TW201937042A - Softener for papermaking, paper, and method for manufacturing paper - Google Patents

Abstract

Provided is a softener for papermaking, with which high levels of softness and strength can be imparted to paper. This softener for papermaking includes at least one of polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil as an A component, and a quaternary cationic surfactant as a B component, the polyoxyalkylene castor oil and the polyoxyalkylene hydrogenated castor oil of the A component both containing at least propylene oxide units.

Description

Softener for papermaking, paper and paper manufacturing method

FIELD OF THE INVENTION The present invention relates to a softening agent for papermaking, a method of producing paper and paper.

BACKGROUND OF THE INVENTION In recent years, household paper such as facial tissue and toilet paper is required to have high flexibility. In addition, general paper such as printing paper and wrapping paper is also required to have softness when used.

In the past, a softener for a paper-based softener (for example, Patent Document 1) and a cationic surfactant-based softener (for example, Patent Documents 2 and 3) are known. ).

However, the softener of the nonionic surfactant is poor in fixability to the pulp. Therefore, in order to obtain the required performance, a large amount of addition is required, and from the viewpoint of manufacturing cost and the like, the problem is considerable.

Further, the cationic surfactant-based softening agent is excellent in the fixing property to the pulp, but there is a problem in that the strength of the paper is liable to be lowered.

As a method for solving such problems, a softener having a nonionic surfactant having an alkyl group and a cationic surfactant is known (Patent Document 4).
[Advanced technical literature]
[Patent Literature]

Japanese Patent Publication No. JP-A-2004-44058, Japanese Patent Application Laid-Open No. Hei. No. Hei.

SUMMARY OF THE INVENTION Problems to be Solved by the Invention The paper treated by the softening agent disclosed in Patent Document 4 cannot be said to be sufficient in terms of achieving both high flexibility and high strength.

Under such circumstances, a main object of the present invention is to provide a softening agent for papermaking which can impart high flexibility and high strength to paper. Further, another object of the present invention is to provide a softening agent for papermaking which can impart flexibility and high water absorbability to paper.
Means to solve the problem

The inventors of the present invention have conducted intensive studies to solve the above problems. As a result, it has been found that a softening agent for papermaking capable of imparting high flexibility and high strength to paper, the softening agent for papermaking comprising at least one of polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil The component A and the level 4 cationic surfactant are referred to as component B, and further, the polyoxyalkylene castor oil of the component A and the polyoxyalkylene hydrogenated castor oil respectively contain at least a propylene oxide unit.

Further, the inventors of the present invention have found a softening agent for papermaking which imparts flexibility and high water absorbency to paper, and the softening agent for papermaking comprises polyoxyethylene-ethyl castor oil and polyoxyethylidene hydrogenated castor oil. At least one is used as the component A, and the level 4 cationic surfactant is used as the component B; and the level 4 cationic surfactant of the component B is selected from the group consisting of dimethyldialkylammonium chloride and trimethylmonoalkyl chloride. At least one of the group consisting of ammonium hydride and a quaternary ammonium salt having an imidazoline ring.

The present invention is based on such knowledge and is further accomplished by repeated discussion.

That is, the present invention provides the invention of the following disclosure.
Item 1. A softening agent for papermaking, comprising:
At least one of polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil as component A, and
The fourth-stage cationic surfactant is a component B; and the polyoxyalkylene-lined castor oil of the component A and the polyoxyalkylene-hydrogenated castor oil respectively contain at least a propylene oxide unit.
Item 2. The softening agent for papermaking according to Item 1, wherein the polyoxyalkylene-lined castor oil of the above-mentioned A component and the polyoxyalkylene hydrogenated castor oil are respectively added, and the molar number of the propylene oxide unit is 1 to 20, the addition molar number of the ethylene oxide unit is from 0 to 50, and the total number of addition moles of the propylene oxide unit and the ethylene oxide unit is from 3 to 50.
Item 3. The softening agent for papermaking according to Item 1 or 2, wherein the aforementioned 4-stage cationic surfactant of the component B is selected from the group consisting of dimethyldialkylammonium chloride and trimethylmonoalkylammonium chloride. And at least one group consisting of a 4-grade ammonium salt having an imidazoline ring.
Item 4. The softening agent for papermaking according to Item 1 or 2, wherein the aforementioned 4-stage cationic surfactant of the component B is N-stearylaminoethyl-N-methyl-2-octadecenyl N-stearoylaminoethyl-N-methyl-2-octadecenyl imidazolinium methyl sulfate.
Item 5. A softening agent for papermaking comprising: at least one of polyoxyethylidene castor oil and polyoxyethylidene hydrogenated castor oil as component A, and
Grade 4 cationic surfactant as component B;
The aforementioned 4-stage cationic surfactant of the above component B is selected from the group consisting of dimethyldialkylammonium chloride, trimethylmonoalkylammonium chloride, and a 4-grade ammonium salt having an imidazoline ring. At least one of them.
The softening agent for papermaking according to any one of items 1 to 5, which is in the form of an aqueous emulsion.
Item 7. A method for producing a paper, comprising: a papermaking step of performing papermaking on a pulp slurry in the presence of the softening agent for papermaking according to any one of items 1 to 6.
The method of producing a paper according to Item 7, wherein in the papermaking step, the total amount of the component A and the component B in the softening agent for papermaking is 0.01 to 5.0 with respect to 100 parts by mass of the absolute dry pulp. Parts by mass.
Item 9. A method of producing a paper comprising the step of adhering a softening agent for papermaking according to any one of Items 1 to 6 to a base paper.
Item 10. A paper obtained by treating the papermaking softening agent according to any one of Items 1 to 6.
Item 11. A paper comprising:
At least one of polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil as component A, and
The fourth-stage cationic surfactant is a component B; and the polyoxyalkylene-lined castor oil of the component A and the polyoxyalkylene-hydrogenated castor oil respectively contain at least a propylene oxide unit.
Item 12. A paper comprising: at least one of polyoxyethylidene ethyl castor oil and polyoxyethylidene hydrogenated castor oil as component A, and
a class 4 cationic surfactant as a component B; and the aforementioned class 4 cationic surfactant of the component B is selected from the group consisting of dimethyldialkylammonium chloride, trimethylmonoalkylammonium chloride, and imidazole At least one of the group consisting of a quaternary ammonium salt of a porphyrin ring.
Item 13. Use of the following composition as a softening agent for papermaking, the use of the composition of the A component and the B component as a softening agent for papermaking;
The composition includes at least one of a polyoxyalkylene chain castor oil and a polyoxyalkylene hydrogenated castor oil as the component A and a level 4 cationic surfactant as the component B; and the aforesaid component A The oxygen-extended alkyl castor oil and the aforementioned polyoxyalkylene hydrogenated castor oil each contain at least a propylene oxide unit.
Item 14. Use of the following composition as a softening agent for papermaking, wherein the composition of the component A and the component B is used as a softening agent for papermaking;
The composition includes at least one of polyoxyethylidene ethyl castor oil and polyoxyethylidene hydrogenated castor oil as the component A and a level 4 cationic surfactant as the component B;
And the aforementioned 4-stage cationic surfactant of the component B is a group selected from the group consisting of dimethyldialkylammonium chloride, trimethylmonoalkylammonium chloride, and a 4-grade ammonium salt having an imidazoline ring. At least one of the groups.
Effect of the invention

