JP7172292B2 - Crepe adhesive and method for producing crepe paper - Google Patents

Description

The present invention relates to a crepe adhesive used for producing paper such as toilet paper, tissue paper, towel paper, and sanitary paper such as kitchen paper, and a method for producing crepe paper using the crepe adhesive. Regarding.

In the manufacture of sanitary paper such as toilet paper, tissue paper, towel paper, kitchen paper, etc., a process (creping) is performed to give the paper fine wrinkles (crepe) in order to give flexibility and bulkiness to the product. Creping consists of a process in which a wet paper is adhered to a rotary cylinder type paper dryer known as a Yankee dryer in the drying process, and after drying, the paper is scraped from the dryer surface with a doctor blade to impart crepe to the paper. At this time, thermosetting resins such as polyamidepolyamine-epihalohydrin resins and polyamidepolyaminepolyurea-epihalohydrin resins have been conventionally used in order to increase the adhesion of the wet paper to the Yankee dryer.

Normally, when creping, a crepe adhesive is applied to the surface of the dryer to form a coating film. In recent years, the speed of paper machines has increased, and in situations where it is difficult to form a coating film, from the viewpoint of production efficiency and paper quality, the adhesion of the wet paper to the dryer is excellent, and the moisture brought in from the wet paper is used for coating. There is a need for crepe adhesives with low film leaching.

Therefore, for example, for the purpose of increasing the adhesive strength, a polyamide epichlorohydrin resin having an amine end using polyamine in excess equivalent to polycarboxylic acid has been proposed (Patent Document 1).

Also, as a technique for increasing the adhesive strength and the water resistance of the film and forming a soft film, an adhesive in which a polyamide epichlorohydrin resin and a softening agent are mixed has been proposed (Patent Document 2).

However, even with these crepe adhesives, the former tends to elute the coating film due to the low water resistance of the film formed on the Yankee dryer, and the latter has poor adhesion of the wet paper to the dryer. was insufficient and the performance was not satisfactory.

Japanese Patent Publication No. 2010-516911 International Publication No. 2015/016350

An object of the present invention is to provide a crepe adhesive which is superior in adhesive strength of a wet paper to a dryer and water resistance of a coating film as compared with conventional adhesives for crepe.

The inventors of the present invention have made intensive studies to solve the above problems, and found that a specific crepe adhesive has excellent adhesive strength to wet paper, excellent water resistance of the formed film, and enables the formation of good crepes. The present inventors have found that the present invention has been completed.

（ここで、Ｒ^３は炭素数３～８のアルキレン基を表す）
＜３＞前記クレープ用接着剤のガラス転移温度が０～４０℃であることを特徴とする前記＜１＞又は＜２＞に記載のクレープ用接着剤、
＜４＞前記＜１＞～＜３＞のいずれか一項に記載のクレープ用接着剤を用いたクレープ紙の製造方法、
＜５＞内添薬品として柔軟剤を用い、紙が衛生用紙であることを特徴とする前記＜４＞に記載のクレープ紙の製造方法、である。 That is, the present invention
<1> A crepe adhesive characterized by containing at least one selected from a polyamidepolyamine/epihalohydrin resin and a polyamidepolyaminepolyurea/epihalohydrin resin and satisfying the following conditions (1) and (2):
(1) The degree of cationization at pH 3 is 5.4 to 9.5 meq/g per solid content
(2) Water resistance evaluated by the following calculation method is 40 to 100%
<Method for calculating water resistance>
A petri dish (weight W1 (g)) prepared so that the uniform film weight was 0.05 g was placed in a tea bag (weight W2 (g)) and placed in water at 50°C for 5 minutes while stirring. After immersion and drying, the weight of the petri dish together with the tea bag (weight W3 (g)) is measured, and the water resistance is calculated from the following formula (1).
Formula (1) Water resistance (%) = 100 - {(W1 + W2) - W3} / 0.05 x 100
W1 (g): weight of the metal petri dish with the film prepared, W2 (g): weight of the tea bag, W3 (g): weight of the tea bag and petri dish after immersion and drying <2> Polyamidepolyamine/epihalohydrin The crepe adhesive according to claim 1, wherein the resin and the polyamidepolyaminepolyurea/epihalohydrin resin are any one of the following (I) to (IV):
(I) reactants of polyalkylenepolyamines (A), dibasic carboxylic acids (B) and epihalohydrin (C) (II) polyalkylenepolyamines (A), dibasic carboxylic acids (B), ureas ( D) and reaction product of epihalohydrin (C) (III) polyalkylenepolyamines (A), dibasic carboxylic acids (B), at least one compound selected from the following (E-1) to (E-3) (E) and reaction product (IV) of epihalohydrin (C): polyalkylenepolyamines (A), dibasic carboxylic acids (B), ureas (D), from the following (E-1) to (E-3) at least one selected compound (E) and a reactant of epihalohydrin (C)

(E-1) An alkylenediamine compound H ₂ N—R ¹ —NH ₂ represented by the following general formula (1) (1)
(Here, R ¹ represents an alkylene group having 2 to 8 carbon atoms)
(E-2) Aminocarboxylic acid compound H ₂ N—R ² —COOH represented by the following general formula (2) (2)
(Here, R ² represents an alkylene group having 2 to 8 carbon atoms)
(E-3) Lactam compound represented by the following general formula (3)

(Here, R ³ represents an alkylene group having 3 to 8 carbon atoms)
<3> The crepe adhesive according to <1> or <2>, wherein the crepe adhesive has a glass transition temperature of 0 to 40°C.
<4> A method for producing crepe paper using the crepe adhesive according to any one of <1> to <3>,
<5> The method for producing crepe paper according to <4>, wherein a softening agent is used as the internal chemical, and the paper is sanitary paper.

