WO2019146698A1

WO2019146698A1 - Softener for papermaking, paper, and method for manufacturing paper

Info

Publication number: WO2019146698A1
Application number: PCT/JP2019/002269
Authority: WO
Inventors: 裕一中嶋; 浩基古澤
Original assignee: 明成化学工業株式会社
Priority date: 2018-01-25
Filing date: 2019-01-24
Publication date: 2019-08-01
Also published as: TW201937042A; KR20200111188A; JP7253259B2; TWI800595B; JPWO2019146698A1; KR102637760B1

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

Paper softener, paper, and method of producing paper

The present invention relates to paper softeners, paper, and methods of making paper.

In recent years, home paper such as tissue paper and toilet paper is required to have high flexibility. Moreover, the softness at the time of use is calculated | required also in general paper like printing paper and wrapping paper.

Conventionally, as softeners for papermaking, softeners of non-ionic surfactant type (for example, patent document 1) and soft agents of cationic surfactant type (for example, patent documents 2, 3) are generally known. ing.

However, non-ionic surfactant-based softeners have poor fixability to the pulp. For this reason, in order to obtain the required performance, a large amount of addition is required, and the problem is large from the viewpoint of manufacturing cost and the like.

Further, although the softening agent of the cationic surfactant type is excellent in the fixing property to the pulp, there is a problem that the strength of the paper is easily reduced.

As a method of solving these problems, a softener (Patent Document 4) in which a nonionic surfactant having an alkyl group and a cationic surfactant are used in combination is known.

Japanese Patent Publication No. 41-9801 Japanese Patent Application Laid-Open No. 48-22701 Japanese Patent Application Laid-Open No. 63-165597 JP 2004-44058 A

The paper treated with the softener disclosed in Patent Document 4 is not sufficient in terms of achieving both high flexibility and high strength.

Under such circumstances, the main object of the present invention is to provide a paper softener which can impart high flexibility and high strength to paper. Another object of the present invention is to provide a softener for papermaking which can impart flexibility and high water absorbency to paper.

The present inventors diligently studied to solve the above-mentioned problems. As a result, it contains at least one of polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil as component A, and a quaternary cationic surfactant as component B, and further, polyoxyalkylene castor oil and poly of component A. Oxyalkylene hydrogenated castor oil, respectively, has been found to be able to impart high softness and high strength to paper, with paper softeners containing at least propylene oxide units.

In addition, the present inventors include, as component A, at least one of polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil and a component B as a quaternary cationic surfactant, and the component B has a quaternary cationic surfactant. A paper softener comprising at least one agent selected from the group consisting of dimethyldialkyl ammonium chloride, trimethyl monoalkyl ammonium chloride, and quaternary ammonium salts having an imidazoline ring, the paper softener having a flexibility to paper It has been found that high water absorbability can be imparted.

The present invention has been completed by further studies based on these findings.

That is, the present invention provides the invention of the aspects listed below.
Item 1. As component A, at least one of polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil,
As a B component, a quaternary cationic surfactant,
Including
The softener for papermaking, wherein the polyoxyalkylene castor oil of the component A and the polyoxyalkylene hydrogenated castor oil each contain at least a propylene oxide unit.
Item 2. The polyoxyalkylene castor oil of the component A and the polyoxyalkylene hydrogenated castor oil each have an addition mole number of propylene oxide units of 1 to 20, and an addition mole number of ethylene oxide units of 0 to 50; The paper softener according to Item 1, wherein a total of the addition mole number of the oxide unit and the ethylene oxide unit is 3 to 50.
Item 3. Item 1 or 2, wherein the quaternary cationic surfactant of the component B is at least one selected from the group consisting of dimethyldialkyl ammonium chloride, trimethyl monoalkyl ammonium chloride, and quaternary ammonium salt having an imidazoline ring. Paper softener as described in.
Item 4. The softener for paper manufacture according to claim 1 or 2, wherein the quaternary cationic surfactant of the component B is N-stearoylaminoethyl-N-methyl-2-octadecenylimidazolinium methyl sulfate.
Item 5. As component A, at least one of polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil,
As a B component, a quaternary cationic surfactant,
Including
The softener for paper making, wherein the quaternary cationic surfactant of the component B is at least one selected from the group consisting of dimethyldialkyl ammonium chloride, trimethyl monoalkyl ammonium chloride, and quaternary ammonium salt having an imidazoline ring. .
Item 6. The softener for papermaking according to any one of Items 1 to 5, which is in the form of an aqueous emulsion.
Item 7. Item 7. A method for producing paper, comprising a paper making step of making a pulp slurry in the presence of the paper making softener according to any one of items 1 to 6.
Item 8. 10. The method according to item 7, wherein the total addition amount of the component A and the component B of the softener for papermaking in the paper making process is 0.01 to 5.0 parts by mass with respect to 100 parts by mass of bone dry pulp. Paper manufacturing method.
Item 9. A method for producing paper, comprising the step of adhering the papermaking softener according to any one of items 1 to 6 on a base paper.
Item 10. A paper treated with the paper softener according to any one of items 1 to 6.
Item 11. As component A, at least one of polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil,
As a B component, a quaternary cationic surfactant,
Including
A paper, wherein the polyoxyalkylene castor oil of the component A and the polyoxyalkylene hydrogenated castor oil each contain at least a propylene oxide unit.
Item 12. As component A, at least one of polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil,
As a B component, a quaternary cationic surfactant,
Including
The paper, wherein the quaternary cationic surfactant of the component B is at least one selected from the group consisting of dimethyldialkyl ammonium chloride, trimethyl monoalkyl ammonium chloride, and a quaternary ammonium salt having an imidazoline ring.
Item 13. Use of a composition containing the components A and B as a softener for papermaking,
The composition contains at least one of polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil as the component A, and a quaternary cationic surfactant as the component B,
The polyoxyalkylene castor oil of the component A and the polyoxyalkylene hydrogenated castor oil each contain at least a propylene oxide unit,
Use of the composition as a softener for papermaking.
Item 14. Use of a composition containing the components A and B as a softener for papermaking,
The composition contains at least one of polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil as the component A, and a quaternary cationic surfactant as the component B,
The quaternary cationic surfactant of the component B is at least one selected from the group consisting of dimethyldialkyl ammonium chloride, trimethyl monoalkyl ammonium chloride, and a quaternary ammonium salt having an imidazoline ring.
Use of the composition as a softener for papermaking.

