JP2013108189A - Paper additive, method of stabilizing paper additive, and paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve viscosity stability of a paper additive that contains a reaction product of an amide-based compound obtained by a reaction of a specific monocarboxylic acid and/or a specific monocarboxylic acid derivative with a polyalkylene polyamine and epihalohydrin, and more preferably to provide a paper additive that is capable of markedly suppressing foaming in papermaking.SOLUTION: There is provided a paper additive containing: a reaction product (A) of an amide-based compound obtained by a reaction of a 6-24C monocarboxylic acid and/or a 6-24C monocarboxylic acid derivative with a polyalkylene polyamine, and epihalohydrin; and a water soluble electrolyte (B).

Description

  The present invention relates to a paper additive, a method for stabilizing a paper additive, and paper, and more particularly, a monocarboxylic acid having 6 to 24 carbon atoms and / or a monocarboxylic acid derivative having 6 to 24 carbon atoms and a polyalkylene. The present invention relates to a paper additive containing a reaction product (A) of epihalohydrin and an aqueous electrolyte (B) obtained by reaction with polyamines, a method for stabilizing paper additive, and paper.

  As a main component of the paper sizing agent, a reaction product (hereinafter referred to as “CAE resin”) of an amide compound obtained by reaction of a carboxylic acid and / or a carboxylic acid ester with a polyalkylene polyamine and an epihalohydrin is useful. Known (for example, see Patent Documents 1 and 2). There are also an opacity improver and a porosity improver other than the size of the CAE resin. It is known that the CAE resin is used as an opacity improver (see, for example, Patent Documents 3 and 4). It is also known to be used as a porosity improver (see, for example, Patent Document 5). However, conventional CAE resins are not sufficiently satisfactory in viscosity stability.

Japanese Patent Publication No.42-2922 Japanese Examined Patent Publication No. 47-11306 JP 61-252400 A Japanese Unexamined Patent Publication No. 2000-273792 JP 61-252400 A

  The present invention relates to an additive for paper containing a reaction product obtained by reacting a specific monocarboxylic acid and / or a specific monocarboxylic acid derivative and a polyalkylene polyamine with an amide compound obtained by reaction with an epihalodolin. Another object of the present invention is to provide a paper additive, a paper additive stabilization method, and paper, which can improve the viscosity stability of the agent and, in a more preferred embodiment, can significantly reduce foaming in papermaking as a paper additive.

  The present inventors provide a paper containing a reaction product obtained by reacting a specific monocarboxylic acid and / or a specific monocarboxylic acid derivative and a polyalkylene polyamine with an amide compound obtained by reaction with an epihalodrine. As a result of intensive investigations on the viscosity stability of additives for additives, viscosity stability can be improved by adding a water-soluble electrolyte to the additive for paper, and as a paper additive by using a specific surfactant. It has been found that foaming in papermaking when used can be significantly reduced, and the present invention has been completed.

That is, the present invention provides <1> a reaction of an amide compound obtained by a reaction of a monocarboxylic acid having 6 to 24 carbon atoms and / or a monocarboxylic acid derivative having 6 to 24 carbon atoms and a polyalkylene polyamine with an epihalohydrin. An additive for paper, characterized by containing the product (A) and a water-soluble electrolyte (B),
<2> The paper additive according to <1>, wherein the water-soluble electrolyte (B) is composed of an acid salt having a pKa of 1 to 13 at 25 ° C.
<3> The above-mentioned <1> or <2> paper additive, wherein the water-soluble electrolyte (B) is a carboxylate.
<4> The additive for paper contains 0.01 to 5% by mass of the water-soluble electrolyte (B), and the viscosity (solid content 15%, temperature 25 ° C.) after storage at 40 ° C. for 1 week is 2 to 50 mPa · s. The paper additive according to any one of the above items <1> to <3>,
<5> The paper additive according to any one of <1> to <4>, further comprising a surfactant (C) having an alkyl group or an alkenyl group having 8 to 24 carbon atoms,
<6> A reaction product (A) of an amide compound obtained by a reaction of a monocarboxylic acid having 6 to 24 carbon atoms and / or a monocarboxylic acid derivative having 6 to 24 carbon atoms and a polyalkylenepolyamine with an epihalohydrin. A method for stabilizing a paper additive, comprising a water-soluble electrolyte (B) composed of an acid salt having a pKa of 1 to 13 at 25 ° C.,
<7> The method for stabilizing a paper additive according to <6>, further comprising a surfactant (C) having an alkyl group or an alkenyl group having 8 to 24 carbon atoms,
<8> Paper containing the paper additive of any one of <1> to <5> above,
Is to provide