According to the present invention, the adhesive strength of the wet paper web to the drier is excellent, so the drying property of the wet paper web is improved, contributing to the improvement of productivity. In addition, since the coating film is less eluted by moisture brought in from wet paper or the like, a uniform coating film can be formed and good crepe can be formed.

In addition, according to the paper manufacturing method of the present invention, even when a softening agent is used as an internal chemical, the wet paper web has a good adhesive strength to the dryer and is a method for manufacturing sanitary paper with a good texture. optimal.

FIG. 1 is a schematic diagram of an embodiment of the water resistance evaluation test of the present invention.

The crepe adhesive of the present invention contains at least one selected from polyamidepolyamine/epihalohydrin resins and polyamidepolyaminepolyurea/epihalohydrin resins.

（ここで、Ｒ^３は炭素数３～８のアルキレン基を表す） Although the polyamidepolyamine/epihalohydrin resin and the polyamidepolyaminepolyurea/epihalohydrin resin are not particularly limited, (I) a reactant of polyalkylenepolyamines (A), dibasic carboxylic acids (B) and epihalohydrin (C); ) Reaction products of polyalkylenepolyamines (A), dibasic carboxylic acids (B), ureas (D) and epihalohydrin (C), (III) polyalkylenepolyamines (A), dibasic carboxylic acids (B ), a reaction product of at least one compound (E) selected from the following (E-1) to (E-3) and an epihalohydrin (C), (IV) polyalkylenepolyamines (A), dibasic carboxylic acids (B), ureas (D), at least one compound (E) selected from the following (E-1) to (E-3), and a reaction product of epihalohydrin (C).
(E-1) An alkylenediamine compound H ₂ N—R ¹ —NH ₂ represented by the following general formula (1) (1)
(Here, R ¹ represents an alkylene group having 2 to 8 carbon atoms)
(E-2) Aminocarboxylic acid compound H ₂ N—R ² —COOH represented by the following general formula (2) (2)
(Here, R ² represents an alkylene group having 2 to 8 carbon atoms)
(E-3) Lactam compound represented by the following general formula (3)

(Here, R ³ represents an alkylene group having 3 to 8 carbon atoms)

Among these, (III) polyalkylenepolyamines (A), dibasic carboxylic acids (B), at least one compound (E) selected from the above (E-1) to (E-3), and epihalohydrin ( C) reactant, (IV) polyalkylenepolyamines (A), dibasic carboxylic acids (B), ureas (D), at least one selected from the above (E-1) to (E-3) and epihalohydrin (C) are preferred.

Polyalkylenepolyamines (A) may have at least two or more alkylene groups and two or more amino groups in the molecule. Examples include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, dipropylenetriamine, tripropylenetetramine, and iminobispropylamine. One of these may be used alone, or two or more thereof may be used in combination. Among these, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine are preferable because they are excellent in adhesive strength.

Dibasic carboxylic acids (B) are dibasic carboxylic acids and/or derivatives thereof having two carboxyl groups in the molecule. Dibasic carboxylic acids include, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, dodecanedioic acid and the like. Industrially, a dibasic carboxylic acid having 5 to 10 carbon atoms is preferred. Derivatives of dibasic carboxylic acids include mono- or diesters of the dibasic carboxylic acids, and acid anhydrides. Mono- or diesters of dibasic carboxylic acids include lower alcohol (methyl, ethyl, propyl) esters preferably having 1 to 5 carbon atoms, particularly preferably 1 to 3 carbon atoms. Examples of acid anhydrides include intramolecular dehydration condensates of free acids and condensates with lower carboxylic acids, preferably lower carboxylic acids having 1 to 5 carbon atoms. One of these may be used alone, or two or more thereof may be used in combination. Among these, adipic acid, glutaric acid dimethyl ester, and adipic acid dimethyl ester are preferable because they are excellent in adhesive strength.

Further, in place of a part of the dibasic carboxylic acids (B), carboxylic acids having 3 or more carboxylic acids in the molecule, such as citric acid and trimellitic acid, as long as they do not interfere with the effects of the present invention, and/or Alternatively, a derivative having a carboxylic acid ester thereof or an anhydride thereof can also be used.

Epihalohydrin (C) includes epichlorohydrin, epibromohydrin and the like, but epichlorohydrin is industrially preferable.

Ureas (D) include urea, thiourea, guanylurea, phenylurea, methylurea, and dimethylurea. Among these, urea is particularly preferred. Instead of some of these ureas (D), compounds having one or more N unsubstituted amide groups capable of transamidation reaction with amino groups, for example, aliphatic amides such as acetamide and propionamide, or benzamide, phenyl Aromatic amides, such as acetic acid amide, and the like can also be used.

(E-1) includes, for example, diaminoethane, diaminopropane, 1,2-diamino-2-methylpropane, 1,3-diamino-2,2-dimethylpropane, diaminobutane, diaminopentane, 1,5 -diamino-2-methylpentane, neopentyldiamine, diaminohexane, diaminooctane and other alkylenediamine compounds.

(E-2) includes, for example, 3-aminopropionic acid, 3-amino-2-methylpropionic acid, 4-aminobutanoic acid, 5-aminopentanoic acid, 6-aminocaproic acid, 7-aminoheptanoic acid, 8 and aminocarboxylic acid compounds such as -aminooctanoic acid and 9-aminononanoic acid.

Examples of (E-3) include lactam compounds such as lactam 4-aminobutanoate, lactam 5-aminopentanoate, lactam 6-aminohexanoate, lactam 7-aminoheptanoate, and lactam 8-aminooctanoate. be done.

The method for producing the polyamidepolyamine/epihalohydrin resin and the polyamidepolyaminepolyurea/epihalohydrin resin is not particularly limited, and can be obtained by a conventional method. Specifically, among the raw materials described above, raw materials other than epihalohydrin (C) are first subjected to a condensation reaction to obtain polyamidepolyamine or polyamidepolyaminepolyurea (hereinafter collectively referred to as "polyamidepolyamine (polyurea)"). ), and then react epihalohydrin (C) with the resulting polyamide polyamine (polyurea) to obtain the desired resin.

