JP4928355B2 - Paper quality improver - Google Patents

Description

  The present invention relates to a paper quality improver for papermaking.

  In recent years, high quality paper with excellent whiteness, opacity, printability, volume, etc. has been demanded, while lightweight paper with low pulp usage is desired for environmental considerations. . In order to solve these problems by the bulkiness of paper, various methods for improving the bulk have been attempted so far, and one of them is the use of a paper quality improver such as a bulking agent.

  For example, Patent Document 1 discloses a monoamine, for the purpose of obtaining a coated paper having a small increase in density even after pressure treatment, high ink absorbability, and excellent color development and water resistance of an ink image. Pulp fiber is a compound obtained by reacting an epihalohydrin or glycidyl ether and / or a compound derived therefrom with a compound having a residue obtained by removing active hydrogen from a polyamine, polyalkyleneimine or a derivative thereof and an acyl group. It is disclosed that low density paper that is attached and imparted with bulkiness is used as a base paper.

  Further, Patent Document 2 discloses a residue obtained by removing active hydrogen from a monoamine, polyamine, polyalkyleneimine or a derivative thereof for the purpose of producing a paper product with high opacity without reducing the strength and size of the paper. A paper opacifying agent characterized by a compound obtained by reacting a compound having a group and an acyl group with epihalohydrin or glycidyl ether and / or a compound derived therefrom is disclosed. And as the manufacture example, tetraethylenepentamine and stearic acid (molar ratio 1/2) are reacted to obtain an intermediate compound, and the intermediate compound is further heated to 90 ° C. to produce epichlorohydrin (molar ratio 1). / 2) is disclosed as a paper opacifier component obtained by dripping.

  Patent Document 3 discloses an aqueous emulsion system in which a polymer compound obtained by reacting a predetermined amide compound with an epihalohydrin in the presence of a cationic polymer and / or an amphoteric polymer is highly concentrated. Is used as an internal additive for paper.

  Patent Document 4 discloses a basic fatty acid amide prepared from a specific fatty acid mixture and a specific amine and quaternized with epichlorohydrin in order to improve the effect of a conventional sizing agent. It is disclosed to use a paper sizing agent comprising an aqueous formulation of the kind and an electrolyte.

JP 2005-188001 A JP 2000-273792 A JP 2006-104609 A Japanese Examined Patent Publication No. 63-30439

  One of the problems in bulky paper production by the bulking agent is that the liquid absorption amount of the coating liquid tends to increase in the step of applying the coating liquid to the surface of the paper immediately after the dryer, such as passing through a predryer. This is thought to be due to an increase in the porosity of the paper when a bulking agent is used. This increase in the amount of liquid absorption increases the drying load after coating, and the papermaking speed cannot be sufficiently increased throughout the production of bulky paper (reduction in papermaking speed). In particular, as a process of applying the coating liquid, liquid absorption in the size press process is a problem. The phenomenon of increasing the liquid absorption amount is noticeable in a two-roll size press where it is difficult to control liquid absorption because of the structure in which paper is passed through the coating liquid.

  An object of this invention is to provide the paper quality improvement agent which can suppress the liquid absorption of a coating liquid, and can obtain a bulky paper, and the manufacturing method of paper using the same.

In the present invention, epichlorohydrin (c) is added to an amide compound obtained by reacting an amine compound (a) containing a polyalkylene polyamine as a main component and a saturated fatty acid (b) having 12 to 40 carbon atoms. A paper quality improver comprising a reaction product obtained by further reaction;
Equivalent amide group (FA) (mgKOH / g) of the reaction product, equivalent of amino group (ToAmV) (mgKOH / g), equivalent of chloride ion (Cl) (mgKOH / g), total chlorine The equivalent amount (TCl) (mgKOH / g) of the reaction product is 0.7 ≦ α <1 and −0.9α + 0.9 ≦ β <− when FA / (ToAmV + Cl + FA) is α and TCl / (ToAmV + Cl + FA) is β. The present invention relates to a paper quality improver satisfying 0.9α + 1.29.

