WO2015016350A1 - Adhésif pour crêpe et procédé de fabrication de papier de crêpe - Google Patents

Adhésif pour crêpe et procédé de fabrication de papier de crêpe Download PDF

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Publication number
WO2015016350A1
WO2015016350A1 PCT/JP2014/070356 JP2014070356W WO2015016350A1 WO 2015016350 A1 WO2015016350 A1 WO 2015016350A1 JP 2014070356 W JP2014070356 W JP 2014070356W WO 2015016350 A1 WO2015016350 A1 WO 2015016350A1
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Prior art keywords
crepe
paper
adhesive
solid content
weight
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PCT/JP2014/070356
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English (en)
Japanese (ja)
Inventor
孝治 吉谷
彩香 勅使河原
Original Assignee
星光Pmc株式会社
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Priority to CN201480029409.4A priority Critical patent/CN105229227B/zh
Priority to JP2015501602A priority patent/JP5854167B2/ja
Publication of WO2015016350A1 publication Critical patent/WO2015016350A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/146—Crêping adhesives
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/52—Epoxy resins
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/56—Polyamines; Polyimines; Polyester-imides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/57—Polyureas; Polyurethanes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/005—Mechanical treatment

Definitions

  • the present invention relates to an adhesive for crepe used when manufacturing paper such as toilet paper, tissue paper, towel paper, and sanitary paper such as kitchen paper.
  • Creping is a process in which a wet fiber web is bonded to a rotary cylinder paper machine dryer known as a Yankee dryer in the drying process, and after drying, the fiber web is scraped off from the dryer surface with a doctor blade, and crepe is applied to the fiber web.
  • a crepe adhesive is applied to the dryer surface to form a film.
  • the coating on the dryer surface is effective to increase the adhesion of the fiber web to the Yankee dryer and to protect the dryer surface against doctor blade contact.
  • thermosetting resins such as polyamide polyamine / epihalohydrin resin and polyamide polyamine polyurea / epihalohydrin resin have been proposed (for example, see Patent Documents 1, 2, and 3).
  • plasticizers for crepe adhesives.
  • an adhesive prepared by mixing a reaction product of adipic acid and methylbis (aminopropylamine) with a polyamide epichlorohydrin resin obtained by reacting epichlorohydrin and a polyhydric alcohol plasticizer has been proposed (for example, , See Patent Document 4).
  • these crepe adhesives are used, there is a problem that the fiber web cannot be uniformly creped because the water resistance of the film formed on the Yankee dryer is weak or the adhesion of the film to the fiber web is weak. It was.
  • the object of the present invention is excellent in adhesion between fiber webs when producing paper, and the paper is easy to disaggregate even though there is little elution of the coating film by moisture brought in from wet paper etc. It is an object of the present invention to provide an adhesive for crepe with less wear of a doctor blade because the formed film is soft.
  • a crepe adhesive comprising a polyamide polyamine / epihalohydrin resin (A) and / or a polyamide polyamine / polyurea / epihalohydrin resin (B) and a softening agent (C), all of the following conditions (1) to (5):
  • a crepe adhesive characterized by filling. (1) 0 to 0.2 mEq of azetidinium group in 1 g of solid content of crepe adhesive (2) The intrinsic viscosity of the crepe adhesive is 0.20 to 0.55 dL / g.
  • a method for producing crepe paper comprising a step, ⁇ 4> ⁇ 3> the method for producing a crepe paper according to ⁇ 3>, wherein a softener is used as an internal additive, and the paper is sanitary paper I will provide a.
  • the present invention is a crepe adhesive containing at least a polyamide polyamine / epihalohydrin resin (A) and / or a polyamide polyamine / polyurea / epihalohydrin resin (B) and a softening agent (C).
  • an adhesive for crepe containing at least a polyamide polyamine / epihalohydrin resin (A) and a softening agent (C) A crepe adhesive containing at least a polyamide polyamine polyurea / epihalohydrin resin (B) and a softener (C);
  • a crepe adhesive containing at least a polyamide polyamine / epihalohydrin resin (A), a polyamide polyamine / polyurea / epihalohydrin resin (B) and a softening agent (C) is also included.
  • a polyamide polyamine / epihalohydrin resin (e) obtained by reacting a polyalkylene polyamine (a) and a dibasic carboxylic acid (b) with an epihalohydrin (c) to a polyamide polyamine (x) ( A) and softener (C)
  • a polyamide polyamine obtained by reacting a polyalkylene polyamine (a), a dibasic carboxylic acid (b) and a urea (d) with a polyamide polyamine polyurea (y) and an epihalohydrin (c)
  • Polyamide polyamine which is a crepe adhesive containing at least a polyurea / epihalohydrin resin (B) and a softener (C), and is naturally obtained by reacting a polyalkylene polyamine (a) and a dibasic carboxylic acid (b).
