JP6532102B2 - Antifouling composition for paper manufacturing process and antifouling method - Google Patents

Description

  The present invention relates to an anti-smudge agent composition for a paper manufacturing process and a method for preventing fouling.

  In the process of producing pulp and paper, a non-water-soluble adhesive substance consisting of an organic resin derived from a natural resin released from wood, pulp or the like, chemicals used in the process of producing pulp and paper is generated as pitch. The pitch is usually dispersed in the form of colloids in the slurry of the papermaking process, but it is considered that external factors such as shear force cause the colloidal state to be broken and coarsened. Since the coarsened pitch is tacky, the adhesion of the pitch to a paper making apparatus such as paper or chest, wire, felt or the like causes paper stains, breaks and the like.

  In order to solve such a problem, many methods have been proposed conventionally (for example, patent documents 1-3 etc.). Patent Document 1 discloses a method of adding a pitch inhibitor made of a copolymer of diallyldimethylammonium chloride and acrylic acid to pulp slurry in order to suppress the precipitation of natural pitch on the surface of a paper machine. . Patent Document 2 discloses a quaternary ammonium selected from polydiallyldimethyl ammonium salts and alkyldimethyl benzyl ammonium salts having an alkyl group having 12 to 18 carbon atoms in order to prevent the backing roll from being soiled in the coated paper production process. There is disclosed a method of adding an antisoiling agent containing a compound as an active ingredient to shower water and spraying it on the surface of a backing roll. In order to prevent pitch stains in the paper / pulp production process, Patent Document 3 discloses a paper / pulp production process water containing a pitch inhibitor comprising polydiallyldimethyl ammonium salt, a nonionic surfactant and a phosphonic acid compound as active ingredients. Discloses a pitch suppression method to be added to

  However, the above method is insufficient in the antifouling effect, and a more effective antifouling agent and antifouling method are desired.

Patent No. 2955388 Patent No. 4366524 Patent No. 4151048

  In such a situation, the problem to be solved by the present invention is to provide an antifouling composition and an antifouling method which are excellent in the antifouling effect of pitch and the like in a paper manufacturing process.

  The inventors of the present invention conducted intensive studies to develop an antifouling composition having excellent antifouling properties such as pitch, and as a result, a specific allyl group-containing ammonium salt, a hydrocarbon group having a specific carbon number and By using a cationic copolymer obtained by copolymerizing a polymerizable carbon-carbon double bond-containing monomer, adhesion of dirt such as pitch can be prevented and the attached dirt is exfoliated. I found it easier. The present invention has been completed as a result of further studies based on such findings.

That is, the present invention relates to the stain preventing agent composition for the paper manufacturing process and the stain preventing method described in the following items 1 to 5.
Item 1. General formula (1):

[In formula, R < ₁ >, R < ₂ > and R < ₃ > are the same or different, and show a hydrogen atom, a C1-C3 alkyl group, or a C2-C4 alkenyl group. X ₁ ^- represents a halide ion, a hydroxide ion, an anion of an inorganic acid or an anion of an organic acid. And a monomer represented by the general formula (2):

Wherein, R ₄ represents a saturated or unsaturated hydrocarbon group or a benzyl group 5 to 22 carbon atoms. R ₅ and R ₆ represents the same or different and each represents a hydrogen atom, an alkenyl group having 2 to 4 carbon atoms, a saturated or unsaturated hydrocarbon group of 5 to 22 carbon atoms or a benzyl group. X ₂ ⁻ represents a halide ion, a hydroxide ion, an anion of an inorganic acid or an anion of an organic acid. And a monomer represented by the general formula (3):

[Wherein, R ₇ represents a hydrogen atom or a methyl group. R ₈ represents an alkyl group having 1 to 18 carbon atoms, a benzyl group or a phenylethyl group. l is an integer of 0 to 40, m is an integer of 0 to 13, and n is an integer of 0 to 6. However, l, m and n are not simultaneously 0, and the sum of l, m and n is an integer of 1 to 59. ] The cationic copolymer obtained by copolymerizing with at least 1 sort (s) of monomer selected from the group which consists of a monomer represented by the molar ratio in the ratio of 95: 5 to 50:50 is obtained The antifouling composition for paper manufacturing processes which is contained as an active ingredient.
Item 2. The soil inhibitor composition according to item 1, further comprising at least one selected from the group consisting of nonionic surfactants and phosphonic acid compounds.
Item 3. The stain inhibitor composition according to Item 2, wherein the non-ionic surfactant is at least one selected from the group consisting of polyoxyalkylene alkyl ether and polyoxyalkylene alkyl amine.
Item 4. At least one selected from the group consisting of 1-hydroxyethane-1,1-diphosphonic acid, aminotrimethylene phosphonic acid, and 1,2,4-tricarboxybutane-2-phosphonic acid as the phosphonic acid compound The antifouling agent composition according to Item 2 above.
Item 5. The stain prevention method which sprays the stain inhibiting agent composition in any one of said claim | item 1-4 to a paper manufacturing apparatus.