When preparing a polyalkylenepolyamine (A), a dibasic carboxylic acid (B), and optionally a compound (E) consisting of a compound (E), per 1.0 mol of the dibasic carboxylic acid (B) It is preferable to react 0.8 to 1.4 mol of polyalkylenepolyamines (A) and, if necessary, 0.1 to 1.0 mol of compound (E).

When preparing a polyalkylenepolyamine (A), a dibasic carboxylic acid (B), a urea (D), and optionally a compound (E), a dibasic carboxylic acid (B) 1.0 mol, polyalkylenepolyamines (A) 0.8 to 1.4 mol and optionally compound (E) 0.1 to 1.0 mol, and a secondary amino group of (A) It is preferable to react 0.05 to 1.0 mol of urea (D) with 1 mol.

The reaction ratio of the epihalohydrin (C) to the polyamidepolyamine (polyurea) is not particularly limited, but in order to obtain a crepe adhesive that has excellent adhesive strength and does not deteriorate the water degradability of toilet paper, polyamidepolyamine (polyurea ) is preferably 0.01 to 1 mol, more preferably 0.05 to 0.4 mol, per 1 mol of the amino group of ).

In the condensation reaction of polyalkylenepolyamines (A), dibasic carboxylic acids (B) and, if necessary, compound (E), dehydration and/or dealcoholization is performed by heating. From the viewpoint of reaction control, the reaction temperature is preferably 110 to 250° C. and the reaction time is preferably 1 to 8 hours. At this time, as a catalyst for the condensation reaction, sulfuric acid, sulfonic acids such as benzenesulfonic acid and paratoluenesulfonic acid, phosphoric acids such as phosphoric acid, phosphonic acid and hypophosphorous acid, and other known catalysts may be used singly or in combination of two or more. Can be used in combination. After the condensation reaction, an aqueous solution is prepared and subjected to the next reaction with epihalohydrin (C).

When epihalohydrin (C) is reacted with polyamidepolyamine (polyurea), it is preferable from the viewpoint of reaction efficiency that the concentration of polyamidepolyamine (polyurea) in the aqueous solution is 10 to 80% by mass. The reaction temperature is appropriately adjusted within the range of 5 to 90° C. according to the reaction concentration.

The aqueous solution viscosity of the polyamide polyamine/epihalohydrin resin and the polyamide polyamine polyurea epihalohydrin resin is in the range of 5 to 300 mPa·s, preferably 10 to 200 mPa·s, based on the viscosity of a 10 mass% solids aqueous solution at 25°C. By doing so, a resin having excellent adhesion can be obtained.

A crepe adhesive can contain a pH adjuster and an electrolyte in order to improve storage stability and control film formation. Examples of pH adjusters include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, particularly halogen-free inorganic acids; organic acids such as formic acid and acetic acid; sodium hydroxide, potassium hydroxide, calcium hydroxide, and water. inorganic bases such as magnesium oxide, sodium carbonate and potassium carbonate; and monoamine compounds such as ammonia, diethylamine, triethylamine, propylamine, butylamine, diisobutylamine, hydroxylamine, ethanolamine and diethanolamine.

Examples of electrolytes include phosphates, sulfates, carboxylates, and the like. Ammonium or alkali metal phosphates and carboxylates are particularly preferred. Furthermore, electrolytes whose aqueous solutions are alkaline are preferred. For example, as phosphates, ammonium salts of phosphoric acid such as diammonium hydrogen phosphate and triammonium phosphate; ammonium polyphosphates such as ammonium pyrophosphate and ammonium tripolyphosphate; Salts; alkali metal salts of phosphoric acid such as disodium hydrogen phosphate, trisodium phosphate, dipotassium hydrogen phosphate and tripotassium phosphate; alkali metal salts of polyphosphate such as sodium tripolyphosphate and potassium pyrophosphate; As carboxylic acid salts, alkali metal salts of formic acid such as sodium formate and potassium formate; alkali metal salts of acetic acid such as sodium acetate and potassium acetate; alkali metal salts of tartaric acid such as disodium tartrate and dipotassium tartrate; and alkali metal salts of citric acid such as trisodium and tripotassium citrate. Among these, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, and tripotassium phosphate are particularly preferred.

The crepe adhesive may contain a plasticizer having a hydroxyl group, if desired. Examples of plasticizers having a hydroxyl group include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycerol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol and the like. .

The degree of cationization of the crepe adhesive at pH 3 indicates the amount of cationic groups such as primary to tertiary amines and quaternary ammonium contained in the polyamide polyamine (polyurea)/epihalohydrin resin. A cationic group exhibits hydrogen bonding ability and electrostatic interaction between resins and between resins and cellulose, and greatly affects the adhesive strength and water resistance of crepe adhesives. Therefore, the degree of cationization at pH 3 of the crepe adhesive should be 5.4 to 9.5 meq per solid content. If it is lower than 5.4 meq, the adhesion strength of the coating film will be lowered, and if it is higher than 9.5 meq, the water resistance of the coating film will be lowered. It is preferably 6.0 to 9.5 meq.

In addition, the crepe adhesive must have a water resistance of 40 to 100% as determined by the following formula (1) in the evaluation of water resistance based on the following measurement method. If the water resistance is less than 40%, the coating film of the crepe adhesive applied on the Yankee dryer is likely to be eluted by moisture brought in from wet paper or the like. Water resistance is preferably 45 to 100%, more preferably 50 to 100%.

