WO2015016350A1

WO2015016350A1 - Adhesive for crepe and method for manufacturing crepe paper

Info

Publication number: WO2015016350A1
Application number: PCT/JP2014/070356
Authority: WO
Inventors: 孝治吉谷; 彩香勅使河原
Original assignee: 星光Pmc株式会社
Priority date: 2013-08-02
Filing date: 2014-08-01
Publication date: 2015-02-05
Also published as: CN105229227B; CN105229227A; JP5854167B2; JPWO2015016350A1

Abstract

The present invention addresses the problem of providing an adhesive for crepe that has outstanding adhesiveness between fiber webs when paper is being manufactured and with which, even if the amount of coating film elution by water infiltrating from wet paper and the like is small, the paper can be easily separated, favorable crepe can be formed, and the amount of abrasion of a doctor blade is small because the film formed is soft. Provided is an adhesive for crepe that comprises a polyamidopolyamine/epihalohydrin resin (A) and/or a polyamidopolyamine polyurea/epihalohydrin resin (B) and a softener (C), and is characterized by fulfilling all designated conditions.

Description

Crepe adhesive and method for producing crepe paper

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.

When manufacturing sanitary paper such as toilet paper, tissue paper, towel paper, kitchen paper, etc., in order to give the product flexibility and bulkiness, it can be subjected to a process (creping) that gives very fine wrinkles (crepes) to the fiber web. . 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. Become.

Normally, when creping is performed, 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.

As the crepe adhesive, 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). On the other hand, attempts have been made to use plasticizers for crepe adhesives. For example, 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). However, when 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.

Japanese Patent No. 2688950 Japanese Patent No. 4831523 Japanese Patent No. 5191046 Japanese Patent Application Laid-Open No. 09-041297

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.

As a result of diligent research to solve the above problems, the present inventors have found that a specific crepe adhesive has excellent adhesion between fiber webs and enables the formation of a good crepe. It came to be completed.

That is, the present invention
<1>
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.
(3) The softener (C) satisfies the following (i) and (ii): (i) a liquid having a boiling point of 150 ° C or higher and 80 ° C;
(Ii) Water-soluble aliphatic polyol or polyethylene glycol dimethyl ether (4) [resin (A) and / or resin (B)]: [softener (C)] = 100: 0.5 to 70 in mass ratio
(5) Water resistance evaluated by the following calculation method is 40 to 100%
<Calculation method of water resistance>
In a tea bag (weight W2 (g)), a petri dish (weight W1 (g)) prepared so as to have a uniform film weight of 0.05 g was immersed in water at 50 ° C. for 5 minutes with stirring. Then, the petri dish is weighed and measured for each tea bag (weight W3 (g)), and water resistance is calculated from the following equation (1).
Formula (1) Water resistance (%) = 100 − {(W1 + W2) −W3} /0.05×100
W1 (g): Weight of the metal petri dish prepared as a film, W2 (g): Weight of the tea bag, W3 (g): Weight of the tea bag and the petri dish after dipping and drying <2>
The crepe adhesive according to the above <1>, wherein the crepe adhesive has a weight average molecular weight of 1,000,000 to 5,000,000;
<3>
A method for producing crepe paper, wherein the crepe adhesive according to <1> or <2> is applied to a dryer surface so as to be 0.01 to 500 mg / m ² per solid content with respect to the area of the fiber web. 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.

Excellent adhesiveness between fiber webs when manufacturing paper, easy to disaggregate paper even though there is little elution of coating film due to moisture brought in from wet paper, etc., enabling formation of good crepes and forming Since the film is soft, it is possible to provide an adhesive for crepes with little wear on the doctor blade.

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).
That is, 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);
Naturally, an embodiment of 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.

Specifically, 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),
Alternatively, 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). 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. Examples include pentamine, pentaethylenehexamine, hexaethyleneheptamine, dipropylenetriamine, tripropylenetetramine, iminobispropylamine, and the like. These may be used alone or in combination of two or more. . Among these, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine are preferable because of excellent adhesiveness. Furthermore, diethylenetriamine is particularly preferable. These may be used alone or in combination of two or more. In addition to polyalkylene polyamine (a), alkylene diamines such as ethylenediamine, propylenediamine or hexamethylenediamine, aminocarboxylic acids having 1 to 6 carbon atoms such as ε-aminocaproic acid, and 1 to 6 carbon atoms such as ε-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. Further, 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. Further, in place of a part of the dibasic carboxylic acid (b), three or more 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.

