JP4831523B2 - Creping adhesive, crepe paper manufacturing method, and crepe paper - Google Patents

Description

  The present invention relates to an adhesive for creping used in the production of sanitary paper such as toilet paper, tissue paper, and towel paper, a method for producing crepe paper using the adhesive, and a crepe paper produced by the production method. About.

  When producing toilet paper, tissue paper, paper towels, etc., the fiber web is subjected to a step of creping (creping) in order to give the product flexibility and bulkiness. Creping is a process in which a damp fiber web is bonded to a rotary cylinder paper dryer known as a Yankee dryer, and after drying, the fiber web is scraped off from the dryer surface with a doctor blade to cause very fine wrinkles on the fiber web. Become.

  In general, as a method for increasing the adhesion of the fiber web to the Yankee dryer during creping, a polyamide polyamine epichlorohydrin resin having thermosetting properties is internally added, or on the surface of the Yankee dryer or on the fiber web. It is done to spray. However, since such a resin causes a cross-linking reaction due to the heat of the Yankee dryer surface, it is difficult to control the adhesion between the fiber web and the Yankee dryer, resulting in difficulty in creping and further in the fiber web. There was a drawback that wet paper strength was developed and the disaggregation of broken paper was worsened.

  Therefore, in order to overcome the above disadvantages, it has been proposed to use an adhesive having a reduced crosslinkable group in a polyamide polyamine / epichlorohydrin resin. For example, Patent Document 1 proposes a technique using a resin obtained by reacting a crosslinkable group in a resin with an organic acid and an inorganic acid, and Patent Document 2 discloses a deficiency equivalent to an amino group of a polyamide polyamine. A technique using a resin reacted with a crosslinking agent has been proposed. However, in the case of using a resin obtained by reacting an acid or amine and a crosslinkable group described in Patent Document 1, unreacted organic acid and inorganic acid remain in the adhesive, and these residual components are fibers. There is a risk of preventing the uniform adhesion of the web and further promoting the corrosion of the surface of the Yankee dryer. Further, Patent Document 2 does not describe a specific amount of the crosslinking agent that reacts with the polyamide polyamine, and does not lead to sufficiently reducing the crosslinkable group.

  A creping adhesive using a polyamide polyamine polyurea / epihalohydrin resin is also known. The polyamide polyamine polyurea / epihalohydrin resin contains a urea residue, and thus has physical and chemical characteristics different from those of the polyamide polyamine / epichlorohydrin resin. For example, Patent Document 3 discloses that a polyamide polyamine polyurea / epihalohydrin resin is treated with a basic substance, so that there are few adsorptive organic halogen compounds (AOX) derived from epihalohydrin and excellent storage stability. In addition, Patent Document 4 discloses a creping that causes less discoloration due to heating by reacting a polyamide polyamine derivative obtained by adding an amino group addition reactive compound such as urea to a polyamide polyamine and epichlorohydrin. Adhesives have been proposed. However, neither of Patent Documents 3 and 4 describes a specific bonding effect.

No. 2688950 Japanese National Patent Publication No. 11-512498 JP 2004-175818 A JP 2004-285544 A

  An object of the present invention is to provide excellent creping between a Yankee dryer and a fiber web when producing crepe paper, enable formation of a good crepe, and excellent disaggregation when reusing crepe paper. It is to provide an adhesive.

  Another object of the present invention is to produce a crepe paper having a good crepe and an excellent disintegration property of a waste paper by using an adhesive for creping having both excellent adhesiveness and excellent disintegration property of the waste paper. It is to provide a way to do.

  Another object of the present invention is to provide a crepe paper that is also excellent in disintegration of damaged paper when recycled.

  As a result of diligent research to solve the above problems, the present inventors use a polyamide polyamine polyurea / epihalohydrin resin in which the contents of urea residues and epihalohydrin residues contained in the resin are controlled within specific ranges, respectively. Based on this finding, the present invention has been completed.

  That is, the present invention provides a creping adhesive as described in the following items (1) to (9) as a means for solving the above-mentioned problems, and further as a preferred embodiment thereof, and production of crepe paper using the adhesive. Methods and crepe paper are provided.

(1) A polyalkylene polyamine residue, a dicarboxylic acid residue, a urea residue and an epihalohydrin residue, and 0.05 g to 6.0 mol of the urea residue and 0.01 to 1 of the epihalohydrin residue in 1000 g of a resin. A creping adhesive characterized by containing a polyamide polyamine polyurea / epihalohydrin resin containing 2 mol.