In addition, the present invention provides an epichlorohydrin (c) to an amide compound obtained by reacting an amine compound (a) containing a polyalkylene polyamine as a main component and a saturated fatty acid (b) having 12 to 40 carbon atoms. A paper quality improver comprising an aqueous dispersion containing a reaction product obtained by further reacting with
Equivalent amide group (FA) (mgKOH / g) of the reaction product, equivalent of amino group (ToAmV) (mgKOH / g), equivalent of chloride ion (Cl) (mgKOH / g), total chlorine The equivalent amount (TCl) (mgKOH / g) of the reaction product is 0.7 ≦ α <1 and −0.9α + 0.9 ≦ β <− when FA / (ToAmV + Cl + FA) is α and TCl / (ToAmV + Cl + FA) is β. 0.9α + 1.29 is satisfied,
The present invention relates to a paper quality improver in which the average particle size of dispersed particles in the aqueous dispersion is 0.1 to 20 μm.

  The present invention also relates to a paper manufacturing method having a size press step, wherein the paper quality improver of the present invention is added in a step prior to the size press step.

  ADVANTAGE OF THE INVENTION According to this invention, the paper quality improvement agent which can suppress the liquid absorption of the coating liquid at the time of papermaking, and can obtain bulky paper, and the manufacturing method of paper using this agent are provided. By using the paper quality improver of the present invention, the liquid absorption of the coating liquid is suppressed, so that the papermaking speed can be increased and the productivity of bulky paper can be improved as compared with the conventional art.

  The paper quality improver of the present invention is added to the pulp slurry at the time of paper making, and by making paper, the liquid absorption of the coating liquid is suppressed in the step of applying the coating liquid immediately after the dryer, and the resulting paper is improved in bulk and size. Is. Hereinafter, the amine compound (a), specific fatty acids (b), and epichlorohydrin (c) used for obtaining the paper quality improver of the present invention will be described.

<Amine compound (a)>
In order to obtain the paper quality improver of the present invention, an amine compound containing polyalkylene polyamine as a main component is used. Among the polyalkylene polyamines, polyethylene polyamine and polyprolene polyamine are preferable.

  Examples of the polyalkylene polyamine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and further dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, and the like. These may be used alone or as a mixture of two or more. Of these, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine are preferable in terms of high bulk performance and availability of raw materials industrially at low cost.

<Fatty acids (b)>
The saturated fatty acids (b) having 12 to 40 carbon atoms (hereinafter sometimes referred to as fatty acids (b)) used for obtaining the paper quality improver of the present invention include saturated fatty acids and saturated fatty acid esters. . The carbon number of the fatty acid in the fatty acids (b) is preferably 12-30, and more preferably 16-24. Moreover, although a linear or branched chain may be sufficient, a linear chain is preferable. For example, palmitic acid, stearic acid, behenic acid and the like can be mentioned. You may contain an unsaturated fatty acid in the range which has a saturated fatty acid as a main component and has the effect of this invention. The saturated fatty acid may be used alone or as a mixture of two or more. As the fatty acid mixture, naturally-derived fatty acids such as coconut oil fatty acids can also be used. Palmitic acid and stearic acid are preferable from the viewpoint of liquid absorbency of the coating liquid.

  Examples of saturated fatty acid esters include esters with monohydric alcohols (preferably methyl) such as methyl esters and ethyl esters, and esters with polyhydric alcohols such as glycerin. Examples of the saturated fatty acid of the saturated fatty acid ester include the aforementioned fatty acids. When the saturated fatty acid ester is reacted with the amine compound (a) as the fatty acid (b) to obtain an amide compound, alcohol is generated from the saturated fatty acid ester as a by-product. From the viewpoint of the storage stability of the paper quality improver of the present invention, the alcohol contained is preferably 5% by weight or less, more preferably 3% by weight or less in the paper quality improver. Therefore, when using an ester of a saturated fatty acid as the fatty acid (b), it is preferable to remove alcohol generated from the amide compound obtained by reacting with the amine compound (a). From the viewpoint of easy removal of alcohol, methyl esters are preferred as saturated fatty acid esters, and specific examples include methyl palmitate and methyl stearate.