According to the present invention, it is possible to provide a paper making softener which can impart high flexibility and high strength to paper. Further, according to the present invention, it is possible to provide a paper making softener which can impart flexibility and high water absorption to paper. Furthermore, according to the present invention, it is also possible to provide a paper treated with these paper softeners, and a method for producing paper.

The paper softener according to the first embodiment of the present invention contains, as component A, at least one of polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil, and as component B, a quaternary cationic surfactant. Furthermore, the polyoxyalkylene castor oil and the polyoxyalkylene hydrogenated castor oil of the component A are each characterized by containing at least a propylene oxide unit. The paper softener according to the first embodiment of the present invention can impart high flexibility and high strength to paper by including such a configuration.

Further, the softening agent for papermaking according to the second embodiment of the present invention comprises, as component A, at least one of polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil, and as component B, a quaternary cationic surfactant and And the quaternary cationic surfactant of component B is at least one selected from the group consisting of dimethyldialkyl ammonium chloride, trimethyl monoalkyl ammonium chloride, and quaternary ammonium salt having an imidazoline ring. There is. The paper softener according to the second embodiment of the present invention can impart flexibility and high water absorbency to paper by having such a configuration.

Hereinafter, the softener for papermaking of the present invention, paper using the softener for papermaking, and a method for producing paper will be described in detail. In the following description, the softener for papermaking according to the first embodiment will be described, and then the softener for papermaking according to the second embodiment will be described. In the description of the softener for papermaking according to the second embodiment, the description of the matters common to the first embodiment will be appropriately omitted.

1. Softener for Paper Making <First Embodiment>
The papermaking softener according to the first embodiment of the present invention contains an A component and a B component. Each of the component A and the component B 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. Moreover, polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil each contain a propylene oxide unit. That is, the "polyoxyalkylene" of polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil contains a propylene oxide unit.

Polyoxyalkylene castor oil is a compound obtained by adding a polyalkylene oxide to castor oil. 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 known and readily commercially available.

In the polyoxyalkylene castor oil and the polyoxyalkylene hydrogenated castor oil, the addition mole number of the propylene oxide unit is not particularly limited, but from the viewpoint of imparting high flexibility and high strength to the paper, each is preferably 1 It is preferably -20, more preferably 2-15, and still more preferably 3-12. In addition, as propylene oxide, 1,2-propylene oxide and 1,3-propylene oxide can be mentioned.

In polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil, other alkylene oxide units may be added in addition to the propylene oxide unit. Other alkylene oxide units include ethylene oxide units and butylene oxide units from the viewpoint of imparting high flexibility and high strength to paper. The butylene oxide includes 1,2-butylene oxide, 2,3-butylene oxide, and isobutylene oxide. The other alkylene oxide units may be contained singly or in combination of two or more. In addition, in polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil, when other alkylene oxide units are added in addition to propylene oxide units, the polyalkylene oxide may be a block copolymer, And a random copolymer.

From the viewpoint of imparting high flexibility and high strength to paper, polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil each have an addition mole number of propylene oxide units of 1 to 20, and other alkylene oxides It is preferable that the addition mole number of the unit is 0 to 50, and the total addition mole number of the propylene oxide unit and the other alkylene oxide unit is 3 to 50. In particular, polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil each have an addition mole number of propylene oxide units of 1 to 20, an addition mole number of ethylene oxide units of 0 to 50, and propylene oxide units and ethylene oxide The total addition mole number of units is preferably 3 to 50, the addition mole number of propylene oxide units is 2 to 15, the addition mole number of ethylene oxide units is 2 to 25, and a propylene oxide unit and an ethylene oxide unit More preferably, the sum of the number of added moles is 4 to 40, the number of added moles of propylene oxide units is 3 to 12, the number of added moles of ethylene oxide units is 3 to 15, and the propylene oxide units and the ethylene oxide units The total number of added moles of is 6 to 27 Preferred in La.