(2) The creping adhesive according to item (1), wherein the polyamide polyamine polyurea / epihalohydrin resin has an azetidinium ring content of 1000 mol or less in 1000 g of the resin.

(3) In the paragraph (1) or (2), the polyamide polyamine polyurea / epihalohydrin resin has a viscosity within a range of 10 to 100 mPa · s based on a viscosity at 25 ° C. of a 15 wt% solid content aqueous solution. The adhesive for creping as described.

(4) The ratio of the polyalkylene polyamine residue to the dicarboxylic acid residue is 0.8 to 1.4 on a molar ratio basis, for creping according to any one of items (1) to (3) adhesive.

(5) The polyamide polyamine polyurea / epihalohydrin resin is a polyamide polyamine polyurea obtained by reacting a polyalkylene polyamine (A), a dicarboxylic acid (B) and a urea (C). Item (1) to Item (4), which is obtained by reacting 0.01 to 0.40 mol of epihalohydrin (D) with respect to 1 mol of the secondary amino group. Adhesive for creping.

(6) The polyamide polyamine polyurea comprises 0.8 to 1.4 mol of the polyalkylene polyamine (A), 1 mol of the dicarboxylic acid (B), and a secondary amino group 1 of the polyalkylene polyamine. The adhesive for creping according to item (5), which is obtained by reacting 0.05 to 1.0 mole of urea (C) with respect to mole.

(7) Using the creping adhesive according to any one of items (1) to (6), the wet fiber web is bonded to a heated Yankee dryer, and after drying, the fiber web is A method for producing a crepe paper, comprising forming a crepe by scraping the surface of a Yankee dryer with a doctor blade.

(8) The method for producing crepe paper according to (7), wherein a creping release agent is used in combination with the creping adhesive.

(9) A crepe paper using the creping adhesive according to any one of items (1) to (6).

  The present invention makes it possible to form a good crepe by providing sufficient adhesion between the Yankee dryer and the fiber web when producing the crepe paper, and to disassemble the broken paper when the crepe paper is recycled. There is an effect that it can be easily performed.

  The creping adhesive of the present invention contains a polyamide polyamine polyurea / epihalohydrin resin, and the resin comprises a polyalkylene polyamine residue, a dicarboxylic acid residue, a urea residue, and an epihalohydrin residue. 0.05 to 6.0 mol of the urea residue, preferably 0.10 to 5.5 mol, more preferably 0.15 to 5.0 mol, and 0.01 to 1.2 mol of the epihalohydrin residue, Preferably it contains 0.05 to 1.0 mol, more preferably 0.1 to 0.9 mol.

  The polyamide polyamine polyurea / epihalohydrin resin used in the present invention is obtained by reacting a polyalkylene polyamine (A), a dicarboxylic acid (B), and a urea (C) with a polyamide polyamine polyurea obtained by reacting an epihalohydrin ( It can be obtained by reacting D). The polyalkylene polyamine residue, dicarboxylic acid residue, and urea residue on the polyalkylene polyamine polyurea / epihalohydrin resin molecule, each part corresponding to one unit of the original polyalkylene polyamines, dicarboxylic acids, ureas, and epihalohydrins, respectively. Or it is called an epihalohydrin residue.

  The urea residue has a function of increasing the adhesiveness of the resin and a function of increasing the hardness of the resin. Urea residues include, for example,> N-CO-N <,> N-CS-N <, and the like. If the urea residue content is 0.05 mol / 1000 g or more of the resin, sufficient adhesion can be ensured during creping, but if it exceeds 6.0 mol / 1000 g of the resin, the hardness of the resin will increase. In addition to being too high, there is a risk of damaging the blade of the doctor blade during creping, and the crepe shape may be disturbed, and a good crepe may not be obtained.