  By using the stain inhibitor composition for the paper production process of the present invention, it is possible to prevent the dirt such as pitch from adhering to the paper production apparatus such as wire and felt, and to make the attached dirt easy to peel off. Therefore, in the paper manufacturing process, the adhesion of stains to these tools can be sufficiently prevented by spraying an aqueous solution containing the stain inhibitor composition of the present invention onto a paper manufacturing apparatus such as a wire or felt. it can.

  Hereinafter, the stain inhibitor composition for the paper production process of the present invention (hereinafter sometimes referred to simply as "stain inhibitor composition") and the stain preventing method will be specifically described.

  The stain inhibitor composition for the paper production process of the present invention has the general formula (1):

[In formula, R < ₁ >, R < ₂ > and R < ₃ > are the same or different, and show a hydrogen atom, a C1-C3 alkyl group, or a C2-C4 alkenyl group. X ₁ ^- represents a halide ion, a hydroxide ion, an anion of an inorganic acid or an anion of an organic acid. ] (Hereinafter also referred to as “monomer (1)”) represented by the general formula (2):

Wherein, R ₄ represents a saturated or unsaturated hydrocarbon group or a benzyl group 5 to 22 carbon atoms. R ₅ and R ₆ represents the same or different and each represents a hydrogen atom, an alkenyl group having 2 to 4 carbon atoms, a saturated or unsaturated hydrocarbon group of 5 to 22 carbon atoms or a benzyl group. X ₂ ⁻ represents a halide ion, a hydroxide ion, an anion of an inorganic acid or an anion of an organic acid. A monomer represented by the formula (hereinafter, also referred to as “monomer (2)”), and a compound represented by the general formula (3):

[Wherein, R ₇ represents a hydrogen atom or a methyl group. R ₈ represents an alkyl group having 1 to 18 carbon atoms, a benzyl group or a phenylethyl group. l is an integer of 0 to 40, m is an integer of 0 to 13, and n is an integer of 0 to 6. However, l, m and n are not simultaneously 0, and the sum of l, m and n is an integer of 1 to 59. And at least one monomer selected from the group consisting of monomers (hereinafter also referred to as “monomer (3)”), in a molar ratio of 95: 5 to 50:50 It is characterized in that a cationic copolymer obtained by copolymerizing in a ratio is contained as an active ingredient.

  The stain inhibitor composition of the present invention is represented by the monomer represented by the general formula (1), the monomer represented by the general formula (2), and / or the general formula (3) By incorporating a cationic copolymer obtained by copolymerizing the above monomers in the ratio as described above as an effective component, dirt such as pitch adheres to the paper manufacturing apparatus such as wire, felt, etc. Can be made easy to peel off the attached dirt.

In the general formula _{(1), R 1, R} 2 and _{R 3} represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms. R ₁ , R ₂ and R ₃ may be identical to or different from each other.

  Specific examples of the alkyl group having 1 to 3 carbon atoms include methyl, ethyl, n-propyl and isopropyl. As the alkyl group having 1 to 3 carbon atoms, methyl, ethyl and the like are preferable.

  As a C2-C4 alkenyl group, a C2-C4 linear or branched alkenyl group is mentioned. Specific examples of the linear alkenyl group having 2 to 4 carbon atoms include vinyl, 1-propenyl, allyl (2-propenyl), 1-butenyl, 2-butenyl, 3-butenyl and the like, Examples of the branched alkenyl group of 2 to 4 include 2-methyl-2-propenyl and the like. As a C2-C4 alkenyl group, a vinyl, an allyl, etc. are preferable.

As R ₁ , R ₂ and R ₃ , a combination of an alkyl group of 1 to 3 carbon atoms, an alkyl group of 1 to 3 carbon atoms, and an alkenyl group of 2 to 4 carbon atoms, an alkenyl group of 2 to 4 carbon atoms, carbon A combination of several to four alkenyl groups, hydrogen atoms, and the like are preferable.

