbon atoms and an unsaturated fatty acid are preferable from the viewpoint of imparting flexibility to paper and suppressing generation of paper dust.

When R ₃ in the general formula (I) is an alkyl group having 1 to 32 carbon atoms, for example, as a quaternizing agent, alkyl halide, dialkyl sulfate, dialkyl carbonate, alkyl sulfonic acid, alkyl phosphate ester, etc. Can be used.

  Specific examples of the alkyl halide include chloromethane, bromomethane, iodomethane, chloroethane, bromoethane, iodoethane, 1-chloropropane, 1-bromopropane, 1-iodopropane, 1-chlorobutane, 1-bromobutane, 1-iodobutane, 1 -Chloropentane, 1-bromopentane, 1-iodopentane, 1-chlorohexane, 1-bromohexane, 1-iodohexane, 1-chloroheptane, 1-bromoheptane, 1-iodoheptane, 1-chlorooctane, 1 -Bromooctane, 1-iodooctane, 1-chlorononane, 1-bromononane, 1-iodononane, 1-chlorodecane, 1-bromodecane, 1-iododecane, 1-chloroundecane, 1-bromoundecane, 1-iodoundecane, 1- Chlorododecane, -Bromododecane, 1-iodododecane, 1-chlorotridecane, 1-bromotridecane, 1-iodotridecane, 1-chlorotetradecane, 1-bromotetradecane, 1-iodotetradecane, 1-chloropentadecane, 1-bromo Pentadecane, 1-iodopentadecane, 1-chlorohexadecane, 1-bromohexadecane, 1-iodohexadecane, 1-chloroheptadecane, 1-bromoheptadecane, 1-iodoheptadecane, 1-chlorooctadecane, 1-bromooctadecane, 1-iodooctadecane, 1-chlorononadecane, 1-bromononadecane, 1-iodononadecane, 1-chloroeicosan, 1-bromoeicosan, 1-iodoeicosan, 1-chlorohenicosan, 1-bromoheneicosan, 1 -Iodohen Ikosa The like may be exemplified.

  Specific examples of the dialkyl sulfate include dimethyl sulfate, diethyl sulfate, di-n-propyl sulfate, di-n-butyl sulfate, di-n-pentyl sulfate, di-n-hexyl sulfate, di-n-heptyl sulfate, Di-n-octyl sulfate, di-n-nonyl sulfate, di-n-decyl sulfate, diundecyl sulfate, didodecyl sulfate, ditridecyl sulfate, ditetradecyl sulfate, dipentadecyl sulfate, dihexadecyl sulfate, diheptadecyl sulfate, dioctadecyl sulfate, di-iso- Examples thereof include propyl sulfuric acid, di-sec-butyl sulfuric acid, and di-tert-butyl sulfuric acid.

  Specific examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate.

  Specific examples of the alkyl sulfonic acid include methyl p-toluenesulfonate, ethyl p-toluenesulfonate, and n-butyl p-toluenesulfonate.

  Specific examples of the phosphoric acid alkyl ester include trimethyl phosphate, triethyl phosphate, ethyldimethyl phosphate, and diethylmethyl phosphate.

When R ₃ in the general formula (I) is a hydroxyalkyl group having 1 to 4 carbon atoms, for example, a halogenated alcohol can be used as a quaternizing agent.

  Specific examples of the halogenated alcohol include chloromethanol, bromomethanol, iodomethanol, 1-chloroethanol, 1-bromoethanol, 1-iodoethanol, 2-chloroethanol, 2-bromoethanol, 2-iodoethanol, 1 -Chloropropanol, 1-bromopropanol, 1-iodopropanol, 2-chloropropanol, 2-bromopropanol, 2-iodopropanol, 3-chloropropanol, 3-bromopropanol, 3-iodopropanol, 1-chlorobutanol, 1 -Bromobutanol, 1-iodobutanol, 2-chlorobutanol, 2-bromobutanol, 2-iodobutanol, 3-chlorobutanol, 3-bromobutanol, 3-iodobutanol, 4-chlorobutanol, 4-bromine Butanol, and the like can be exemplified 4-iodo-butanol.