Component B is a quaternary cationic surfactant. The quaternary cationic surfactant is not particularly limited as long as it is used as a softener for papermaking, and known surfactants having a quaternary cation can be used.

From the viewpoint of imparting high flexibility and high strength to paper by being used in combination with the component A, preferred quaternary cationic surfactants include dimethyldialkyl ammonium chloride, trimethyl monoalkyl ammonium chloride, and an imidazoline ring. The quaternary ammonium salt which it has is mentioned.

In the dimethyldialkyl ammonium chloride, the two alkyl groups (dialkyls) are not particularly limited, but from the viewpoint of imparting high flexibility and high strength to the paper, an alkyl group preferably having 6 to 24 carbon atoms, respectively, More preferably, it is an alkyl group having 6 to 18 carbon atoms. Specific examples of the alkyl group include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl (lauryl) group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl (cetyl, palmityl) group, Heptadecyl group, octadecyl (stearyl) group, nonadecyl group, eicosyl group, heneicosyl group, docosyl (behenyl) group, tricosyl group, tetracosyl group and the like. The two alkyl groups may be identical or different. Also, these alkyl groups may be linear or branched. Specific examples of dimethyldialkyl ammonium chloride include dimethyl distearyl ammonium chloride, dimethyl dilauryl ammonium chloride, dimethyl dicetyl ammonium chloride, dimethyl dipalmityl ammonium chloride, dimethyl distearyl ammonium chloride, dimethyl dioleyl ammonium chloride, dimethyl dibehenyl Ammonium chloride etc. are mentioned.

In the trimethylalkyl ammonium chloride, the alkyl group is not particularly limited, but preferably an alkyl group having 6 to 24 carbon atoms, more preferably a carbon number, from the viewpoint of imparting high flexibility and high strength to paper. Are 6 to 18 alkyl groups. Specific examples of the alkyl group include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl (lauryl) group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl (cetyl, palmityl) group, Heptadecyl group, octadecyl (stearyl) group, nonadecyl group, eicosyl group, heneicosyl group, docosyl (behenyl) group, tricosyl group, tetracosyl group and the like. The alkyl group may be linear or branched. Specific examples of trimethyl alkyl ammonium chloride include trimethyl stearyl ammonium chloride, trimethyl mono lauryl ammonium chloride, trimethyl monocetyl ammonium chloride, trimethyl mono palmityl ammonium chloride, trimethyl mono stearyl ammonium chloride, trimethyl mono oleyl ammonium chloride, trimethyl mono behenyl ammonium Chloride etc. are mentioned.

As a quaternary ammonium salt which has an imidazoline ring, the quaternary ammonium salt represented by following General formula (1) is mentioned.

In the general 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 the carbon number an alkenyl group of 1 ~ 24, X ^- is a sulfate ion, anions such as chloride ion.

As a quaternary ammonium salt having an imidazoline ring, from the viewpoint of imparting high flexibility and high strength to paper, preferably N-stearoylaminoethyl-N-methyl-2-octadecenylimidazolium methyl sulfate, 1-hydroxyethyl-1-ethyl-2-oleylimidazoline ethyl sulfate, 1-hydroxyethyl-1-methyl-2-oleylimidazoline chloride, 1-hydroxyethyl-1-ethyl-2-laurylimidazoline ethyl sulfate.

Furthermore, examples of quaternary cationic surfactants include monomethyl ester quaternary salt, dimethyl diester quaternary salt, trimethyl diester quaternary salt and the like. Examples of the monomethyl ester quaternary salt include those obtained by diesterizing triethanolamine with a fatty acid having 7 to 25 carbon atoms, preferably 11 to 23 carbon atoms, such as stearic acid, and quaternizing it with dimethyl sulfate; Examples of the salt include those obtained by diesterizing N-methyldiethanolamine with a fatty acid having 7 to 25 carbon atoms, preferably 11 to 23 carbon atoms, such as oleic acid, and quaternizing with methyl chloride, and the trimethyldiester quaternary salt includes Examples thereof include 3-dimethylamino-1,2-propanediol which is diesterified with a fatty acid having 7 to 25 carbon atoms, preferably 11 to 23 carbon atoms, such as oleic acid, and quaternized with methyl chloride.

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

Second Embodiment
The softener according to the second embodiment of the present invention is also the same as the first embodiment except that at least one of polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil as component A and component B as component B And a class cationic surfactant.