  Viscosity stability of a paper additive containing a reaction product obtained by reacting a specific monocarboxylic acid and / or a specific monocarboxylic acid derivative with a polyalkylenepolyamine and an amide-based compound and epihalodrine. In a more preferred embodiment, it is possible to provide a paper additive capable of significantly reducing foaming in papermaking as a paper additive.

  The present invention provides a reaction product (A) of an amide compound obtained by reacting a monocarboxylic acid having 6 to 24 carbon atoms and / or a monocarboxylic acid derivative having 6 to 24 carbon atoms with a polyalkylene polyamine and an epihalohydrin. And a water-soluble electrolyte (B). A paper additive, a method for stabilizing a paper additive, and paper.

  Examples of the monocarboxylic acid having 6 to 24 carbon atoms and the monocarboxylic acid derivative having 6 to 24 carbon atoms used in the present invention include fatty acids having 6 to 24 carbon atoms, acid anhydrides of fatty acids having 6 to 24 carbon atoms, and carbon numbers. Examples thereof include esters of 6 to 24 fatty acids.

The fatty acid may be any of straight-chain fatty acids having 6 to 24 carbon atoms, fatty acids having a branched chain, saturated fatty acids, and unsaturated fatty acids. Among these various fatty acids, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid are particularly preferable. These may be used alone or in combination of two or more.
Examples of fatty acid acid anhydrides include the acid anhydrides of the above fatty acids.

  Examples of fatty acid esters include the lower alcohol esters of the above fatty acids. Examples of the lower alcohol ester of fatty acid include fatty acid methyl ester, fatty acid ethyl ester, and fatty acid propyl ester. The fatty acid ester in the present invention can be obtained by a conventionally known esterification reaction between a fatty acid and an alcohol. These may be used alone or in combination of two or more.

  In the present invention, an aliphatic dibasic carboxylic acid can be used in combination as a part of the monocarboxylic acid and / or monocarboxylic acid derivative other than those described above. Examples of the aliphatic dibasic carboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like. Also, alkenyl succinic anhydride and alkenyl ketene dimer can be used in combination. These may be used alone or in combination of two or more.

  Polyalkylene polyamines used in the present invention include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, dipropylenetriamine, tripropylenetetramine, hexamethylenediamine, iminobis. Examples thereof include propylamine and alkylene oxide adducts of these amines, and these may be used alone or in combination of two or more. Among these, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine are preferable, and tetraethylenepentamine is particularly preferable. These may be used alone or in combination of two or more.

  The reaction molar ratio of the carboxylic acid and / or carboxylic acid ester and the polyalkylene polyamine is not particularly limited, but the reaction of the monocarboxylic acid and / or the monocarboxylic acid derivative with respect to the amino group of the polyalkylene polyamine. The amount is 0.3-0.99 equivalent, preferably 0.4-0.8 equivalent.

  The reaction between the monocarboxylic acid and / or the monocarboxylic acid derivative and the polyalkylene polyamine is carried out by heating to 100 to 200 ° C. The reaction time is usually 0.5 to 10 hours, and preferably 2 to 6 hours. There is no restriction on the method of mixing the carboxylic acid and / or carboxylic acid ester and the polyalkylene polyamine during the reaction, and usually the carboxylic acid and / or carboxylic acid ester is gradually added to the polyalkylene polyamine to smoothly carry out the reaction. The method of proceeding is preferred. A catalyst for the amidation reaction is not particularly required, but as a catalyst for the amidation reaction, a sulfonic acid such as sulfuric acid, benzenesulfonic acid, paratoluenesulfonic acid, or a catalyst usually used for the amidation reaction such as phosphoric acid is used. May be used. The amount used is usually 0.005 to 0.1 mol, preferably 0.01 to 0.05 mol, per mol of polyalkylene polyamine.

