JP5621956B2 - Water squeezing improver for paper - Google Patents

Description

  The present invention relates to a water squeezing improver for paper, and more specifically, when added to a pulp slurry, the water squeezing improver having an excellent water squeezing effect without affecting the strength or thickness of the paper. About.

  In the paper manufacturing process, in order to increase the papermaking efficiency and productivity, it is strongly required to improve the dewaterability of the papermaking process. The dehydration in the papermaking process can be divided into filtration dehydration (drainage) at the wire part, filtration dehydration (water pressing) at the press part, and dry dehydration (dryability) at the dryer part. Conventionally, as means for improving the dewaterability of the papermaking process, for example, a polymer compound such as high molecular weight polyacrylamide imparted with ionicity (for example, see Patent Documents 1 and 2), a Hoffman degradation product of polyacrylamide, polyethyleneimine And the like, and a combination of an amphoteric polymer exhibiting cationic properties and a cationic polymer (see, for example, Patent Document 3). Further, a drying efficiency improver (for example, see Patent Document 4) composed of a compound that brings about a specific paper quality improving effect is disclosed. However, these dehydrating effects are not fully satisfied.

  In addition, a reaction product of an amide compound obtained by reaction of polyalkylene polyamines with a monocarboxylic acid and epihalohydrin (hereinafter sometimes abbreviated as “CAE resin”) is a main component of the paper sizing agent. It is known (see, for example, Patent Documents 5 and 6) that it is useful. Moreover, it is known as an opacity improver (see, for example, Patent Documents 7 and 8) and a porosity improver (see, for example, Patent Document 9) as uses other than the size of CAE resin, and also peels paper from a dryer drum. Although it is also known that it is useful for improving the performance (see, for example, Patent Document 10), there is no description about the ability to improve dehydration, and the ability to improve dewaterability is not at a satisfactory level. There was a problem that the strength decreased due to the increase in the strength. In order to compensate for this decrease in strength, a paper manufacturing method (for example, see Patent Document 11) in which a CAE resin and a specific paper strength enhancer are separately added to paper has been proposed. In addition, even if they were used as a water squeezing improver, it was not a satisfactory dehydration improvement level.

JP-A 61-6395 JP 61-6396 A JP-A-5-78997 Japanese Patent No. 3387033 (Japanese Patent Laid-Open No. 2001-123391) Japanese Patent Publication No.42-2922 JP 47-11306 A JP 61-252400 A Japanese Unexamined Patent Publication No. 2000-273792 JP 61-252400 A JP 59-30997 JP 2008-179910 A

  This invention makes it a subject to provide the water squeezing improvement agent which has the outstanding water squeezing improvement effect, without affecting the intensity | strength of paper or the thickness of paper, when it adds to a pulp slurry.

The present inventors have found that a specific CAE resin has an excellent effect of improving water squeezing without affecting the strength of the paper and the thickness of the paper, and have completed the present invention.

Means for solving the above-mentioned problems are:
(1) A reaction product of an amide compound obtained by reaction of polyalkylene polyamines with monocarboxylic acids and epihalohydrin, and the monocarboxylic acids contain at least 60% by weight of saturated monocarboxylic acids having 6 to 12 carbon atoms The reaction amount of the monocarboxylic acid with respect to one amino group of the polyalkylenepolyamine is 0.3 to 0.8 equivalent, and the active hydrogen of the residual amino group amount in the amide compound is equivalent to that of the epihalohydrin. A water squeezing improver for paper, characterized in that the amount is 0.4 to 1.2 equivalents,
(2) A reaction product of an amide compound obtained by reaction of polyalkylene polyamines with monocarboxylic acids and epihalohydrin, where the monocarboxylic acids are unsaturated monocarboxylic acids having 6 to 12 carbon atoms and 18 carbon atoms. A reactant (A) component containing at least 60% by weight of a monocarboxylic acid and having an amount of epihalohydrin of 0.4 to 1.2 equivalents relative to the active hydrogen of the residual amino group in the amide compound, and cationic And / or the amphoteric acrylamide polymer (B) component, and the weight ratio of the solid content of the component (A) to the component (B) is (A) :( B) = 99: 1 to 60:40. Paper water squeezing improver,
(3) The water squeezing improver for paper according to (2), wherein the ratio of the cation equivalent and the anion equivalent of the acrylamide polymer (B) component is anion equivalent / cation equivalent = 0/100 to 60/40,
(4) The water squeezing improver according to any one of (1) to (3), wherein the standard bulk improvement degree is smaller than 0.02 g / cm ³ .