However, in the paper softener according to the second embodiment, the quaternary cationic surfactant of the component B is a group consisting of dimethyldialkyl ammonium chloride, trimethyl monoalkyl ammonium chloride, and a quaternary ammonium salt having an imidazoline ring. Since at least one selected is used, the polyoxyalkylene castor oil and the polyoxyalkylene hydrogenated castor oil of the component A may or may not contain propylene oxide units, respectively. . That is, in the paper softener according to the second embodiment, the "polyoxyalkylene" of the polyoxyalkylene castor oil of component A and the polyoxyalkylene hydrogenated castor oil may contain a propylene oxide unit, It does not have to be included. For example, in the paper softener according to the second embodiment, the "polyoxyalkylene" may be composed only of polyoxyethylene.

In the paper softener according to the second embodiment, when the polyoxyalkylene castor oil of component A and the polyoxyalkylene hydrogenated castor oil each contain a propylene oxide unit, as the component A, the first embodiment. The same as is preferably exemplified.

In the paper softener according to the second embodiment, when the polyoxyalkylene castor oil and the polyoxyalkylene hydrogenated castor oil of the component A do not each contain a propylene oxide unit, they are combined with the component B to be described later in the paper. On the other hand, it is preferable that polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil are polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil, respectively, from the viewpoint of imparting flexibility and high water absorption.

In polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil, the addition mole number of the ethylene oxide unit is not particularly limited, but in view of imparting flexibility and high water absorbency to paper in combination with B component described later And preferably 1 to 20, more preferably 2 to 15, and still more preferably 3 to 12, respectively.

Also in the second embodiment, the B component is a quaternary cationic surfactant, but from the viewpoint of imparting flexibility and high water absorbency to paper, dimethyldialkyl ammonium chloride, trimethyl monoalkyl ammonium chloride, and It is at least one selected from the group consisting of quaternary ammonium salts having an imidazoline ring. In the softener for papermaking of the second embodiment, by combining the above-described A component and these B components, it is possible to impart flexibility and high water absorbency to paper.

In the softener for papermaking of the second embodiment, the blending ratio of component A and component B (component A: component B, mass ratio) is preferably from the viewpoint of imparting flexibility and high water absorbency to paper. And 100: 0.5 to 100: 40, more preferably 100: 1 to 100: 35, still more preferably 100: 2 to 100: 25.

The paper softener according to the first and second embodiments may contain other additives in addition to the components A and B, respectively. As other additives, known additives to be mixed with a softener for paper making can be used, and examples thereof include dry paper strength improvers, wet paper strength improvers, coagulants, thickeners and the like. When other additives are contained, as a ratio of the additive in the softener for paper making of the first and second embodiments, the coagulant is, for example, 100 parts by mass of the total of the A component and the B component. The amount is 1 to 200 ppm and the viscosity is 0.05 to 0.15 parts by mass. Here, as a coagulant, polydiallyldimethyl ammonium chloride (pDADMAC) or a derivative thereof, a copolymer of diallyl dimethyl ammonium chloride and another monomer, polyacrylamide, polyamine, polyethylene imine, 2- (methacryloyloxy) ethyltrimethyl ammonium chloride Polymers, modified polyethylene imine and the like can be mentioned. Examples of the tackifier include polyethylene oxide-based tackifiers ("Alcox" series manufactured by Meisei Chemical Co., Ltd.) and the like.

The paper softener according to the first and second embodiments may or may not contain a solvent in addition to the component A and the component B, respectively. The solvent is not particularly limited, but preferably includes water and an alcohol such as isopropyl alcohol. A solvent may use only 1 type and may mix and use 2 or more types. It is preferable to disperse | distribute A component and B component in a solvent. For example, by using water as a solvent, the softener for papermaking of the first and second embodiments may be in the form of an aqueous emulsion in which the A component and the B component are dispersed in a solvent containing water, respectively. it can.

No particular limitation is imposed on the method for dispersing the component A and the component B in water in the first and second embodiments, respectively. The phase inversion emulsification method, a surfactant or an inorganic salt is added. The later phase inversion emulsification method, mechanical dispersion method of dispersing by mechanical method, etc. may be mentioned. Examples of the mechanical dispersion method include methods of uniformly dispersing by means of various known emulsifying machines such as homomixer, high pressure discharge type homogenizer, high shear type rotary emulsifying and dispersing machine, ultrasonic emulsifying machine and the like. The dispersion method may be one type only or two or more types in combination.

When the softener for papermaking of the first and second embodiments is in the form of an aqueous emulsion, respectively, as the total content of the component A and the component B in the softener for papermaking of the first and second embodiments Is preferably 10 to 40% by mass, more preferably 15 to 30% by mass.

From the viewpoint of imparting high flexibility, high strength, and high water absorption to paper, the softener for papermaking of the present invention has the constitution of both of the softeners for papermaking of the first and second embodiments. It is particularly preferred to be satisfactory.

2. Paper and Method for Producing the Same The paper of the present invention is suitably produced, for example, by a method comprising a paper making process for making a pulp slurry in the presence of the paper making softener of the first and second embodiments, respectively. Can. The paper of the present invention can also be suitably produced, for example, by adhering the paper making softener of the first and second embodiments to a base paper. Furthermore, using these production methods in combination, first, a base paper is prepared by a paper making process for making a pulp slurry in the presence of the softener for paper making of the first and second embodiments, and then the obtained base paper It can also be produced by adhering the paper making softener of the first and second embodiments to a base paper. The details of the paper softener according to the first and second embodiments are as described above.