According to the present invention, it is possible to provide a softening agent for papermaking which can impart high flexibility and high strength to paper. Moreover, according to the present invention, it is possible to provide a softening agent for papermaking which can impart flexibility and high water absorbability to paper. Further, according to the present invention, it is also possible to provide a paper treated with the softening agent for papermaking and a method for producing the paper.

BEST MODE FOR CARRYING OUT THE INVENTION The softening agent for papermaking according to the first embodiment of the present invention is characterized in that it comprises at least polyoxyalkylene-lined castor oil and polyoxyalkylene hydrogenated castor oil. One is a component A and the fourth-level cationic surfactant is a component B; and further, the polyoxyalkylene castor oil of the component A and the polyoxyalkylene hydrogenated castor oil each contain at least a propylene oxide unit. By having such a configuration, the softening agent for papermaking according to the first embodiment of the present invention can impart high flexibility and high strength to paper.

Further, a softening agent for papermaking according to a second embodiment of the present invention is characterized in that it comprises at least one of polyoxyethylene-ethyl castor oil and polyoxyethylidene hydrogenated castor oil as an A component and a 4-stage cation interface. The active agent is used as the component B; and the level 4 cationic surfactant of the component B is selected from the group consisting of dimethyldialkylammonium chloride, trimethylmonoalkylammonium chloride, and 4-grade ammonium having an imidazoline ring. At least one of the groups consisting of salts. By having such a configuration, the softening agent for papermaking according to the second embodiment of the present invention can impart flexibility and high water absorbability to paper.

Hereinafter, the softening agent for papermaking of the present invention, the paper using the softening agent for papermaking, and the method for producing paper will be described in detail. In the following description, the softening agent for papermaking according to the first embodiment will be described, and the softening agent for papermaking according to the second embodiment will be described. In the description of the softening agent for papermaking according to the second embodiment, the description is a matter common to the first embodiment, and the description thereof will be appropriately omitted.

1. Softener for papermaking <First embodiment>
The softening agent for papermaking according to the first embodiment of the present invention contains the component A and the component B. The A component and the B component may be used alone or in combination of two or more.

The component A is at least one of polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil. Further, the polyoxyalkylene castor oil and the polyoxyalkylene hydrogenated castor oil each contain a propylene oxide unit. That is, the polyoxyalkylene castor oil and the polyoxyalkylene of the polyoxyalkylene hydrogenated castor oil contain a propylene oxide unit.

Polyoxyalkylene castor oil is a compound obtained by adding castor oil to a polyalkylene oxide. Further, polyoxyalkylene hydrogenated castor oil is a compound obtained by adding a polyalkylene oxide to hydrogenated castor oil. Castor oil and hydrogenated castor oil are well known, and commercially available products can be easily obtained.

In the polyoxyalkylene-lined castor oil and the polyoxyalkylene hydrogenated castor oil, the addition molar number of the propylene oxide unit is not particularly limited, and the paper is imparted with high flexibility and high strength. From the viewpoints, it is preferably from 1 to 20, more preferably from 2 to 15, still more preferably from 3 to 12. Further, examples of the propylene oxide include 1,2-propylene oxide and 1,3-propylene oxide.

In the polyoxyalkylene castor oil and the polyoxyalkylene hydrogenated castor oil, other alkylene oxide units may be added in addition to the propylene oxide unit. The other alkylene oxide unit may, for example, be an ethylene oxide unit or a butylene oxide unit from the viewpoint of imparting high flexibility and high strength to paper. As the butylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and epoxy isobutane can be mentioned. The other alkylene oxide unit may be contained alone or in combination of two or more types. Further, in the polyoxyalkylene castor oil and the polyoxyalkylene hydrogenated castor oil, in the case of addition of other alkylene oxide units in addition to the propylene oxide unit, the polyalkylene oxide may be a block copolymerization. The material may also be a random copolymer.