  The imidazolinium type betaine contained in the chemical | medical agent of this invention is represented by the said general formula (II).

In the general formula (II), R ₆ is any one of hydrogen, an alkyl group having 1 to 32 carbon atoms, or an alkenyl group.

In the general formula (II), R ₇ is an alkylene group having 1 to 4 carbon atoms.

In the general formula (II), R ₈ is CH ₂ CH ₂ NHCOR ₉ (R ₉ is hydrogen, an alkyl group or an alkenyl group having 1 to 32 carbon atoms), CH ₂ CH ₂ OR ₁₀ (R ₁₀ is hydrogen) , An acyl group having 1 to 33 carbon atoms, and an alkyl carboxylate having 1 to 4 carbon atoms in the alkyl group).

Similarly, in the synthesis of imidazolinium-type betaine represented by the general formula (II), a compound in which R ₈ is CH ₂ CH ₂ NHCOR ₉ is obtained by reacting diethylenetriamine with a fatty acid and then diamidating it. It can be obtained by synthesizing the compound (condensation reaction) to synthesize an imidazoline compound and reacting the imidazoline compound with a quaternizing agent. In addition, a compound in which R ₈ is CH ₂ CH ₂ OR ₁₀ is amidated by reacting N- (2-aminoethyl) -2-aminoethanol with a fatty acid, and then an intramolecular cyclization reaction (condensation reaction). Thus, an imidazoline compound can be synthesized and obtained by reacting the imidazoline compound with a quaternizing agent.

In this case, as the fatty acid, a saturated fatty acid having 1 to 33 carbon atoms, an unsaturated fatty acid, and a mixture of a saturated fatty acid and an unsaturated fatty acid can be used. As the quaternizing agent, halogenated carboxylic acids such as chloroacetic acid and chloropropionic acid can be used. A compound in which R ₁₀ is an alkyl carboxylate can be obtained by reacting a compound in which R ₁₀ is hydrogen with 2 moles of a halogenated carboxylic acid. Alkyl carboxylate salts include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as calcium and magnesium; ammonium salts; organic amine salts such as monoethanolamine, diethanolamine and triethanolamine. .

  Furthermore, it is preferable that the chemical | medical agent of this invention contains a nonionic surfactant. Examples of the nonionic surfactant include fatty acid ethoxylates having 12 to 22 carbon atoms, castor oil ethoxylate, polyoxyethylene nonylphenyl ether, polyoxyalkylene alkyl (C12 to C22) ether, polyoxyethylene sorbitan fatty acid ester, and the like. 1 type or 2 types or more can be illustrated.

  And the mass ratio of the total of the imidazoline type quaternary ammonium salt represented by the general formula (I) and the imidazolinium type betaine represented by the general formula (II) and the nonionic surfactant is: It is preferable that it is 25: 75-99: 1. In this case, it is possible to reliably obtain papers that are excellent in flexibility and in which the generation of paper dust is suppressed.

  Next, the method of the present invention will be described.

  The method of the present invention is a method of imparting flexibility to papers and suppressing the generation of paper dust in the papermaking process, and includes the step of adding the above-described agent of the present invention to an aqueous pulp slurry.

  It is preferable that the addition amount of the chemical | medical agent of this invention is 0.01-2 mass% with respect to the raw material pulp. When the added amount of the drug is within this range, it is possible to reliably obtain papers that are excellent in flexibility and in which the generation of paper dust is suppressed.

  As a method for evaluating the flexibility of paper, for example, “JAPAN TAPPI Paper Pulp Test Method No. 34: 2000 Paper-Softness Test Method” can be mentioned. Regarding the flexibility of paper made by adding the agent of the present invention, the resistance of the paper measured by the above test method is a decrease rate of 10% or more with respect to the resistance of the paper made only with pulp. Some are preferable, and those with a reduction rate of 20% or more are more preferable.

  The method of using the agent of the present invention is not particularly limited, and it can be diluted with industrial water or the like, or can be added as it is without being diluted. In any case, a method similar to a general paper manufacturing method can be adopted except that the agent of the present invention is used.