  In order to obtain the paper additive of the present invention, the amide compound obtained as described above and epihalohydrin are reacted at 30 to 100 ° C. As a reaction solvent, water or a mixed solvent of water and an organic solvent can be used. In order to stabilize the emulsion of the paper additive obtained in the present invention, it is preferable to contain a surfactant, and further to reduce low molecular organic chlorine compounds such as DCP (1,3-dichloro-2-propanol). Therefore, it is preferable to perform the following primary reaction and secondary reaction.

  Water or a mixed solvent of water and an organic solvent is used as a reaction solvent, and the mixture of the amide compound and the reaction solvent is kept at 30 ° C. to 69 ° C., and epihalohydrin is added thereto to advance the reaction. After adding the epihalohydrin, the reaction temperature is further maintained at 30 ° C. to 69 ° C. to proceed with the reaction. This reaction is referred to as a primary reaction for convenience. The primary reaction time is preferably 5 minutes to 3 hours. If the reaction time is less than 5 minutes, the effect of lowering the content of DCP in the CAE resin may not be sufficient, while the content of DCP in the CAE resin obtained even if the primary reaction time exceeds 3 hours. The amount does not drop so much, it simply increases the reaction time and is not economical.

  After making it react by primary reaction, it heats up to 70 to 100 degreeC, and advances reaction, keeping the temperature. This reaction is referred to as a secondary reaction for convenience. The reaction time of the secondary reaction may be sufficient for the reaction to be completed, and is usually 1 hour to 8 hours.

  As the reaction solvent used in the present invention, water or a mixed solvent of water and an organic solvent is used. Examples of the organic solvent include methanol, ethanol, isopropyl alcohol, etc. Among them, isopropyl alcohol is preferable. These may be used alone or mixed with water, or two or more of them may be used in combination with water. The amount of water and organic solvent used and the mixing ratio may be the amount and mixing ratio required to uniformly dissolve and disperse the amide compound at the reaction temperature. Usually, the reaction between the amide compound and epihalohydrin is carried out by the reaction of the amide compound. The concentration is 5 to 90%, and the mixing ratio of water and organic solvent is 0 to 100 g with respect to 100 g of water.

In the reaction of the amide compound with epihalohydrin, the molar amount of epihalohydrin relative to the active hydrogen of the remaining amino group of the amide compound is 0.05 to 1.2 equivalents, preferably 0.2 to 1.0 equivalents. is there. If the molar amount of the epihalohydrin is less than 0.05 equivalent, the viscosity of the CAE resin is increased and fluidity may be lost, resulting in inconvenience that handling becomes difficult. There may be a disadvantage that the content of DCP increases.

Here, the residual amino group can be calculated by measuring the amine value of the amino compound.

Residual amino group = Amine number = (V × F × 0.5 × 56.1) / S
However, V: titration volume of 1/2 N hydrochloric acid methanol solution (cc)
F: 1/2 titer of normal hydrochloric acid methanol solution S: solid content of collected sample (g)
Examples of the epihalohydrin used in the present invention include epichlorohydrin, epibromohydrin, etc. Among them, epichlorohydrin is preferable.

  As the surfactant used in the present invention, conventionally known surfactants can be used, and examples thereof include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. . Among these, nonionic surfactants and cationic surfactants are preferably used. In particular, cationic surfactants are preferable because they are excellent in fixing to pulp fibers and lead to foaming reduction in the papermaking system. The surfactant can be added to the amide compound before the reaction with the epihalohydrin, or during the reaction of the amide compound and the epihalohydrin, after the reaction between the amide compound and the epihalohydrin is completed. %, Particularly preferably in the range of 0.5 to 5%. If the surfactant content exceeds 10%, it is difficult to reduce foaming during papermaking.

Examples of the nonionic surfactant include a compound represented by the following general formula (1) (hereinafter referred to as Compound I). These may be used alone or in combination of two or more.
General formula (1)

(In the formula, -A ¹¹ -represents -O- or -COO-, R ¹¹ represents an alkyl group having 5 to 23 carbon atoms or an alkenyl group having 5 to 23 carbon atoms, and R ¹² represents 6 carbon atoms. Represents an acyl group having 24 to 24 alkyl groups or an alkenyl group having 6 to 24 carbon atoms, an alkyl group having 6 to 24 carbon atoms or an alkenyl group having 6 to 24 carbon atoms, or a hydrogen group, and B ¹¹ O represents an oxyethylene group And / or an oxypropylene group, and one or two of oxyethylene group and oxypropylene group may be added, and k is 1 to 100, preferably 10 to 80, where k is an average addition. Number of moles.)