From the viewpoint of imparting high flexibility and high strength to the paper, the polyoxyalkylene castor oil and the polyoxyalkylene hydrogenated castor oil, respectively, preferably have a molar number of propylene oxide units added thereto. 1 to 20, the addition mole number of the other alkylene oxide unit is from 0 to 50, and the total addition mole number of the propylene oxide unit to the other alkylene oxide unit is from 3 to 50. Polyoxyalkylene-based castor oil and polyoxyalkylene hydrogenated castor oil, respectively, particularly preferably, the addition molar number of the propylene oxide unit is from 1 to 20, and the molar number of the ethylene oxide unit is added. 0 to 50, and the addition mole number of the propylene oxide unit to the ethylene oxide unit is 3 to 50; more preferably, the addition mole number of the propylene oxide unit is 2 to 15, epoxy B The addition molar number of the alkane unit is from 2 to 25, and the total number of addition moles of the propylene oxide unit to the ethylene oxide unit is from 4 to 40; further preferably, the addition of the propylene oxide unit is Molar. The number is from 3 to 12, the addition molar number of the ethylene oxide unit is from 3 to 15, and the total number of addition moles of the propylene oxide unit to the ethylene oxide unit is from 6 to 27.

The B component is a grade 4 cationic surfactant. The level 4 cationic surfactant is not particularly limited as long as it is used as a softening agent for papermaking, and a known surfactant having a grade 4 cation can be used.

From the viewpoint of imparting high flexibility and high strength to the paper by the combination with the component A, a preferred class 4 cationic surfactant is dimethyldialkylammonium chloride or the like. a monoalkylammonium chloride, and a quaternary ammonium salt having an imidazoline ring.

In the dimethyldialkylammonium chloride, two alkyl (dialkyl) groups are not particularly limited, and from the viewpoint of imparting high flexibility and high strength to paper, respectively, Preferred is an alkyl group having 6 to 24 carbon atoms, more preferably an alkyl group having 6 to 18 carbon atoms. Specific examples of the alkyl group include hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl , pentadecyl, hexadecyl (cetyl, palmityl), heptadecyl, octadecyl (stearyl), nonadecyl, eicosyl, A monoalkyl group, a decyl dialkyl (tetracosyl) group, a perylene trialkyl group, a perylene tetraalkyl group, and the like. The two alkyl groups may be the same or different. Further, the alkyl groups may be linear or branched. Specific examples of the dimethyldialkylammonium chloride include dimethyl distearyl ammonium chloride, dimethyl dilauryl ammonium chloride, and dimethyl dicetyl ammonium chloride. And dimethyldipalmityl ammonium chloride, dimethyl distearyl ammonium chloride, dimethyl dioleyl ammonium chloride, dimethyl di(docosyl) ammonium chloride, and the like.

In the trimethylalkylammonium chloride, the alkyl group is not particularly limited, and from the viewpoint of imparting high flexibility and high strength to paper, respectively, it is preferable to have a carbon number of 6 to 24, respectively. The alkyl group is more preferably an alkyl group having 6 to 18 carbon atoms. Specific examples of the alkyl group include hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl , pentadecyl, hexadecyl (cetyl, palmity), heptadecyl, octadecyl (stearyl), nonadecyl, eicosyl, decyl, anthracene A dialkyl (docosyl) group, a perylene trialkyl group, a perylene tetraalkyl group or the like. Further, the alkyl group may be linear or branched. Specific examples of the trimethylalkylammonium chloride include trimethyl stearyl ammonium chloride, trimethyl monolauryl ammonium chloride, trimethyl cetyl ammonium chloride, and three. Methyl monopalmityl ammonium chloride, trimethyl monostearyl ammonium chloride, trimethyl monooleyl ammonium chloride, trimethyl mono (docosyl) ammonium chloride (trimethyl monobehenyl ammonium chloride) and the like.

The quaternary ammonium salt having the imidazoline ring may be a quaternary ammonium salt represented by the following formula (1).

In the formula (1), R ¹ is an alkyl group having 6 to 24 carbon atoms or an alkenyl group having 6 to 24 carbon atoms, and R ² is an alkyl group having 1 to 24 carbon atoms or a carbon number of 1 to 24 Alkenyl, X ^- is an anion such as a sulfate ion or a chloride ion.

In the case of the quaternary ammonium salt having an imidazoline ring, from the viewpoint of imparting high flexibility and high strength to the paper, N-stearylaminoethyl-N-methyl group is preferred. N-stearoylaminoethyl-N-methyl-2-octadecenyl imida zolium methyl sulfate, 1-hydroxyethyl-1-ethyl-2-oleyl imidazoline B Sulfate, 1-hydroxyethyl-1-methyl-2-oleylimidazolium chloride, 1-hydroxyethyl-1-ethyl-2-lauryl imidazoline ethyl sulfate.

Further, as the class 4 cationic surfactant, a monomethyl ester grade 4 salt, a dimethyl diester grade 4 salt, a trimethyl diester grade 4 salt, or the like can also be mentioned. In the case of the monomethyl ester grade 4 salt, a fatty acid having a carbon number of 7 to 25, preferably 11 to 23, such as stearic acid, a diesterification of triethanolamine and using dimethyl sulfate can be used. For the dimethyl diester 4-grade salt, a fatty acid having a carbon number of 7 to 25, preferably 11 to 23, such as oleic acid, and N-methyldiethanolamine can be used. Esterification, and 4-stage formation using methyl chloride; in the case of trimethyl diester 4-grade salt, a fatty acid having a carbon number of 7 to 25, preferably 11 to 23, such as oleic acid, is used. The 3-dimethylamino-1,2-propanediol was subjected to diesterification and was subjected to four stages using methyl chloride.