  The type of paper obtained by the method of the present invention is not particularly limited. Specifically, for example, tissue paper, toilet paper, paper diapers, paper towels, household thin paper such as kitchen paper, PPC paper, inkjet printing paper, pressure-sensitive paper, laser printer paper, foam paper, thermal transfer paper, thermal recording base paper, Recording paper such as pressure-sensitive recording paper, photographic paper and its base paper, art paper, coated paper such as cast coated paper, high-quality coated paper, packaging paper such as kraft paper, pure white roll paper, other notebook paper, book paper, various printing Examples include various paper (paper) such as paper and newspaper, paperboard for paper containers such as Manila balls, white balls, and chip balls, and paperboard such as liners and gypsum board base paper.

  Pulp raw materials for producing paper include chemical pulp such as kraft pulp or sulfite pulp, high-yield pulp such as crushed wood pulp, mechanical pulp or thermomechanical pulp, newspaper wastepaper, magazine wastepaper, cardboard wastepaper Examples include waste paper pulp such as ink waste paper. Such paper may also contain a mixture of pulp raw material and rock wool, asbestos, or synthetic fibers such as polyamide, polyimide, polyester, polyolefin, and polyvinyl alcohol.

  In the method of the present invention, if necessary, for example, additives such as fillers, sulfate bands, sizing agents, dry paper strength improvers, wet paper strength improvers, humectants, yield improvers, and drainage improvers are also added. , It may be used to develop the physical properties required for each paper type. These may be used alone or in combination of two or more. These additives may be used before, after, or simultaneously with the addition of the agent of the present invention to the aqueous slurry of paper. It can also be used by adding to an aqueous slurry.

  Examples of the filler include clay, talc, calcium carbonate and the like, and these may be used alone or in combination of two or more.

  Sizing agents include fatty acid soap sizing agents such as sodium stearate, rosin, fortified rosin, aqueous emulsion of rosin ester, aqueous emulsion of alkenyl succinic anhydride, aqueous emulsion of 2-oxetanone, aqueous emulsion of paraffin wax, carboxylic acid Sizing agents obtained by the reaction of polyamines with polyamines, aqueous emulsions of reaction products of aliphatic oxyacids with aliphatic amines or aliphatic alcohols, and anionic and cationic styrenic sizing agents A seed | species or 2 or more types can be illustrated.

  Examples of the dry paper strength improver include anionic polyacrylamide, cationic polyacrylamide, amphoteric polyacrylamide, cationized starch, and amphoteric starch. These may be used alone or in combination of two or more. Also good.

  Examples of the wet paper strength improver include one or more of polyamide / epichlorohydrin resin, melamine / formaldehyde resin, urea / formaldehyde resin, and the like.

  Examples of humectants include polyhydric alcohols such as glycerin, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, sorbitol, and polyethylene glycol. One or more of them can be exemplified. It is preferable to add a polyhydric alcohol having a molecular weight of 600 or less to the drug of the present invention because the viscosity of the drug is reduced and handling becomes easy.

  As a yield improver, anionic, cationic or amphoteric high molecular weight polyacrylamide may be used, silica sol and cationized starch may be used in combination, or bentonite and cationic high molecular weight polyacrylamide may be used in combination. it can. These may be used alone or in combination of two or more.

  Examples of the drainage improver include one or more of polyethyleneimine, cationic, amphoteric or anionic polyacrylamide.

  The agents and methods of the present invention are not limited to the above embodiments.

  Hereinafter, although the chemical | medical agent and method of this invention are demonstrated in detail with an Example, the chemical | medical agent and method of this invention are not limited to a following example.

<1> Component of drug (1) About the imidazoline type quaternary ammonium salt represented by the above general formula (I), R _{1 to} R ₅ and X of the compounds used in Examples and Comparative Examples are shown in Table 1. . Beef tallow fatty acid (PM810 manufactured by Miyoshi Oil Co., Ltd.) was used as the fatty acid raw material of R ₁ and R ₄ of Compound I-2.