Examples of ureas (d) used in the present invention include urea, thiourea, guanylurea, phenylurea, methylurea, dimethylurea and the like. Of these, urea is particularly preferred industrially. As a part of these ureas (d), in place of the ureas (d), 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. In particular, the polyalkylene polyamine (a) is preferably 43 to 54%, the dibasic carboxylic acid (b) is 42 to 52 mol%, and 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. For example, the polyalkylene polyamine (a), the dibasic carboxylic acid (b), and the urea (d) can be reacted simultaneously. Alternatively, 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 By reacting at 1 mol% or less and epihalohydrin (c) 1 to 11 mol%, an adhesive for crepes having excellent film properties can be obtained. In particular, the 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, and 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. From the viewpoint of reaction control, the reaction temperature is preferably 110 to 250 ° C. and the reaction time is 1 to 8 hours. 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.

When the polyamide polyamine (x) and / or the polyamide polyamine polyurea (y) is reacted with the epihalohydrin (c), 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). By continuing the reaction until 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. When the viscosity of the reaction liquid falls within this viscosity range, 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. 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 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. When there are more azetidinium groups (hereinafter sometimes abbreviated as AZR) than 0.2 mEq in 1 g of solid content, 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. Here, 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 | membrane excellent in adhesiveness.

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 mass ratio of the adhesive for a crepe of the present invention needs to be “resin (A) and / or resin (B)”: “softener (C)” = 100: 0.5 to 70. Preferably, the mass ratio is “resin (A) and / or resin (B)”: “softener (C)” = 100: 5 to 30, more preferably 100: 5 to 20. If the mass ratio of the softening agent (C) is less than 0.5, the effect of softening the coating film cannot be obtained, and if it exceeds 70, the adhesiveness is significantly lowered.

In the crepe adhesive of the present invention, the water resistance required by the following formula (1) needs to be 40 to 100% in the following evaluation of water resistance.
In a tea bag (weight W2 (g)), a petri dish (weight W1 (g)) prepared so as to have a uniform film weight of 0.05 g was immersed in water at 50 ° C. for 5 minutes with stirring. Then, the petri dish is weighed and measured for each tea bag (weight W3 (g)), and water resistance is calculated from the following equation (1).
Formula (1) Water resistance (%) = 100 − {(W1 + W2) −W3} /0.05×100
W1 (g): Weight of metal petri dish with coating prepared, W2 (g): Weight of tea bag, W3 (g): Weight of tea bag and petri dish after immersion / drying If water resistance is in the above range 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. Examples of the release agent for crepe 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.

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. When 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.

As a paper suitable for creping using the adhesive for crepes of the present invention, 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. In the case of toilet paper or tissue paper, 0.2 to 0.3 g / cm ³ is preferable. In addition, the longitudinal dry tear length (JIS P 8113) is preferably 0.3 to 2.5 km, and toilet paper or tissue paper is preferably 0.2 to 0.8 km from the viewpoint of water decomposability. Furthermore, when used as sanitary paper, it is preferable that the water absorption (Japanese Industrial Standards JIS S 3104) 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. Moreover, you may contain the mixture of synthetic fibers, such as the said pulp raw material, polyamide, a polyimide, polyester, polyolefin, and polyvinyl alcohol.

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. In addition, 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.

Examples of the softener 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. Among these, fatty acid amide epihalohydrin resin (S1) is preferable because of its excellent flexibility effect in the present invention. These 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.

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these examples. In each example, “%” is “% by mass” unless otherwise specified.

Example 1
<Production of polyamide polyamine (x-1)>
In 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).

<Manufacture of crepe adhesive>
7.4 g (0.08 mol) of epichlorohydrin was added to the total amount of the polyamidepolyamine aqueous solution (x-1) obtained above, 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 45 mPa · s, the reaction was terminated to obtain a polyamide polyamine / epichlorohydrin resin (A-1). Next, 12 g of propylene glycol (5% by mass relative to 100% by mass of the resin (A-1) solid content) was added as a softening agent (C), and the solid content was adjusted to 15% with water. An adhesive was obtained.