  In the paper quality improver of the present invention, a size effect is manifested in the paper quality improver itself, and the size of the resulting paper can be improved, or the amount of the sizing agent used in combination can be reduced. For example, when an alkyl ketene dimer is used as a sizing agent internally added before the size press step, the amount added is preferably 0 to 0.05 parts by weight, more preferably 0 to 0.03 parts by weight with respect to 100 parts by weight of the pulp. But enough size performance can be obtained.

<Epichlorohydrin (c)>
As the epichlorohydrin (c) used for obtaining the paper quality improver of the present invention, commercial products such as industrial raw materials and reagents can be used.

<Paper quality improver>
The paper quality improver of the present invention is a reaction obtained by reacting epichlorohydrin (c) under predetermined conditions with an amide compound obtained by reacting the amine compound (a) with the saturated fatty acids (b). Consists of products.

  Reaction product amide group equivalent (FA) (mgKOH / g), amino group equivalent (ToAmV) (mgKOH / g), chloride ion equivalent (Cl) (mgKOH / g), and total chlorine When the equivalent weight (TCl) (mgKOH / g) is FA / (ToAmV + Cl + FA) is α and TCl / (ToAmV + Cl + FA) is β, the reaction products are 0.7 ≦ α <1 and −0.9α + 0.9 ≦ β <−0.9. In order to satisfy α + 1.29, preferably 0.73 ≦ α <0.90 and −0.9α + 0.90 ≦ β <−0.9α + 1.05, and more preferably 0.73 ≦ α <0.85 and −0.9α + 0.91. Epichlorohydrin (c) is reacted with the amide compound obtained by reacting the amine compound (a) with the saturated fatty acids (b) so as to satisfy ≦ β <−0.9α + 1.05.

  That is, in the present invention, epichlorohydrin (c) is added to an amide compound obtained by reacting an amine compound (a) containing polyalkylene polyamine as a main component and a saturated fatty acid (b) having 12 to 40 carbon atoms. The amide group equivalent (FA) (mgKOH / g), the amino group equivalent (ToAmV) (mgKOH / g) and the chloride ion equivalent (Cl ) (MgKOH / g) and total chlorine equivalent (TCl) (mgKOH / g) where FA / (ToAmV + Cl + FA) is α and TCl / (ToAmV + Cl + FA) is β, 0.7 ≦ α <1, -0.9α + 0 A method for producing a paper quality improver is provided which includes a step of obtaining a reaction product satisfying .9 ≦ β <−0.9α + 1.29.

  The form of the amino group after the reaction of the amine compound (a) is any structure of an unreacted amino group, a quaternary salt or hydrochloride, and an amide group, and the number of quaternary salts or hydrochlorides is chloride. Since it corresponds to the number of object ions, it corresponds to ToAmV, Cl, and FA, respectively. Therefore, the total amount of ToAmV + Cl + FA corresponds to the number of amino groups of the amine compound (a) whose main component is the polyalkylene polyamine of the raw material. Values for ToAmV, Cl and FA are according to the methods of the examples.

  Since FA corresponds to the number of alkyl groups in the saturated fatty acids (b) as a raw material, it can be adjusted by the amount of the saturated fatty acids, and FA increases as the number of saturated fatty acids increases.

  Since TCl corresponds to the number of chlorine in epichlorohydrin (c), it can be adjusted by the amount of epichlorohydrin, and increasing the epichlorohydrin increases TCl.

  Therefore, the values of α and β can be set to target values by adjusting the ratio of the raw materials during the reaction. α is an index of the degree of amidation of the amine compound (a), and β is an index of the ratio of epichlorohydrin to the amine compound (a). If α is less than 0.7, the liquid absorption suppressing effect of the coating liquid decreases. This is thought to be because the degree of hydrophobicity of the reaction product is reduced. Β is an index of alkylation and crosslinking of an amide compound by epichlorohydrin (c), and epichlorohydrin (c) reacts with an amino group that has not been amidated, and therefore α is an index of amidation. The preferred range varies depending on the value of. If β is less than −0.9α + 0.9, it is considered that the fixability of the reaction product to the pulp decreases. When β exceeds −0.9α + 1.29, impurities derived from epichlorohydrin (c) increase. The impurities may be removed after obtaining the reaction product, but the values of α and β are values before the removal.