In the paper making process, the total addition amount of the component A and the component B of the softener for paper making of the first and second embodiments is preferably 0.01 to 5.0 with respect to 100 parts by mass of bone dry pulp. There are mentioned parts by mass, more preferably 0.01 to 2.0 parts by mass, and still more preferably 0.05 to 0.5 parts by mass. In addition, when the softeners for papermaking of the first and second embodiments are attached to the base paper, the total addition amount of the component A and the component B to be attached to the base paper is preferably in these ranges. That is, 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. The amount is 0 parts by mass, more preferably 0.05 to 0.5 parts by mass.

Papermaking of pulp slurry can be carried out by a method using a known paper machine. The paper machine may be any device capable of dewatering the pulp slurry on a wire. Examples of the paper machine include suction breast formers (yen net type, long mesh type), twin wire formers, circle net formers (C wrap, S wrap), crescent formers, and the like. In addition to a continuous paper machine such as a Fourdrinier paper machine, after adding a pulp slurry to a forming frame formed of a wire, it is dewatered from the lower portion of the wire to produce a formed body by a batch type pulp mold Molding machines are also included in that category.

The method of attaching the paper making softener according to the first and second embodiments to the surface of the base paper is not particularly limited as long as the component A and the component B adhere to the surface of the base paper, for example, the spray method Coating by a flexo method or gravure method, size press, gate roll coater, bill blade coater, calender coating, and the like.

Examples of applications of the paper of the present invention include household paper such as tissue paper, toilet paper, towel paper, and kitchen paper, and general paper such as printing paper and wrapping paper. The paper treated with the paper softener of the first embodiment combines high flexibility and high strength, and the paper treated with the paper softener of the second embodiment has the flexibility and The combination of high water absorbability makes them particularly suitable for use as tissue paper and toilet paper among household paper.

Pulp materials constituting the paper or base paper of the present invention include softwood bleached kraft pulp (NBKP), hardwood bleached kraft pulp (LBKP), ground pulp (GP), thermomechanical pulp (TMP), chemithermomechanical Pulp (CTMP), deinked pulp (DIP), etc. may be mentioned. Moreover, waste pulp such as newspaper waste paper, magazine waste paper, corrugated waste paper, deinked waste paper, etc. can also be used as a pulp raw material. In addition, the paper of the present invention may contain a mixture of the above-described pulp raw material and rock wool, asbestos, or synthetic fibers such as polyamide, polyimide, polyester, polyolefin, and polyvinyl alcohol.

In manufacturing the paper of the present invention, various additives such as fillers, sulfate bands, sizing agents, dry strength improvers, wet strength improvers, moisturizers, retention improvers, freeness improvers, etc. You may use as needed in order to express the physical property requested | required of a species. These may be used alone or in combination of two or more. Also, these additives may be mixed in advance with the softeners for paper making of the first and second embodiments and added to the pulp slurry to produce the paper of the present invention, or to be adhered to the base paper. it can.

As the filler, kaolin, calcined kaolin, derivatized kaolin, illite, ground calcium carbonate, light calcium carbonate, light calcium carbonate-silica composite, magnesium carbonate, barium carbonate, titanium dioxide, zinc oxide, silicon oxide, amorphous And inorganic fillers such as aluminum hydroxide, calcium hydroxide and magnesium hydroxide. The filler may be used alone or in combination of two or more.

As sizing agents, sizing agents for fatty acid soaps such as sodium stearate, rosin, fortified rosin, aqueous emulsion of rosin ester, aqueous emulsion of alkenyl succinic anhydride, aqueous emulsion of 2-oxetanone, aqueous emulsion of paraffin wax, carboxylic acid Cationic sizing agents obtained by the reaction of a polyvalent amine, an aqueous emulsion of a reactant of an aliphatic oxy acid and an aliphatic amine or aliphatic alcohol, and anionic and cationic styrenic sizing agents. Only one type of sizing agent may be used, or two or more types may be mixed and used.

Examples of the dry strength improver include anionic polyacrylamide, cationic polyacrylamide, amphoteric polyacrylamide, cationized starch, amphoteric starch and the like. Only one type of dry strength improver may be used, or two or more types may be mixed and used.

Examples of wet paper strength improvers include polyamide epichlorohydrin resins, melamine formaldehyde resins, and urea formaldehyde resins. Moreover, you may use together anionic polyacrylamide. Only one type of wet strength agent may be used, or two or more types may be mixed and used.

Humectants include polyhydric alcohols such as glycerin, sorbitol and polyethylene glycol. A moisturizer may use only 1 type and may mix and use 2 or more types.

As the retention aid, anionic, cationic or amphoteric high molecular weight polyacrylamide can be used, silica sol and cationized starch can be used in combination, or bentonite and cationic high molecular weight polyacrylamide can be used in combination. The retention aid may be used alone or in combination of two or more.