  The compound represented by the general formula (1) is, for example, an alcohol having 6 to 24 carbon atoms, preferably 10 to 22 alcohols, or ethylene oxide in 1 mol of a fatty acid having 6 to 24 carbon atoms, preferably 10 to 22 carbon atoms, and It can be obtained by adding propylene oxide, and further, the alkylene oxide adduct is esterified with 1 mol of a fatty acid having 6 to 24 carbon atoms, preferably 10 to 22 carbon atoms, or 6 to 24 carbon atoms, preferably Can be obtained by etherification with 10 to 22 alcohols or 1 mole of alkyl halide having 6 to 24 carbon atoms, preferably 10 to 22 carbon atoms. The addition form of ethylene oxide and / or propylene oxide may be random or block, and is an alcohol having 6 to 24 carbon atoms, preferably 10 to 22 carbon atoms or 1 mol of fatty acid having 6 to 24 carbon atoms, preferably 10 to 22 carbon atoms. 1 to 100 mol, preferably 10 to 80 mol.

  The alcohol having 6 to 24 carbon atoms may be any of linear alcohol, branched chain alcohol, saturated alcohol, and unsaturated alcohol. Among these various alcohols, alcohols having 10 to 22 carbon atoms are preferable, and lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, and oleyl alcohol are particularly preferable. These may be used alone or in combination of two or more.

  The fatty acid having 6 to 24 carbon atoms may be any of linear fatty acid, fatty acid having a branched chain, saturated fatty acid, and unsaturated fatty acid. Among these various fatty acids, fatty acids having 10 to 22 carbon atoms are preferable, and lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid are particularly preferable. These may be used alone or in combination of two or more.

Mention may be made of cationic surfactants represented by the following general formulas (2) to (4).
General formula (2)
In the general formula ^{(2), R 21} represents an alkyl or alkenyl group having 8 to 24 carbon ^{atoms, B 21} O and ^{B 22} O represents an oxyethylene group and / or an oxypropylene group, an oxyethylene group and oxypropylene One or two of the groups may be added, and l and m are the average number of moles added, and the sum of l and m is 1 to 70, preferably 10 to 60.
General formula (3)
In the general formula (3), R ³¹ and R ³² represent an alkyl group or alkenyl group having 8 to 24 carbon atoms, B ³¹ O represents an oxyethylene group and / or an oxypropylene group, and the oxyethylene group and the oxypropylene group 1 type or 2 types may add, n is an average addition mole number, and shows that it is 1-70, Preferably it is 10-60.

General formula (4)

In the general formula (4), R ⁴¹ represents an alkyl group or alkenyl group having 8 to 24 carbon atoms, Y represents an alkylene group having 2 to 6 carbon atoms, and B ⁴¹ O, B ⁴² O and B ⁴³ O oxyethylene Group and / or oxypropylene group, one or two of oxyethylene group and oxypropylene group may be added, o to q are the average number of moles added, and the sum of o to q is 1 to 70, preferably 10-60.

  The paper additive of the present invention contains a water-soluble electrolyte (B) from the viewpoint of viscosity stability of the additive. The water-soluble electrolyte (B) is preferably added during or after the reaction between the amide compound and the epihalohydrin. The content of the water-soluble electrolyte (B) is preferably in the range of 0.01 to 5% by mass, particularly 0.05 to 2% by mass as the concentration contained in the paper additive.