  • X is reacted with a polyamidopolyamine / epihalohydrin resin (A) obtained by reacting an epihalohydrin (c) with a polyalkylene polyamine (a), a dibasic carboxylic acid (b) and a urea (d).
  • A polyamidopolyamine / epihalohydrin resin obtained by reacting an epihalohydrin (c) with a polyalkylene polyamine (a), a dibasic carboxylic acid (b) and a urea (d).
  • Polyamide polyamine polyurea (y) and epihalohydrin (c) obtained Creping adhesive comprising at least obtained by reacting polyamidepolyaminepolyurea-epihalohydrin resin (B) and softening agent (C) also included.
  • the polyalkylene polyamine (a) used in the present invention may be any one having at least two alkylene groups and two or more amino groups in the molecule, such as diethylenetriamine, triethylenetetramine, tetraethylene.
  • diethylenetriamine, triethylenetetramine, tetraethylene examples include pentamine, pentaethylenehexamine, hexaethyleneheptamine, dipropylenetriamine, tripropylenetetramine, iminobispropylamine, and the like. These may be used alone or in combination of two or more. .
  • diethylenetriamine, triethylenetetramine, and tetraethylenepentamine are preferable because of excellent adhesiveness.
  • diethylenetriamine is particularly preferable. These may be used alone or in combination of two or more.
  • alkylene diamines such as ethylenediamine, propylenediamine or hexamethylenediamine
  • aminocarboxylic acids having 1 to 6 carbon atoms such as ⁇ -aminocaproic acid, and 1 to 6 carbon atoms such as ⁇ -caprolactam. Lactams of aminocarboxylic acids can also be used.
  • the dibasic carboxylic acids (b) used in the present invention include two dibasic carboxylic acids and / or derivatives thereof in the molecule.
  • Examples of the derivatives include mono- or diesters of these dibasic carboxylic acids, or acid anhydrides.
  • Examples of the dibasic carboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, dodecanedioic acid and the like.
  • a dibasic carboxylic acid having a number of 5 to 10 is preferred.
  • examples of mono- or diesters of dibasic carboxylic acid include lower alcohol (methyl, ethyl, propyl) esters preferably having 1 to 5 carbon atoms, particularly preferably 1 to 3 carbon atoms.
  • examples of the acid anhydride include an intramolecular dehydration condensate of a free acid and a condensate of a lower carboxylic acid, preferably a lower carboxylic acid having 1 to 5 carbon atoms.
  • Particularly preferred industrially preferred dibasic carboxylic acids (b) include adipic acid, glutaric acid dimethyl ester, and adipic acid dimethyl ester. Said dibasic carboxylic acid (b) can be used 1 type or in combination of 2 or more types.
  • carboxylic acids and / or carboxylic acids thereof in the molecule such as citric acid and trimellitic acid, may be used as long as the effects of the present invention are not hindered.
  • Acid esters or derivatives having acid anhydrides thereof can also be used.
  • ureas (d) used in the present invention include urea, thiourea, guanylurea, phenylurea, methylurea, dimethylurea and the like. Of these, urea is particularly preferred industrially.
  • compounds having one or more N unsubstituted amide groups that can undergo an amide exchange reaction with an amino group for example, aliphatic amides such as acetamide and propionamide Or aromatic amides such as benzamide and phenylacetamide can also be used.
  • the epihalohydrin (c) used in the present invention includes epichlorohydrin, epibromohydrin and the like, but industrially epichlorohydrin is preferable.
  • the polyamide polyamine / epihalohydrin resin (A) in the present invention is obtained by reacting a polyalkylene polyamine (a) and a dibasic carboxylic acid (b) with a polyamido polyamine (x) and an epihalohydrin (c). The resulting resin.
  • the polyamide polyamine / epihalohydrin resin (A) of the present invention is preferably a polyalkylene polyamine (a) 38 to 58 mol%, a dibasic carboxylic acid (b) 37 to 55 mol%, and an epihalohydrin (c) 1 to 14 mol. %, A crepe adhesive having excellent film properties can be obtained.
  • the polyalkylene polyamine (a) is preferably 43 to 54%
  • the dibasic carboxylic acid (b) is 42 to 52 mol%
  • the epihalohydrin (c) is preferably 1 to 10 mol%.
  • the polyamide polyamine polyurea / epihalohydrin resin (B) in the present invention is a polyamide polyamine polyurea (y) obtained by reacting a polyalkylene polyamine (a), a dibasic carboxylic acid (b), and a urea (d). And epihalohydrin (c).