  According to the present invention, by adding to the pulp slurry, it is possible to provide a water squeezing improver comprising the specific CAE resin of the present invention that exhibits an excellent water squeezing improvement effect. Furthermore, when paper making is performed using a pulp slurry to which the water squeezing improver is added, a water squeezing improver excellent in water squeezing is provided without reducing the strength of the obtained paper and without affecting the thickness of the paper. can do.

  The dryer section in the paper making process consumes a great deal of energy to perform the drying described above. By using the water squeezing improver according to the present invention, the water squeezing in the press part is improved, and the paper moisture brought into the dryer part can be reduced. As a result, the steam unit consumption in the dryer part is reduced. In addition, the papermaking speed can be improved, which can contribute to the reduction of the total energy cost in the production process.

    Polyalkylene polyamines used in the present invention include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, dipropylenetriamine, tripropylenetetramine, hexamethylenediamine, iminobis. Examples include propylamine and alkylene oxide adducts of these amines, which can form amide compounds by reacting with monocarboxylic acids. 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 monocarboxylic acid of the present invention may be a derivative such as an ester of a monocarboxylic acid capable of forming an amide compound by reacting with not only a monocarboxylic acid but also a polyalkylene polyamine. In the embodiment of the aqueous improver, the monocarboxylic acids contain at least 60% by weight, preferably at least 80% by weight of saturated monocarboxylic acids having 6 to 12 carbon atoms, more preferably 6 to 12 carbon atoms. In the embodiment of the paper water squeezing improver according to claim 2, wherein the monocarboxylic acid is at least a saturated monocarboxylic acid having 6 to 12 carbon atoms and an unsaturated monocarboxylic acid having 18 carbon atoms. 60% by weight, preferably at least 80% by weight, more preferably 6 to 12 carbon saturated monocalcium Unsaturated monocarboxylic acids emissions acids and carbon 18 is only.

  The saturated monocarboxylic acid having 6 to 12 carbon atoms may be either a linear saturated monocarboxylic acid having 6 to 12 carbon atoms or a saturated monocarboxylic acid having a branched chain. By reacting with a polyalkylene polyamine, an amide type Any derivative such as an ester of a saturated monocarboxylic acid having 6 to 12 carbon atoms capable of forming a compound may be used. Of these various saturated monocarboxylic acids, caproic acid, caprylic acid, capric acid, and lauric acid are particularly preferable. These may be used alone or in combination of two or more.

Examples of the unsaturated monocarboxylic acid having 18 carbon atoms include oleic acid, linoleic acid, and linolenic acid. Of these, oleic acid is preferred.

    The reaction ratio of polyalkylene polyamines to monocarboxylic acids is such that the reaction amount of monocarboxylic acids is 0.3 to 0.8 equivalent to one amino group of polyalkylene polyamines. When the amount is less than 0.3 equivalent, the water squeezing effect is not sufficient, and when it exceeds 0.8 equivalent, the fixability to the pulp is deteriorated and the water squeezing effect may not be sufficient. .

A part of the monocarboxylic acid in the amide compound obtained by the reaction of the polyalkylenepolyamines of the present invention and the monocarboxylic acid can be replaced with a dibasic carboxylic acid.

The dibasic carboxylic acids are two dibasic carboxylic acids and / or derivatives thereof in the molecule as long as they can form amide compounds by reacting with polyalkylene polyamines. Examples of the derivatives include monoesters, diesters, and acid anhydrides of these dibasic carboxylic acids. 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. Moreover, as monoester and diester of dibasic carboxylic acid, Preferably it is C1-C5, Most preferably, C1-C3 lower alcohol (methyl, ethyl, propyl) ester can be mentioned. 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 include adipic acid, glutaric acid dimethyl ester, and adipic acid dimethyl ester. The above dibasic carboxylic acids can be used alone or in combination of two or more.

  The molar ratio of monocarboxylic acids to dibasic carboxylic acids is monocarboxylic acids / dibasic carboxylic acids = 100/0 to 60/40. When the proportion of monocarboxylic acids is less than 60%, sufficient water squeezing is possible. I can't get it.