  The water-soluble electrolyte (B) in the present invention refers to a compound that ionically dissociates in water. A suitable water-soluble electrolyte (B) is composed of an acid salt having a pKa at −25 ° C. of −4 to 13, preferably 1 to 13, and more preferably 3 to 10. The pKa of the present invention is an acid dissociation constant in water at 25 ° C., and indicates pKa n in the case of an n salt of a polyvalent acid. Specifically, in the case of disodium citrate, the pKa2 of citric acid is expressed as pKa2. It is shown. Specifically, formic acid, acetic acid, lactic acid, gluconic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartaric acid, maleic acid, fumaric acid, itaconic acid, citric acid, phthalic acid, acetic acid, benzoic acid, salicylic acid, Carboxylic acids such as gallic acid and diethyl barbituric acid, amino acids such as glycine, alanine, valine, leucine, serine, glutamic acid and aspartic acid, ethanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, m-xylenesulfonic acid, etc. Organic sulfonic acid, aminosulfonic acid such as taurine, acid agent such as hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, carbonic acid, silicic acid, aluminate, etc., alkanol such as monoethanolamine, diethanolamine, triethanolamine Inorganic bases such as amine, ammonia, sodium hydroxide, potassium hydroxide, Which alkali agent, neutralized product salt of the above acid agent and alkali agent, such as sodium citrate, potassium benzoate, ammonium chloride, sodium carbonate, dipotassium phosphate, monoethanolamine sulfate, No. 1 sodium silicate, No. 2 Examples include sodium silicate, No. 3 sodium silicate, and the like. Among these, it is preferable to blend an acid agent selected from carboxylic acids and / or a neutralized product salt thereof. Specifically, sodium acetate (pKa = 4.8), ammonium acetate (pKa = 4.8), potassium acetate (pKa = 4.8), sodium citrate (monosodium citrate (pKa1 = 3.1) , Disodium citrate (pKa2 = 4.8) and trisodium citrate (pKa3 = 6.4), sodium malate (monosodium malate (pKa1 = 3.4) and disodium malate (Means pKa2 = 5.1)), sodium formate (pKa = 3.8), sodium adipate (monosodium adipate (pKa1 = 4.4) and disodium adipate (pKa2 = 5.4)) Means).

  The CAE resin can be dispersed by a conventionally known method. In that case, said water-soluble electrolyte (B) may be added previously, and may be added after dispersion | distribution. As a conventionally known dispersion method, it can be dispersed by phase inversion emulsification, addition of a surfactant, phase inversion emulsification after adding a surfactant, or a mechanical method. These may be used alone or in combination of two or more methods. Examples of the mechanical method include a method of uniformly dispersing with various known emulsifiers such as a homomixer, a high-pressure discharge type homogenizer, a high shear type rotary emulsifier / disperser, and an ultrasonic emulsifier.

  The paper containing the paper additive of the present invention is not particularly limited, and examples thereof include various papers and paperboard. Paper types include PPC paper, inkjet printing paper, laser printer paper, form paper, thermal transfer paper, thermal recording base paper, pressure sensitive recording base paper, etc., photographic paper and its base paper, art paper, cast coated paper, high quality Paper containers such as coated paper such as coated paper, wrapping paper such as kraft paper, pure white roll paper, other paper such as notebook paper, book paper, various printing papers, newspaper paper, manila balls, white balls, chip balls, etc. Paperboard such as paperboard, liner, and gypsum board base paper. In addition to paper, modified wood and inorganic building materials can be used, and examples include particle board, hard board, insulation board, rock wool board and the like.

  In producing the paper of the present invention, the additive for production of the present invention is usually added at a use ratio of 0.1 to 3% by weight in solid content with respect to the solid content of pulp raw material. Further, the manufacturing additive of the present invention may be applied to a paper substrate with a size press, a gate roll coater, a shim sizer or the like.

  The paper of the present invention is a bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high yield pulp such as pulverized wood pulp, mechanical pulp or thermomechanical pulp, newspaper waste paper, magazine waste paper, cardboard Waste paper pulp such as waste paper or deinked waste paper can be contained. Moreover, you may contain the mixture of the said pulp raw material and synthetic fibers, such as rock wool, asbestos, or polyamide, a polyimide, polyester, polyolefin, and polyvinyl alcohol.

  In producing the paper of the present invention, additives such as fillers, sizing agents, dry paper strength agents, wet paper strength improvers, yield improvers, and drainage improvers also have the physical properties required for each paper type. In order to express, you may use as needed. These may be used alone or in combination of two or more. Further, these can be mixed with the paper additive of the present invention and added to the paper stock, and the mixing method is not particularly limited.