[Measuring method]
<I> Crepe adhesive so that the solid content is 0.05 g, placed in a metal petri dish with an inner diameter of 6.5 cm (weight: W1 (g)), and dried by heating (108 ° C., 90 minutes) while maintaining a horizontal position. to form a crepe adhesive film that evenly covers the entire bottom surface of the metal petri dish.
<B> Place the metal petri dish on which the uniform film is formed in <B> into the tea bag (weight W2 (g)). 500 mL of hot water at 50° C. is adjusted in a 500 mL beaker, a teabag containing a metal petri dish with a film formed is attached to the tip of the stirrer, and the metal petri dish is completely immersed and rotated at 100 rpm for 5 minutes.
<ha> Dry the tea bag containing the metal petri dish after <b> with a circulating hot air dryer (108 ° C, 90 minutes), measure its weight (weight W3 (g)), The water resistance is calculated from the formula (1).
Formula (1) Water resistance (%) = 100 - {(W1 + W2) - W3} / 0.05 x 100
W1 (g): weight of metal petri dish with film preparation, W2 (g): weight of tea bag, W3 (g): weight of tea bag and petri dish after immersion and drying

As the tea bag, it is preferable to use a polyethylene polyester tea bag with a string of about 95×70 mm, and the tea bag containing a metal petri dish is preferably attached vertically to the stirring rod as shown in FIG.

It is preferable that the glass transition point of the crepe adhesive is 0 to 40° C., particularly 10 to 40° C., since excellent adhesive strength can be readily exhibited.

Specific methods for applying the crepe adhesive to paper include a method of spraying onto the wet paper in front of the Yankee dryer in the manufacturing process, a method of spraying directly onto the surface of the Yankee dryer, and a method of combining these methods. There is It is preferable to spray directly onto the surface of the Yankee dryer because the effect as an adhesive for crepes can be easily obtained.

The crepe adhesive may be used in combination with a crepe release agent to control the adhesion of the wet paper to the Yankee dryer surface. Examples of release agents for crepes include silicone oils, hydrocarbon oils, oxidized waxes, paraffin waxes, polyethylene waxes, cationic surfactants, anionic surfactants, and amphoteric surfactants. These can be used singly or in combination of two or more.

When the crepe adhesive is sprayed directly onto 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 , especially 0.1, based on the solid content of the resin. By making it to 300 mg/m ² , it becomes easier to obtain a uniform coating film suitable for creping. If it is outside this range, a sufficient coating film may not be formed, or dirt may accumulate on the coating film, making creping difficult.

The method of using the adhesive for crepe in the present invention is to apply it to paper as described above, but as another embodiment, it is used by adding (internally adding) to paper stock (pulp slurry), or both internally adding and coating. It is also possible to use in When the crepe adhesive is added internally, the solid content of the crepe adhesive is usually 0.01 to 1% by mass, preferably 0.01 to 0.5% by mass, relative to the pulp solid content. It should be added.

Paper suitable for creping using the crepe adhesive of the present invention has a basis weight of 10 to 45 g/m ² and a density of 0.1 to 0.4 g/cm ³ from the viewpoint of texture. In the case of toilet paper and tissue paper, it is preferably 0.2 to 0.3 g/cm ³ . In addition, the longitudinal dry tearing length (JIS P 8113) is preferably 0.3 to 2.5 km, and in the case of toilet paper and tissue paper, it is preferably 0.2 to 0.8 km from the viewpoint of water disintegration. Furthermore, when used as sanitary paper, it is preferable that the water absorbency (Japanese Industrial Standards JIS S 3104) is 1 to 10 seconds when two papers are stacked, from the viewpoint of the wiping effect during use.

The paper to be creped with the adhesive for crepe of the present invention is preferably sanitary paper such as toilet paper, tissue paper, towel paper, kitchen paper, etc., and the pulp raw material is bleached or unbleached chemical paper such as kraft pulp or sulfite pulp. Bleached or unbleached high-yield pulp such as pulp, groundwood, mechanical or thermomechanical pulp, and waste paper pulp such as waste newspaper, magazine, corrugated waste or deinked waste paper can be included. It may also contain a mixture of the pulp material and synthetic fibers such as polyamide, polyimide, polyester, polyolefin and polyvinyl alcohol.
When producing paper to be creped using the crepe adhesive of the present invention, softeners, fillers, sizing agents, dry strength improvers, wet strength improvers, retention improvers, bulking agents, and paper thickness improvers Additives such as opacifying agents and drainage improvers may also be used as necessary in order to develop 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 softening agent internally or externally because it provides a paper having excellent texture.

Examples of softening agents include fatty acid amide epihalohydrin resins (S1), quaternary ammonium salts having alkyl groups and/or alkenyl groups (S2), and alkylene oxide reactants of fatty acids and/or fatty alcohols (S3). Among these, the fatty acid amide epihalohydrin resin (S1) is preferred in the present invention because of its excellent softening effect. These may be used alone or in combination of two or more. Generally, it may be added to the paper at a ratio of 0.01 to 1% by mass, preferably 0.01 to 0.5% by mass, in terms of solid content relative to the pulp solid content.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, % in each example is mass %.

<(I) Reaction product of polyalkylenepolyamines (A), dibasic carboxylic acids (B) and epihalohydrin (C)>
(Example 1)
124 g (1.2 mol) of diethylenetriamine as polyalkylenepolyamines (A) and 0.52 g of 95% sulfuric acid were charged into a 500 mL four-necked round bottom flask equipped with a thermometer, a reflux condenser, a stirrer, and a nitrogen inlet tube. , While stirring, add 146 g (1.0 mol) of adipic acid as dibasic carboxylic acid (B), raise the temperature while removing the generated water from the system under a nitrogen stream, and react at 175 ° C. for 4 hours. After that, water was gradually added to adjust the solid content to 50% to obtain an aqueous polyamidopolyamine solution.
Next, a 1000 mL four-necked round-bottomed flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was charged with 200 g of the aqueous polyamide polyamine solution, water was added to adjust the solid content to 35%, and epichlorohydrin was added. 20.2 g (equivalent to 0.4 mol of epichlorohydrin per 1 mol of amino groups of polyamide polyamine) was added dropwise over 30 minutes. At this time, the temperature of the reaction solution was kept at 25° C. or lower. After dropping, the temperature was raised to 30° C. and kept at the same temperature for 1 hour. Water was then added to 25% solids and adjusted to pH 7.0 with sulfuric acid. After that, the temperature was raised to 60° C., and when the viscosity at 15% time reached 50 mPa·s, 10 g of water and 5 g of 30% sulfuric acid were added and cooled. After cooling to around room temperature, the pH and solid content were adjusted with sulfuric acid and water to obtain a crepe adhesive containing a polyamide polyamine/epihalohydrin resin. Table 2 shows the solid content concentration, viscosity and pH.