Examples of the drainage improver include polyethylene imine, cationic or amphoteric or anionic polyacrylamide and the like. Only one type of the drainage improving agent may be used, or two or more types may be mixed and used.

In addition, when applying the paper making softener of the first and second embodiments to a base paper, it can be used in combination with known additives used for surface coating of the base paper. Specific examples of such additives include surface strength improvers such as starch, polyvinyl alcohol and acrylamide polymers, dyes, coating colors, moisturizers, surface sizing agents, and anti-slip agents.

Hereinafter, the present invention will be described in detail by way of Examples and Comparative Examples. However, the present invention is not limited to the examples.

Example 1
Charge 524 g of castor oil and 1.0 g of special grade potassium hydroxide to an autoclave (made by stainless steel made by pressure resistant glass industry), and add 150 g of ethylene oxide and 327 g of propylene oxide at 150 ° C. After cooling to 85 ° C., 1.1 g of 90% acetic acid was added, and after stirring for 30 minutes, Compound A-1 as Component A was obtained. Subsequently, 87.3 g of ion-exchanged water, 2.7 g of Cortamine D86P as a component B (a 75% product of Kao's product distearyldimethyl ammonium chloride) and 10 g of a compound A-1 (component A) are sequentially added to a 500 ml glass beaker at 60 ° C. After stirring for 30 minutes, the mixture was cooled to 40 ° C. or less to obtain 100 g of a softener for papermaking in the form of an aqueous emulsion (the total content of components A and B is 10% by mass). The ratio (mass ratio) of the component A to the component B is shown in Table 1.

Example 2
552 g of hardened castor oil was charged into an autoclave and heated to 90 ° C. and dissolved, then 1.0 g of special grade potassium hydroxide was charged, and a mixture of 311 g of ethylene oxide and 137 g of propylene oxide was gradually dropped over 3 hours at 150 ° C. After completion of the dropwise addition, the mixture was cooled to 85 ° C., 1.1 g of 90% acetic acid was added, and the mixture was stirred for 30 minutes to obtain Compound A-2 as Component A. Subsequently, 82.9 g of ion-exchanged water, 7.1 g of Cortamine 86W (Kao product stearyltrimethylammonium chloride 28% product) as component B and 10 g of compound A-2 (component A) are sequentially added to a 200 ml glass beaker at 30 ° C. After stirring for a minute, the mixture was cooled to 40 ° C. or less to obtain 100 g of a softener for papermaking in the form of an aqueous emulsion (the total content of components A and B is 10% by mass). The ratio (mass ratio) of the component A to the component B is shown in Table 1.

[Example 3]
In an autoclave, 542 g of hardened castor oil and dissolved by heating to 90 ° C., 1.0 g of special grade potassium hydroxide is charged, 202 g of propylene oxide is added over 3 hours at 170 ° C., and after cooling to 130 ° C., 255 g of ethylene oxide is 4 hours The reaction mixture was added, and cooled to 85 ° C. after completion of the reaction, and then 1.1 g of 90% acetic acid was added to obtain Compound A-3 as Component A. Then, in an 200 ml glass beaker, 85.6 g of ion-exchanged water and 4.4 g of cation SF-75 PA (manufactured by Sanyo Chemical Industries, Ltd. 75% of N-stearoylaminoethyl-N-methyl-2-octadecenylimidazolinium methyl sulfate) Then, 10 g of Compound A-3 (A component) was sequentially added and stirred for 30 minutes at 60 ° C., followed by cooling to 40 ° C. or less, for papermaking in the form of an aqueous emulsion (total content of A component and B component is 10 mass%) 100 g of softener was obtained. The ratio (mass ratio) of the component A to the component B is shown in Table 1.

Example 4
518 g of hardened castor oil and 1.0 g of special grade potassium hydroxide are charged in an autoclave, 385 g of propylene oxide is added over 5 hours at 170 ° C., and after cooling to 130 ° C., 97 g of ethylene oxide is added over 2 hours. After cooling to 85 ° C., 1.1 g of 90% acetic acid was added to obtain compound A-4 (component A). Thereafter, in the same manner as in Example 3, except that Compound A-4 was used instead of Compound A-3 as Component A, a form of an aqueous emulsion (the total content of Components A and B was 10% by mass) 100 g of a softener for papermaking of The ratio (mass ratio) of the component A to the component B is shown in Table 1.

[Comparative Examples 1 to 4]
10 g of the component A and / or the component B and 90 g of ion-exchanged water were stirred for 30 minutes at normal temperature so as to obtain the ratio (mass ratio) of the component A and the component B shown in Table 2; 100 g of a softener for papermaking in a form (the total content of the components A and B being 10% by mass) was obtained.

In Tables 1 and 2, "EO" means ethylene oxide units and "PO" means propylene oxide units. Further, the number of moles after “EO” and “PO” means the number of moles of addition of ethylene oxide units and propylene oxide units, for example, the notation “6 moles of EO” means the number of moles of addition of ethylene oxide units. Is meant to be 6.