  • the reaction of the polyalkylene polyamine (a), the dibasic carboxylic acid (b) and the urea (d) can be performed in any order or simultaneously.
  • the polyalkylene polyamine (a), the dibasic carboxylic acid (b), and the urea (d) can be reacted simultaneously.
  • polyalkylene polyamine (a) and ureas (d) are reacted to obtain polyalkylene polyamine polyurea (z), and then the polyalkylene polyamine polyurea (z) is reacted with dibasic carboxylic acids (b). Can be made. Furthermore, the polyalkylene polyamine (a) and the dibasic carboxylic acid (b) can be reacted to obtain a polyamide polyamine (x), and the polyamide polyamine (x) and the urea (d) can be reacted.
  • the polyamide polyamine polyurea / epihalohydrin resin (B) of the present invention is preferably a polyalkylene polyamine (a) 28 to 58 mol%, a dibasic carboxylic acid (b) 24 to 55 mol%, and a urea (d) 37
  • a polyalkylene polyamine (a) is 33 to 54%
  • the dibasic carboxylic acid (b) is 28 to 52 mol%
  • the urea (d) is 35 mol% or less
  • the epihalohydrin (c) is 1 to 10 mol%. preferable.
  • the condensation reaction of the polyalkylene polyamine (a) and the dibasic carboxylic acid (b), or the polyalkylene polyamine (a) and the urea (d), or the polyamide polyamine (x) and the urea (d) Dehydration and / or dealcoholization and / or deammonia reaction is performed.
  • the reaction temperature is preferably 110 to 250 ° C. and the reaction time is 1 to 8 hours.
  • sulfonic acids such as sulfuric acid, benzenesulfonic acid, and paratoluenesulfonic acid
  • phosphoric acids such as phosphoric acid, phosphonic acid, and hypophosphorous acid
  • other known catalysts may be used alone or in combination. These can be used in combination.
  • the concentration of the reaction solution is preferably 10 to 80% by mass, and the reaction temperature depends on the reaction concentration. Although adjustment is necessary as appropriate, it is usually preferred to carry out at 5 to 90 ° C.
  • the reaction between the polyamide polyamine (x) and / or the polyamide polyamine polyurea (y) and the epihalohydrin (c) is carried out by reacting the resulting polyamide polyamine / epihalohydrin resin (A) and / or polyamide polyamine polyurea / epihalohydrin resin (B).
  • the viscosity is within the range of 10 to 350 mPa ⁇ s, preferably 50 to 250 mPa ⁇ s, based on the viscosity at 25 ° C. of an aqueous solution containing 15% by mass of solid content, a resin having excellent adhesive strength can be obtained. Be able to.
  • the reaction is stopped by adding water to the reaction liquid and cooling it to obtain an aqueous solution of resin (A) and / or resin (B).
  • the aqueous solution of the crepe adhesive of the present invention can be adjusted in pH to improve storage stability and control film formation.
  • the pH can be adjusted by adding a pH adjuster.
  • the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, especially inorganic acids not containing halogen; organic acids such as formic acid and acetic acid; sodium hydroxide, potassium hydroxide, calcium hydroxide, water
  • Preferable examples include inorganic bases such as magnesium oxide, sodium carbonate and potassium carbonate; monoamine compounds such as ammonia, diethylamine, triethylamine, propylamine, butylamine, diisobutylamine, hydroxyamine, ethanolamine and diethanolamine.
  • the azetidinium group should be 0 to 0.2 mEq, preferably 0 to 0.1 mEq in 1 g of the solid content of the crepe adhesive of the present invention.
  • AZR azetidinium group
  • a wet paper strength effect is manifested when used as an adhesive for crepes, and water disintegration of toilet paper and the like is achieved. Adversely affect.
  • the intrinsic viscosity of the crepe adhesive should be 0.20 to 0.55 dL / g, preferably 0.25 to 0.5 dL / g.
  • the intrinsic viscosity is a physical quantity that depends on the molecular weight, shape, and size of the polymer chain that is independently dissolved in the solvent. If it is this range, when using as an adhesive for crepes, it will become easy to form the film
  • the softener (C) contained in the crepe adhesive is It must be (i) a boiling point of 150 ° C. or higher and liquid at 80 ° C., and (ii) a water-soluble aliphatic polyol or polyethylene glycol dimethyl ether.
  • the softener (C) is preferably ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycerol, 1,3-butanediol, 1,4-butanediol, diethylene glycol dimethyl ether, triethylene.
  • Examples thereof include glycol dimethyl ether and tetraethylene glycol dimethyl ether, and polyethylene glycol, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether are particularly preferable.