(2) Table 2 shows R _{6 to} R ₁₀ of the compounds used in Examples and Comparative Examples for the imidazolinium type betaine represented by the general formula (II).

(3) Table 3 shows the types of nonionic surfactants (A to E) added to the drugs of Examples and Comparative Examples.

(4) Table 4 shows tetraalkyl quaternary ammonium salts (F to H) used as comparative examples.

<2> Test method and evaluation method (1) Test paper production method In the aqueous slurry of regenerated bleached pulp composed of 70% hardwood pulp and 30% softwood pulp, the chemicals and nonionic surfactants listed in Table 5 After adding the amounts shown in Table 5 and stirring, paper was made using a handmade paper machine to obtain a paper with a basis weight of 40 g / m ² .

(2) Flexibility evaluation method In accordance with “JAPAN TAPPI Paper Pulp Test Method No. 34: 2000 Paper-Softness Test Method”, the resistance of the paper was measured with a handle ohmmeter and the front and back sides of the paper were obtained. Measured in total 20 times, 5 times each in the vertical and horizontal directions, the average value was obtained, and the flexibility was reduced as follows according to the decrease rate from the average value of the resistance of the paper made from only the pulp measured in the same manner. evaluated.
A: The average value of the test is 20% or more lower than the average value of the pulp alone.
○: The average value of the test is 10% or more and less than 20% compared to the average value of the pulp alone.
(Triangle | delta): The reduction rate is 5% or more and less than 10% compared with the average value of only a pulp for a test.
X: The average value of the test is equivalent to the average value of only the pulp, or the decrease rate of the average value is less than 5%.

(3) Paper dust generation suppression effect evaluation method For the obtained paper, a transparent adhesive tape (adhesive strength: about 4 N / 10 cm) is adhered to the cut surface when 50 sheets of paper dust are generated by cutting. Then, paper dust was collected by a method of peeling and pasting on a black paper mount, and the amount of paper dust attached to the adhesive tape was visually observed. Based on the amount of paper dust of paper made only with pulp without adding a chemical that has the effect of suppressing paper dust generation, ○ when the amount of paper dust generated is equivalent to this standard, ◎ when less than this standard, A case where the amount was slightly higher than this criterion was evaluated as Δ, and a case where the amount was larger than this criterion was evaluated as ×.

<3> Results The results are shown in Table 5, Table 6, Table 7, and Table 8.

Examples 1 to 19 in which one kind of imidazoline-type quaternary ammonium salt represented by the general formula (I) and R _{1 to} R ₅ and X satisfying the predetermined conditions in the present invention are used as a drug are good and flexible (Evaluation: ◎ or ○), and it was confirmed that the generation of paper dust was comparable to the case of pulp alone (evaluation: ○ or △), or suppressed (evaluation: ◎). .

Example 20 in which two kinds of imidazoline type quaternary ammonium salts represented by the general formula (I) and R _{1 to} R ₅ and X satisfy the predetermined conditions in the present invention is used as a drug has good flexibility. It was confirmed (◎) that generation of paper dust was suppressed (evaluation: ○).

Examples 21 to 27 in which one kind of imidazolinium type betaine represented by the general formula (II) and R _{6 to} R ₁₀ satisfying the predetermined condition in the present invention are used as a drug have good flexibility. (Evaluation: ま た は or ○) It was confirmed that the generation of paper dust was suppressed to the same level (evaluation: Δ) compared to the case of pulp alone.

The drug is represented by the general formula (I), and R _{1 to} R ₅ and X are each represented by _one imidazoline-type quaternary ammonium salt satisfying the predetermined condition in the present invention, the general formula (II), and R ₆ example 28 to R ₁₀ is used by mixing a predetermined condition is satisfied imidazolinium type betaines one in the present invention has a good flexibility (evaluation: ◎), also suppressed the generation of paper dust (Evaluation: ○).

  On the other hand, it was confirmed that Comparative Example 1 containing only pulp has poor flexibility (evaluation: x).