In the softening agent for papermaking of the first embodiment, the blending ratio of the component A to the component B (component A: component B, mass ratio) is from the viewpoint of imparting high flexibility and high strength to the paper. It is preferably 100:0.5 to 100:40, more preferably 100:1 to 100:35, still more preferably 100:2 to 100:25.

<Second embodiment>
In the same manner as in the first embodiment, the softening agent for papermaking according to the second embodiment of the present invention comprises at least one of polyoxyethylene-ethyl castor oil and polyoxyethylidene hydrogenated castor oil as the component A. A level 4 cationic surfactant is used as the B component.

However, in the softening agent for papermaking according to the second embodiment, the fourth-stage cationic surfactant of the component B is selected from the group consisting of dimethyldialkylammonium chloride and trimethylmonoalkylammonium chloride. And at least one of the group consisting of a 4-grade ammonium salt having an imidazoline ring. Therefore, the polyoxyalkylene-extended castor oil of the component A and the polyoxyalkylene hydrogenated castor oil may not contain or contain a ring, respectively. Oxypropane unit. In the softening agent for papermaking according to the second embodiment, the "polyoxyalkylene" of the polyoxyalkylene-based castor oil of the component A and the polyoxyalkylene hydrogenated castor oil of the component A may or may not be included. Contains propylene oxide units. For example, in the softening agent for papermaking according to the second embodiment, the "polyoxyalkylene group" may be composed only of polyoxyethylene.

In the softening agent for papermaking according to the second embodiment, the polyoxyalkylene chain castor oil of the component A and the polyoxyalkylene hydrogenated castor oil of the component A each contain a propylene oxide unit, and the component A is preferably exemplified. The same as the first embodiment.

In the softening agent for papermaking according to the second embodiment, when the polyoxyalkylene-extended castor oil of the component A and the polyoxyalkylene hydrogenated castor oil are contained, respectively, the propylene oxide unit is not contained, and B will be described later. The combination of the components, the polyoxyalkylene castor oil and the polyoxyalkylene hydrogenated castor oil, respectively, preferably polyoxyethylene ethyl castor oil and poly, from the viewpoint of imparting softness and high water absorbability to the paper. Oxygen extended ethyl hydrogenated castor oil.

In the polyoxyethylene-ethyl castor oil and the polyoxyethylidene hydrogenated castor oil, the addition molar number of the ethylene oxide unit is not particularly limited, and is combined with the component B described later. From the viewpoint of imparting flexibility and high water absorbency, respectively, it is preferably from 1 to 20, more preferably from 2 to 15, still more preferably from 3 to 12.

In the second embodiment, the component B is also a fourth-order cationic surfactant, but is selected from dimethyldialkylammonium chloride from the viewpoint of imparting flexibility and high water absorbability to paper. At least one of the group consisting of trimethylmonoalkylammonium chloride and a quaternary ammonium salt having an imidazoline ring. In the softening agent for papermaking according to the second embodiment, the A component and the B component described above are combined to impart flexibility and high water absorbability to the paper.

In the softening agent for papermaking of the second embodiment, the blending ratio of the component A and the component B (component A: component B, mass ratio) is from the viewpoint of imparting flexibility and high water absorbability to the paper. It is preferable that it is 100:0.5 to 100:40, more preferably 100:1 to 100:35, still more preferably 100:2 to 100:25.

The softening agents for papermaking according to the first and second embodiments may contain other additives in addition to the components A and B, respectively. As the other additives, known additives to be blended in the softening agent for papermaking can be used, and examples thereof include a dry paper strength enhancer, a wet paper strength enhancer, a coagulant, and an adhesive. In the case of containing other additives, the ratio of the additives in the softening agent for papermaking according to the first and second embodiments is set to 1 for the total of 100 parts by mass of the A component and the B component, respectively. 200 ppm, the viscosity is set to 0.05 to 0.15 parts by mass. Here, as the coagulating agent, polydiallyldimethylammonium chloride (pDADMAC) or a derivative thereof, a copolymer of diallyldimethylammonium chloride and another monomer, and polypropylene may be mentioned. Amidoxime, polyamine, polyethylene imine, 2-(methacryloxy)ethyltrimethylammonium chloride polymer, modified polyethyleneimine, and the like. As the adhesive, a polyethylene oxide adhesive ("ALKOX" series manufactured by Mingcheng Chemical Co., Ltd.) or the like can be mentioned.

In the softening agent for papermaking according to the first and second embodiments, a solvent may or may not be contained in addition to the components A and B, respectively. The solvent is not particularly limited, and preferably an alcohol such as water or isopropyl alcohol. The solvent may be used alone or in combination of two or more. The component A and the component B are preferably dispersed in a solvent. For example, the softening agent for papermaking of the first and second embodiments can be used in the form of an aqueous emulsion in which the component A and the component B are dispersed in a solvent containing water, by using water as a solvent.

In the softening agent for papermaking of the first and second embodiments, the method of dispersing the component A and the component B in water is not particularly limited, and a phase inversion emulsification method is mentioned. A phase inversion emulsification method in which a surfactant or an inorganic salt is added, or a mechanical dispersion method in which dispersion is carried out by a mechanical method. The mechanical dispersion method is a method of uniformly dispersing by various known emulsifiers such as a homomixer, a high-pressure discharge type homogenizer, a high-shear rotary emulsification disperser, and an ultrasonic emulsifier. . The dispersion method may be one type of method or two or more types may be used in combination.

In the case where the softening agent for papermaking of the first and second embodiments is in the form of an aqueous emulsion, respectively, the total content of the A component and the B component in the softening agent for papermaking according to the first and second embodiments are respectively It is preferably from 10 to 40% by mass, more preferably from 15 to 30% by mass.