  • the water resistance required by the following formula (1) needs to be 40 to 100% in the following evaluation of water resistance.
  • a tea bag weight W2 (g)
  • a petri dish weight W1 (g)
  • a uniform film weight of 0.05 g was immersed in water at 50 ° C. for 5 minutes with stirring.
  • the petri dish is weighed and measured for each tea bag (weight W3 (g)), and water resistance is calculated from the following equation (1).
  • Water resistance (%) 100 ⁇ ⁇ (W1 + W2) ⁇ W3 ⁇ /0.05 ⁇ 100
  • the coating film is less likely to be eluted by moisture brought in from wet paper or the like, and the coating film is easily formed on the Yankee dryer.
  • the weight average molecular weight of the crepe adhesive of the present invention is preferably from 1 to 5 million, particularly from 1.5 to 4.5 million in order to obtain excellent adhesion.
  • the weight average molecular weight in this invention is based on the measurement described in the Example.
  • Specific methods for applying the crepe adhesive of the present invention to paper include a method of spraying wet paper in front of a Yankee dryer in a manufacturing process, a method of spraying directly on the surface of a Yankee dryer, and a combination of these methods. There is a way to do it. Spraying directly on the surface of the Yankee dryer is preferable because the effect as an adhesive for crepe is easily obtained.
  • the crepe adhesive of the present invention can be used in combination with a crepe release agent in order to control the adhesive force of the fiber web to the surface of the Yankee dryer.
  • a crepe release agent examples include silicone oil, hydrocarbon oil, oxidized wax, paraffin wax, polyethylene wax, cationic surfactant, anionic surfactant, and amphoteric surfactant. These can be used alone or in combination of two or more.
  • the crepe adhesive of the present invention When the crepe adhesive of the present invention is sprayed directly on the surface of the Yankee dryer, the crepe adhesive is diluted 10 to 1000 times, and the spray amount is 0.01 to 500 mg / m 2 based on the solid content of the resin.
  • a content of 0.1 to 300 mg / m 2 is preferable because a uniform coating film suitable for creping is easily obtained. Outside this range, when a sufficient coating film is not formed or dirt is deposited on the coating film, creping becomes difficult in all cases.
  • the method of using the crepe adhesive in the present invention is application to paper as described above. However, as another embodiment, it is used by adding (internal addition) to a paper material (pulp slurry), or both internal addition and application. Can also be used.
  • the crepe adhesive is added internally, it is usually 0.01 to 1% by mass, preferably 0.01 to 0.5% by mass, based on the solid content of the crepe adhesive, based on the pulp solid content. What is necessary is just to add.
  • the basis weight of the paper is 10 to 45 g / m 2 and the density is 0.1 to 0.4 g / cm 3 from the viewpoint of texture.
  • the longitudinal dry tear length JIS P 8113
  • toilet paper or tissue paper is preferably 0.2 to 0.8 km from the viewpoint of water decomposability.
  • the water absorption Japanese Industrial Standards JIS S 3104
  • the water absorption is 1 to 10 seconds when two sheets are stacked, from the viewpoint of the wiping effect when used.
  • the paper to be creped using the crepe adhesive of the present invention is preferably sanitary paper such as toilet paper, tissue paper, towel paper, kitchen paper, and bleached or unbleached chemicals such as kraft pulp or sulfite pulp as a pulp raw material.
  • Waste paper pulp such as bleached or unbleached high yield pulp such as pulp, groundwood pulp, mechanical pulp or thermomechanical pulp, newspaper waste paper, magazine waste paper, corrugated waste paper or deinked waste paper can be contained.
  • a softener In producing a paper to be creped using the crepe adhesive of the present invention, a softener, a filler, a sizing agent, a dry paper strength improver, a wet paper strength improver, a yield improver, a bulk enhancer, and a paper thickness improver.
  • additives such as an opacifying agent and a freeness improver may be used as necessary in order to develop the physical properties required for each paper type. These may be used alone or in combination of two or more. Among them, it is preferable to add a softener internally or externally because paper having excellent texture can be obtained.
  • the softener examples include a fatty acid amide epihalohydrin resin (S1), a quaternary ammonium salt (S2) having an alkyl group and / or an alkenyl group, an alkylene oxide reactant (S3) of a fatty acid and / or an aliphatic alcohol, and the like.
  • fatty acid amide epihalohydrin resin (S1) is preferable because of its excellent flexibility effect in the present invention.
  • S1 may be used alone or in combination of two or more. Usually, it may be added to the paper in a proportion of 0.01 to 1% by mass, preferably 0.01 to 0.5% by mass, based on the solid content of the pulp.