The epihalohydrin residue has a function of crosslinking the resin and increasing the molecular weight, and a function of giving wet paper strength to the crepe paper by reacting with the fiber web by the heat of the Yankee dryer during creping. The epihalohydrin residues, for example _{-CH 2 -CH (OH) -CH 2} -, - CH 2 -CH (OH) -CH 2 X (. X is represents a halogen atom) include azetidinium ring. If the content of the epihalohydrin residue is 0.01 mol / 1000 g or more of the resin, the resin can be cross-linked by epihalohydrin and the molecular weight can be increased, so that an appropriate adhesive force can be ensured. / If the resin exceeds 1000 g, the crepe paper may exhibit excessive wet paper strength and may make it difficult to disassemble the damaged paper. In particular, since the azetidinium ring in the resin contributes to the development of wet paper strength, the content of the azetidinium ring in the resin is 0.5 mol / resin 1000 g or less, preferably 0.4 mol / resin 1000 g or less. Is preferred.

  The polyalkylene polyamines (A) may be those having at least two alkylene groups and two or more amino groups in the molecule. For example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobis Examples thereof include propylamine, and among them, diethylenetriamine is preferable. These can be used alone or in combination of two or more. Further, in place of a part of the polyalkylene polyamines (A), an alkylene diamine such as ethylene diamine, propylene diamine or hexamethylene diamine; an aminocarboxylic acid having 1 to 6 carbon atoms such as ε-aminocaproic acid; and ε-caprolactam A lactam of an aminocarboxylic acid having 1 to 6 carbon atoms can also be used.

  The dicarboxylic acids (B) may be those having two carboxyl groups in the molecule. For example, saturated or unsaturated aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, dodecanedioic acid, itaconic acid, maleic acid, fumaric acid, etc. Acids; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; acid anhydrides of the above acids; lower alcohols having 1 to 5 carbon atoms, especially 1 to 3 carbon atoms (methyl alcohol, ethyl alcohol) , Propyl alcohol) and other dicarboxylic acid derivatives. Of these, glutaric acid, adipic acid, glutaric acid methyl ester and adipic acid methyl ester are preferred. These can be used alone or in combination of two or more.

  Examples of ureas (C) include urea, thiourea, guanylurea, phenylurea, methylurea, dimethylurea and the like. Of these, urea is preferred. In place of a part of ureas (C), compounds having at least one N unsubstituted amide group capable of undergoing an amide exchange reaction with an amino group, for example, aliphatic amides such as acetamide and propionamide, benzamide, and phenylacetic acid Aromatic amides such as amides can also be used.

  In the synthesis of the polyamide polyamine polyurea, the polyalkylene polyamines (A), the dicarboxylic acids (B), and the ureas (C) can be reacted in any order or simultaneously. For example, a method of reacting (A) and (B) and then reacting (C), a method of reacting (A) and (C), and reacting with (B), (A) and (B ) And (C) may be used at the same time.

Upon synthesizing polyamide polyamine urea, polyalkylene polyamines (A) 0.8 to 1.4 dicarboxylic acids moles (B) 1.0 mole, to the second amino group 1 mole of (A) A reaction ratio of 0.05 to 1.0 mol of ureas (C) is preferable. With this reaction ratio, a resin excellent in adhesiveness can be obtained.

  The reaction of the polyalkylene polyamines (A), the dicarboxylic acids (B) and the ureas (C) is carried out in such a way that the resulting polyamide polyamine polyurea has a viscosity of 100 to 1, It is preferable to continue until it has a viscosity within the range of 000 mPa · s, whereby a resin having excellent adhesiveness can be obtained.

  When reacting the amino group of the polyalkylene polyamines (A) or polyalkylene polyamine polyurea with the carboxyl group of the dicarboxylic acids (B), use the heat of reaction generated at the time of charging the raw materials or heat from the outside. Dehydration and / or dealcoholization reaction. The reaction temperature is preferably 110 to 250 ° C., more preferably 120 to 180 ° C., but the temperature condition depends on whether (B) is a free acid or a derivative such as an anhydride or an ester. At this time, as a catalyst for the polycondensation reaction, sulfonic acids such as sulfuric acid, benzenesulfonic acid, and paratoluenesulfonic acid, phosphoric acids such as phosphoric acid, phosphonic acid, and hypophosphorous acid, and other known catalysts may be used alone or in combination. These can be used in combination. The amount used is preferably 0.005 to 0.1 mol, more preferably 0.01 to 0.05 mol, per 1 mol of polyalkylene polyamine.

  When the polyalkylene polyamine (A) or the amino group of the polyalkylene polyamine polyurea is reacted with the urea (C), an amide exchange reaction is performed while removing generated ammonia out of the system. The reaction temperature at this time is preferably from 80 to 180 ° C., more preferably from 100 to 160 ° C., from the viewpoint that the reaction easily proceeds moderately.