From the viewpoint of imparting high flexibility and high strength to paper, and further imparting high water absorbability, the softening agent for papermaking of the present invention preferably satisfies both the softening agents for papermaking of the first and second embodiments. The constituents.

2. Paper and method for producing the same The paper of the present invention can be provided, for example, in the presence of a softening agent for papermaking according to the first and second embodiments, by a papermaking step for performing papermaking on a pulp slurry. And suitably manufactured. Moreover, the paper of the present invention can be suitably produced by, for example, attaching the softening agent for papermaking of the first and second embodiments to the base paper. Further, by using these manufacturing methods, first, the base paper is prepared by subjecting the pulp slurry to papermaking in the presence of the softening agent for papermaking according to the first and second embodiments, and secondly, the obtained paper is obtained by the pairing. The base paper can also be produced by attaching the softening agent for papermaking of the first and second embodiments to the base paper. The details of the softening agents for papermaking according to the first and second embodiments are as described above.

In the papermaking step, the total addition amount of the component A and the component B of the softening agent for papermaking according to the first and second embodiments is preferably 0.01 to 5.0 by mass per 100 parts by mass of the absolute dry pulp. It is more preferably 0.01 to 2.0 parts by mass, still more preferably 0.05 to 0.5 parts by mass. In addition, when the softening agents for papermaking of the first and second embodiments are attached to the base paper, the total amount of the components A and B adhered to the base paper is preferably in such a range. In the paper of the present invention, the total content of the component A and the component B is preferably 0.01 to 5.0 parts by mass, more preferably 0.01 to 2.0 parts by mass, still more preferably 0.05 to 0.5, per 100 parts by mass of the absolute dry pulp. Parts by mass.

The papermaking of the pulp slurry can be carried out by a method using a known paper machine. The paper machine is a device capable of dehydrating the pulp slurry on a wire. As the paper machine, a suction breast former (round net type, long net type), a twin wire former (twin wire former), a rotary net former (C-shaped coating (C-) can be mentioned. Wrap), S-wrap, crescent former, etc. Moreover, in addition to the continuous paper machine like the long net paper machine, the scope also includes a batch type pulp mold forming machine, etc., the batch type pulp mold forming machine is adding the pulp slurry to the line. After forming the formed frame, dehydration is performed from the lower portion of the wire to produce a molded body.

In addition, the method of adhering the softening agent for papermaking of the first embodiment and the second embodiment to the surface of the base paper is not particularly limited as long as the components A and B adhere to the surface of the base paper, for example, A coating by a spray method, a coating by a flexography method or a gravure method, a size press, a gate roll coater, and a Bill coater can be used. Coating by calendering, etc.

Examples of the use of the paper of the present invention include household paper such as tissue paper, toilet paper, paper towel, kitchen paper towel, and general paper such as printing paper and wrapping paper. The paper treated with the softening agent for papermaking according to the first embodiment has both high flexibility and high strength, and the paper treated with the softening agent for papermaking according to the second embodiment has both softness and high water absorption. Therefore, it is particularly suitable for use as a tissue paper or toilet paper among household papers.

As the pulp raw material constituting the paper or base paper of the present invention, bleached kraft pulp (NBKP) of conifer, bleached kraft pulp (LBKP) of hardwood, groundwood pulp (GP), thermomechanical pulp (TMP) ), Chemi-Thermo Mechanical Pulp (CTMP), Deinked Pulp (DIP), and the like. Further, as the pulp raw material, waste paper pulp such as newspaper waste paper, magazine waste paper, corrugated waste paper, and deinked waste paper can also be used. Further, the paper of the present invention may further contain a mixture of the above-mentioned pulp raw material and rock wool, asbestos, or synthetic fibers such as polyamide, polyimine, polyester, polyolefin, and polyvinyl alcohol.

In the manufacture of the paper of the present invention, in order to express the physical properties required in various paper types, it can also be used as needed: filler, aluminum sulfate, sizing agent, dry paper strength enhancer, moist paper strength enhancer, moisturizer Various additives such as yield improver and water filter enhancer. These may be used alone or in combination of two or more. Moreover, these additives can be added to the pulp slurry in advance by mixing with the softening agent for papermaking of the first and second embodiments, and the paper of the present invention can be produced and attached to the base paper.

In terms of fillers, kaolin, calcined kaolin, delaminated kaolin, illite, heavy calcium carbonate, light calcium carbonate, light calcium carbonate-yttria composite, magnesium carbonate, carbonic acid An inorganic filler such as ruthenium, titanium dioxide, zinc oxide, ruthenium oxide, amorphous ruthenium oxide, aluminum hydroxide, calcium hydroxide or magnesium hydroxide. The filler may be used alone or in combination of two or more.

As the sizing agent, there may be mentioned a sizing agent of a fatty acid soap such as sodium stearate, an aqueous emulsion of rosin, a fortified rosin, a rosin ester, an aqueous emulsion of an alkenyl succinic anhydride, a 2-oxa compound. An aqueous emulsion of 2-oxetanone, an aqueous emulsion of paraffin, a cationic sizing agent obtained by the reaction of a carboxylic acid with a polyvalent amine, a reaction of an aliphatic oxyacid with an aliphatic amine or an aliphatic alcohol An aqueous emulsion of an object, an anionic or cationic styrene sizing agent, and the like. The sizing agent may be used alone or in combination of two or more types.

Examples of the dry paper strength enhancer include anionic polypropylene decylamine, cationic polypropylene decylamine, amphoteric polypropylene decylamine, cationized starch, amphoteric starch, and the like. The dry paper strength enhancer may be used in a single type or in a mixture of two or more types.

Examples of the wet paper strength enhancer include polyamine, epichlorohydrin resin, melamine, formaldehyde resin, and urea/formaldehyde resin. Further, an anionic polypropylene decylamine may also be used in combination. The wet paper strength enhancer may be used in a single type or in a mixture of two or more types.