  The reaction product (paper quality improver) according to the present invention preferably has a melting point of 50 ° C. or higher. If the melting point is 50 ° C. or higher, it becomes solid at room temperature and the effective component is almost 100%, which is preferable in terms of storage and transportation. The melting point of the reaction product is measured by the method described later using the measuring device of FIG. The paper quality improver comprising the reaction product of the present invention can be produced by a method including the steps (I) and (II) described below.

  A method for measuring the melting point will be described. The sample is melted at the lowest possible temperature and sucked up to about 10 mm into a capillary ("ME-18552" manufactured by Mettler (hard glass, length 76 mm, inner diameter 1.3 mm, wall thickness 0.2 mm)). Cool at 10 ° C. or lower for 24 hours or at least 2 hours to solidify the sample in the capillary. The capillary tube is attached to the apparatus shown in FIG. 1, and the temperature rise is started in a place where there is no vibration. The temperature is raised to about 10 ° C. before the expected melting point, and then the temperature is raised at a rate of 1 ° C. per minute. Read the temperature at which the sample began to rise up the capillary (one decimal place) and use it as the melting point. The bath solution uses water. The unit of the numerical values in FIG. 1 is mm.

<Process (I)>
Step (I) is a step of obtaining an amide compound by reacting an amine compound (a) with a saturated fatty acid having 12 to 40 carbon atoms (b) at 100 to 230 ° C. In view of the reaction rate of amidation, it is preferable to carry out the reaction until the acid value becomes 5 mgKOH / g or less.

  In step (I), the amounts of the amine compound (a) and the saturated fatty acids (b) having 12 to 40 carbon atoms are adjusted so as to satisfy the range of α.

<Process (II)>
Step (II) is a step of reacting the amide compound obtained in step (I) with epichlorohydrin (c) at 50 to 140 ° C. Epichlorohydrin (c) is preferably added dropwise to the amide compound and reacted so as to be within the above temperature range. This alkylates and / or bridges the amide compound. Step (II) includes a method in which epichlorohydrin (c) is added dropwise to a melt of amide compound or water added.

  In step (II), the amount of epichlorohydrin (c) is adjusted so as to satisfy the range of β.

<Process (III)>
When the reaction product is a solid, the method for producing a paper quality improver of the present invention preferably further includes the following step (III).
Process (III):
A step of forming the reaction product obtained in step (II) into a flaky product having an average major axis of 3 to 30 mm, an average minor axis of 1 to 15 mm, and an average thickness of 0.1 to 5 mm

  Step (III) is a step of converting the reaction product obtained in step (II) into a flaky product (flakes) that is easy to handle. Specifically, first, the reaction product obtained in the step (II) is formed into a plate shape in a molten state, and then solidified while being held below the melting point to obtain a plate-like reaction product. As a method of forming the reaction product into a plate shape in a molten state, for example, the reaction product obtained in step (II) is heated to a melting point or higher to obtain a molten state, and the molten liquid is discharged from a nozzle such as stainless steel. An example is a method of developing on a flat plate with a thickness suitable for subsequent pulverization or dispersion in water, and then cooling and solidifying by maintaining it below the melting point. The temperature of the flat plate such as stainless steel can be adjusted to adjust the thickness and the speed of solidification. Next, the solidified plate-like reaction product can be pulverized to a desired size with a flaker or the like to obtain a paper quality improver having a desired size. From the viewpoint of workability of addition and dispersibility in water by mixing with warm water, the average major axis of the flaky material is preferably 3 to 30 mm, and more preferably 5 to 25 mm. The average minor axis is preferably 1 to 15 mm, more preferably 2 to 10 mm. The average thickness is preferably 0.1 to 5 mm, more preferably 0.1 to 3 mm. Accordingly, the particles preferably have an average major axis of 3 to 30 mm, an average minor axis of 1 to 15 mm, and an average thickness of 0.1 to 5 mm, an average major axis of 5 to 25 mm, an average minor axis of 2 to 10 mm, and an average thickness of 0.1 to 3 mm. Is more preferable. The long diameter is the longest diameter of each particle, and the short diameter is the longest diameter orthogonal to the long diameter. The thickness is the longest diameter orthogonal to the major axis and the minor axis. The average major axis, the average minor axis, and the average thickness are average values obtained by measuring 100 particles.