X ₁ ⁻ represents a halide ion, a hydroxide ion, an anion of an inorganic acid or an anion of an organic acid. As a halide ion, a fluoride ion, a chloride ion, a bromide ion, an iodide ion etc. are mentioned. Examples of the anion of the inorganic acid include sulfate ion, nitrate ion and phosphate ion. Examples of the anion of the organic acid include formate ion, acetate ion and oxalate ion.

  Specifically, allyldimethylamine hydrochloride, allyltrimethylammonium chloride, allyldiethylamine hydrochloride, allyldimethylamine sulfate, allyldimethylamine acetate, diallylamine hydrochloride as the monomer represented by the general formula (1) Salts, diallylamine sulfate, diallyldimethylammonium chloride (DADMAC), diallyldiethylammonium chloride, diallyldimethylammonium bromide, diallyldimethylammonium sulfate, diallyldimethylammonium nitrate, triallylamine hydrochloride (Tri-AAC), triallylmethyl ammonium chloride , Triallylethyl ammonium chloride, triallyl methyl ammonium bromide, triallyl methyl ammonium sulfate , Triallyl methyl ammonium nitrate, tetra allyl ammonium chloride, tetra allyl ammonium sulfate, tetra allyl ammonium nitrate, tetra allyl ammonium acetate, tetra allyl ammonium oxalate and the like.

  Among these, diallyldimethylammonium chloride (DADMAC), diallylamine hydrochloride, triallylamine hydrochloride (Tri-AAC) and the like are preferable. Monomer (1) can be used individually by 1 type or in mixture of 2 or more types.

In general formula (2), R ₄ represents a saturated or unsaturated hydrocarbon group or a benzyl group 5 to 22 carbon atoms.

  As a C5-C22 saturated or unsaturated hydrocarbon group, a linear, branched or cyclic hydrocarbon group is mentioned. Specific examples of the linear saturated hydrocarbon group include n-pentyl, n-hexyl, n-octyl, n-decyl, lauryl, stearyl and the like. Examples of branched saturated hydrocarbon groups include isopentyl, isostearyl and the like. Examples of cyclic saturated hydrocarbon groups include cyclohexyl, cyclopentyl and the like. As a linear unsaturated hydrocarbon group, specifically, 4-pentenyl, 3-hexenyl, 5-hexenyl, 3-octenyl, 7-octenyl, 5-decenyl, 9-decenyl, tetradeca-9-enoyl Hexadeca-9-enoyl, octadeca-9-enoyl and the like. Examples of branched unsaturated hydrocarbon groups include isopentenyl and the like. Examples of cyclic unsaturated hydrocarbon groups include cyclohexenyl, cyclopentenyl and the like. As a C5-C22 saturated or unsaturated hydrocarbon group, n-octyl, lauryl, stearyl etc. are preferable.

R ₅ and _{R 6} represents a hydrogen atom, an alkenyl group having 2 to 4 carbon atoms, a saturated or unsaturated hydrocarbon group of 5 to 22 carbon atoms or a benzyl group. R ₅ and R ₆ may be identical to or different from each other.

  As a C2-C4 alkenyl group, the thing similar to the C2-C4 alkenyl group of the said General formula (1) can be used. Specific examples of the alkenyl group having 2 to 4 carbon atoms include vinyl, 1-propenyl, allyl (2-propenyl), 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-2-propenyl and the like. Be As a C2-C4 alkenyl group, a vinyl, an allyl, etc. are preferable.

The saturated or unsaturated hydrocarbon group having 5 to 22 carbon atoms can be the same as the saturated or unsaturated hydrocarbon group having 5 to 22 carbon atoms of R ₄ . Specific examples of the saturated or unsaturated hydrocarbon group having 5 to 22 carbon atoms include linear saturated hydrocarbon groups such as n-pentyl, n-hexyl, n-octyl, n-decyl, lauryl and stearyl. Branched saturated hydrocarbon groups such as isopentyl, isohexyl and isostearyl; cyclic saturated hydrocarbon groups such as cyclohexyl and cyclopentyl; 4-pentenyl, 3-hexenyl, 5-hexenyl, 3-octenyl, 7- Linear unsaturated hydrocarbon groups such as octenyl, 5-decenyl, 9-decenyl, tetradeca-9-enoyl, hexadeca-9-enoyl, octadeca-9-enoyl, etc. Branched unsaturated carbonization such as isopentenyl And a hydrogen group; and cyclic unsaturated hydrocarbon groups such as cyclohexenyl and cyclopentenyl. As a C5-C22 saturated or unsaturated hydrocarbon group, n-octyl, lauryl, stearyl etc. are preferable.