The humectant may, for example, be a polyhydric alcohol such as glycerin, sorbitol or polyethylene glycol. The humectant may be used alone or in combination of two or more.

For the yield enhancer, an anionic, cationic or amphoteric high molecular weight polyacrylamide may be used, or a cerium oxide sol and a cationized starch may be used in combination, or a bentonite and a cationic high molecular weight polypropylene may be used in combination. amine. The yield improver may be used in only one type or in a mixture of two or more types.

The water-repellent enhancer may, for example, be polyethyleneimine, cationic or amphoteric or anionic polypropylene decylamine. The water-supplementing agent may be used in a single type or in a mixture of two or more types.

Moreover, when the softening agent for papermaking of the first embodiment and the second embodiment is applied to the base paper, it can be used in combination with a known additive which can be applied to the surface of the base paper. Specific examples of such additives include surface paper strength enhancers such as starch, polyvinyl alcohol, and acrylamide polymers, dyes, coating colors, humectants, and surfaces. Sizing agents, as well as anti-slip agents.
[Examples]

The present invention will be described in detail below by showing examples and comparative examples. However, the invention is not limited by the examples.

[Example 1]
524g of castor oil, 1.0g of special grade potassium hydroxide were fed into the autoclave (made of stainless steel made of pressure-resistant industrial glass), and it was slowly mixed at 150 ° C for 3 hours. 149g of ethylene oxide and 327g of epoxy were pre-mixed. When propane was added, the mixture was cooled to 85 ° C after the completion of the dropwise addition, and 1.1 g of 90% acetic acid was added thereto, and the mixture was stirred for 30 minutes to obtain a compound A-1 as the component A. Next, 87.3 g of ion-exchanged water, 2.7 g of Quartamin D86P as a component B (a product of Kao's commercial distearyl dimethylammonium chloride 75%), and 10 g of a compound A-1 (component A) were sequentially added in a 500 ml glass beaker. After stirring at 60 ° C for 30 minutes, the mixture was cooled to 40 ° C or lower to obtain a softening agent for papermaking in the form of 100 g of an aqueous emulsion (the total content of the component A and the component B was 10% by mass). The ratio (mass ratio) of the A component to the B component is shown in Table 1.

[Embodiment 2]
552 g of hydrogenated castor oil was fed into the autoclave, heated to 90 ° C and dissolved, and then 1.0 g of special grade potassium hydroxide was fed thereto, and slowly dropped at 150 ° C for 3 hours, and 311 g of ethylene oxide and 137 g were previously mixed. In the case of the propylene oxide, after the completion of the dropwise addition, the mixture was cooled to 85 ° C, and 1.1 g of 90% acetic acid was added thereto, and after stirring for 30 minutes, the compound A-2 as the component A was obtained. Then, in a 200 ml glass beaker, 82.9 g of ion-exchanged water, 7.1 g of Quartamin 86W as a component B (28% of Kaoki stearyl trimethylammonium chloride), and 10 g of compound A-2 (component A) were sequentially added. After stirring at 60 ° C for 30 minutes, the mixture was cooled to 40 ° C or lower to obtain a softening agent for papermaking in the form of 100 g of an aqueous emulsion (the total content of the component A and the component B was 10% by mass). The ratio (mass ratio) of the A component to the B component is shown in Table 1.

[Example 3]
In an autoclave, 542 g of hydrogenated castor oil was heated to 90 ° C and dissolved, and then 1.0 g of special grade potassium hydroxide was fed, and 202 g of propylene oxide was added at 170 ° C for 3 hours, and after cooling to 130 ° C, 255 g was added for 4 hours. Ethylene oxide was cooled to 85 ° C after the completion of the reaction, and then 1.1 g of 90% acetic acid was added to obtain a compound A-3 as the component A. Next, 85.6 g of ion-exchanged water and 4.4 g of cationic SF-75PA (Sanyo Chemical Industrial Products N-stearyl decylaminoethyl-N-methyl-2-octadecyl imidazole) were sequentially added in a 200 ml glass beaker. 10 g of the compound A-3 (component A) and 10 g of the compound A-3 (component A) were stirred at 60 ° C for 30 minutes, and then cooled to 40 ° C or lower to obtain a form of 100 g of an aqueous emulsion (component A and B). A softening agent for papermaking having a total content of the components of 10% by mass. The ratio (mass ratio) of the A component to the B component is shown in Table 1.

[Example 4]
518 g of hydrogenated castor oil and 1.0 g of special potassium hydroxide were fed into the autoclave, and 385 g of propylene oxide was added at 170 ° C for 5 hours. After cooling to 130 ° C, 97 g of ethylene oxide was added over 2 hours. After cooling to 85 ° C, 1.1 g of 90% acetic acid was added to obtain a compound A-4 (component A). In the same manner as in Example 3, except that the compound A-4 was used instead of the compound A-3 as the component A, 100 g of an aqueous emulsion (the total content of the component A and the component B was 10% by mass) was obtained. Softener for papermaking. The ratio (mass ratio) of the A component to the B component is shown in Table 1.

[Comparative Examples 1 to 4]
In a ratio of the ratio of the component A to the component B (mass ratio) shown in Table 2, 10 g of the component A and/or the component B were stirred with 90 g of ion-exchanged water at room temperature for 30 minutes, and 100 g of an aqueous emulsion was obtained. A softening agent for papermaking having a form (the total content of the A component and the B component is 10% by mass).