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.

<Manufacture of crepe adhesive>
18.5 g (0.2 mol) of epichlorohydrin was added to the total amount of the polyamidepolyamine aqueous solution (x-2) obtained above, 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 50 mPa · s, the reaction was terminated to obtain a polyamide polyamine / epichlorohydrin resin (A-3). Next, 61 g of glycerin (so that it becomes 20% by mass with respect to 100% by mass of the resin (A-3) solid content) is added as a softener (C), and the pH is 5 with 15% sulfuric acid and water, and the solid content is 15%. An adjusted crepe adhesive 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.

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.

Example 6
<Production 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).

<Manufacture of crepe adhesive>
8.3 g (0.09 mol) of epichlorohydrin was added to the total amount of the polyamidepolyaminepolyurea aqueous solution (y-1) obtained above, 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 95 mPa · s, the reaction was terminated to obtain a polyamide polyamine polyurea / epichlorohydrin resin (B-1). . Next, 59 g of glycerin (so that it becomes 20% by mass with respect to 100% by mass of the resin (B-1) solid content) was added as a softening agent (C), and the solid content was adjusted to 15% with water. An agent was obtained.

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).

<Manufacture of crepe adhesive>
8.3 g (0.09 mol) of epichlorohydrin was added to the total amount of the polyamidepolyaminepolyurea aqueous solution (y-2) obtained above, 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 65 mPa · s, the reaction was terminated to obtain a polyamide polyamine polyurea / epichlorohydrin resin (B-2). . Next, 60 g of glycerin (20% by mass with respect to 100% by mass of resin (B-2) solid content) was added to obtain an adhesive for crepes having a solid content adjusted to 15% with water.

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.

<Manufacture of crepe adhesive>
5.6 g (0.06 mol) of epichlorohydrin was added to the total amount of the polyamidepolyamine aqueous solution (x-3) obtained above, 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 60 mPa · s, the reaction was terminated to obtain a polyamide polyamine / epichlorohydrin resin (A-6). Next, 56 g of glycerin (20% by mass with respect to 100% by mass of the resin (A-6) solid content) was added to obtain an adhesive for crepes having a solid content adjusted to 15% with water.

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.

<Manufacture of crepe adhesive>
Epichlorohydrin 11.1 g (0.12 mol) was added to the total amount of the polyamidepolyamine aqueous solution (x-4) obtained above, 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 60 mPa · s, the reaction was terminated to obtain a polyamide polyamine / epichlorohydrin resin (A-7). Next, 59 g of glycerin (so that the resin (A-7) solid content is 20% by mass) is added as a softening agent (C), and a crepe adhesive whose solid content is adjusted to 15% with water is added. 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). Next, 59 g of polyethylene glycol (degree of polymerization: 200) is added as a softening agent (C) (20% by mass with respect to 100% by mass of resin (A-9) solid content), and the solid content is made 15% with water. An adjusted crepe adhesive was obtained.

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). Next, 59 g of 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. Got.

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 1 (when the amount of AZR in the crepe adhesive is too large and out of range)
Epichlorohydrin (37 g, 0.4 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 100 mPa · s, the reaction was terminated to obtain a polyamide polyamine / epichlorohydrin resin (A-12). Next, as a softener (C), 64 g of propylene glycol (20% by mass with respect to 100% by mass of resin (A-12) solid content) was added, and 15% sulfuric acid and water were added to adjust the pH to 3.2. A crepe adhesive having a solid content adjusted to 15% 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. 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%. 450 g of an aqueous solution (y-3) was obtained.

<Manufacture of crepe adhesive>
A four-necked round bottom flask equipped with a thermometer, reflux condenser, stirrer and dropping funnel was charged with 200 g of polyamide polyamine polyurea aqueous solution (y-3), and 5.5 g of epichlorohydrin (resin B) at 20 ° C. The composition ratio of 0.13 mol of epichlorohydrin to 1 mol of adipic acid was added, and then heated to 30 ° C. and kept at the same temperature for 10 minutes. Polyamide polyamine polyurea / epichlorohydrin Resin (B-3) was obtained. Next, 122 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 15 % Of crepe adhesive 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). Next, 112.5 g of the polyamide polyamine aqueous solution (x-5) and 241.0 g of water were charged into a four-necked flask equipped with a thermometer, a cooler, and a stirrer, and 10.5 g of epichlorohydrin (resin A The composition ratio was 0.44 mol of epichlorohydrin per mol of adipic acid). Thereafter, the temperature was raised to 50 ° C. and maintained for 12 hours to obtain a polyamide polyamine / epichlorohydrin resin (A-13). Next, 1.0 g (0.01 mol) of 98% sulfuric acid was added at the same temperature to obtain a crepe adhesive whose solid content was adjusted to 15% with water.