  Conventionally, Comparative Examples 2 to 4 using compounds F to H that have been used as paper softeners have been confirmed to generate a lot of paper dust, although they are given flexibility (evaluation:）). (Evaluation: x).

Further, Comparative Examples 5 and 6 using an imidazoline type quaternary ammonium salt represented by the general formula (I), in which R ₁ and R ₂ do not satisfy the predetermined conditions in the present invention, generate slightly more paper dust. However, it was confirmed that the flexibility was poor (evaluation: x).

Furthermore, Comparative Example 7 and R ₁₀ using one kind of imidazolinium type betaine represented by the general formula (II), in which R ₆ and R ₉ do not satisfy the predetermined condition in the present invention satisfy the predetermined condition in the present invention. In Comparative Example 8 in which one type of imidazolinium-type betaine that was not satisfied was used, the generation of paper dust was slightly high (evaluation: Δ), but it was confirmed that the flexibility was poor (evaluation: x).

As mentioned above, it is one or more of imidazoline type quaternary ammonium salt represented by general formula (I) and imidazolinium type betaine represented by general formula (II), and R ₁ by to R _{10, X} is used an agent of a predetermined condition is satisfied the present invention, it is possible to impart flexibility to paper, and it was confirmed that it is possible to suppress the paper dust generation.

Claims (5)

An imidazoline type fourth agent represented by the following general formula (I), which is an agent capable of imparting flexibility to paper and suppressing the generation of paper dust in the papermaking process by being added to an aqueous pulp slurry. A drug comprising one or more of a quaternary ammonium salt and an imidazolinium type betaine represented by the following general formula (II).

(In the above general formula (I),
R ₁ represents any one of hydrogen, an alkyl group having _{1 to} 32 carbon atoms, or an alkenyl group,
R ₂ represents CH ₂ CH ₂ NHCOR ₄ (R ₄ represents hydrogen, an alkyl group having 1 to 32 carbon atoms or an alkenyl group), CH ₂ CH ₂ OR ₅ (R ₅ represents hydrogen, carbon, Any one of the acyl groups represented by formulas 1 to 33).
R ₃ represents any one of hydrogen, an alkyl group having 1 to 32 carbon atoms, and a hydroxyalkyl group having 1 to 4 carbon atoms,
X ⁻ represents any one of a halogen anion, an alkyl sulfate anion, a sulfonate anion, a phosphate anion, and an alkyl carbonate anion. )

(In the above general formula (II),
R ₆ represents any one of hydrogen, an alkyl group having 1 to 32 carbon atoms, or an alkenyl group,
R ₇ represents an alkylene group having 1 to 4 carbon atoms,
R ₈ represents CH ₂ CH ₂ NHCOR ₉ (R ₉ represents any one of hydrogen, an alkyl group having 1 to 32 carbon atoms or an alkenyl group), CH ₂ CH ₂ OR ₁₀ (R ₁₀ represents hydrogen, carbon, Represents an acyl group having 1 to 33 or an alkyl carboxylate having 1 to 4 carbon atoms in the alkyl group). )   Further, a nonionic surfactant is included, the total of the imidazoline type quaternary ammonium salt represented by the general formula (I) and the imidazolinium type betaine represented by the general formula (II), and a nonionic The drug according to claim 1, wherein the mass ratio to the active surfactant is 25:75 to 99: 1. In the imidazoline type quaternary ammonium salt represented by the general formula (I), R ₁ is an alkyl group or alkenyl group having 11 to 21 carbon atoms, R ₂ is CH ₂ CH ₂ NHCOR ₄ (R ₄ is 11 to 11 carbon atoms). 21 alkyl or alkenyl group), according to claim 1 or 2 agents R ₃ is equal to or an alkyl group having 1 to 21 carbon atoms.   A method for imparting flexibility to papers and suppressing the generation of paper dust in a papermaking process, comprising the step of adding the agent according to any one of claims 1 to 3 to an aqueous pulp slurry. And how to. The method according to claim 4, wherein the amount of the drug added is 0.01 to 2% by mass with respect to the pulp.