  The reaction product obtained in the step (II) can be used as it is as a paper quality improver. Further, when the reaction product is a solid, it is preferable to form particles having an appropriate shape and size (powder, granules, flakes, pellets, etc.) from the viewpoint of workability and dispersibility in water. As a method for obtaining an appropriate shape and size, for example, a method of solidifying powder and granule once and then pulverizing with a pulverizer, a method of thinly extending and solidifying in a flaky shape, and then pulverizing with a pulverizer For example, there may be mentioned a method in which a liquid droplet is dropped on a flat plate in a liquid state and solidified. Among these, a flaky shape obtained by the step (III) is preferable.

<Process (IV)>
The method for producing a paper quality improver of the present invention may further include the following step (IV).
Process (IV):
A paper quality improver by dispersing the reaction product obtained in steps (I) and (II) or the flaky reaction product obtained in steps (I) to (III) in water having a temperature equal to or higher than its melting point. Of obtaining an aqueous dispersion of

  Step (IV) is a step of obtaining an aqueous dispersion containing the paper quality improver of the present invention in water from the reaction product obtained in step (II) or step (III). Here, the aqueous dispersion refers to an emulsion or suspension. Specifically, the paper quality improver obtained in step (II) or step (III) is mixed with water having a temperature equal to or higher than the melting point of the reaction product obtained in step (II) or step (III). A method of dispersing is mentioned. By dispersing in water at a temperature equal to or higher than the melting point, the paper quality improver can be dispersed in water as smaller particles, resulting in added workability, storage stability of the dispersion, and paper quality improver during pulp sheet production. Affinity to pulp can be improved. For mixing and dispersing, an emulsifier such as a line mixer, a homomixer, and a high-pressure homogenizer can be used. For example, in a laboratory scale, it is possible to use an emulsifier such as Robotics (made by Special Machine).

  From the viewpoint of storage stability and viscosity of the aqueous dispersion, the solid content in the aqueous dispersion is preferably 3 to 60% by weight, more preferably 5 to 55% by weight, and further 10 to 50% by weight. preferable.

  When obtaining the aqueous dispersion of the paper quality improver of the present invention, an emulsifier can be used in combination. Examples of the emulsifier include a cationic compound, an anionic compound, an amphoteric compound, and a nonionic compound, and a nonionic compound is preferable from the viewpoint of low foamability during paper production. Examples of the nonionic compound include a surfactant having an oxyethylene group and / or an oxypropylene group. It can be used by mixing with the paper quality improver obtained in step (II) or step (III). Further, it can be contained during the production of the aqueous dispersion in the step (IV).

  When the paper quality improver is an aqueous dispersion, a dispersion method that is usually performed can be adopted in addition to the step (IV). The reaction product may be dispersed alone, or it may be dispersed using an emulsifier or a dispersant as long as it does not adversely affect the performance. The average particle diameter (median diameter) of the dispersed particles (emulsified particles) in the aqueous dispersion is preferably from 0.1 to 20 μm, more preferably from 0.1 to 10 μm. If the average particle size is 0.1 μm or more, the yield is good and efficient, and if it is 20 μm or less, the performance is good.

<Manufacturing method of pulp sheet>
The paper quality improver of the present invention is added in any of the paper making processes, and may be added as it is, or may be added as a dispersion dispersed in water or the like as necessary.

  The paper quality improver of the present invention can be widely applied to pulp raw materials such as mechanical pulp such as thermomechanical pulp (TMP), virgin pulp such as chemical pulp such as LBKP, and waste paper pulp.

  The paper quality improver of the present invention is added in any step prior to the size press step. It is added before the process of forming a paper layer by draining a thin liquid of pulp raw material as it travels over the wire mesh. It is a disintegrator and beater such as a pulper and refiner, a mixing chest, a machine chest, and a head box. May be added to tanks such as water tanks and white water tanks, or pipes connected to these facilities, but it is desirable to add them to the pulp raw material uniformly, such as by adding refiners, mixing chests, machine chests, and head boxes. . It is preferable that the paper quality improver of the present invention is made into a paper as it is after being added to the pulp raw material and remains largely in the pulp sheet. The type of the paper machine is not particularly limited in order to exert the effect of the paper quality improver of the present invention. For example, the long net type, the circular net type, the short net type, the twin wire type, and the inclined wire type paper machine. Machine. Moreover, about a wire part, a gap former, a hybrid former, etc. are mentioned, for example.