  Examples of the filler include clay, talc, and calcium carbonate. These may be used alone or in combination of two or more. As sizing agents, fatty acid soap sizing agents such as sodium stearate, rosin, fortified rosin, rosin ester sizing agent, alkenyl succinic anhydride aqueous emulsion, 2-oxetanone aqueous emulsion, paraffin wax aqueous emulsion, carboxylic acid And an aqueous emulsion of a reaction product of an aliphatic oxyacid and an aliphatic amine or an aliphatic alcohol, a cationic styrene-based sizing agent, and the like. These may be used alone or in combination of two or more.

  Examples of the dry paper strength improver include anionic polyacrylamide, cationic polyacrylamide, amphoteric polyacrylamide, cationized starch, and amphoteric starch. These may be used alone or in combination of two or more. Also good. Examples of the wet paper strength improver include polyamide / epichlorohydrin resin, melamine / formaldehyde resin, and urea / formaldehyde resin. These may be used alone or in combination with anionic polyacrylamide.

  Examples of the yield improver include anionic, cationic or amphoteric high molecular weight polyacrylamide, combined use of silica sol and cationized starch, and combined use of bentonite and cationic high molecular weight polyacrylamide. These may be used alone or in combination of two or more. Examples of the drainage improver include polyethyleneimine, cationic, amphoteric or anionic polyacrylamide. These may be used alone or in combination of two or more.

  In addition, with a size press, gate roll coater, bill blade coater, calendar, etc., surface paper strength improvers such as starch, polyvinyl alcohol and acrylamide polymers, dyes, coating colors, surface sizing agents, anti-slip agents, etc., as necessary May be applied. These may be used alone or in combination of two or more. Moreover, you may use a sulfuric acid sulfate before adding the paper additive of this invention, after adding, or simultaneously adding.

  Hereinafter, although an example and a comparative example of the present invention are given and explained concretely, the present invention is not limited to these examples. In each example, “%” means “% by weight” unless otherwise specified.

Production Example 1
Diethylenetriamine 10.3 g (0.1 mol), tetraethylenepentamine 170 g (0.9 mol), 75% phosphoric acid 0 in a 2 L four-necked round bottom flask equipped with a thermometer, reflux condenser, stirrer and dropping funnel .218 g (0.005 mol) was charged and the temperature was raised to 130 ° C., and then beef tallow fatty acid {stearic acid / palmitic acid mixture (mixing weight ratio 65/35)} 714 g (2.3 mol) was gradually added. The temperature was raised to 180 ° C., and the reaction was carried out for 2 hours while removing generated water out of the system to obtain an amide compound. The acid value of the obtained amide compound was 6, and the residual amino group amount was 2.3 mmol / g.

Production Example 2
A 2 L four-necked round bottom flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel was charged with 189 g (1 mol) of tetraethylenepentamine and 0.218 g (0.005 mol) of 75% phosphoric acid at 130 ° C. After the temperature was increased to 847 g (3 mol) of oleic acid was gradually added. The temperature was raised to 180 ° C., and the reaction was carried out for 2 hours while removing generated water out of the system to obtain an amide compound. The acid value of the obtained amide compound was 8, and the amount of residual amino groups was 1.9 mmol / g.

Example 1
In a 1 L four-necked round bottom flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, 100 g of the product obtained in Production Example 1 (0.23 mol as amino group) and poly (surfactant) as surfactant (C) 5 g of oxyethylene (40) coconut alkyl ether and 245 g of water were added and stirred at 80 ° C. for 1 hour. After cooling to 60 ° C., 8.4 g (0.091 mol) of epichlorohydrin was added and stirred for 30 minutes. Subsequently, after the reaction solution was reacted at 80 ° C. for 1 hour, 45.2 g of 10% aqueous sodium acetate solution was added as a water-soluble electrolyte (B) while cooling the reaction solution, and water was added so that the solid content was 15%. And adjusted. This was directly used as a paper additive. Table 1 shows the viscosity immediately after production and the viscosity after storage at 40 ° C. for 7 days, foamability and bulkiness effect.

Examples 2-17, Comparative Examples 1-2
The procedure of Example 1 was repeated except that the types and amounts of the amide compound (A), water-soluble electrolyte (B) and surfactant (C) shown in Table 1 were used. Table 1 shows the viscosity immediately after production, the viscosity after storage at 40 ° C. for 7 days, the bulkiness effect, and the foamability.