Comparative Example 4 (when the intrinsic viscosity of the crepe adhesive is low and out of range)
To the total amount of the 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. Next, 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). Next, 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))
In a 3 L four-necked round bottom flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, 103 g (1 mol) of diethylenetriamine as a polyalkylene polyamine, and coconut oil oleic acid {olein as a monocarboxylic acid having 6 to 24 carbon atoms 559 g (2 mol) of acid / linoleic acid / palmitic acid (mixing mass ratio 70/20/10)} was gradually added. 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.
Next, 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. for 1 hour, the reaction solution was cooled and adjusted by adding water so that the solid content was 30% by mass. The concentration was 30%, the viscosity was 350 mPa · s, the melting point. A paper softening agent having a particle size of 4 μm was obtained at 29 ° C.

<Measurement of molecular weight>
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. Column: SHODEX SB806M HQ manufactured by Showa Denko KK
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

<Measurement of intrinsic viscosity>
The reduced specific viscosity η _sp / C at a measurement temperature of 25 ° C. was measured using an Ubbelohde viscometer for 1N ammonium chloride aqueous solutions having a solid content concentration of 1%, 0.5%, and 0.2% of the adhesive for crepe in the examples. The intrinsic viscosity [η] was determined.
η _sp / C = [η] + k ′ [η] ² × C
Where C is the concentration, [η] is the intrinsic viscosity, and k ′ is the Huggins constant.

<Measurement of AZR content>
¹ HNMR of a sample obtained by adding a known amount of methanol to the crepe adhesive was measured, and the AZR amount was determined from the proton ratio of methanol and AZR. A sample obtained by adding 0.01 g of methanol to 1 g of the solid content of the crepe adhesive was used.

<Water resistance>
In a tea bag (weight W2 (g)), a petri dish (weight W1 (g)) prepared so as to have a uniform film weight of 0.05 g was immersed in water at 50 ° C. for 5 minutes with stirring. Then, the petri dish is dried, the weight of the petri dish is measured for each tea bag (weight W3 (g)), and water resistance is calculated from the following formula (1).
Formula (1) Water resistance (%) = 100 − {(W1 + W2) −W3} /0.05×100
W1 (g): Weight of the metal petri dish prepared as a film, W2 (g): Weight of the tea bag, W3 (g): Weight of the tea bag and the petri dish after soaking and drying

<Evaluation test of adhesive strength>
The 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. (area 0.2 cm ² ), dried for 1 minute, and then a half paper (basis weight) on which 2 μL of water was dropped to the plate so that the coated surface was 300 gf / cm ² 30 g / m ² , thickness 0.07 mm, 5 μL drop size 12 seconds), and the load required for peeling was evaluated with a probe tack tester. The evaluation results are shown in Tables 1 and 2.
In addition, it is preferable that the adhesive strength is higher. This test is adopted because it is easy to obtain the same tendency as when the crepe adhesive is applied to a dryer.

<Method for evaluating film hardness>
The solid content of 0.13 g of the crepe adhesive in Examples 1 to 13 and Comparative Examples 1 to 6 was placed in a metal petri dish having an inner diameter of 6.5 cm and dried by heating (110 ° C., 2 hours) to form a crepe adhesive film. Was prepared. The pencil is scratched with a hard core 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, 6B in order, and the hardness of the pencil with no scars is evaluated. did. Those that were not damaged by 6H were set to 15, those that were not damaged by 6B by scratching with a soft pencil in order were set to 2, and those that were damaged by 6B were set to 1. The lower the numerical value, the softer it was, and it was rated on a 15-point scale. The evaluation results are shown in Tables 1 and 2.