  The pulp sheet production method using the paper quality improver of the present invention can be based on a known method, but from the viewpoint of workability, the paper quality improver of the present invention is dissolved or dispersed in water or an aqueous solvent. It is preferable to add to the pulp slurry and make paper in the form. In particular, it is preferable to carry out papermaking by dispersing the paper quality improver of the present invention in water having a temperature equal to or higher than its melting point and adding the dispersion to the pulp slurry. The addition amount of the paper quality improver of the present invention is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, based on 100 parts by weight of pulp, in terms of solid content, from the viewpoint of the paper quality improvement effect. More preferably 2 parts by weight or more. Moreover, 20 weight part or less is preferable from a viewpoint of hold | maintaining the original characteristic of a pulp sheet, 10 weight part or less is more preferable, and 2 weight part or less is still more preferable. Therefore, from the viewpoint of maintaining the paper quality improvement effect and the original properties of the pulp sheet, 0.05 to 20 parts by weight is preferable, 0.1 to 10 parts by weight is more preferable, and 0.2 to 2 parts per 100 parts by weight of pulp. Part by weight is more preferred. The paper quality improver solution or dispersion of the present invention is preferably added so as to have this ratio during papermaking.

  In the production of the pulp sheet in the present invention, a sizing agent, a filler, a yield improver, a drainage improver, a paper strength improver, and the like, which are used in general paper making, may be added. In particular, in order for the paper quality improver of the present invention to exhibit its function, it is important to fix to pulp, and if necessary, an agent that promotes fixing (hereinafter referred to as a fixing accelerator) can be used. . Examples of such agents include aluminum sulfate, cationized starch, compounds having an acrylamide group, polyethyleneimine, and the like. The addition amount of the fixing accelerator is preferably 0.001 to 5 parts by weight and more preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the pulp. Moreover, it is preferable to use 0.005-1 weight part with respect to 100 weight part of paper quality improvement agents of this invention.

  The paper quality improver of the present invention is effective in improving the paper making speed when used in a paper machine equipped with a size press equipment among coating equipment. That is, in the paper manufacturing method having a size press step, it is preferable to add the paper quality improver of the present invention before the size press step. Further, when the paper quality improver of the present invention is used, the addition amount in the step of adding the alkyl ketene dimer prior to the size press step is 0 to 0.05 parts by weight, further 0 to 0.03 parts by weight with respect to 100 parts by weight of the pulp. Paper with excellent size performance can be obtained even within this range. The step of adding the paper quality improver of the present invention and the step of adding the alkyl ketene dimer may be performed at the same time or one of them.

  The pulp sheet obtained by using the paper quality improver of the present invention is a newspaper paper, non-coating material in the item classification described in the Paper Pulp Technology Handbook (issued by the Paper Pulp Technology Association, pages 455-460, 1992). It is suitably used for paper or paperboard such as printing paper, fine coating printing paper, coating printing paper, information paper, cardboard paper, white board paper, packaging paper and the like. Particularly, it is suitably used for non-coating printing paper, fine coating printing paper, and coating printing paper used for books and publishing applications.

Production Example 1 (Synthesis of paper quality improver 1)
Palmitic acid / stearic acid mixture (Kao Lunac S-40) 1061.1 g (3.854 mol) and tetraethylenepentamine 208.5 g (total amine value 1251.9 mgKOH / g, 4.652 mol as amino group) in a flask After preparation and substitution with nitrogen, amidation was carried out at 200 ° C. and normal pressure under nitrogen flow. After confirming that the acid value was less than 5, it was cooled to 95 ° C., and 19 g of water was added for hydrolysis to obtain a polyamidoamine (total amine value 55 mgKOH / g). Next, 99.86 g (1.079 mol) of epichlorohydrin was added dropwise at 90 to 100 ° C., and further aged at 110 ° C. for 3 hours to obtain a paper quality improver 1. This paper quality improver 1 has an amide group equivalent (FA) of 181.1 mgKOH / g, an amino group equivalent (ToAmV) of 40.6 mgKOH / g, a chloride ion equivalent (Cl) of 7.96 mgKOH / g, The equivalent (TCl) was 45.6 mgKOH / g, α [FA / (ToAmV + Cl + FA)] was 0.79, and β [TCl / (ToAmV + Cl + FA) was 0.20.