The reaction between polyalkylene polyamines and monocarboxylic acids and the reaction between polyalkylene polyamines, monocarboxylic acids and dibasic carboxylic acids are 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 limitation on the method of mixing the polyalkylene polyamines with the monocarboxylic acids and the dibasic carboxylic acids to be used as necessary during the reaction. Usually, the polyalkylene polyamines are mixed with the dibasic carboxylic acids and the monocarboxylic acids. A method in which the reaction is smoothly carried out by gradually adding them and a method in which the reaction is smoothly carried out by gradually adding monocarboxylic acids to the reaction product of the dibasic carboxylic acid and the polyalkylene polyamine are preferred. A catalyst for the amidation reaction is not particularly required. However, as the catalyst for the amidation reaction, sulfonic acids such as sulfuric acid, benzenesulfonic acid and paratoluenesulfonic acid, or a catalyst usually used for the amidation reaction are used. May be. The amount used is usually 0.005 to 0.1 mol, preferably 0.01 to 0.05 mol, per 1 mol of polyalkylene polyamines.

Examples of the epihalohydrin used in the present invention include epichlorohydrin, epibromohydrin, etc. Among them, epichlorohydrin is preferable.

The amount of epihalohydrin used in the present invention is 0.4 to 1.2 equivalents relative to the active hydrogen of the remaining amino group of the amide compound. When the molar amount of epihalohydrin is less than 0.4 equivalent, the effect of improving water squeezing is insufficient, and when the amount exceeds 1.2 equivalents, not only does the effect of improving water squeezing reach a peak, but also low molecules in the CAE resin. There may be a disadvantage that the content of the organic halogen compound is increased.

The residual amino group in the present invention is obtained by measuring and calculating the amine value of an amino compound.
Residual amino group = amine value = (V × F × 0.5 × 56.1) / S
However, V: 1/2 titration of normal hydrochloric acid in methanol (cc)
F: 1/2 titer of normal hydrochloric acid methanol solution S: solid content of collected sample (g)

In the present invention, as the acrylamide polymer, at least (meth) acrylamide (meaning at least one kind of methacrylamide and acrylamide, hereinafter “(meth)” is used according to this) as an acrylamide is a polymerization component. And a copolymer of acrylamides and a cationic monomer, or a copolymer of acrylamides, a cationic monomer and an anionic monomer.

Examples of the cationic monomer include N, N-dialkylaminoalkyl (meth) acrylate and N, N-dialkylaminoalkyl (meth) acrylamide. Examples of N, N-dialkylaminoalkyl (meth) acrylate include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth) acrylate. Examples of N, N-dialkylaminoalkyl (meth) acrylamide include N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) Acrylamide etc. are mentioned, These can be used individually or in mixture of 2 or more types, respectively.

Further, the cationic monomer may be an acid chloride by an organic acid or an inorganic acid, a partial by a quaternizing agent, or a complete quaternized compound. The quaternization reaction can be performed on the monomer before polymerization, and can also be performed on a copolymer obtained by polymerization. As the quaternizing agent, alkyl halide, benzyl halide, glycidyl ether compound, dimethyl sulfate, epichlorohydrin, alkylene oxide, monochloroacetic acid, 3-chloro-2-hydroxypropyltrimethylammonium chloride, glycidyltrimethylammonium chloride, etc. are used. be able to.

Examples of the anionic monomer include monomers having a carboxylic acid group such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride, and salts thereof. (In the case of polyvalent carboxylic acid monomers, a part or all of them are salts), styrene sulfonic acid, (meth) allyl sulfonic acid, vinyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meta ) Sulfoethyl acrylate, sulfopropyl (meth) acrylate, sulfate of hydroxyethyl (meth) acrylate, sulfate of hydroxypropyl (meth) acrylate, sulfate of polyoxyalkylene (meth) acrylate, polyoxyethylene Alkylpropenyl ether sulfate Monomers having a sulfonic acid group such as sodium and alkali metal salts and ammonium salts such as sodium and potassium, acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, acid phosphooxyethylene glycol (meth) Monomers having a phosphonic acid group such as acrylate, alkali metal salts such as sodium and potassium, and ammonium salts thereof can be used, and these can be used alone or in combination of at least two or more. Among these, monomers having carboxylic acid groups and salts thereof (in the case of polyvalent carboxylic acid monomers, part or all of which are salts), monomers having sulfonic acid groups, and alkali metal salts such as sodium and potassium, Preference is given to using ammonium salts.

The ratio of the cation equivalent to the anion equivalent in the cationic and / or amphoteric acrylamide polymer (B) obtained by polymerizing a monomer containing at least acrylamides is preferably 100/0 to 40/60. When the ratio of the anion equivalent exceeds 60%, when mixed with the CAE resin (A) of the present invention, the viscosity greatly increases and handling may be difficult.