  The polyamide polyamine polyurea / epihalohydrin resin used in the present invention can be obtained by reacting the above-mentioned polyamide polyamine polyurea with an epihalohydrin (D).

  Epihalohydrins (D) include 1,3-dihalogeno-2-propanol derived from epihalohydrin in addition to epihalohydrin. Examples of the epihalohydrin include epichlorohydrin and epibromohydrin. Examples of the 1,3-dihalogeno-2-propanol derived from epihalohydrin include 1,3-dichloro-2-propanol. Of these, epichlorohydrin is preferred.

The reaction ratio of the epihalohydrins (D) to the polyamide polyamine polyurea is preferably 0.01 to 0.40 mol, more preferably 0.05 to 0.1 mol with respect to 1 mol of the secondary amino group of the polyamide polyamine polyurea . 0.30. When the molar ratio of (D) is more than 0.40 mol, the resulting polyamide polyamine polyurea / epihalohydrin resin has a strong cross-linking property, so that the adhesive strength to the Yankee dryer becomes too strong, or conversely, Adhesive strength may be insufficient due to deterioration of water swellability, and not only the control of creping becomes difficult, but also the disintegration property of the waste paper may be deteriorated due to the wet paper strength enhancing effect. If the molar ratio of (D) is less than 0.01 mol, the adhesive strength of the resulting resin may be insufficient.

  The reaction between the polyamide polyamine polyurea and the epihalohydrins (D) is preferably performed at a reaction solution concentration of 15 to 80% by weight and a reaction temperature of 5 to 90 ° C. In particular, in order to increase the reaction efficiency between the polyamide polyamine polyurea and the epihalohydrins (D), the reaction temperature when the epihalohydrins (D) are added to the polyamide polyamine polyurea is carried out in the range of 5 to 40 ° C. In the cross-linking reaction, it is preferable that the reaction temperature is 40 to 90 ° C., and the resulting polyamide polyamine polyurea / epihalohydrin resin is increased in molecular weight to increase its viscosity.

  The reaction between the polyamide polyamine polyurea and the epihalohydrin (D) is 10 to 100 mPa · s, preferably 15 to 15 μm, based on the viscosity of the 15% by weight aqueous solution of the polyamide polyamine polyurea / epihalohydrin resin obtained at 25 ° C. By continuing the reaction until it has a viscosity in the range of 80 mPa · s, it becomes easy to obtain a resin excellent in adhesive strength. When the viscosity of the reaction solution falls within this viscosity range, water is added to the reaction solution to stop the reaction and cool.

  The creping adhesive of the present invention is preferably adjusted to a solid content of 15 to 50% by weight by adding water to the polyamide polyamine polyurea / epihalohydrin resin obtained by the above reaction.

  The creping adhesive of the present invention is preferably adjusted within the range of pH 2 to 10 from the viewpoint of improving storage stability. The pH can be adjusted by adding a pH adjuster. Examples of 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 Examples thereof include inorganic bases such as magnesium oxide, sodium carbonate and potassium carbonate; monoamine compounds such as diethylamine, triethylamine, propylamine, butylamine, diisobutylamine, hydroxyamine, ethanolamine and diethanolamine.

  The method of using the adhesive for creping of the present invention includes a method of adding to a pulp slurry, a method of spraying wet paper in front of a Yankee dryer, a method of spraying directly on the surface of a Yankee dryer, and a combination of these methods. Can be applied as appropriate according to the type of paper to be produced, the machine conditions used for papermaking, and the desired operating conditions such as paper quality, speed and temperature.

  The creping adhesive of the present invention can be used in combination with a creping release agent in order to control the adhesive force of the fiber web to the surface of the Yankee dryer. Examples of the creping release agent include silicone oil, hydrocarbon oil, surfactant, ethylene glycol, propylene glycol, diethylene glycol, glycerol, pyrrolidone, triethanolamine, diethanolamine, polyethylene glycol, dipropylene glycol and the like. These can be used alone or in combination of two or more.