X ₂ ^- represents a halide ion, a hydroxide ion, an anion of an inorganic acid or an anion of an organic acid. As a halide ion, a fluoride ion, a chloride ion, a bromide ion, an iodide ion etc. are mentioned. Examples of the anion of the inorganic acid include sulfate ion, nitrate ion and phosphate ion. Examples of the anion of the organic acid include formate ion, acetate ion and oxalate ion.

  Specific examples of the monomer represented by the above general formula (2) include allyl lauryl amine hydrochloride (ALAC), allyl stearyl amine hydrochloride (ASAC), allyl trioctyl ammonium chloride, allyl trioctadecyl ammonium chloride, Allyldibenzylamine hydrochloride, allyldicyclohexylamine hydrochloride, allyltricyclohexylammonium chloride, diallyldioctylammonium chloride, diallyldioctadecylammonium chloride, diallylbenzylamine hydrochloride, diallylcyclohexylamine hydrochloride, diallyldicyclohexylammonium chloride, diallyldioctylammonium chloride Bromide, diallyl dioctyl ammonium sulfate, diallyl dioctyl ammonium nitrate Triallyl dodecyl Nmo chloride, triallyl octadecyl Nmo chloride, triallyl dodecyl Nmo bromide, triallyl dodecyl Nmo iodonium sulfate, triallyl dodecyl Nmo iodonium nitrate, and the like.

  Among these, allyl lauryl amine hydrochloride (ALAC), allyl stearyl amine hydrochloride (ASAC) and the like are preferable. Monomer (2) can be used individually by 1 type or in mixture of 2 or more types.

In the general formula (3), R ₇ represents a hydrogen atom or a methyl group.

R ₈ represents an alkyl group having 1 to 18 carbon atoms, a benzyl group or a phenylethyl group.

  As a C1-C18 alkyl group, a C1-C18 linear, branched or cyclic alkyl group is mentioned. Specific examples of the linear alkyl group include methyl, ethyl, n-propyl, n-hexyl, n-octyl, n-decyl, lauryl, stearyl and the like. Examples of branched alkyl groups include isopropyl, isobutyl, tert-butyl, isohexyl and the like. Examples of cyclic alkyl groups include cyclohexyl, cyclopentyl and the like. As an alkyl group having 1 to 18 carbon atoms, methyl, ethyl and the like are preferable.

  l shows the average added mole number of oxymethylene group, and is an integer of 0-40. As l, preferably, it is an integer of 10 to 30. m shows the average added mole number of oxyethylene group, It is an integer of 0-13. Preferably, m is an integer of 1 to 10. n shows the average added mole number of oxybutylene group, and is an integer of 0-6. As n, Preferably, it is an integer of 1-4. However, l, m and n are not simultaneously 0, and the sum of l, m and n is an integer of 1 to 59. The sum of l, m and n is preferably an integer of 10 to 44.

  As a monomer represented by the general formula (3), polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polybutylene glycol (meth) acrylate, poly (ethylene glycol / propylene glycol) (meth) acrylate, Ethylene glycol polypropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, lauroxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, etc. may be mentioned. In the present specification, “(meth) acrylate” indicates acrylate or methacrylate.

  Among these, methoxy polyethylene glycol (meth) acrylate and the like are preferable. Monomer (3) can be used individually by 1 type or in mixture of 2 or more types.

  The cationic copolymer comprises a monomer (1) and at least one monomer selected from the group consisting of the monomers (2) and (3) in a monomer (1 ): Monomer (2) and / or (3) can be obtained by copolymerization in the ratio of 95: 5 to 50:50. That is, the cationic copolymer is a copolymer of the monomer (1) and the monomer (2), a copolymer of the monomer (1) and the monomer (3), or It can be any of those obtained by copolymerizing the monomer (1), the monomer (2) and the monomer (3). When both the monomer (2) and the monomer (3) are contained, they are mixed at a molar ratio of monomer (2): monomer (3) = 1: 10 to 10: 1. And the total amount of them is in the above ratio.

  The copolymerization is preferably performed by a radical polymerization reaction. As the radical polymerization reaction, conventionally known methods can be widely used. For example, in a solvent, using a radical polymerization initiator, the monomer (1) and the monomer (2) and / or (3) can be mixed and reacted in the above ratio.