  The weight ratio of the CAE resin (A) of the present invention to the cationic and / or amphoteric acrylamide polymer (B) is such that the solid content weight ratio of the CAE resin (A) to the acrylamide polymer (B) is (A) :( B) = 99: 1 to 60:40, preferably (A) :( B) = 99: 1 to 80:20. If the proportion of the component (A) is less than 60%, a sufficient water squeezing effect may not be obtained.

As the water squeezing improver for paper containing the CAE resin (A) of the present invention and the acrylamide polymer (B), it is used for paper in which the acrylamide polymer (B) is mixed in advance when the CAE resin (A) is produced. It can also be set as a water squeezing improver, and can also be made into a paper squeezing improver mixed with an acrylamide polymer (B) after the production of the CAE resin (A).

The water squeezing improver of the present invention preferably has a standard bulk improvement of less than 0.02 g / cm ³ . When the standard bulk improvement is 0.02 g / cm ³ or more, the paper strength may be reduced.

The water squeezing improver of the present invention can be dispersed by a conventionally known method as required. As a conventionally known dispersion method, it can be dispersed by phase inversion emulsification, addition of a surfactant or inorganic salt, phase inversion emulsification after adding a surfactant or inorganic salt, 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.

  As the surfactant, a conventionally known surfactant can be used, and examples thereof include a nonionic surfactant in which an oxyalkylene group is added to a higher alcohol or a higher fatty acid. Examples of inorganic salts include sodium and calcium hydrochlorides, sulfates and carbonates. These may be used individually by 1 type, and may use 2 or more types together.

The paper squeezing improver of the present invention is added to a paper stock (pulp slurry), and a paper is obtained by making paper. Except for using the water squeezing improver for paper of the present invention, the same conditions as those for a general paper or paperboard production method can be employed.

The water squeezing improver for paper of the present invention may be usually added at a usage rate of 0.005% to 0.3% in solid content with respect to the pulp solid content. If it is less than 0.005%, a sufficient squeezing effect may not be obtained, and if it exceeds 0.3%, the strength may decrease.

Thus, when the obtained water squeezing improver of the present invention is added to a pulp slurry, it exhibits an excellent squeezing effect without affecting the strength of the paper.

  Although it does not restrict | limit especially as paper containing the water squeezing improvement agent for papers of this invention, Various paper and paperboard are mentioned. 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 Coated paper such as coated paper, wrapping paper such as kraft paper, pure white roll paper, tissue paper, toilet paper, towel paper, household paper such as kitchen paper, other notebook paper, book paper, various printing paper, newspaper paper, etc. Examples include various paper (paper), paperboard for paper containers such as Manila balls, white balls and chip balls, and paperboard such as liners 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.

  Paper containing the water squeezing improver for paper of the present invention is a high yield of bleached or unbleached bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, groundwood pulp, mechanical pulp or thermomechanical pulp. Waste paper pulp such as pulp, newspaper waste paper, magazine waste paper, cardboard 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 the paper of the present invention, additives such as a filler, a sizing agent, a dry paper strength improver, a wet paper strength improver, a yield improver, a bulking agent, a paper thickness improver, an opacifier, and a drainage improver Alternatively, it 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. These can be mixed with the paper water squeezing improver 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.

Sizing agents include fatty acid soap sizing agents such as sodium stearate, rosin, reinforced rosin, and rosin ester sizing agents, aqueous emulsions of alkenyl succinic anhydride, aqueous emulsions of 2-oxetanone, aqueous emulsions of paraffin wax, Examples thereof include a cationic sizing agent obtained by the reaction of a carboxylic acid and a polyvalent amine, an aqueous emulsion of a reaction product of an aliphatic oxyacid and an aliphatic amine or an aliphatic alcohol, and a cationic styrene sizing agent. 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 or 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 ban earth before adding the water squeezing improver for papers of this invention, after adding, or adding simultaneously.

  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.

Synthesis example 1
401.22 g of water, 136.61 g (39.79 mol%) of 50% aqueous acrylamide solution, 40.58 g (4.50 mol%) of 76% acryloyloxyethyldimethylbenzylammonium chloride aqueous solution as a cationic monomer, 1% N, N A mixture of 4.84 g (0.013 mol%) of 5'-methylenebisacrylamide aqueous solution and 19.10 g (0.250 mol%) of 5% sodium methallylsulfonate aqueous solution is adjusted to pH 4.0 with 20% aqueous sulfuric acid solution. . Next, the temperature was raised to 65 ° C. under introduction of nitrogen gas, and 6.64 g of 5% ammonium persulfate aqueous solution was added to initiate the reaction. Subsequently, 135.39 g of water separately charged at 85 ° C., 181.43 g (52.847 mol%) of a 50% aqueous acrylamide solution, and 7.85 g (2.50 mol) of itaconic acid as an anionic monomer were prepared. %) A monomer aqueous solution consisting of 7.64 g (0.10 mol%) of a 5% sodium methallylsulfonate aqueous solution was added dropwise over 30 minutes using a dropping funnel. After completion of the dropwise addition, the mixture was reacted at a reaction temperature of 90 ° C. for 2 hours to obtain an acrylamide polymer having a solid content of 20.6% and a viscosity (25 ° C., using Brookfield rotary viscometer) of 7400 mP · s.