  As the surfactant, for example, a conventionally known cationic surfactant, anionic surfactant, amphoteric surfactant, or nonionic surfactant can be used. Specifically, as the cationic surfactant, for example, a long-chain alkylamine salt, a modified amine salt, a tetraalkyl quaternary ammonium salt, a trialkylbenzyl quaternary ammonium salt, an alkylimidazolium salt, an alkylpyridinium salt, an alkyl Examples include quinolium salts, alkylphosphonium salts, and alkylsulfonium salts. Examples of amphoteric surfactants include various betaine surfactants. Examples of the anionic surfactant include alkyl sulfonate, alkyl sulfate ester salt, alkyl phosphate ester salt, polyoxyalkylene alkyl sulfate ester salt, polyoxyalkylene alkyl aryl sulfate ester salt, polyoxyalkylene aralkyl aryl sulfate ester salt. , Alkyl-aryl sulfonates and various sulfosuccinic acid ester surfactants. Nonionic surfactants include, for example, fatty acid sorbitan esters, their polyalkylene oxide adducts, fatty acid polyglycol esters, various polyalkylene oxide type nonionic surfactants (polyoxyethylene fatty acid esters, polyoxyethylene fatty acid amides, polyoxyethylenes). Oxyethylene aliphatic alcohol, polyoxyethylene aliphatic amine, polyoxyethylene aliphatic mercaptan, polyoxyethylene alkyl aryl ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene aralkyl aryl ether, etc.).

  When the creping adhesive of the present invention is used as an internal additive, moderate adhesiveness can be obtained by adding 0.001 to 5% by weight of the solid content per dry weight of the pulp to the aqueous dispersion of the pulp or the white water of the fan pump part. It is preferable because it is obtained and easily creped. The creping adhesive to be added is preferably diluted 1 to 200 times.

When spraying the creping adhesive on the wet paper in front of the Yankee dryer, or when spraying directly on the surface of the Yankee dryer, it is preferable to dilute the creping adhesive 10 to 1000 times, and the spray amount is 0.01 to 500 mg / m ² , particularly 0.1 to 300 mg / m ² is preferable based on the solid content of the resin.

  In the case of using the creping adhesive of the present invention, pulp raw materials include bleached and unbleached chemical pulp such as kraft pulp and sulfite pulp; bleached and unbleached high yield of groundwood pulp, mechanical pulp, thermomechanical pulp, etc. Pulp: Used paper pulp such as used newspaper, magazine used paper, cardboard used paper, and deinked used paper can be used, and these can be used alone or in combination of two or more.

  Also, additives such as fillers, dyes, dry paper strength improvers, yield improvers, sizing agents and wet paper strength improvers, softeners, moisturizers, paper thickness improvers, etc. are also required for pulp slurries made from the above raw material pulp It may be used according to. Furthermore, with a size press, gate roll coater, bill blade coater, and calendar, etc., surface paper strength improvers such as starch, polyvinyl alcohol, and acrylamide polymers, surface sizing agents, dyes, coating colors, and anti-slip coating are applied as necessary. You may do it.

  The crepe paper produced by the production method of the present invention is suitable for applications such as toilet paper, tissue paper, towel paper, sanitary paper such as napkin base paper.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these examples. In each example, “%” means “% by weight” unless otherwise specified.

<Measurement method of content of various residues and azetidinium ring>
(1) The content of epihalohydrin residues in the resin was calculated by measuring the total halogen content in the polyamide polyamine polyurea epihalohydrin resin aqueous solution.
(2) Composition analysis of polyalkylene polyamine residue, adipic acid residue, urea residue and epihalohydrin residue using ¹³ C-NMR chart of polyamide polyamine polyurea epihalohydrin resin and the result of total halogen content in resin aqueous solution The urea residue content in the resin was calculated.
(3) The content of the azetidinium ring was calculated from the ¹ H-NMR chart of the polyamide polyamine polyurea epihalohydrin resin.

Example 1
A 500 mL four-necked round bottom flask equipped with a thermometer, a condenser, a stirrer, and a 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. Next, the 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%. The containing liquid (A) was obtained.

In another 500 ml four-necked flask equipped with a thermometer, reflux condenser, stirrer and dropping funnel, 200 g of polyamide polyamine-containing liquid (A) (0.3 mol as a secondary amino group) was charged at 20 ° C. After adding 5.5 g (0.06 mol) of epichlorohydrin, the mixture was heated to 30 ° C. and kept at the same temperature for 10 minutes. Next, 122 g of water was added, heated to 50 ° C. and held at the same temperature until the viscosity reached 200 mPa · s (25 ° C.), then 30% sulfuric acid and water were added to adjust the pH to 6, solid content (polyamide) A creping adhesive having a polyamine polyurea / epihalohydrin resin) adjusted to 30% was obtained. In 1000 g of the polyamide polyamine polyurea / epihalohydrin resin contained in the creping adhesive, the urea residue content was 0.8 mol and the epihalohydrin residue content was 0.5 mol. Moreover, the azetidinium ring was not able to be confirmed from the chart of ¹ HNMR.