Production Examples 2-14
According to Production Example 1, the amounts of amine compound (a), saturated fatty acids (b) and epichlorohydrin (c) are adjusted, and α [FA / (ToAmV + Cl + FA)] and β [TCl / (ToAmV + Cl + FA)] are obtained. As shown in Table 1, paper quality improvers were produced.

<Production of water dispersion>
The paper quality improver produced in Production Examples 1 to 14 was made into an aqueous dispersion having a predetermined average particle diameter (median diameter) using a homomixer (specialized robotics). In addition, the average particle diameter of the water dispersion was measured by LA-910 of Horiba.

<Evaluation>
(1) Tightness and sizing degree (1-1) Papermaking method LBKP was disaggregated and beaten with a beater at room temperature to obtain an LBKP slurry having a pulp concentration of 2.2% by weight. Canadian Standard Freeness was 430ml. The LBKP slurry was weighed so that the basis weight of the sheet after papermaking was 100 g / m ² when it was absolutely dry, and then cationized starch (CATO308, manufactured by NSC Japan) 1.0% (weight basis, vs. pulp, below) The same), industrial sulfuric acid band 0.5%, light calcium carbonate 20%, sizing agent (alkyl ketene dimer, indicated as AKD in the table) in the amount shown in Table 1, and paper quality improver in the amount shown in Table 1. Added with stirring. After diluting with water so that the pulp concentration becomes 0.5% by weight, and adding 0.03% of a cationic polyacrylamide yield improver (Percoll 47, manufactured by Ciba Specialty Chemicals) with stirring Paper was made with a 150-mesh wire with a round tappi paper machine and coached to obtain wet paper. The wet paper after paper making was pressed with a press at 3.5 kg / cm ² for 2 minutes and dried at 105 ° C. for 2 minutes using a drum dryer to obtain a pulp sheet. The obtained pulp sheet was conditioned at 23 ° C. and a humidity of 50% RH for 1 day, and then the tightness and sizing degree were measured by the following methods. The results are shown in Table 1.

(1-2) Tenacity The basis weight (g / m ² ) and thickness (mm) of the resulting conditioned pulp sheet were measured, and the tenacity (g / cm ³ ) was determined by the following formula.
Calculation formula: (tensity) = (basis weight) / (thickness) × 0.001
The smaller the absolute value, the higher the bulk, and the 0.02 difference in the strength is fully recognized as a significant difference.

(1-3) Sizing degree The degree of sizing of the conditioned pulp sheet obtained by the papermaking method was measured according to JIS-8122.

(2) Dynamic water absorption The same operation as the paper making method was performed up to the press. After pressing, the wet paper is cut into a size of 5 cm × 5 cm and dried at 105 ° C. using a halogen moisture meter manufactured by METTLER TOLEDO Co., Ltd., and the moisture in the paper is estimated to be more than 0 to about 5%. The drying operation is stopped when the weight is reached, and 3 microliters of 60 ° C. warm water is quickly dropped from above using a syringe with the moisture meter set, and the time until the paper completely penetrates into the paper. Was measured. Then, the drying operation was restarted, and the weight was further dried until there was no weight loss, and the weight of moisture in the paper was 0% (absolute dry weight). The moisture in the paper at the time when the penetration time was measured was calculated from the weight when the penetration time was measured and the dry weight. The water content in the paper is the weight of water with respect to the absolute dry weight in%. Measure 5 samples with different moisture in the paper, take the moisture in the paper on the X-axis and the penetration time on the Y-axis, draw a moisture-penetration time curve in the paper, and determine the penetration time at 1% moisture in the paper, Dynamic water absorption was evaluated. The results are shown in Table 1. In this evaluation method, the longer the permeation time, the lower the paper water absorption in the coating process for the paper immediately after the dryer (that is, the dynamic water absorption is suppressed), and the paper making speed is improved.