Synthesis Examples 2-4
An acrylamide polymer was obtained in the same manner as in Synthesis Example 1 except that the types and amounts of the cationic monomer and the anionic monomer in Synthesis Example 1 were changed to those shown in Table 1.

In Table 1, (Note 1) DABz: N-benzyl-N, N-dimethyl- (2-acryloyloxy) ethylammonium chloride, (Note 2) DM: N, N-dimethylaminoethyl methacrylate.

Synthesis Example 5 (Acrylamide polymer of Production Example 2 of JP2008-179910)
A reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and two dropping funnels was charged with 350 g of ion-exchanged water, and then in one dropping funnel, a monomer solution (pH adjusted to 3) ( 179 g of acrylamide, 11 g of 62.5% sulfuric acid, 12.8 g of 80% aqueous acrylic acid solution, 2.3 g of sodium methallylsulfonate, 22.4 g of dimethylaminoethyl methacrylate, 2.8 g of dimethylacrylamide and 340 g of ion-exchanged water ) And another dropping funnel were charged with a polymerization initiator solution (ammonium persulfate 0.3 g, ion-exchanged water 100 g). Next, after removing oxygen in the reaction system through a nitrogen gas introduction tube, the reaction system is heated to 90 ° C., and the monomer solution and the polymerization initiator solution are dropped into the reaction system from the dropping funnels over about 3 hours. did. After completion of the dropwise addition, a polymerization initiator solution (ammonium persulfate 0.45 g, ion-exchanged water 10 g) was further charged from the other dropping funnel, and the reaction system was kept warm for 1 hour to complete the polymerization reaction. Subsequently, 80 g of ion-exchanged water was added to obtain an acrylamide polymer having a solid content concentration of 20.4% by weight and a viscosity of 5400 mPa · s.

Example 1
In a 1 liter four-necked round bottom flask equipped with a thermometer, a condenser, a stirrer, and a nitrogen inlet tube, 235.4 g of tetraethylenepentamine (amine number 1320 1.11 mol) and 620.4 g of lauric acid (3 .10 mol) was added, the temperature was raised to 170 ° C., and the reaction was carried out for 7 hours while removing the generated water. After charging 50.0 g of this amide compound, 2.5 g of isopropyl alcohol, and 242.5 g of water into a 1000 ml four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, the temperature was raised to 80 ° C., Stir for 1 hour. 11.3 g of epichlorohydrin (0.82 equivalents relative to the remaining amino group of 0.12 mol) was added, reacted at 80 ° C. for 4 hours, then cooled and made of a 20% solids CAE resin paper A water squeezing improver was obtained.

Examples 2-8, Comparative Examples 1-4
It consists of CAE resin like Example 1 except having replaced the kind of monocarboxylic acid of the said Example 1, the ratio of monocarboxylic acid and amine, and the reaction equivalent of epichlorohydrin into what was shown in Table 2. A water squeezing improver for paper was obtained.

In Table 2, (Note 1): Numbers in parentheses are reaction equivalents of saturated monocarboxylic acid having 6 to 12 carbon atoms to one amino group of polyalkylene polyamines,
(Note 2): Monocarboxylic acid composition of coconut fatty acid: C8 / C10 / C12 / C14 / C16 / C18 = 6/6/50/18/10/2 (% by weight). Here, C8 is caprylic acid which is a saturated monocarboxylic acid having 8 carbon atoms, C10 is capric acid which is a saturated monocarboxylic acid having 10 carbon atoms, C12 is lauric acid which is a saturated monocarboxylic acid having 12 carbon atoms, C14 is Myristic acid which is a saturated monocarboxylic acid having 14 carbon atoms, C16 is palmitic acid which is a saturated monocarboxylic acid having 16 carbon atoms, and C18 is stearic acid which is a saturated monocarboxylic acid having 18 carbon atoms.
It is shown that.