(Example 2)
Creping in the same manner as in Example 1 except that 2.8 g (0.03 mol) of epichlorohydrin was added to 200 g of the polyamine-polyurea-containing liquid (A) (0.3 mol as a secondary amino group). An adhesive was obtained. In 1000 g of the polyamide polyamine polyurea / epihalohydrin resin contained in the creping adhesive, the urea residue content was 0.8 mol and the epihalohydrin residue content was 0.3 mol. Moreover, the azetidinium ring was not able to be confirmed from the chart of ¹ HNMR.

(Example 3)
Except for adding 10.5 g (0.11 mol) of epichlorohydrin to 200 g (0.3 mol as a secondary amino group) of the polyamide-polyamine-polyurea-containing liquid (A), A creping adhesive was obtained. In 1000 g of the polyamide polyamine polyurea / epihalohydrin resin contained in the creping adhesive, the urea residue content was 0.7 mol and the epihalohydrin residue content was 0.9 mol. From the ¹ HNMR chart, the azetidinium ring was 0.3 mol / 1000 g of resin.

Example 4
A polyamide polyamine polyurea-containing liquid (B) having a solid content of 50% was obtained in the same manner as in Example 1 except that urea was changed to 24 g (0.4 mol).

Creping as in Example 1 except that 2.1 g (0.02 mol) of epichlorohydrin was added to 200 g of the polyurea-polyurea-containing liquid (B) (0.12 mol as the secondary amino group). An adhesive was obtained. In 1000 g of the polyamide polyamine polyurea / epihalohydrin resin contained in the creping adhesive, the urea residue content was 1.5 mol and the epihalohydrin residue content was 0.2 mol. Moreover, the azetidinium ring was not able to be confirmed from the chart of ¹ HNMR.

(Example 5)
A 500 mL four-necked round bottom flask equipped with a thermometer, a condenser, a stirrer and a nitrogen inlet tube was charged with 94.9 g (0.92 mol) of diethylenetriamine and 11.6 g (0.1 mol) of hexamethylenediamine and stirred. Then, 146.1 g (1 mol) of adipic acid was added, and the temperature was raised while removing generated water out of the system, and the reaction was carried out at 170 ° C. for 5 hours. Next, the 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%. A containing liquid (C) was obtained.

Creping in the same manner as in Example 1 except that 4.7 g (0.05 mol) of epichlorohydrin was added to 200 g (0.25 mol as a secondary amino group) of the polyamide-polyamine-polyurea-containing liquid (C). An adhesive was obtained. In 1000 g of the polyamide polyamine polyurea / epihalohydrin resin contained in the creping adhesive, the urea residue content was 0.8 mol and the epihalohydrin residue content was 0.2 mol. Moreover, the azetidinium ring was not able to be confirmed from the chart of ¹ HNMR.

(Example 6)
A polyamide polyamine polyurea-containing liquid (D) having a solid content of 50% was obtained in the same manner as in Example 5 except that 11.3 g (0.1 mol) of ε-caprolactam was added instead of hexamethylenediamine.

For creping, in the same manner as in Example 1, except that 200 g of a polyamidopolyamine-polyurea-containing liquid (D) (0.16 mol as a secondary amino group) was added and 3 g (0.03 mol) of epichlorohydrin was added. An adhesive was obtained. In 1000 g of the polyamide polyamine polyurea / epihalohydrin resin contained in the creping adhesive, the urea residue content was 0.8 mol and the epihalohydrin residue content was 0.3 mol. Moreover, the azetidinium ring was not able to be confirmed from the chart of ¹ HNMR.

(Example 7)
A creping adhesive was obtained in the same manner as in Example 4 except that 30% potassium hydroxide was added instead of 30% sulfuric acid to adjust the pH to 10. In 1000 g of the polyamide polyamine polyurea / epihalohydrin resin contained in the creping adhesive, the content of urea residues was 1.5 mol and the content of epihalohydrin residues was 0.3 mol. Moreover, the azetidinium ring was not able to be confirmed from the chart of ¹ HNMR.