  • Example 1 ⁇ Production of polyamide polyamine (x-1)>
  • a four-necked round bottom flask equipped with a thermometer, reflux condenser, stirrer, and nitrogen inlet tube 103 g (1 mol) of diethylenetriamine (hereinafter sometimes abbreviated as “DETA”), 0.52 g of 95% sulfuric acid (0 0.005 mol) was added, and while stirring, 146 g (1 mol) of adipic acid was added. Under nitrogen flow, the temperature was raised while removing generated water out of the system, and the reaction was carried out at 175 ° C. for 3 hours. Gradually added to adjust the solid content to 35% to obtain a polyamide polyamine aqueous solution (x-1).
  • DETA diethylenetriamine
  • Example 2 Epichlorohydrin (12 g, 0.13 mol) was added to the total amount of the polyamide polyamine aqueous solution (x-1) obtained in the same manner as in Example 1, and the temperature was raised to 30 ° C. and kept at the same temperature for 1 hour. Next, water was added to adjust the solid content to 15%, the temperature was raised to 70 ° C., and when the viscosity reached 470 mPa ⁇ s, the reaction was terminated to obtain a polyamide polyamine / epichlorohydrin resin (A-2). Next, 99 g of propylene glycol (30% by mass relative to 100% by mass of resin (A-2) solid content) was added as a softener (C), and the solid content was adjusted to 15% with water. An adhesive was obtained.
  • Example 3 ⁇ Production of polyamide polyamine (x-2)> A four-necked round bottom flask equipped with a thermometer, reflux condenser, stirrer, and nitrogen inlet tube was charged with 108 g (1.05 mol) of diethylenetriamine and 0.52 g (0.005 mol) of 95% sulfuric acid and stirred with adipine. 146 g (1 mol) of acid was added, the temperature was raised while removing the generated water out of the system under a nitrogen stream, and after reacting at 175 ° C. for 6 hours, water was gradually added to adjust the solid content to 35%. A polyamide polyamine aqueous solution (x-2) was obtained.
  • Example 4 7.4 g (0.08 mol) of epichlorohydrin was added to the total amount of the polyamide polyamine aqueous solution (x-2) obtained in the same manner as in Example 3, and the temperature was raised to 30 ° C. and kept at the same temperature for 1 hour. Next, water was added to adjust the solid content to 15%, the temperature was raised to 70 ° C., and when the viscosity reached 20 mPa ⁇ s, the reaction was terminated to obtain a polyamide polyamine / epichlorohydrin resin (A-4). Next, 58 g of glycerin as a softening agent (C) (20% by mass with respect to 100% by mass of resin (A-4) solid content) was added, and the solid content was adjusted to 15% with water. Got.
  • C softening agent
  • Example 5 14.8 g (0.16 mol) of epichlorohydrin was added to the total amount of the polyamide polyamine aqueous solution (x-2) obtained in the same manner as in Example 3, and the temperature was raised to 30 ° C. and kept at the same temperature for 1 hour. Next, water was added to adjust the solid content to 15%, the temperature was raised to 70 ° C., and when the viscosity reached 510 mPa ⁇ s, the reaction was terminated to obtain a polyamide polyamine / epichlorohydrin resin (A-5). Next, 60 g of glycerin as a softening agent (C) was added (so that the resin (A-5) had a solid content of 20% by mass with respect to 100% by mass), and the solid content was adjusted to 15% with water. Got.
  • glycerin as a softening agent (C) 60 g of glycerin as a softening agent (C) was added (so that the resin (A-5) had a solid content
  • Example 6 Provide of polyamide polyamine polyurea (y-1)> A four-necked round bottom flask equipped with a thermometer, reflux condenser, stirrer, and nitrogen inlet tube was charged with 105 g (1.02 mol) of diethylenetriamine and 0.52 g (0.005 mol) of 95% sulfuric acid, and agitated while stirring. 146 g (1 mol) of acid was added, and the temperature was raised while removing the generated water out of the system under a nitrogen stream. After reacting at 175 ° C. for 6 hours, water was gradually added to adjust the solid content to 98%. Next, 12 g (0.2 mol) of urea was added and reacted at 125 ° C. for 2 hours, and then water was gradually added to adjust the solid content to 35% to obtain a polyamide polyamine polyurea aqueous solution (y-1).