Example 10
In a 1 liter four-necked round bottom flask equipped with a thermometer, a condenser, a stirrer, and a nitrogen inlet tube, 321 g of tetraethylenepentamine (amine value 1320 1.51 mol) and 109.4 g of adipic acid (0.75) were added. The reaction mixture was heated to 170 ° C. and reacted for 2 hours while removing generated water, and further 437.5 g (3.02 mol) of caprylic acid was added, followed by further reaction at 170 ° C. for 5 hours. After charging 50.0 g of this amide compound, 2.5 g of isopropyl alcohol, and 248.8 g of water into a 500 ml four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, the temperature was raised to 50 ° C. Stir for 1 hour. Epichlorohydrin (13.9 g) (0.8 equivalents relative to the remaining amino group) was added and reacted at 50 ° C. for 3 hours and further at 80 ° C. for 3 hours, and then cooled to a solid content of 20%. A water squeezing improver for paper was obtained.

Example 11, Comparative Example 5
It consists of CAE resin like Example 1 except having changed the kind of monocarboxylic acid of the said Example 10, the ratio of monocarboxylic acid and amine, and the reaction equivalent of epichlorohydrin into what was shown in Table 3. A water squeezing improver for paper was obtained.

(Note 1) The numbers in parentheses in Table 3 are reaction equivalents of carboxylic acid to one amino group of polyalkylene polyamines.

Example 12
By mixing 20 g of the acrylamide polymer obtained in Synthesis Example 1 with 80 g of the paper squeezing improver made of the CAE resin obtained in Example 3, and mixing with a stirrer for 1 hour, the CAE resin and the acrylamide system are mixed. A water squeezing improver for paper having a solid content ratio of 8/2 and a solid content of 20% was obtained.

Examples 12 to 21, Comparative Example 5
Except that the water squeezing improver for paper comprising the CAE resin obtained in Example 3 of Example 12 and the type and ratio of the acrylamide polymer obtained in Synthesis Example 1 were changed to those shown in Table 4. In the same manner as in Example 12, a water squeezing improver for paper was obtained.

Comparative Example 6 (Example 3 of JP 61-252400 A)
In a 0.5 liter four-necked round bottom flask equipped with a thermometer, a condenser, a stirrer, and a nitrogen inlet tube, 170 g (0.62 mol) of oleic acid was melted, and 43.8 g of triethylenetetramine (amine number 1537). 0.3 mol) is added with stirring. The temperature was raised to 190 ° C. under nitrogen to remove all volatile substances and reacted for 6 hours to obtain a basic amide. 201.6 g of this basic amide is heated to 120 ° C., 70 g of water and then 16 g of formic acid are added, and the mixture is stirred at 110 ° C. for 1 hour. In succession, 1182 g of water preheated to about 95 ° C. are added, and the purified emulsion is stirred for 1 hour under gentle stirring and cooled to 40 ° C. Further, a mixed solution of 1.2 g of sodium chloride and 92 g of water was added to obtain a CAE resin.

Comparative Example 7 (Example 4 of JP 2000-273792 A)
31.6 g of diethylenetriamine, 161.6 g of a mixture of stearic acid and lauric acid at a molar ratio of 1/1, and 0.5 g of paratoluenesulfonic acid as a catalyst were attached to a dehydrating tube, a thermometer, and a nitrogen gas blowing tube. The product was taken into a multi-necked flask, gradually heated with a mantle heater, and dehydrated at 200 ° C. for 5 hours while blowing nitrogen gas to obtain an intermediate compound. After taking 138.0 g of this compound into a four-necked flask equipped with a condenser, a thermometer and a dropping funnel, and heating to 90 ° C. with a mantle heater, 23.1 g of epichlorohydrin (molar ratio 1/1) The solution was added dropwise while maintaining the temperature. After completion of dropping, the reaction was carried out for 4 hours while maintaining the temperature at 90 ° C. to obtain a CAE resin.

Comparative Example 8 (Example 2 of JP 59-30997)
After adding 146 g (1.0 mol) of triethylenetetramine to 88 g (0.6 mol) of adipic acid and reacting at 150 ° C. for 2 hours, 227 g (0.8 mol) of stearic acid was added, and an additional 4 at 150 ° C. The reaction was carried out for a period of time, and water was distilled off. To the obtained amide compound, 1500 g of water was gradually added to obtain an emulsion, and then 199 g (1.08 mol) of epichlorohydrin was added and reacted at 90 ° C. for 8 hours. Next, 2750 g of water was added to obtain a CAE resin having a solid content of 10%.