(Comparative Example 1)
A 500 mL four-necked round bottom flask equipped with a thermometer, a condenser, a stirrer, and a 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. Subsequently, water was gradually added to obtain a polyamide polyamine-containing liquid (E) having a solid content of 50%.

A thermometer, a reflux condenser, a stirrer, and another 500 ml four-necked flask were charged with 200 g of a polyamide polyamine-containing liquid (E) (0.49 mol as a secondary amino group) and epichlorohydride at 20 ° C. After adding 46 g (0.50 mol) of phosphorus, the mixture was heated to 30 ° C. and kept at the same temperature for 1 hour. Next, 233 g of water was added and heated to 50 ° C., and maintained at the same temperature until the viscosity reached 200 mPa · s (25 ° C.), then 30% sulfuric acid and water were added to adjust the pH to 6, and the solid content to 30%. A creping adhesive was prepared. The content of the epihalohydrin residue in 1000 g of the polyamide polyamine / epihalohydrin resin contained in the creping adhesive was 3.1 mol. From the ¹ HNMR chart, the azetidinium ring was 2.0 mol / 1000 g of resin.

(Comparative Example 2)
A creping adhesive was prepared in the same manner as in Comparative Example 1 except that 17 g (0.18 mol) of epichlorohydrin was added to 200 g of the polyamide polyamine-containing liquid (E) (0.49 mol as the secondary amino group). Obtained. The content of the epihalohydrin residue in 1000 g of the polyamide polyamine / epihalohydrin resin contained in the creping adhesive was 0.7 mol. From the ¹ HNMR chart, the azetidinium ring was 1.2 mol / 1000 g of resin.

(Comparative Example 3)
Adhesion for creping in the same manner as in Example 1 except that 15 g (0.16 mol) of epichlorohydrin is added to 200 g (0.3 mol as a secondary amino group) of the polyamide-polyamine-polyurea-containing liquid (A). An agent was obtained. In 1000 g of the polyamide polyamine / epihalohydrin resin contained in the creping adhesive, the urea residue content was 0.7 mol and the epihalohydrin residue content was 1.3 mol. From the ¹ HNMR chart, the azetidinium ring was 1.0 mol / 1000 g of resin.

(Comparative Example 4)
A polyamide polyamine polyurea-containing liquid (F) having a solid content of 50% is obtained in the same manner as in Example 1 except that 206 g (2 mol) of diethylenetriamine, 146 g (1 mol) of adipic acid and 60 g (1 mol) of urea are used. It was.

Adhesion for creping was carried out in the same manner as in Example 1 except that 54 g (0.58 mol) of epichlorohydrin was added to 200 g (0.58 mol as a secondary amino group) of the polyamide-polyamine-polyurea-containing liquid (F). An agent was obtained. In 1000 g of the polyamide polyamine polyurea / epihalohydrin resin contained in the creping adhesive, the urea residue content was 1.7 mol and the epihalohydrin residue content was 3.5 mol. Moreover, the azetidinium ring was not able to be confirmed from the chart of ¹ HNMR.

  Properties of the polyamide polyamine polyurea-containing liquids (A) to (F) are shown in Table 1.

実施例１〜７及び比較例１〜４で得たそれぞれのクレーピング用接着剤について、接着強度の指標としてＴ字剥離強度、離解性の指標として湿潤紙力強度を測定した。測定結果を表２に示した。

For each of the adhesives for creping obtained in Examples 1 to 7 and Comparative Examples 1 to 4, T-peel strength was measured as an adhesive strength index, and wet paper strength was measured as a disaggregation index. The measurement results are shown in Table 2.

<Evaluation method of adhesive strength>
0.1g of sample liquid containing 0.1% adhesive and 0.02% mineral oil type mold release agent "CR6104" (manufactured by Seiko PMC Co., Ltd.) is sprayed on aluminum foil (3 x 11 cm) with a sprayer. Heat-dried on the plate. Wet paper (3 x 12 cm) is attached to the surface of the aluminum foil from which the sample has been dried, and heat-pressed at 120 ° C for 3 minutes to 100 kgf / cm ² to remove excess moisture from the wet paper and simultaneously remove the aluminum foil and paper. Glued. The peel strength when peeling paper from an aluminum foil It measured based on TAPPI-19- (2) -B method. The stronger the peel strength, the better the adhesive strength for creping.