(Examples 2-5)
A crepe adhesive containing a polyamide polyamine/epihalohydrin resin was obtained in the same manner as in Example 1, except that the raw material composition was changed as shown in Table 1. Table 2 shows the solid content concentration, viscosity and pH.

(Example 6)
54 g (0.525 mol) of diethylenetriamine and 112 g (0.525 mol) of tetraethylenepentamine as polyalkylenepolyamines (A) were placed in a 500 mL four-necked round bottom flask equipped with a thermometer, a reflux condenser, a stirrer, and a nitrogen inlet tube. Then, 0.52 g of 95% sulfuric acid was charged, 146 g (1.0 mol) of adipic acid was added as a dibasic carboxylic acid (B) while stirring, and the resulting water was removed from the system under a nitrogen stream. After heating and reacting at 175° C. for 4 hours, water was gradually added to adjust the solid content to 50% to obtain an aqueous polyamide polyamine solution.
Next, a 1000 mL four-necked round-bottomed flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was charged with 200 g of the polyamide polyamine aqueous solution, water was added to adjust the solid content to 35%, and the temperature was raised to 30°C. After warming, 6.2 g of epichlorohydrin (equivalent to 0.09 mol of epichlorohydrin per 1 mol of amino groups of polyamide polyamine) was added and the mixture was kept at the same temperature for 1 hour. Then, water was added to adjust the solid content to 15%, and after heating to 60° C., the reaction was terminated when the viscosity reached 50 mPa·s to obtain a crepe adhesive containing a polyamide polyamine/epihalohydrin resin. Table 2 shows the solid content concentration, viscosity and pH.

(Examples 7 to 11)
A crepe adhesive was obtained in the same manner as in Example 6, except that the raw material composition was changed as shown in Table 1. Table 2 shows the solid content concentration, viscosity and pH.

(Example 12)
223 g (1.05 mol) of tetraethylenepentamine as polyalkylenepolyamines (A) and 0.52 g of 95% sulfuric acid were placed in a 500 mL four-necked round bottom flask equipped with a thermometer, reflux condenser, stirrer, and nitrogen inlet tube. was charged, and with stirring, 146 g (1.0 mol) of adipic acid was added as a dibasic carboxylic acid (B), and the temperature was raised to 175 ° C. for 4 hours under a nitrogen stream while removing the generated water from the system. After the reaction, water was gradually added to adjust the solid content to 50%, thereby obtaining an aqueous polyamide polyamine solution.
Next, a 1000 mL four-necked round-bottomed flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was charged with 200 g of the polyamide polyamine aqueous solution, water was added to adjust the solid content to 35%, and the temperature was raised to 30°C. After warming, 6.8 g of epichlorohydrin (equivalent to 0.09 mol of epichlorohydrin per 1 mol of amino groups of polyamide polyamine) was added, and the mixture was kept at the same temperature for 1 hour. Then, water was added to adjust the solid content to 15%, and after heating to 60° C., the reaction was terminated when the viscosity reached 50 mPa·s to obtain an aqueous polyamide polyamine/epihalohydrin resin solution. Then, 10.6 g of glycerol (10% by mass based on 100% by mass of resin solids) was added as a plasticizer having a hydroxyl group, and a crepe adhesive adjusted to a solids content of 15% with water was obtained. Table 2 shows the solid content concentration, viscosity and pH.

<(II) Reaction product of polyalkylenepolyamines (A), dibasic carboxylic acids (B), ureas (D) and epihalohydrin (C)>
(Example 13)
255 g (1.2 mol) of tetraethylenepentamine as polyalkylenepolyamines (A) and 0.52 g of 95% sulfuric acid were placed in a 500 mL four-necked round bottom flask equipped with a thermometer, a reflux condenser, a stirrer, and a nitrogen inlet tube. 146 g (1.0 mol) of adipic acid was added as a dibasic carboxylic acid (B) with stirring, and the temperature was raised to 175° C. for 4 After reacting for a period of time, water was gradually added to adjust the solid content to 98%. Then, 36 g of urea (equivalent to 0.2 mol of urea per 1 mol of the secondary amino group of the polyalkylenepolyamine used) was added as urea (D) and reacted at 125° C. for 2 hours, and water was gradually added. In addition, the solid content was adjusted to 50% to obtain a polyamide-polyamine-polyurea aqueous solution.
Next, a 1000 mL four-necked round-bottomed flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was charged with 200 g of the aqueous polyamide-polyamine-polyurea solution, and water was added to adjust the solid content to 35%. 22.8 g of hydrin (equivalent to 0.4 mol of epichlorohydrin per 1 mol of amino groups of polyamide polyamine polyurea) was added dropwise over 30 minutes. At this time, the temperature of the reaction solution was kept at 25° C. or lower. After dropping, the temperature was raised to 30° C. and kept at the same temperature for 1 hour. Water was then added to 25% solids and adjusted to pH 7.0 with sulfuric acid. After that, the temperature was raised to 60° C., and when the viscosity at 15% time reached 50 mPa·s, 10 g of water and 5 g of 30% sulfuric acid were added and cooled. After cooling to around room temperature, the pH and solid content were adjusted with sulfuric acid and water to obtain a crepe adhesive containing a polyamide polyamine polyurea/epihalohydrin resin. Table 2 shows the solid content concentration, viscosity and pH.