  • Example 7 ⁇ Production of polyamide polyamine polyurea (y-2)> A four-necked round bottom flask equipped with a thermometer, reflux condenser, stirrer, and nitrogen inlet tube was charged with 105 g (1.02 mol) of diethylenetriamine and 0.52 g (0.005 mol) of 95% sulfuric acid, and agitated while stirring. 146 g (1 mol) of acid was added, and the temperature was raised while removing the generated water out of the system under a nitrogen stream. After reacting at 175 ° C. for 6 hours, water was gradually added to adjust the solid content to 98%. Next, 24 g (0.4 mol) of urea was added and reacted at 125 ° C. for 2 hours, and then water was gradually added to adjust the solid content to 35% to obtain a polyamide polyamine polyurea aqueous solution (y-2).
  • Example 8 ⁇ Production of polyamide polyamine (x-3)> A four-necked round bottom flask equipped with a thermometer, reflux condenser, stirrer, and nitrogen inlet tube was charged with 101 g (0.98 mol) of diethylenetriamine and 0.52 g (0.005 mol) of 95% sulfuric acid, and agitated with stirring. 146 g (1 mol) of acid was added, the temperature was raised while removing the generated water out of the system under a nitrogen stream, and after reacting at 175 ° C. for 6 hours, water was gradually added to adjust the solid content to 35%. A polyamide polyamine aqueous solution (x-3) was obtained.
  • Example 9 ⁇ Production of polyamide polyamine (x-4)> A four-necked round bottom flask equipped with a thermometer, reflux condenser, stirrer, and nitrogen inlet tube was charged with 108 g (1.05 mol) of diethylenetriamine and 0.52 g (0.005 mol) of 95% sulfuric acid and stirred with adipine. 146 g (1 mol) of acid was added, the temperature was raised while removing the generated water out of the system under a nitrogen stream, and after reacting at 175 ° C. for 6 hours, water was gradually added to adjust the solid content to 35%. A polyamide polyamine aqueous solution (x-4) was obtained.
  • Example 10 11.1 g (0.12 mol) of epichlorohydrin was added to the total amount of the polyamide polyamine aqueous solution (x-4) obtained in the same manner as in Example 9, and the temperature was raised to 30 ° C. and kept at the same temperature for 1 hour. Next, water was added to adjust the solid content to 15%, the temperature was raised to 70 ° C., and when the viscosity reached 80 mPa ⁇ s, the reaction was terminated to obtain a polyamide polyamine / epichlorohydrin resin (A-8). Next, 59 g of propylene glycol (20% by mass with respect to 100% by mass of resin (A-8) solid content) was added as a softening agent (C), and the solid content was adjusted to 15% with water. Got.
  • Example 11 11.1 g (0.12 mol) of epichlorohydrin was added to the total amount of the polyamide polyamine aqueous solution (x-4) obtained in the same manner as in Example 9, and the temperature was raised to 30 ° C. and kept at the same temperature for 1 hour. Next, water was added to adjust the solid content to 15%, the temperature was raised to 70 ° C., and when the viscosity reached 80 mPa ⁇ s, the reaction was terminated to obtain a polyamide polyamine / epichlorohydrin resin (A-9).
  • Example 12 11.1 g (0.12 mol) of epichlorohydrin was added to the total amount of the polyamide polyamine aqueous solution (x-4) obtained in the same manner as in Example 9, and the temperature was raised to 30 ° C. and kept at the same temperature for 1 hour. Next, water was added to adjust the solid content to 15%, the temperature was raised to 70 ° C., and when the viscosity reached 80 mPa ⁇ s, the reaction was terminated to obtain a polyamide polyamine / epichlorohydrin resin (A-10).
  • diethylene glycol dimethyl ether (so as to be 20% by mass with respect to 100% by mass of the resin (A-10) solid content) was added as a softening agent (C), and the solid content was adjusted to 15% with water.
  • Example 13 11.1 g (0.12 mol) of epichlorohydrin was added to the total amount of the polyamide polyamine aqueous solution (x-4) obtained in the same manner as in Example 9, and the temperature was raised to 30 ° C. and kept at the same temperature for 1 hour. Next, water was added to adjust the solid content to 15%, the temperature was raised to 70 ° C., and when the viscosity reached 80 mPa ⁇ s, the reaction was terminated to obtain a polyamide polyamine / epichlorohydrin resin (A-11). Next, 59 g of triethylene glycol dimethyl ether (20% by mass with respect to 100% by mass of resin (A-11) solid content) was added as a softening agent (C), and the solid content was adjusted to 15% with water. An adhesive was obtained.
  • Comparative Example 2 (corresponding to Example 1 of the prior art, Japanese Patent No. 483523) ⁇ Production of polyamide polyamine polyurea (y-3)> A four-necked round bottom flask equipped with a thermometer, reflux condenser, stirrer, and nitrogen inlet tube was charged with 105.3 g (1.02 mol) of diethylenetriamine, and 146.1 g (1 mol) of adipic acid was added with stirring. The temperature was raised while removing the generated water out of the system, and the reaction was carried out at 170 ° C. for 3 hours.