[Example 5]
82.9 g of ion-exchanged water, 7.1 g of Cortamine 86 W (Kao product stearyltrimethylammonium chloride 28% product) as component B and 10 g of compound A-3 (component A) in a 200 ml glass beaker, and stirring at 60 ° C. for 30 minutes The mixture was cooled to 40 ° C. or less to obtain 100 g of a softener for papermaking in the form of an aqueous emulsion (the total content of A component and B component is 10% by mass). The proportions (mass ratios) of the component A and the component B are shown in Table 3.

[Example 6]
Add 87.3 g of ion-exchanged water, 2.7 g of Cortamine D86P (75% Kao's product distearyldimethyl ammonium chloride) as Component B, and 10 g of Braunone BR-410 (Compound A-5) as Component A in a 200 ml glass beaker 60 After stirring at 30 ° C. for 30 minutes, the solution was cooled to 40 ° C. or less to obtain 100 g of a softener for papermaking in the form of an aqueous emulsion (the total content of components A and B is 10% by mass). The proportions (mass ratios) of the component A and the component B are shown in Table 3.

[Example 7]
In a 200-ml glass beaker, 82.9 g of ion-exchanged water, 7.1 g of Cortamine 86 W (Kao product stearyltrimethylammonium chloride 28% product) as component B, and 10 g of braunone CW-10 (compound A-6) as component A are sequentially added to 60 ° C. After stirring for 30 minutes, the mixture was cooled to 40.degree. C. or less to obtain 100 g of a softener for papermaking in the form of an aqueous emulsion (the total content of components A and B is 10% by mass). The proportions (mass ratios) of the component A and the component B are shown in Table 3.

Example 8
75.7 g of ion-exchanged water, 14.3 g of Cortamine 86 W (Kao product stearyltrimethyl ammonium chloride 28% product) as component B, and 10 g of braunone CW-10 (compound A-6) as component A in a 200 ml glass beaker at 60 ° C. After stirring for 30 minutes, the mixture was cooled to 40.degree. C. or less to obtain 100 g of a softener for papermaking in the form of an aqueous emulsion (the total content of components A and B is 10% by mass). The proportions (mass ratios) of the component A and the component B are shown in Table 3.

[Example 9]
85.6 g of ion-exchanged water in a 200 ml glass beaker, cation SF-75PA as component B (manufactured by Sanyo Chemical Industries, Ltd. N-stearoylaminoethyl-N-methyl-2-octadecenylimidazolinium methyl sulfate 75%) 4. 4 g, 10 g of braunone CW-10 (compound A-6) as component A are sequentially added, stirred at 60 ° C. for 30 minutes, cooled to 40 ° C. or less, and the form of aqueous emulsion (total content of components A and B is 10 100% by mass of the paper softener was obtained. The proportions (mass ratios) of the component A and the component B are shown in Table 3.

Comparative Example 5
87.9 g of ion-exchanged water, 2.1 g of Liposocard C / 25 (Lion product dipolyoxyethylene palm alkyl methyl ammonium chloride 95% product) as component B in a 200 ml glass beaker, and 10.0 g of compound A-5 are sequentially added to 60 ° C. After stirring for 30 minutes, the mixture was cooled to 40.degree. C. or less to obtain 100 g of a softener for papermaking in the form of an aqueous emulsion (the total content of components A and B is 10% by mass).

Comparative Example 6
In an 200-ml glass beaker, 85.8 g of ion-exchanged water, 4.2 g of Liposocard C / 25 (Lion product dipolyoxyethylene palm alkyl methyl ammonium chloride 95% product) as component B, and 10.0 g of compound A-6 are sequentially added at 60 ° C. After stirring for 30 minutes, the mixture was cooled to 40.degree. C. or less to obtain 100 g of a softener for papermaking in the form of an aqueous emulsion (the total content of components A and B is 10% by mass).

Comparative Example 7
The case where the softener for papermaking was not used was referred to as Comparative Example 7.

In Tables 3 and 4, "EO" means ethylene oxide units and "PO" means propylene oxide units. Further, the number of moles after “EO” and “PO” means the number of moles of addition of ethylene oxide units and propylene oxide units, for example, the notation “6 moles of EO” means the number of moles of addition of ethylene oxide units. Is meant to be 6.

[Papermaking method]
Weigh hardwood bleached kraft pulp (LBKP) and softwood bleached kraft pulp (NBKP) to a mass ratio of 7: 3 and beat it to a Canadian standard freeness of 450 ml using a disintegrator (manufactured by Kumagai Riki) The concentration was adjusted to 1.0%. After weighing so as to have a basis weight of 20 g / m ² , the softeners obtained above were each added to the pulp in an amount of 0.1% by mass on a pure basis (total addition amount of A component and B component is 0.1 % By mass) and stirred for 1 minute. Next, add 0.1% of a net content of Alcox SW (registered trademark, manufactured by Meisei Chemical Industry Co., Ltd.) to the pulp in a square sheet machine, make a paper using 100 mesh, and press at 0.35 MPa for 1 minute The resultant was dried at 105 ° C. for 60 seconds with a drum dryer to obtain a pulp sheet (paper).