  Examples of the solvent include water, ethanol and the like.

  As a radical polymerization initiator, For example, inorganic or organic peroxides, such as potassium persulfate, ammonium persulfate, t-butyl hydroperoxide, etc .; 2,2'-azobis [2- (2-imidazolin-2-yl) propane] Dihydrochloride, 2,2′-azobis [N- (2-carboxyl) -2-methylpropionamidine] hydrate, 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-] And imidazolin-2-yl] propane} dihydrochloride, 2,2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride and the like.

  The polymerization temperature is usually about 25 to 90 ° C, preferably about 40 to 80 ° C. It can be heated to control the molecular weight of the target polymer. The reaction time is usually about 1 to 48 hours, preferably about 3 to 10 hours.

  After completion of the reaction, the resulting mixture can be appropriately filtered, washed, dried and the like to obtain a copolymer. Alternatively, it is possible to formulate the anti-stain agent composition in the state of the obtained mixture.

  The anti-soiling agent composition of the present invention is conveniently used as a preparation obtained by diluting the above-mentioned cationic copolymer as an active ingredient with a suitable solvent. The stain inhibitor composition of the present invention is preferably an aqueous solution containing the above cationic copolymer and water. The content of the cationic copolymer in the anti-soiling agent composition of the present invention is not particularly limited, and usually about 5 to 40% by weight, preferably about 10 to 20% by weight, in the composition. If the content of the cationic copolymer is within the above range, a sufficient antifouling effect can be obtained.

  The stain inhibitor composition of the present invention preferably contains, in addition to the cationic copolymer described above, at least one selected from the group consisting of nonionic surfactants and phosphonic acid compounds. The anti-soiling effect can be further improved by further adding a nonionic surfactant and / or a phosphonic acid compound to the anti-soiling agent composition.

  As the nonionic surfactant, one comprising an alkylene oxide adduct to a compound having active hydrogen is preferable. As the alkylene oxide, ethylene oxide, propylene oxide, butylene oxide or mixed adducts thereof are used.

  Examples of the compound having active hydrogen include aliphatic alcohol, alkylphenol, sorbitan fatty acid ester, glycerin fatty acid ester, polyhydric alcohol fatty acid ester such as pentaerythritol fatty acid ester, fatty acid, fatty acid amide, aliphatic amine and the like. Each of the fatty acids constituting the compound may be either saturated or unsaturated.

  Examples of alkylene oxide adducts to compounds having active hydrogen as described above include polyoxyalkylene alkyl ethers that are alkylene oxide adducts to aliphatic alcohols, and polyoxyalkylene alkyl phenyl ethers that are adducts to alkyl phenols. Polyoxyalkylene sorbitan fatty acid ester which is an adduct to sorbitan fatty acid ester, polyoxyalkylene glycerin fatty acid ester which is an adduct to glycerin fatty acid ester, polyoxyalkylene pentaerythritol fatty acid ester which is an adduct to pentaerythritol fatty acid ester A polyoxyalkylene fatty acid ester which is an adduct to a fatty acid, a polyoxyalkylene fatty acid amide which is an adduct to a fatty acid amide, an addition to an aliphatic amine Polyoxyalkylene alkylamine such as is can be exemplified. Examples of the alkylene oxide to be added include ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof. Among these, polyoxyalkylene alkyl ethers and polyoxyalkylene alkyl amines are preferable, and polyoxyalkylene alkyl ethers or polyoxyalkylene alkyl amines, in which the number of moles of oxyethylene groups is 5 to 20, are more preferable. These nonionic surfactants can be used alone or in combination of two or more.

  In the case where the stain inhibitor composition of the present invention contains a nonionic surfactant, it is preferable to blend it at a ratio of about 25 to 500 parts by weight with respect to 100 parts by weight of the cationic copolymer. More preferably, it is 100 to 300 parts by weight with respect to 100 parts by weight of the cationic copolymer.

  Specific examples of phosphonic acid compounds include aminotrimethylenephosphonic acid (ATMP), ethylenediaminetetramethylenephosphonic acid, trimethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, diethylenetriaminepenta (methylenephosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid (HEDP), 1-hydroxypropane-1,1-diphosphonic acid, 1-aminopropane-1,1-diphosphonic acid, and 1,2,4-tricarboxybutane- 2-phosphonic acid (PBTC) etc. are mentioned. Among these, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotrimethylenephosphonic acid (ATMP), 1,2,4-tricarboxybutane-2-phosphonic acid (PBTC) and the like are preferable. These phosphonic acid compounds can be used singly or in combination of two or more.