  • reaction solution was cooled to 130 ° C., 12 g (0.2 mol) of urea was added, and deammonia reaction was performed at the same temperature for 2 hours, and then water was gradually added to polyamide polyamine polyurea having a solid content of 50%. 450 g of an aqueous solution (y-3) was obtained.
  • Comparative Example 3 (corresponding to Example 1 of Japanese Patent No. 591046, which is a prior art) A four-necked round bottom flask equipped with a thermometer, a condenser, and a stirrer was charged with 108.2 g (1.05 mol) of diethylenetriamine, 146.1 g (1.00 mol) of adipic acid, and 146.1 g of water. A dehydration reaction was performed at 160 to 170 ° C. for 6 hours to obtain a polyamide polyamine aqueous solution. Water was added thereto to obtain 440 g of a 50% polyamide polyamine aqueous solution (x-5).
  • Comparative Example 4 (when the intrinsic viscosity of the crepe adhesive is low and out of range)
  • a polyamide polyamine aqueous solution (x-4) obtained in the same manner as in Example 9 3.7 g (0.04 mol) of epichlorohydrin was added, and the temperature was raised to 30 ° C. and kept at the same temperature for 1 hour.
  • water was added to adjust the solid content to 15%, the temperature was raised to 70 ° C., and when the viscosity reached 45 mPa ⁇ s, the reaction was terminated to obtain a polyamide polyamine / epichlorohydrin resin (A-14).
  • 57 g of propylene glycol (20% by mass with respect to 100% by mass of resin (A-14) solid content) was added to obtain an adhesive for crepe having a solid content adjusted to 15% with water.
  • Comparative Example 5 (when the water resistance evaluation value of the crepe adhesive is out of range) 7.4 g (0.08 mol) of epichlorohydrin was added to the total amount of the polyamide polyamine aqueous solution (x-4) obtained in the same manner as in Example 9, and the temperature was raised to 30 ° C. and kept at the same temperature for 1 hour. Next, water was added to adjust the solid content to 15%. After the temperature was raised to 70 ° C., when the viscosity reached 45 mPa ⁇ s, 10.8 g of 98% sulfuric acid was added to terminate the reaction, and the polyamide polyamine / epichlorohydrin resin ( A-15) was obtained. Next, 58 g of propylene glycol (20% by mass with respect to 100% by mass of resin (A-15) solid content) was added, and the pH was adjusted to 15% with 15% sulfuric acid and water, and the solid content was adjusted to 15%. An adhesive was obtained.
  • Comparative Example 6 when the intrinsic viscosity of the crepe adhesive is high and out of range 14.8 g (0.16 mol) of epichlorohydrin was added to the total amount of the polyamide polyamine aqueous solution (x-4) obtained in the same manner as in Example 9, and the temperature was raised to 30 ° C. and kept at the same temperature for 1 hour. Next, water was added to adjust the solid content to 15%. After the temperature was raised to 70 ° C., when the viscosity reached 640 mPa ⁇ s, 10.8 g of 98% sulfuric acid was added to terminate the reaction, and the polyamide polyamine / epichlorohydrin resin ( A-16) was obtained. Next, 59 g of propylene glycol (20% by mass with respect to 100% by mass of resin (A-16) solid content) was added, and the pH was adjusted to 15% with 15% sulfuric acid and water, and the solid content was adjusted to 15%. An adhesive was obtained.
  • Synthesis Example 1 (Production Example of Softening Agent Corresponding to Fatty Acid Amide Epihalohydrin (S1))
  • S1 Fatty Acid Amide Epihalohydrin
  • the temperature was raised to 180 ° C., and reaction was performed for 3 hours while removing generated water out of the system to obtain an amide compound.
  • the amount of residual amino groups of the obtained amide compound was 2 mmol / g.
  • 100 g of the amide compound (0.16 mol as an amino group), 5 g of polyoxyethylene (45) stearylamine (the numbers in parentheses indicate the average number of moles added of polyoxyethylene), 100 g of water, and epihalohydrins as epihalohydrins.
  • Chlorohydrin (5.9 g, 0.064 mol) was added at 50 ° C., and the mixture was stirred for 30 minutes. Subsequently, after the reaction solution was reacted at 70 ° C.
  • reaction solution was cooled and adjusted by adding water so that the solid content was 30% by mass.
  • concentration was 30%
  • viscosity was 350 mPa ⁇ s
  • melting point was obtained at 29 ° C.
  • the weight average molecular weight of the crepe adhesive in the present invention is obtained by the GPC-MALS method in which a multi-angle light scattering detector is connected to GPC under the following measurement conditions.