(Example 14)
223 g (1.05 mol) of tetraethylenepentamine as polyalkylenepolyamines (A) and 0.52 g of 95% sulfuric acid were placed in a 500 mL four-necked round bottom flask equipped with a thermometer, a reflux condenser, a stirrer, and a nitrogen inlet tube. was charged, and with stirring, 146 g (1.0 mol) of adipic acid was added as a dibasic carboxylic acid (B), and the temperature was raised to 175 ° C. for 4 hours under a nitrogen stream while removing the generated water from the system. After the reaction, water was gradually added to adjust the solid content to 98%. Next, 27 g of urea (equivalent to 0.2 mol of urea per 1 mol of the secondary amino group of the polyalkylene polyamine used) was added as urea (D) and reacted at 125° C. for 2 hours, and water was gradually added. In addition, the solid content was adjusted to 50% to obtain a polyamide-polyamine-polyurea aqueous solution.
Next, a 1000 mL four-necked round-bottomed flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel was charged with 200 g of the aqueous polyamide-polyamine-polyurea solution, and water was added to adjust the solid content to 35%. 6.2 g of epichlorohydrin (equivalent to 0.09 mol of epichlorohydrin per 1 mol of the amino group of the polyamide polyamine polyurea) was added, and the mixture was kept at the same temperature for 1 hour. Next, water was added to adjust the solid content to 15%, and the temperature was raised to 60°C. When the viscosity reached 50 mPa·s, the reaction was terminated to obtain a crepe adhesive containing an aqueous solution of polyamide polyamine polyurea/epihalohydrin resin. rice field. Table 2 shows the solid content concentration, viscosity and pH.

(Example 15)
A crepe adhesive was obtained in the same manner as in Example 14, except that the raw material composition was changed as shown in Table 1. Table 2 shows the solid content concentration, viscosity and pH.

<(III) Reaction product of polyalkylenepolyamines (A), dibasic carboxylic acids (B), compound (E) and epihalohydrin (C)>
(Example 16)
223 g (1.05 mol) of tetraethylenepentamine as polyalkylenepolyamines (A) and 0.52 g of 95% sulfuric acid were placed in a 500 mL four-necked round bottom flask equipped with a thermometer, reflux condenser, stirrer, and nitrogen inlet tube. 146 g (1.0 mol) of adipic acid as a dibasic carboxylic acid (B) and 23 g (0.2 mol) of ε-caprolactam as a compound (E) are added with stirring, and the resulting water is added under a nitrogen stream. was removed from the system, the temperature was raised, and the mixture was reacted at 175°C for 4 hours, and then water was gradually added to adjust the solid content to 50% to obtain an aqueous polyamidepolyamine solution.
Next, a 1000 mL four-necked round-bottomed flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was charged with 200 g of the polyamide polyamine aqueous solution, water was added to adjust the solid content to 35%, and the temperature was raised to 30°C. After warming, 7.0 g of epichlorohydrin (equivalent to 0.09 mol of epichlorohydrin per 1 mol of amino groups of polyamide polyamine) was added, and the mixture was kept at the same temperature for 1 hour. Then, water was added to adjust the solid content to 15%, and after heating to 60° C., the reaction was terminated when the viscosity reached 50 mPa·s to obtain a crepe adhesive containing a polyamide polyamine/epihalohydrin resin. Table 2 shows the solid content concentration, viscosity and pH.

(Examples 17-22)
A crepe adhesive was obtained in the same manner as in Example 16, except that the raw material composition was changed as shown in Table 1. Table 2 shows the solid content concentration, viscosity and pH.

<(IV) Polyalkylenepolyamines (A), dibasic carboxylic acids (B), ureas (D), at least one compound (E) selected from the following (E-1) to (E-3) and reaction product of epihalohydrin (C)>
(Example 23)
108 g (1.05 mol) of diethylenetriamine as polyalkylenepolyamines (A) and 0.52 g of 95% sulfuric acid were charged into a 500 mL four-necked round bottom flask equipped with a thermometer, a reflux condenser, a stirrer, and a nitrogen inlet tube. 146 g (1.0 mol) of adipic acid as a dibasic carboxylic acid (B) and 23 g (0.2 mol) of ε-caprolactam as a compound (E) were added with stirring, and the resulting water was removed from the system under a stream of nitrogen. After the temperature was raised while removing to 175° C. for 4 hours, water was gradually added to adjust the solid content to 98%. Next, 1.8 g of urea (equivalent to 0.2 mol of urea per 1 mol of the secondary amino group of the polyalkylenepolyamine used) was added as urea (D) and reacted at 125° C. for 2 hours, and then water was added. It was gradually added to adjust the solid content to 50%, thereby obtaining an aqueous polyamide-polyamine-polyurea solution.
Next, a 1000 mL four-necked round-bottomed flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel was charged with 200 g of the aqueous polyamide-polyamine-polyurea solution, and water was added to adjust the solid content to 35%. , 5.3 g of epichlorohydrin (equivalent to 0.09 mol of epichlorohydrin per 1 mol of amino groups of polyamide polyamine polyurea) was added, and the mixture was kept at the same temperature for 1 hour. Next, water was added to adjust the solid content to 15%, and after the temperature was raised to 60° C., the reaction was terminated when the viscosity reached 50 mPa·s to obtain a crepe adhesive containing a polyamide polyamine polyurea/epihalohydrin resin. . Table 2 shows the solid content concentration, viscosity and pH.