[Table 1]

[Table 2]

In Tables 1 and 2, "EO" means an ethylene oxide unit, and "PO" means a propylene oxide unit. Moreover, the number of moles after "EO" and "PO" means the number of addition moles of the ethylene oxide unit and the propylene oxide unit, for example, the description of "EO6 Moer" means epoxy B. The addition molar number of the alkane unit is 6.

[Example 5]
82.9 g of ion-exchanged water, 7.1 g of Quartamin 86W (a product of Kao's commercial stearyl trimethylammonium chloride 28%) were added in sequence as a B component and 10 g of a compound A-3 (component A) in a 200 ml glass beaker. After stirring at 60 ° C for 30 minutes, the mixture was cooled to 40 ° C or lower to obtain a softening agent for papermaking in the form of 100 g of an aqueous emulsion (the total content of the component A and the component B was 10% by mass). The ratio (mass ratio) of the A component to the B component is shown in 3.

[Embodiment 6]
87.3 g of ion-exchanged water, 2.7 g of Quartamin D86P (a product of Kao's commercial distearyl dimethylammonium chloride 75%) were added in sequence as a B component, 10 g of Brownen BR-410 (Compound A) in a 200 ml glass beaker. -5) The component A was stirred at 60 ° C for 30 minutes, and then cooled to 40 ° C or lower to obtain a softening agent for papermaking in the form of 100 g of an aqueous emulsion (the total content of the component A and the component B was 10% by mass). The ratio (mass ratio) of the A component to the B component is shown in 3.

[Embodiment 7]
In a 200 ml glass beaker, 82.9 g of ion-exchanged water, 7.1 g of Quartamin 86W (a product of Kao's commercial stearyl trimethylammonium chloride 28%) was added as a component B, and 10 g of Brownen CW-10 (Compound A- 6) As a component A, the mixture was stirred at 60 ° C for 30 minutes, and then cooled to 40 ° C or lower to obtain a softening agent for papermaking in the form of 100 g of an aqueous emulsion (the total content of the component A and the component B was 10% by mass). The ratio (mass ratio) of the A component to the B component is shown in 3.

[Embodiment 8]
75.7 g of ion-exchanged water, 14.3 g of Quartamin 86W (28% of Kaoki stearyl trimethylammonium chloride) were added as a B component and 10 g of Brownen CW-10 (Compound A-) in a 200 ml glass beaker. 6) As a component A, the mixture was stirred at 60 ° C for 30 minutes, and then cooled to 40 ° C or lower to obtain a softening agent for papermaking in the form of 100 g of an aqueous emulsion (the total content of the component A and the component B was 10% by mass). The ratio (mass ratio) of the A component to the B component is shown in 3.

[Embodiment 9]
85.6 g of ion-exchanged water and 4.4 g of cationic SF-75PA (Sanyo Chemical Industrial Products N-stearyl decylaminoethyl-N-methyl-2-octadecyl imidazoline) were sequentially added to a 200 ml glass beaker. As a component A, 10 g of Brownon CW-10 (compound A-6) as a component B, and stirred at 60 ° C for 30 minutes, and then cooled to 40 ° C or lower to obtain 100 g of water system. A softening agent for papermaking in the form of an emulsion (the total content of the A component and the B component is 10% by mass). The ratio (mass ratio) of the A component to the B component is shown in 3.

[Comparative Example 5]
In a 200 ml glass beaker, 87.9 g of ion-exchanged water and 2.1 g of LIPOTHOQUAD C/25 (a product of Lion's product dimerized oxygen-ethylhexylmethylmethylammonium chloride 95%) were added as a component B, 10.0 g. The compound A-5 was stirred at 60 ° C for 30 minutes, and then cooled to 40 ° C or lower to obtain a softening agent for papermaking in the form of 100 g of an aqueous emulsion (the total content of the component A and the component B was 10% by mass).

[Comparative Example 6]
In a 200 ml glass beaker, 85.8 g of ion-exchanged water and 4.2 g of LIPOTHOQUAD C/25 (a product of Lion's product dimerized oxygen-extended ethyl coconut alkyl ammonium chloride 95%) were sequentially added as a component B, 10.0 g. The compound A-6 was stirred at 60 ° C for 30 minutes, and then cooled to 40 ° C or lower to obtain a softening agent for papermaking in the form of 100 g of an aqueous emulsion (the total content of the component A and the component B was 10% by mass).

[Comparative Example 7]
The case where the softening agent for papermaking was not used was designated as Comparative Example 7.

[table 3]

[Table 4]

In Tables 3 and 4, "EO" means an ethylene oxide unit, and "PO" means a propylene oxide unit. Further, the number of moles after "EO" and "PO" means the molar number of addition of an ethylene oxide unit and a propylene oxide unit, for example, the description of "EO6 Moer" means ethylene oxide. The addition of the unit has a molar number of 6.

[Paper method]
The broadleaf bleached kraft pulp (LBKP) and the conifer bleached kraft pulp (NBKP) were weighed in a mass ratio of 7:3, and beaten with a dissolving machine (Kumani mechanism) to make the Canadian Standard Freeness 450 ml. And the concentration was adjusted to 1.0%. The amount of the base weight was 20 g/m ² , and the softener obtained in the above was added to the pulp in an amount of 0.1% by mass (the total amount of the A component and the B component was 0.1 mass). %) and stirred for 1 minute. Next, ALKOX SW (registered trademark, manufactured by Mingcheng Chemical Industry Co., Ltd.) was used to add 0.1% pure pulp to the pulp using a square sheet machine, and papermaking was carried out using 100 mesh, and pressed at 0.35 MPa for 1 minute, and dried at 105 ° C using a tumble dryer. After drying for 60 seconds, a pulp sheet (paper) was obtained.

[Evaluation method]
The obtained pulp sheet was conditioned for 24 hours in a standard state (temperature: 23 ° C, humidity: 50%), and the following items were evaluated. The results are shown in Tables 1 to 4.