  • GPC body LC1100 series manufactured by Agilent Technologies Inc.
  • Eluent N / 10 phosphate buffer (pH 3) containing N / 10 sodium nitrate
  • Detector 1 Multi-angle light scattering detector DAWN manufactured by Wyatt Technology Detector 2: Suggested refractive index detector RI-101 manufactured by Showa Denko KK
  • crepe adhesives of Examples 1 to 13 and Comparative Examples 1 to 6 were 0.3 g / m 2 as a solid content, and the crepe agent CR6154 (manufactured by Seiko PMC Co., Ltd., crepe release agent) as an active ingredient 0.25 g / m 2 and coated on a plate heated to 100 ° C.
  • Table 5 shows the Young's modulus of the obtained handmade paper. Young's modulus: Ultrasonic wave propagation velocity V was measured with an orientation measuring instrument SST-2500 manufactured by Nomura Corporation, and the Young's modulus was obtained from the following formula. The lower the number, the more flexible the paper. Relative notation was made assuming that the Young's modulus of the paper without the softener was 100. Young's modulus ⁇ V 2 ( ⁇ : density)
  • Softener 1 oleic acid EO (4) PO (12) oleyl ether corresponding to softener (S3).
  • EO is ethylene oxide
  • PO is propylene oxide
  • the numerical value in () indicates the average added molar amount.
  • Softener 2 ... Dioleyldimethylammonium chloride equivalent to softener (S2)
  • Examples and Comparative Example 1 from Tables 1 to 4 By comparing Examples and Comparative Example 1 from Tables 1 to 4, compared to the case where the amount of AZR of the crepe adhesive is outside the scope of the present invention, the Examples of the present invention have a disaggregation property and adhesive strength. It is clear that the film surface is softer than that of Comparative Example 1. By comparing Examples and Comparative Examples 2 and 3 from Tables 1 to 4, the examples of the present invention have better disaggregation and adhesive strength than the prior art, and the coating surface is softer than the prior art. I understand. By comparing Examples and Comparative Example 4 from Tables 1 to 4, the examples of the present invention have higher disaggregation and adhesive strength than the case where the intrinsic viscosity of the crepe adhesive is low and outside the scope of the present invention. It turns out that it is favorable.

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Abstract

La présente invention concerne le problème consistant à fournir un adhésif pour crêpe ayant une capacité d'adhésion exceptionnelle entre les nappes de fibres lors de la fabrication du papier et avec lequel, même si la quantité d'élution du film de revêtement par de l'eau d'infiltration, provenant du papier humide et similaires, est faible, le papier peut être facilement séparé, un crêpe de bonne qualité peut être formé, et la quantité d'abrasion d'une lame de racloir est faible parce que le film formé est doux. Selon l'invention, l'adhésif pour crêpe comprend une résine de polyamidopolyamine/épihaolhydrine (A) et/ou une résine de polyamidopolyamine polyurée/épihalohydrine (B) et un adoucissant (C), et est caractérisé en ce qu'il satisfait à toutes les conditions mentionnées.
PCT/JP2014/070356 2013-08-02 2014-08-01 Adhésif pour crêpe et procédé de fabrication de papier de crêpe WO2015016350A1 (fr)

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JP2018528279A (ja) * 2015-06-25 2018-09-27 エコラブ ユーエスエイ インク 官能性架橋樹脂を含有するクレープ加工用接着剤
CN108859503A (zh) * 2018-08-10 2018-11-23 青岛理工大学 废纸回用铅笔生产装置
JP2020033672A (ja) * 2018-08-30 2020-03-05 星光Pmc株式会社 クレープ用接着剤及びクレープ紙の製造方法

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JPH0941297A (ja) * 1995-04-25 1997-02-10 Hercules Inc クレーピング剥離剤
JP2002506937A (ja) * 1998-03-17 2002-03-05 ザ、プロクター、エンド、ギャンブル、カンパニー クレープ加工補助剤および紙をクレープ加工する方法
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Publication number Priority date Publication date Assignee Title
JP2018528279A (ja) * 2015-06-25 2018-09-27 エコラブ ユーエスエイ インク 官能性架橋樹脂を含有するクレープ加工用接着剤
CN108859503A (zh) * 2018-08-10 2018-11-23 青岛理工大学 废纸回用铅笔生产装置
JP2020033672A (ja) * 2018-08-30 2020-03-05 星光Pmc株式会社 クレープ用接着剤及びクレープ紙の製造方法
JP7172292B2 (ja) 2018-08-30 2022-11-16 星光Pmc株式会社 クレープ用接着剤及びクレープ紙の製造方法

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