  When the stain inhibitor composition of the present invention contains a nonionic surfactant, it is preferable to blend it in a ratio of about 15 to 200 parts by weight with respect to 100 parts by weight of the cationic copolymer. More preferably, it is 50 to 100 parts by weight with respect to 100 parts by weight of the cationic copolymer.

  The above-described anti-soiling agent composition is used to prevent adhesion of dirt such as pitch to the paper manufacturing apparatus in the paper manufacturing process. When used, it is preferred to use the stain inhibitor composition further diluted with water. It is also possible to add an organic solvent, if necessary. The stain inhibitor composition is preferably diluted with water so that the concentration of the cationic copolymer is about 0.0005 to 0.2% by weight.

  By spraying the anti-smudge composition onto the papermaking apparatus, the papermaking apparatus can be prevented from becoming dirty. Thus, the present invention provides a method of preventing soiling by spraying the soilproofing agent composition onto a papermaking apparatus. When spraying on a paper manufacturing apparatus, it is preferable to use the liquid which diluted the antifouling agent composition with water.

  Examples of the paper manufacturing apparatus include felts and rolls of a press part in a paper machine. For example, by adding the stain inhibitor composition to paper manufacturing process water, in particular, shower water of a roll or a felt, it is possible to effectively prevent stains such as pitch of a felt, a roll and the like. Thus, in the paper manufacturing process, the adhesion of stains to these tools can be sufficiently prevented by spraying the antifouling composition of the present invention onto a paper manufacturing apparatus such as a wire or felt. .

  In addition to direct spraying on a felt or the like, the stain inhibitor composition can also prevent dirt adhesion in the paper making process by adding it to the pulp slurry before paper making.

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples.
Synthesis Example 1
A 500 mL separable flask equipped with an overhead stirrer and a condenser was charged with 185 g (1.0 mol) of laurylamine, 210 g of ion exchanged water, and 40.3 g (1.01 mol) of sodium hydroxide, and the water bath was stirred. The internal temperature was raised to 50.degree. To this was added 78 g (1.02 mol) of allyl chloride dropwise over 30 minutes, and the reaction exotherm was allowed to react while cooling with a water bath. After completion of the dropwise addition, the internal temperature was kept at 50 ° C. for 1 hour to complete the reaction. The mixture was cooled to 30 ° C., and the upper oil layer and the aqueous layer were separated by a separatory funnel. Further, by drying under reduced pressure, unreacted allyl chloride was distilled off to obtain 200 g of allyl laurylamine as a yellow oil.

  91 g of allyl laurylamine obtained above and 130 g of ethanol are charged into a 1 L separable flask equipped with an overhead stirrer and a nitrogen inlet tube, and hydrochloric acid (35% while cooling so that the internal temperature does not exceed 60 ° C. 42 g was added dropwise to prepare allyl laurylamine hydrochloride (ALAC) solution. While blowing in nitrogen gas at 100 mL / min, the temperature was raised to 60 ° C. with a water bath to deoxidize the system. This includes 90.5 g of a 65% aqueous solution of diallyldimethylammonium chloride (DADMAC), 10 g of a 70% aqueous solution of triallylamine hydrochloride (TAA.HCl), and a polymerization initiator 2,2'-azobis (2-methylpropionamidine) dihydrochloride. 40 g of a 20% aqueous solution was separately added in 5 portions and polymerized for 5 hours. The internal temperature is further raised to 75 ° C., and polymerization is carried out until there is no unreacted monomer, and when the polymerization rate reaches 100% by colloid titration, 596.2 g of purified water is added, 0.3 g of a 48% aqueous sodium hydroxide solution Was adjusted to pH 5.0 to obtain a pale yellow milky white cationic copolymer (1) having a solid content of 18% by weight. Incidentally, the cationic copolymer (1) having a solid content of 18% by weight is a state in which the copolymer (1) is dissolved in a solvent such as water and the solid content (copolymer) in the solution is Is contained at a rate of 18% by weight.