Comparative Example 9 (CAE resin of Production Example 1 of JP2008-179910)
After charging 1095.2 g of stearic acid into a reaction vessel equipped with a stirrer, dehydration tube, cooling tube, thermometer and nitrogen gas introduction tube and heating and melting it, 166.6 g of triethylenetetramine was added to the reaction system under a nitrogen atmosphere. The temperature was raised to 180 ° C. Next, the reaction system was maintained at 180 ° C. while removing the reaction product water, and after 3 hours, it was confirmed that generation of the reaction product water was not observed, and then cooled to room temperature to obtain an amide compound. 100 g of this amide compound was sampled and charged into the same reaction vessel, and further 20 g of isopropyl alcohol was added to keep the reaction system at 80 ° C. Next, 1247 g of ion-exchanged water at 80 ° C. is added, and the reaction system is vigorously stirred to prepare a suspension solution. Then, 52.7 g of epichlorohydrin is added, and the reaction system is kept at 80 ° C. for 4 hours. By holding, CAE resin was obtained. To the same reaction system, 24.0 g of a nonionic surfactant (trade name: Epan 720, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added and stirred, and the resulting solution was emulsified using a high-pressure emulsifier to obtain a CAE resin. Got.

Example 22
(Evaluation of paper quality)
After adding 1.0% sulfuric acid band to the pulp slurry with LBKP adjusted to Canadian Standard Freeness 400 and having a concentration of 2.4%, the paper squeezing improver of Example 1 was added to the pulp. Then, cationized starch (manufactured by Nippon NSC Co., Ltd., CATO304, 0.8% based on pulp) was added to the pulp. After diluting this pulp slurry with tap water adjusted to pH 7.5 to a concentration of 0.6%, an organic cationic retention agent (manufactured by Seiko PMC Co., Ltd., 150 ppm with respect to RD7153 pulp) was added and stirred. After that, paper was made with a square sheet machine to obtain handmade paper with a basis weight of 80 g / m ² . The obtained handmade paper was conditioned at 23 ° C. and RH 50% for 24 hours, and then the internal strength was measured by the following method. In addition, the addition rate of the said chemical | medical agent is a solid content weight ratio with respect to a pulp dry weight. Table 5 shows the measurement results.
Internal strength: TAPPINo. Based on 54-93

(Evaluation of water extraction)
After adding 1.0% sulfuric acid band to the pulp slurry with LBKP adjusted to Canadian Standard Freeness 400 and having a concentration of 2.4%, the paper squeezing improver of Example 1 was added to the pulp. Then, cationized starch (manufactured by Nippon NSC Co., Ltd., CATO304, 0.8% based on pulp) was added to the pulp. After diluting this pulp slurry with tap water adjusted to pH 7.5 to a concentration of 0.6%, an organic cationic retention agent (manufactured by Seiko PMC Co., Ltd., 150 ppm with respect to RD7153 pulp) was added and stirred. Then, the paper was made to have a basis weight of 160 g / m ² and the weight W1 after the couch was measured. The paper after this couch was pressed for 3 minutes at 4.2 kgf / cm ² using a flat press machine, and the weight W2 was measured. The wet paper was dried at 100 ° C. for 120 seconds using a drum dryer, and then the weight W0 was measured.

Using the following formulas (1) and (2), the difference in moisture content before and after pressing (water content before pressing−water content after pressing) was calculated. It shows that it is excellent in water squeezing, so that this value is large.
Moisture ratio before pressing: (W1-W0) / W1 * 100 (Formula 1)
Moisture content after pressing: (W2-W0) / W2 * 100 (Formula 2)

(Standard bulk improvement)
LBKP is disaggregated in a constant amount at 25 ± 3 ° C. in a beater and beaten to 460 ± 10 ml with Canadian standard freeness (JISP8121) to obtain an LBKP slurry having a pulp concentration of 1.0% by weight. The pulp slurry was weighed so that the basis weight of the LBKP content of the sheet after papermaking was 80 ± 0.5 g / m ^2, and after adjusting the pH to 4.5 with aluminum sulfate, A 1.0 wt% ethanol solution is added to 0.5 parts by weight (pure content) with respect to 100 parts by weight of pulp, and a wet sheet is obtained by making paper with a 150 mesh wire (area 200 cm ² ) using a round tappi paper machine. . ^Two filter papers (diameter 185 mm) having a basis weight of 320 ± 20 g / m ² are stacked on the wet sheet, and a coach plate is further stacked thereon to perform coaching, and then the wet sheet is taken out. Next, the wet sheet is sandwiched between the above two filter papers and pressed at a pressure of 340 ± 10 kPa for 5 minutes. After pressing, only the sheet is dried at 105 ± 3 ° C. for 2 minutes using a mirror dryer. The dried sheet is conditioned for 5 hours at 20 ± 1 ° C. and humidity 65 ± 2%.
The weight of the conditioned sheet is measured, and the basis weight (g / m ² ) is determined by the following calculation formula (1).
Basis weight (g / m ² ) = sheet weight / 0.02 (1)
Next, the thickness of the conditioned sheet is measured at 10 points with a pressure of 54 ± 5 kPa using a paper micrometer, and the average value obtained is defined as the thickness (mm).
The tension d (g / cm ³ ) is obtained from the basis weight and thickness obtained above by the following formula (2).
d = (basis weight) / (thickness) × 0.001 (2)
Also, squeezing capability without the addition of compounds to be the aqueous enhancer similarly the sheet is prepared, the bulk density was determined in the same manner and d _0.
Bulk density was determined by the d, from d _0, we obtain the standard bulk improvement of the following equation (3).
Standard bulk improvement (g / cm ³ ) = d ₀ −d (3).