(Comparative example 1)
A crepe adhesive containing a polyamide polyamine/epihalohydrin resin was obtained in the same manner as in Example 1, except that the raw material composition was changed as shown in Table 1. Table 2 shows the solid content concentration, viscosity and pH.

(Comparative example 2)
A crepe adhesive containing a polyamide polyamine/epihalohydrin resin was obtained in the same manner as in Example 6, except that the raw material composition was changed as shown in Table 1. Table 2 shows the solid content concentration, viscosity and pH.

(Comparative Example 3)
A crepe adhesive was obtained in the same manner as in Example 16, except that the raw material composition was changed as shown in Table 1. Table 2 shows the solid content concentration, viscosity and pH.

(Comparative Example 4)
Example 12 of Japanese Patent Application Publication No. 2010-516911, Ex. With reference to No. 47A, a crepe adhesive containing a polyamidepolyamine-epihalohydrin resin was obtained in the same manner as in Example 6, except that the raw material composition was changed as shown in Table 1. Table 2 shows the solid content concentration, viscosity and pH.

(Comparative Example 5)
A crepe adhesive was obtained in the same manner as in Example 12 except that the raw material composition was changed as shown in Table 1 with reference to Example 11 of WO 2015/016350. Table 2 shows the solid content concentration, viscosity and pH.

(Comparative Example 6)
A crepe adhesive was obtained in the same manner as in Example 14, except that the raw material composition was changed as shown in Table 1. Table 2 shows the solid content concentration, viscosity and pH.

For each crepe adhesive obtained in Examples 1 to 23 and Comparative Examples 1 to 6, the degree of cationization at pH 3, glass transition point, water resistance, and adhesive strength were measured by the methods described below. Table 2 shows the measurement results.

<Method for measuring degree of cationization at pH 3>
Measurements of the degree of cationization of the crepe adhesive at pH 3 were obtained by colloidal titration using a particle surface charge detector and an automatic titrator. The measurement conditions are as follows.

[machine]
Particle surface charge detector: PCD03 (manufactured by Mutec)
Automatic titrator: DL50 Titrators (manufactured by METTLER TOLEDO)

[Measuring method]
The crepe adhesive was diluted to 0.1% by weight with deionized water, and 10 g of the sample solution was added to the measurement cell of the particle surface charge detector. After adjusting the sample solution in the measurement cell to pH X (where X is 2.5 to 3) using 15N acetic acid aqueous solution, use 1/1000N polyvinyl potassium sulfate (PVSK) aqueous solution. Titrate. A constant amount (0.01 mL) of the PVSK aqueous solution is always dropped at one time by the automatic titrator. Using the amount (V1) of the 1/1000N PVSK aqueous solution used for titration, the degree of cationization (V2) at pH X is calculated by the following formula (1). Similarly, a sample solution adjusted to pH Y (where Y is 3 to 3.5) is also measured. At that time, using the amount (V3) of the 1/1000N PVSK aqueous solution used for titration, the degree of cationization (V4) at pH Y (where Y is 3 to 3.5) is calculated by the following formula (2). .
The degree of cationization at pH 3 is calculated by the following formula (3).
Formula (1) Degree of cationization at pH X (V2) (meq/g) = (V1/1000)/0.002
Formula (2) Degree of cationization at pH Y (V4) (meq/g) = (V3/1000)/0.002
Formula (3) Degree of cationization at pH 3 (meq/g) = {(V4-V2)/(YX)} x 3 + V2-{(V4-V2)/(YX)} x X

<Evaluation of water resistance>
<I> Crepe adhesive so that the solid content is 0.05 g, placed in a metal petri dish with an inner diameter of 6.5 cm (weight: W1 (g)), and dried by heating (108 ° C., 90 minutes) while maintaining a horizontal position. to form a crepe adhesive film that evenly covers the entire bottom surface of the metal petri dish.
<B> Place the metal petri dish on which the uniform film is formed in <B> into the tea bag (weight W2 (g)). 500 mL of hot water at 50° C. is adjusted in a 500 mL beaker, a teabag containing a metal petri dish with a film formed is attached to the tip of the stirrer, and the metal petri dish is completely immersed and rotated at 100 rpm for 5 minutes.
<ha> Dry the tea bag containing the metal petri dish after <b> with a circulating hot air dryer (108 ° C, 90 minutes), measure its weight (weight W3 (g)), The water resistance is calculated from the formula (1).
Formula (1) Water resistance (%) = 100 - {(W1 + W2) - W3} / 0.05 x 100
W1 (g): weight of metal petri dish with film preparation, W2 (g): weight of tea bag, W3 (g): weight of tea bag and petri dish after immersion and drying

For the evaluation of water resistance, a polyethylene polyester tea bag with a string of about 95×70 mm was used as the tea bag, and the tea bag containing a metal Petri dish was attached vertically to a stirring bar as shown in FIG.

<Adhesion strength evaluation test>
The adhesive strength of the crepe adhesive was measured using a tacking tester TAC-II (manufactured by Lesca Co., Ltd.). A plate heated to 90° C. so that the solid content of the crepe adhesive is 2.0 g/m ² and the active ingredient of the crepe agent CR6106 (manufactured by Seiko PMC Co., Ltd., crepe release agent) is 0.5 g/m ² . (Area of 0.2 cm ² ) and dried for ¹ minute ^. A probe tack tester was used to evaluate the load required for pressing and peeling from a drop size of 12 seconds). It should be noted that the adhesive strength is preferably as high as possible. In addition, this test is adopted because it is easy to obtain the same tendency as when applying a crepe adhesive to a dryer. The adhesive strength is preferably 130 gf or more, particularly 140 gf or more.

<Method for measuring glass transition point>
Using a differential scanning calorimeter (DSC6220, manufactured by Hitachi High-Tech Science Co., Ltd.), the crepe adhesive dried under the conditions of 110 ° C.-90 minutes was dried at an operating speed of 20 ° C./min while purging with nitrogen in an open pan. Measured at ~180°C. The Tg values in Table 2 indicate the onset temperature from the second heating cycle.