(Composition example 2)
In a 1 L separable flask equipped with an overhead stirrer and a nitrogen inlet tube, 82 g of allyloctylamine and 130 g of ethanol are charged, and 37.4 g of hydrochloric acid (35%) while cooling so that the internal temperature does not exceed 60 ° C. The solution was added dropwise to prepare an allyloctylamine hydrochloride (AOAC) solution. While blowing in nitrogen gas at 100 mL / min, the temperature was raised to 60 ° C. with a water bath to deoxidize the system. In this, 103 g of a 65% aqueous solution of diallyldimethyl ammonium chloride (DADMAC), 11.5 g of a 70% aqueous solution of triallylamine hydrochloride (TAA.HCl), and a polymerization initiator 2,2'-azobis (2-methylpropionamidine) dihydrochloride 40 g of a 20% aqueous solution of a salt was each added in five portions and polymerized for 10 hours. The internal temperature is further raised to 75 ° C., and polymerization is performed until there is no unreacted monomer. When the polymerization rate reaches 100% by colloid titration, 595.8 g of purified water is added, and 0.3 g of a 48% aqueous sodium hydroxide solution is added. By adding and adjusting to pH 5.0, a pale yellow and milky white cationic copolymer (2) having a solid content of 18% by weight was obtained. Incidentally, the cationic copolymer (2) having a solid content of 18% by weight is a state in which the copolymer (2) is dissolved in a solvent such as water, and the solid content (copolymer) in the solution is Is contained at a rate of 18% by weight.

(Composition example 3)
In a 1-L separable flask equipped with an overhead stirrer, a nitrogen inlet tube, and a condenser, 194 g of a 65% aqueous solution of diallyldimethylammonium chloride (DADMAC) and 597.5 g of ion-exchanged water are added, and nitrogen is blown at 100 mL / min. The temperature was raised to 70 ° C. with a water bath to deoxygenate the system. To this, 153.5 g of methoxy polyethylene glycol methacrylate and 40 g of a 20% aqueous solution of a polymerization initiator 2,2'-azobis (2-methylpropionamidine) dihydrochloride were each separately added in 5 portions and polymerized for 10 hours. Further, the internal temperature is raised to 80 ° C., 15 g of a 20% aqueous solution of a polymerization initiator 2,2′-azobis (2-methylpropionamidine) dihydrochloride is added and polymerized, and polymerization is carried out until there is no unreacted monomer. When the polymerization rate reached 100% by colloid titration, it was cooled to terminate the polymerization, and a colorless cationic copolymer (3) having a solid content of 30% by weight was obtained. Incidentally, the cationic copolymer (3) having a solid content of 30% by weight is a state in which the copolymer (3) is dissolved in a solvent such as water, and the solid content (copolymer) in the solution is Is contained in a proportion of 30% by weight.

(Examples 1 to 6)
Cationic copolymer obtained in Synthesis Examples 1 to 3, polyoxyethylene stearylamine (oxyethylene group = 20 mol, active ingredient 100%) (Kao Co., Ltd. Ameite 320 (product name)), 1-hydroxyethane -1, 1-diphosphonic acid (HEDP) (made by Chelest Co., Ltd., Chelesto PH-210 (product name), 60% of active ingredient) and water are compounded in the ratio described in Table 1; An antifoulant composition was obtained.

(Comparative Examples 1 to 6)
Polydiallyldimethylammonium chloride (DADMAC) with a molecular weight of 20,000 (manufactured by Senka Co., Ltd., Unisense FPA 100L (product name), solid content 27% by weight), polydiallyldimethylammonium chloride (DADMAC) with a molecular weight of 200,000 (Senka Co., Ltd.) Product, Unisense FPA 1001 L (product name), solid content 43% by weight), polyoxyethylene stearylamine (oxyethylene group = 20 mol, active ingredient 100%) (manufactured by Kao Corporation, Ameto 320 (product name)), 1- Hydroxyethane-1,1-diphosphonic acid (HEDP) (manufactured by Chelest Co., Ltd., Chelesto PH-210 (product name), active ingredient 60%) and water are blended in the proportions described in Table 1, Comparative Examples 1 to 6 The antifoulant composition of