(3) Physical properties of paper quality improver (reaction product) Amide equivalent (FA) (mgKOH / g), amino group equivalent (ToAmV) (mgKOH / g), chloride of paper quality improver (reaction product) The equivalent (Cl) of product ions (mgKOH / g) and the equivalent (TCl) of total chlorine (mgKOH / g) were measured as follows to determine α and β. The results are shown in Table 1.
Equivalent amino group (ToAmV): 0.5 to 1.5 g of a sample was dissolved in 50 mL of butanol and titrated with a 0.2 mol / l HClO ₄ -acetic acid solution using an automatic potentiometric titrator.
Equivalent of total chlorine (TCl): 0.5-1.5 g of sample is dissolved in 25 mL of 20 g / L sodium 1-butanol solution, and air-cooled tube is attached and gently boiled on a hot plate for about 1.5 hours. . Cool to room temperature and wash with water and alcohol while washing the air-cooled tube, dissolve in a 300 ml flask, make up to about 200 ml with ethanol and water, and then add 15 ml of 25% nitric acid solution. It determined by titrating with a 0.1 mol / l silver nitrate standard solution with an automatic potentiometric titrator.
Equivalent chloride ion (Cl): 0.5-1.5 g of sample is dissolved in 80 mL of water, and about 15 mL of 25% nitric acid solution is added. This was determined by titrating with an automatic potentiometric titrator using a 0.1 mol / l silver nitrate standard solution.
・ Equivalent amide group (FA): 30-35 mg of a sample is precisely weighed, dissolved in ¹ g of deuterated chloroform containing p-dinitrobenzene as an internal standard, and p appearing at around 8.4 pm using ¹ H-NMR. -It calculated | required by measuring the integrated value of the methyl group of the alkyl-group terminal derived from the fatty acid which appears in the vicinity of 0.9 ppm with respect to the integrated value of dinitrobenzene.

Schematic showing an apparatus for measuring the melting point of fatty acids or paper quality improvers

Explanation of symbols

A: Measuring tube B: Cork stopper C: Vent hole D: Thermometer E: Auxiliary thermometer F: Bath solution G: Capillary tube H: Side tube

Claims (4)

Obtained by further reacting epichlorohydrin (c) with an amide compound obtained by reacting a polyalkylene polyamine as a main component with an amine compound (a) and a saturated fatty acid having 12 to 40 carbon atoms (b). A paper quality improver comprising a reaction product obtained,
Equivalent amide group (FA) (mgKOH / g) of the reaction product, equivalent of amino group (ToAmV) (mgKOH / g), equivalent of chloride ion (Cl) (mgKOH / g), total chlorine The equivalent amount (TCl) (mgKOH / g) of the reaction product is 0.7 ≦ α <1 and −0.9α + 0.9 ≦ β <− when FA / (ToAmV + Cl + FA) is α and TCl / (ToAmV + Cl + FA) is β. Paper quality improver that satisfies 0.9α + 1.29. Obtained by further reacting epichlorohydrin (c) with an amide compound obtained by reacting a polyalkylene polyamine as a main component with an amine compound (a) and a saturated fatty acid having 12 to 40 carbon atoms (b). A paper quality improver comprising an aqueous dispersion containing the reaction product obtained,
Equivalent amide group (FA) (mgKOH / g) of the reaction product, equivalent of amino group (ToAmV) (mgKOH / g), equivalent of chloride ion (Cl) (mgKOH / g), total chlorine The equivalent amount (TCl) (mgKOH / g) of the reaction product is 0.7 ≦ α <1 and −0.9α + 0.9 ≦ β <− when FA / (ToAmV + Cl + FA) is α and TCl / (ToAmV + Cl + FA) is β. 0.9α + 1.29 is satisfied,
A paper quality improver in which the average particle size of dispersed particles in the aqueous dispersion is 0.1 to 20 μm.   A paper manufacturing method comprising a size press step, wherein the paper quality improver according to claim 1 or 2 is added in a step prior to the size press step.   The paper manufacturing method according to claim 3, further comprising a step of adding 0 to 0.05 part by weight of an alkyl ketene dimer to 100 parts by weight of pulp in a step prior to the size press step.

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