From Table 2, it can be seen that the examples of the present invention reach the desired levels of both adhesive strength and water resistance compared to the comparative examples that do not satisfy the conditions of the present invention.

From Table 2, by comparing Examples 8 and 14 with Examples 16 to 23, when compound (E) is used as a raw material for polyamide polyamine (polyurea)/epihalohydrin resin, adhesive strength and water resistance are improved. Both are found to be superior.

From Table 2, Examples 2 to 11 and 13 to 23, in which the glass transition temperature of the adhesive for crepe satisfies 0 to 40°C, have water resistance of 45% or more and adhesion compared to Examples 1 and 12, which do not. It can be seen that the strength is 140 gf or more, which is more preferable.

<Preparation of softener>
(Synthesis example 1)
103 g (1 mol) of diethylenetriamine as a polyalkylenepolyamine and coconut oil oleic acid (oleic Acid/linoleic acid/palmitic acid (mixed mass ratio 70/20/10)} 559 g (2 mol) was gradually added. The temperature was raised to 180° C., and the reaction was carried out for 3 hours while removing the generated water out of the system to obtain an amide compound. The amount of residual amino groups in the resulting amide compound was 2 mmol/g.
Next, 100 g of the above amide compound (0.16 mol as an amino group), 5 g of polyoxyethylene (45) stearylamine (the number in parentheses indicates the average number of added moles of polyoxyethylene), 100 g of water, and epichloro as an epihalohydrin. 5.9 g (0.064 mol) of hydrin was added at 50° C. and stirred for 30 minutes. Subsequently, the reaction solution was heated to 70° C. and reacted for 1 hour, and then water was added to adjust the solid content to 30% by mass while cooling the reaction solution. A paper softening agent having a temperature of 29° C. and a particle size of 4 μm was obtained.

<Evaluation results of adhesive strength assuming the use of softener>
In the adhesive strength evaluation test, except that 2 μL of water dropped on the Japanese paper is changed to a 0.5% concentration aqueous solution using the softener shown in Table 3, in the same manner as in the adhesive strength evaluation test. An evaluation was carried out. Table 3 shows the evaluation results.

Softener 1: Oleic acid EO(4)PO(12) oleyl ether corresponding to softener (S3). EO is ethylene oxide, PO is propylene oxide, and the numbers in parentheses indicate the average addition mol amount.

Softener 2: dioleyldimethylammonium chloride corresponding to softener (S2)

As can be seen from Table 3, when the crepe adhesive of the present invention is used, the adhesive strength is high even when a softener is used. Therefore, the amount of softening agent used can be increased, which is advantageous in terms of texture (softness, touch). That is, the method for producing crepe paper using the softening agent as the internal chemical and the adhesive for crepe of the present invention is suitable for producing sanitary paper.

1: Stirrer 2: Stirring rod 3: Metal petri dish 4: Tea bag 5: Tea bag string

Claims (5)

Dibasic carboxylic acid containing at least one selected from polyamidepolyamine/epihalohydrin resins and polyamidepolyaminepolyurea/epihalohydrin resins and used in obtaining polyamidepolyamine/epihalohydrin resins and polyamidepolyaminepolyurea/epihalohydrin resins as reactants A crepe adhesive, wherein the acid is adipic acid and satisfies the following conditions (1) and (2).
(1) The degree of cationization at pH 3 is 5.4 to 9.5 meq/g per solid content
(2) Water resistance evaluated by the following calculation method is 40 to 100%
<Method for calculating water resistance>
A petri dish (weight W1 (g)) prepared so that the uniform film weight was 0.05 g was placed in a tea bag (weight W2 (g)) and placed in water at 50°C for 5 minutes while stirring. After immersion and drying, the weight of the petri dish together with the tea bag (weight W3 (g)) is measured, and the water resistance is calculated from the following formula (1).
Formula (1) Water resistance (%) = 100 - {(W1 + W2) - W3} / 0.05 x 100
W1 (g): weight of metal petri dish with film preparation, W2 (g): weight of tea bag, W3 (g): weight of tea bag and petri dish after immersion and drying 2. The crepe adhesive according to claim 1, wherein the polyamine/epihalohydrin resin and the polyamidepolyaminepolyurea/epihalohydrin resin are any one of the following (I) to (IV).
(I) Reaction products of polyalkylenepolyamines (A), adipic acid (B) and epihalohydrin (C)
(II) Reaction products of polyalkylenepolyamines (A), adipic acid (B), ureas (D) and epihalohydrin (C) (III) polyalkylenepolyamines (A), adipic acid (B), the following (E -1) Reaction product of at least one compound (E) selected from to (E-3) and epihalohydrin (C)
(IV) polyalkylenepolyamines (A), adipic acid (B), ureas (D), at least one compound (E) selected from the following (E-1) to (E-3) and epihalohydrin ( C) reactants
(E-1) An alkylenediamine compound H ₂ N—R ¹ —NH ₂ represented by the following general formula (1) (1)
(Here, R1 represents an alkylene group having 2 to 8 carbon atoms)
(E-2) Aminocarboxylic acid compound H ₂ N—R ² —COOH represented by the following general formula (2) (2)
(Here, R ² represents an alkylene group having 2 to 8 carbon atoms)
(E-3) Lactam compound represented by the following general formula (3)

(Here, R ³ represents an alkylene group having 3 to 8 carbon atoms)
The crepe adhesive according to claim 1 or 2, wherein the crepe adhesive has a glass transition temperature of 0 to 40°C. A method for producing crepe paper using the crepe adhesive according to any one of claims 1 to 3. 5. The method for producing crepe paper according to claim 4, wherein a softening agent is used as the internal chemical, and the paper is sanitary paper.

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