(Soil adhesion prevention test)
(1) The soil component obtained by actually using the paper company and extracting the soiled dirt component with ethanol: benzene = 1: 2 (volume ratio) is again ethanol: benzene = 1: 2 (volume) The mixture was dissolved in the mixed solvent (ratio) to prepare a 5% soil extract.
(2) Test water (150 ml) obtained by diluting each of the antifouling agents of Examples 1 to 6 and Comparative Examples 1 to 6 with ion exchange water in a 200 ml beaker so that the concentration of the cationic copolymer becomes 100 ppm. Created. A polyethylene plate (20 × 60 × 1 mm) was immersed in test water and stirred at 25 ° C., 600 rpm for 30 minutes.
(3) A 5% soil extract was added to the test water so as to be 100 ppm, and stirred at 25 ° C., 600 rpm for 60 minutes.
(4) Stirring was stopped, and left still for 60 minutes.
(5) Stirring was resumed, the polyethylene plate was taken out, immersed in Sudan Black B staining solution (manufactured by Kishida Chemical Co., Ltd.) for 5 minutes, washed with deionized water, and then dried at 70 ° C.
(6) A polyethylene plate of the same size (20 × 60 mm) printed with a straight line in the form of a grid so as to equally divide the entire area of the polyethylene plate by 100 on the treated polyethylene plate is superimposed, and stains can be visually confirmed The number of grids was measured and evaluated by the following AE.
A: Dirt component adhesion rate to polyethylene plate is less than 1% of polyethylene plate area B: Dirt component adhesion rate to polyethylene plate is 1% to less than 5% of polyethylene plate area C: Dirt component adhesion rate to polyethylene plate 5% or more and less than 10% of the polyethylene plate area D: The dirt component adhesion rate to the polyethylene plate is 10% or more and less than 25% of the polyethylene plate area E: The dirt component adhesion rate to the polyethylene plate is 25% or more of the polyethylene plate area

(Peelability test)
(1) The test water (150 ml) prepared in the above-mentioned anti-soiling test was heated to 40 ° C., and the felt, which was actually used by a paper company and to which the fouling component was attached, was immersed for 2 minutes.
(2) The felt was taken out, a cloth tape was applied, the upper and lower sides were sandwiched by a SUS plate, and pressure was applied at 4 kgf / m ² .
(3) The double clip was held between cloth tapes, and the peeling resistance (g) at the time of peeling with a force gauge was measured.

  The results are shown in Table 2.

  From Table 2, since the antifouling agents of Examples 1 to 6 contain the cationic copolymer of the present invention, the antifouling agents of Comparative Examples 1 to 6 which do not contain the cationic copolymer of the present invention As compared with the above, it is understood that the adhesion of the stain is effectively prevented and the peeling resistance of the stain is small.

Claims (5)

General formula (1):

[In formula, R < ₁ >, R < ₂ > and R < ₃ > are the same or different, and show a hydrogen atom, a C1-C3 alkyl group, or a C2-C4 alkenyl group. X ₁ ^- represents a halide ion, a hydroxide ion, an anion of an inorganic acid or an anion of an organic acid. And a monomer represented by the general formula (2):

Wherein, R ₄ represents a saturated or unsaturated hydrocarbon group or a benzyl group 5 to 22 carbon atoms. R ₅ and R ₆ represents the same or different and each represents a hydrogen atom, an alkenyl group having 2 to 4 carbon atoms, a saturated or unsaturated hydrocarbon group of 5 to 22 carbon atoms or a benzyl group. X ₂ ⁻ represents a halide ion, a hydroxide ion, an anion of an inorganic acid or an anion of an organic acid. And a monomer represented by the general formula (3):

[Wherein, R ₇ represents a hydrogen atom or a methyl group. R ₈ represents an alkyl group having 1 to 18 carbon atoms, a benzyl group or a phenylethyl group. l is an integer of 0 to 40, m is an integer of 0 to 13, and n is an integer of 0 to 6. However, l, m and n are not simultaneously 0, and the sum of l, m and n is an integer of 1 to 59. ] The cationic copolymer obtained by copolymerizing with at least 1 sort (s) of monomer selected from the group which consists of a monomer represented by the molar ratio in the ratio of 95: 5 to 50:50 is obtained The antifouling composition for paper manufacturing processes which is contained as an active ingredient.   The stain inhibitor composition according to claim 1, further comprising at least one selected from the group consisting of nonionic surfactants and phosphonic acid compounds.   The stain inhibitor composition according to claim 2, wherein the nonionic surfactant is at least one selected from the group consisting of polyoxyalkylene alkyl ethers and polyoxyalkylene alkyl amines.   At least one selected from the group consisting of 1-hydroxyethane-1,1-diphosphonic acid, aminotrimethylene phosphonic acid, and 1,2,4-tricarboxybutane-2-phosphonic acid as the phosphonic acid compound The antifouling agent composition according to claim 2.   A method for preventing stains, comprising spraying the stain inhibitor composition according to any one of claims 1 to 4 onto a paper manufacturing apparatus.