<Soft> 1 ← 2 (6B) ← 7 (B) → 15 (6H) <Hard>
Figures in parentheses indicate the hardness of pencils that do not have scars that are subject to numerical values.
A lower numerical value is preferable because there is less abrasion of the blade, and 6 or less is preferable.
This test is adopted because it is easy to obtain the same tendency as when the crepe adhesive is applied to a dryer.

<Preparation of handmade paper and evaluation results of paper quality>
By measuring the wet tear length of the handmade paper internally added with the crepe adhesive, the water disintegrability of the crepe adhesive can be easily evaluated. Adhesion for crepes prepared in Examples 1 to 13 and Comparative Examples 1 to 6 on a paper stock having a concentration of 2.4% by mass adjusted to a beating degree (CSF) of bleached kraft pulp (hardwood / conifer = 9/1) The agent was added so that it might become 0.1 mass% with respect to pulp solid content. After stirring, the paper was made with a square sheet machine to obtain handmade paper with a basis weight of 65 g / m ² . The wet tear lengths of the obtained handmade paper are shown in Tables 3 and 4. The larger the value of the wet tear length, the worse the water disintegrability, so the smaller the value, the better. This evaluation is called disaggregation.
Wet tear length: according to JIS P8135

After adding 0.1% by mass of the crepe adhesive described in Table 5 to the solid content of pulp, 0.3% by mass of the various softening agents described in Table 5 were added to the above handmade paper. In the same manner, hand-made paper was obtained. 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 ∝ρV ² (ρ: density)

Softener 1 oleic acid EO (4) PO (12) oleyl ether corresponding to softener (S3). EO is ethylene oxide, PO is propylene oxide, and the numerical value in () indicates the average added molar amount.
Softener 2 ... Dioleyldimethylammonium chloride equivalent to softener (S2)

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.
By comparing Examples and Comparative Example 5 from Tables 1 to 4, compared to the case where the water resistance evaluation value of the crepe adhesive is out of the range of the present invention, the examples of the present invention have a disaggregation property and an adhesive strength. It can be seen that the film surface is softer than that of Comparative Example 5.
By comparing Examples and Comparative Example 6 from Tables 1 to 4, the inherent viscosity of the crepe adhesive is high, and the examples of the present invention have better disaggregation and adhesive strength than those outside the scope of the present invention. Further, it can be seen that the surface of the film is softer than Comparative Example 6.
From Tables 1 to 4, it can be seen that a molecular weight of 1,000,000 to 5,000,000 is good and preferable by comparing Examples 1 and 2 other than Example 2.

Claims

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) Content of azetidinium group in 1 g of solid content of crepe adhesive is 0 to 0.2 mEq
(2) The intrinsic viscosity of the crepe adhesive is 0.20 to 0.55 dL / g.
(3) The softener (C) satisfies the following (i) and (ii): (i) a liquid having a boiling point of 150 ° C or higher and 80 ° C;
(Ii) Water-soluble aliphatic polyol or polyethylene glycol dimethyl ether (4) [resin (A) and / or resin (B)]: [softener (C)] = 100: 0.5 to 70 in mass ratio
(5) Water resistance evaluated by the following calculation method is 40 to 100%
<Calculation method of water resistance>
In a tea bag (weight W2 (g)), a petri dish (weight W1 (g)) prepared so as to have a uniform film weight of 0.05 g was immersed in water at 50 ° C. for 5 minutes with stirring. Then, the petri dish is weighed and measured for each tea bag (weight W3 (g)), and water resistance is calculated from the following equation (1).
Formula (1) Water resistance (%) = 100 − {(W1 + W2) −W3} /0.05×100
W1 (g): Weight of the metal petri dish prepared as a film, W2 (g): Weight of the tea bag, W3 (g): Weight of the tea bag and the petri dish after soaking and drying
The crepe adhesive according to claim 1, wherein the crepe adhesive has a weight average molecular weight of 1,000,000 to 5,000,000.
A method for producing a crepe paper, wherein the crepe adhesive according to claim 1 or 2 is applied to a dryer surface such that the amount of the crepe adhesive is 0.01 to 500 mg / m 2 per solid content relative to the area of the fiber web. A method for producing crepe paper, comprising a step of applying.
4. The method for producing crepe paper according to claim 3, wherein a softener is used as the internal chemical and the paper is sanitary paper.