<Bulky effect, foamability>
Each of the paper additives obtained in Examples 1 to 17 and Comparative Examples 1 and 2 was subjected to a papermaking test using a square sheet machine. The foaming state of white water obtained by papermaking was judged visually (× ... high foaming, Δ ... not much foaming, ○ ... low foaming), and the density of the obtained paper (conforms to JISP8118) Was measured.

<Paper making conditions>
Pulp used: Bleached kraft pulp (conifer / hardwood = 1/9) concentration 2.4%
Degree of beating (CSF) 410
Addition rate of chemicals and order of addition: all addition rates are obtained in 10% of calcium carbonate solid content (TP121 manufactured by Okutama Kogyo Co., Ltd.) → 0.5% of cationized starch → Examples 1-17 and Comparative Examples 1-2 Any paper additive 1% → Paper-making basis weight on square sheet machine: 80 g / m ²
Drying conditions: 100 ° C x 100 sec (using a drum dryer)

  The pKa at 25 ° C. of the water-soluble electrolyte (B) in Table 1 is 3.4 (pKa1) for monosodium malate, −3.7 (pKa) for calcium chloride, and 2.0 (for disodium sulfate). pKa2), sodium chloride -3.7 (pKa), sodium bicarbonate 6.4 (pKa1), sodium dihydrogen phosphate 2.2 (pKa1), sodium acetate 4.8 (pKa), ammonium acetate 4.8 (pKa), potassium acetate 4.8 (pKa), disodium citrate 4.8 (pKa2), sodium formate 3.8 (pKa), monosodium adipate 4.4 (pKa1) ).

The density of the handmade paper when only the paper additive was not added in the chemical addition was 0.69 g / cm ² .

  The coconut alkyl group in Table 1 is a mixture of an alkyl group having 6 to 18 carbon atoms or an alkenyl group, and mainly contains a lauryl group. Moreover, the number in () of the name of surfactant in Table 1 shows the average addition mole number of an oxyethylene group. The content of (B) in Table 1 indicates the concentration of the water-soluble electrolyte (B) contained in the paper additive.

  As is apparent from the results shown in Table 1, the paper additive of the present invention exhibits an excellent effect in reducing the density of paper and has no significant increase in viscosity even after 1 week at 40 ° C. There is a merit that the restriction accompanying transportation and the like can be remarkably reduced. Furthermore, Examples 2 to 9 and Examples 11 to 17 using the compound (C) can be remarkably reduced in foaming properties in papermaking, and thus are very useful in practice. .

Claims (8)

Reaction product (A) of amide compound obtained by reaction of monocarboxylic acid having 6 to 24 carbon atoms and / or monocarboxylic acid derivative having 6 to 24 carbon atoms and polyalkylenepolyamine, and epihalohydrin, and water-soluble electrolyte A paper additive comprising (B). The paper additive according to claim 1, wherein the water-soluble electrolyte (B) is composed of an acid salt having a pKa of 1 to 13 at 25 ° C. The paper additive according to claim 1 or 2, wherein the water-soluble electrolyte (B) is a carboxylate. The paper additive contains 0.01 to 5% by mass of the water-soluble electrolyte (B), and the viscosity after storage for 1 week at 40 ° C. (solid content 15%, temperature 25 ° C.) is in the range of 2 to 50 mPa · s. The paper additive according to any one of claims 1 to 3, wherein the paper additive is used. Furthermore, surfactant (C) which has a C8-C24 alkyl group or an alkenyl group is contained, The additive for paper of any one of Claims 1-4 characterized by the above-mentioned. A reaction product (A) of an amide compound obtained by reacting a monocarboxylic acid having 6 to 24 carbon atoms and / or a monocarboxylic acid derivative having 6 to 24 carbon atoms with a polyalkylene polyamine and an epihalohydrin has a temperature of 25 ° C. A method for stabilizing a paper additive, characterized by containing a water-soluble electrolyte (B) composed of an acid salt having a pKa of 1 to 13. The method for stabilizing a paper additive according to claim 6, further comprising a surfactant (C) having an alkyl group or an alkenyl group having 8 to 24 carbon atoms. A paper comprising the paper additive according to any one of claims 1 to 5.