Examples 23-32, Comparative Examples 10-13, 15-22
Evaluation of paper quality and water squeezing were performed in the same manner as in Example 22 except that the water squeezing improver used in Example 22 was changed to that shown in Table 5. The results are shown in Tables 5 and 6.

Examples 33-42 and Comparative Example 14
Evaluation of paper quality and evaluation of water squeezing were performed in the same manner as in Example 22 except that the water squeezing improver used in Example 22 was changed to that shown in Table 5. The results are shown in Tables 5 and 6. In addition, regarding the standard bulk improvement degree, these water squeezing improvers mixed with acrylamide polymers cannot be uniformly dissolved in ethanol, and some of them are precipitated as a lump, so that the water squeezing improvers Was added to the pulp as an aqueous solution instead of the 1.0 wt% ethanol solution, and the standard bulk improvement was measured.

Comparative Example 24
After changing the water squeezing improver used in Example 22 to the water squeezing improver of Comparative Example 10, and after adding the water squeezing improver, the acrylamide polymer of Synthesis Example 4 was 0.05% with respect to the pulp. Except for the addition, the paper quality and water squeezing were evaluated in the same manner as in Example 22. The results are shown in Table 6.

In Table 6, (Note 1): Compound used in Example 1-5 of Japanese Patent No. 3387033,
(Note 2): Compound used in Example 1-9 of Japanese Patent No. 3387033.

  From the result of Table 4, Examples 1-42 of the water squeezing improver for paper of this invention are 0.5% of difference of the moisture content before and behind a press compared with the comparative example 21 which does not add the squeezing improver. As described above, even in Comparative Example 1 in which the internal strength is the greatest decrease, it is a decrease of 2.5% or less with respect to the blank, and there is no adverse effect on the strength. On the other hand, with respect to the water squeezing improver for paper of the present invention, the amount of epihalohydrin or the carbon chain length of monocarboxylic acids, or the mixing ratio of CAE resin and acrylamide polymer deviates from the scope of the present invention. (Excluding Comparative Example 12) and Comparative Examples 19 and 20 which are compounds described in Examples of Japanese Patent No. 3387033, the difference in moisture content before and after pressing is 0.5% or less, and the water squeezing improvement for paper of the present invention is improved. It turns out that the water-squeezing improvement effect of Examples 1-42 of an agent is remarkably higher than that. In Comparative Example 12, the difference in moisture content before and after pressing is 0.8%, but the degree of decrease in internal strength is about 12% lower than that in Comparative Example 1, and the negative effect on paper strength is great. I understand that.

Claims (3)

It is a reaction product of an amide compound obtained by the reaction of polyalkylene polyamines and monocarboxylic acids and epihalohydrin, and the monocarboxylic acids are saturated monocarboxylic acids having 6 to 12 carbon atoms and unsaturated monocarboxylic acids having 18 carbon atoms. A reactant (A) component in which the amount of epihalohydrin is 0.4 to 1.2 equivalents with respect to the active hydrogen in the amount of residual amino groups in the amide compound, cationic and / or It contains an amphoteric acrylamide polymer (B) component, and the solid content weight ratio of the component (A) to the component (B) is (A) :( B) = 99: 1 to 60:40. Water squeezing improver for paper. The ratio of the acrylamide polymer (B) component of the cation equivalent and an anion equivalent, aqueous improver squeezing capability for paper according to claim 1, characterized in that the anion equivalent / cation equivalent = 0 / 100-60 / 40. The water squeezing improver according to claim 1 or 2 , wherein the standard bulk improvement degree is smaller than 0.02 g / cm ³ .