[softness]
The softness of each pulp sheet was judged by eight skilled reviewers based on the following evaluation criteria, and the average value was rounded off. The results are shown in Tables 1 to 4.
5: Especially good
4: Excellent
3: ordinary
2: Slightly worse
1: difference

[Tensile Strength]
The tensile strength of each pulp sheet was measured by a method according to JIS P8113 by a standard temperature of 23 ° C and a humidity of 50%. The measurement was carried out under the conditions of a test piece width of 15 mm, a test length (average interval of the nip line) of 150 mm, and a tensile speed of the test piece of 30 mm/min, using AUTOGRAPH AG-X manufactured by Shimadzu Corporation. The results are shown in Tables 1 to 4.

[Clark stiffness]
The carat stiffness of each pulp sheet was measured by a method according to JIS 8143 at a standard temperature of 23 ° C and a humidity of 50%. The smaller the value, the higher the softness. The results are shown in Tables 1 to 4.

[Practical water absorption]
Each pulp sheet was cut into 7 cm × 7 cm and subjected to weight measurement. 100 ml of distilled water (25 ° C) was placed in a glass petri dish (150 mm in diameter), and the cut pulp sheet was immersed for 30 seconds, and then quickly taken out with a tweezers, and excess water was taken up by a filter paper, and then the weight was measured after 15 seconds. A larger value indicates a higher water absorption. The results are shown in Tables 1 to 4.
Practical water absorption (%) = [(weight of sheet after water absorption - weight of sheet before water absorption) / (weight of sheet before water absorption)] × 100

Claims (14)

A softening agent for papermaking, which comprises: At least one of polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil as component A, and a grade 4 cationic surfactant as component B; The polyoxyalkylene-lined castor oil of the above component A and the polyoxyalkylene hydrogenated castor oil each contain at least a propylene oxide unit. The softening agent for papermaking according to claim 1, wherein the polyoxyalkylene chain castor oil of the above-mentioned component A and the polyoxyalkylene hydrogenated castor oil are respectively added, and the molar number of the propylene oxide unit is 1 to 20. The addition mole number of the ethylene oxide unit is from 0 to 50, and the total number of addition moles of the propylene oxide unit to the ethylene oxide unit is from 3 to 50. The softening agent for papermaking according to claim 1 or 2, wherein the aforementioned 4-stage cationic surfactant of the component B is selected from the group consisting of dimethyldialkylammonium chloride, trimethylmonoalkylammonium chloride, and At least one of the group consisting of a 4-grade ammonium salt having an imidazoline ring. The softening agent for papermaking according to claim 1 or 2, wherein the aforementioned 4-stage cationic surfactant of the component B is N-stearylaminoethyl-N-methyl-2-octadecyl imidazoline N-stearoylaminoethyl-N-methyl-2-octadecenyl imidazolinium methyl sulfate. A softening agent for papermaking, comprising: at least one of polyoxyethylidene ethyl castor oil and polyoxyethylidene hydrogenated castor oil as component A, and Grade 4 cationic surfactant as component B; The aforementioned 4-stage cationic surfactant of the above component B is selected from the group consisting of dimethyldialkylammonium chloride, trimethylmonoalkylammonium chloride, and a 4-grade ammonium salt having an imidazoline ring. At least one of them. The softening agent for papermaking according to any one of claims 1 to 5, which is in the form of an aqueous emulsion. A paper manufacturing method comprising the papermaking step of performing papermaking on a pulp slurry in the presence of a softening agent for papermaking according to any one of claims 1 to 6. The method for producing a paper according to claim 7, wherein in the papermaking step, the total amount of the component A and the component B in the softening agent for papermaking is 0.01 to 5.0 parts by mass based on 100 parts by mass of the absolute dry pulp. . A method of producing a paper comprising the step of adhering a softening agent for papermaking according to any one of claims 1 to 6 to a base paper. A paper obtained by treating a papermaking softener according to any one of claims 1 to 6. a paper comprising: at least one of polyoxyalkylene alkyl castor oil and polyoxyalkylene hydrogenated castor oil as component A, and a grade 4 cationic surfactant as component B; The polyoxyalkylene-lined castor oil of the above component A and the polyoxyalkylene hydrogenated castor oil each contain at least a propylene oxide unit. A paper that contains: At least one of polyoxylated ethyl castor oil and polyoxyethylidene hydrogenated castor oil is used as component A, and a grade 4 cationic surfactant as component B; The aforementioned 4-stage cationic surfactant of the above component B is selected from the group consisting of dimethyldialkylammonium chloride, trimethylmonoalkylammonium chloride, and a 4-grade ammonium salt having an imidazoline ring. At least one of them. Use of the following composition as a softening agent for papermaking, the use of the composition of the A component and the B component as a softening agent for papermaking; The composition includes at least one of polyoxyalkylene-lined castor oil and polyoxyalkylene hydrogenated castor oil as the component A, and a level 4 cationic surfactant as the component B; The polyoxyalkylene-lined castor oil of the above component A and the polyoxyalkylene hydrogenated castor oil each contain at least a propylene oxide unit. Use of the following composition as a softening agent for papermaking, the use of the composition of the A component and the B component as a softening agent for papermaking; The composition comprising at least one of polyoxyethylidene ethyl castor oil and polyoxyethylidene hydrogenated castor oil as the component A and a level 4 cationic surfactant as the component B; The aforementioned 4-stage cationic surfactant of the above component B is selected from the group consisting of dimethyldialkylammonium chloride, trimethylmonoalkylammonium chloride, and a 4-grade ammonium salt having an imidazoline ring. At least one of them.