〔Evaluation method〕
The resulting pulp sheet was conditioned for 24 hours under standard conditions (temperature 23 ° C., humidity 50%), and then evaluated for the following items. The results are shown in Tables 1 to 4.

[Flexibility]
The flexibility of each pulp sheet was judged by eight skilled monitors based on the following evaluation criteria, and the average value was rounded off. The results are shown in Tables 1 to 4.
5: Particularly excellent 4: Excellent 3: Normal 2: Slightly inferior 1: Poor

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

[Clark stiffness]
The Clark stiffness of each pulp sheet was measured at a temperature of 23 ° C. and a humidity of 50%, which is a standard state, according to a method in accordance with JIS 8143. The smaller the value, the more flexible it is. The results are shown in Tables 1 to 4.

[Practical water absorption]
Cut each pulp sheet into 7 cm x 7 cm and measure the weight. 100 ml of distilled water (25 ° C.) was placed in a glass petri dish (diameter 150 mm), and the cut pulp sheet was immersed for 30 seconds, then quickly taken out with tweezers, and after absorbing excess water with filter paper, it was weighed 15 seconds later. The larger the value, the higher the water absorbability. The results are shown in Tables 1 to 4.
Practical water absorption (%) = [(sheet weight after water absorption-sheet weight before water absorption) / (sheet weight before water absorption)] × 100

Claims

As component A, at least one of polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil,
As a B component, a quaternary cationic surfactant,
Including
The softener for papermaking, wherein the polyoxyalkylene castor oil of the component A and the polyoxyalkylene hydrogenated castor oil each contain at least a propylene oxide unit.
The polyoxyalkylene castor oil of the component A and the polyoxyalkylene hydrogenated castor oil each have an addition mole number of propylene oxide units of 1 to 20, and an addition mole number of ethylene oxide units of 0 to 50; The paper softener according to claim 1, wherein a total of the addition mole number of the oxide unit and the ethylene oxide unit is 3 to 50.
The quaternary cationic surfactant of the component B is at least one selected from the group consisting of dimethyldialkyl ammonium chloride, trimethyl monoalkyl ammonium chloride, and a quaternary ammonium salt having an imidazoline ring. Paper softener according to 2.
The paper softener according to claim 1 or 2, wherein the quaternary cationic surfactant of component B is N-stearoylaminoethyl-N-methyl-2-octadecenylimidazolinium methyl sulfate.
As component A, at least one of polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil,
As a B component, a quaternary cationic surfactant,
Including
The softener for paper making, wherein the quaternary cationic surfactant of the component B is at least one selected from the group consisting of dimethyldialkyl ammonium chloride, trimethyl monoalkyl ammonium chloride, and quaternary ammonium salt having an imidazoline ring. .
A paper softener according to any of claims 1 to 5, in the form of an aqueous emulsion.
A method for producing paper comprising a paper making step of making a pulp slurry in the presence of the paper making softener according to any one of claims 1 to 6.
The method according to claim 7, wherein in the paper making process, a total addition amount of the component A and the component B of the softener for papermaking is 0.01 to 5.0 parts by mass with respect to 100 parts by mass of bone dry pulp. Method for producing the described paper.
A method for producing paper, comprising the step of adhering the papermaking softener according to any one of claims 1 to 6 to a base paper.
A paper treated with the papermaking softener according to any one of claims 1 to 6.
As component A, at least one of polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil,
As a B component, a quaternary cationic surfactant,
Including
A paper, wherein the polyoxyalkylene castor oil of the component A and the polyoxyalkylene hydrogenated castor oil each contain at least a propylene oxide unit.
As component A, at least one of polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil,
As a B component, a quaternary cationic surfactant,
Including
The paper, wherein the quaternary cationic surfactant of the component B is at least one selected from the group consisting of dimethyldialkyl ammonium chloride, trimethyl monoalkyl ammonium chloride, and a quaternary ammonium salt having an imidazoline ring.
Use of a composition containing the components A and B as a softener for papermaking,
The composition contains at least one of polyoxyalkylene castor oil and polyoxyalkylene hydrogenated castor oil as the component A, and a quaternary cationic surfactant as the component B,
The polyoxyalkylene castor oil of the component A and the polyoxyalkylene hydrogenated castor oil each contain at least a propylene oxide unit,
Use of the composition as a softener for papermaking.
Use of a composition containing the components A and B as a softener for papermaking,
The composition contains at least one of polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil as the component A, and a quaternary cationic surfactant as the component B,
The quaternary cationic surfactant of the component B is at least one selected from the group consisting of dimethyldialkyl ammonium chloride, trimethyl monoalkyl ammonium chloride, and a quaternary ammonium salt having an imidazoline ring.
Use of the composition as a softener for papermaking.