<Evaluation method for disintegrating scrap paper>
Test papers were prepared under the following papermaking conditions using the creping adhesives of the above Examples and Comparative Examples as the creping adhesives, and the Noble and Wood handmade paper machine as the papermaking machine. The disaggregation test of the obtained test paper was performed according to the following conditions. The measurement results are shown in Table 2. The longer the time, the more difficult it is to disaggregate, and the result of the measurement is ◯ within 150 seconds, and the case where it is longer than 150 seconds is indicated as x.
○ Paper used under papermaking conditions: Bleached kraft pulp (Conifer / Hardwood = 3/7)
Degree of beating (Canadian Standard Freeness) 410ml
Creping adhesive addition rate (resin content): 0.1% (vs. pulp solid content)
Papermaking basis weight: 30 g / m ²
Drying conditions: 100 ° C x 120 sec (using a drum dryer)
○ Conditions of disaggregation test Add 300 ml of water (25 ° C) to a 500 ml beaker, and stir with a rotor (a disk having a diameter of 35 mm and a thickness of 12 mm) so that the rotation speed is 600 rpm. A piece of test paper (5 cm square) was added while stirring, and the time until the test paper was loosened was measured.
The shorter the time until the test paper is loosened, the better the disaggregation. The case where the time until unraveling was 150 seconds or less was marked with ◯, and the case where the time was over 150 seconds was marked with ×.

  It is preferable that the adhesive strength exceeds 100 mN / 3 cm, and the judgment of the disaggregation test becomes ◯.

  As is apparent from the results shown in Table 2, when the creping adhesives of Examples 1 to 7 of the present invention are used, the adhesive strength is sufficiently strong as about 260 to 350 mN / 3 cm and exceeds 150 seconds in the disaggregation test. It is possible to achieve both adhesiveness and disaggregation, while using the creping adhesives of Comparative Examples 1 to 3, although the adhesive strength is sufficiently strong, it exceeds 150 seconds in the disaggregation test. When the adhesive for creping of Example 4 is used, although the disaggregation test is within 150 seconds, the adhesive strength is less than 100 mN / 3 cm, and it becomes difficult to achieve both adhesion and disaggregation.

Claims (9)

  It consists of a polyalkylene polyamine residue, a dicarboxylic acid residue, a urea residue and an epihalohydrin residue, and 0.05 g to 6.0 mol of the urea residue and 0.01 to 1.2 mol of the epihalohydrin residue in 1000 g of resin. A creping adhesive comprising a polyamidopolyamine polyurea / epihalohydrin resin containing   2. The creping adhesive according to claim 1, wherein the polyamide polyamine polyurea / epihalohydrin resin has an azetidinium ring content of 1,000 mol or less in 1000 g of the resin.   3. The adhesive for creping according to claim 1, wherein the polyamide polyamine polyurea / epihalohydrin resin has a viscosity in a range of 10 to 100 mPa · s based on a viscosity at 25 ° C. of a 15 wt% solid content aqueous solution.   The creping adhesive according to any one of claims 1 to 3, wherein a ratio of the polyalkylene polyamine residue to the dicarboxylic acid residue is 0.8 to 1.4 on a molar ratio basis. The polyamide polyamine polyurea / epihalohydrin resin is converted into a polyamide polyamine polyurea obtained by reacting a polyalkylene polyamine (A), a dicarboxylic acid (B), and a urea (C) . The adhesive for creping according to any one of claims 1 to 4, which is obtained by reacting 0.01 to 0.40 mol of epihalohydrin (D) with respect to 1 mol of a primary amino group. The polyamide polyamine polyurea is used in an amount of 0.8 to 1.4 mol of the polyalkylene polyamine (A), 1 mol of the dicarboxylic acid (B), and 1 mol of the secondary amino group of the polyalkylene polyamine. The creping adhesive according to claim 5, which is obtained by reacting 0.05 to 1.0 mole of urea (C).   A wet fiber web is adhered to a Yankee dryer using the creping adhesive according to any one of claims 1 to 6, and after drying, the fiber web is scraped off from the surface of the Yankee dryer with a doctor blade. A method of producing a crepe paper, comprising forming a crepe by   The method for producing a crepe paper according to claim 7, wherein a creping release agent is used in combination with the creping adhesive.   A crepe paper using the creping adhesive according to any one of claims 1 to 6.