JP2007177372A - Paper production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pulp treating agent capable of imparting excellent softness and smoothness to paper having a basis weight of 5-30 g/m<SP>2</SP>and frequently used as home paper. <P>SOLUTION: The paper production method has a step (I) to treat pulp fiber with a pulp treating agent obtained by compounding an alkoxysilane of formula (1): R<SP>1</SP><SB>p</SB>Si(OR<SP>2</SP>)<SB>4-p</SB>, an organic acid and water to obtain paper having a basis weight of 5-30 g/m<SP>2</SP>. Not less than 50 wt.% of the alkoxysilane of formula (1) is selected from a trialkoxysilane of formula (2): R<SP>1</SP>Si(OR<SP>2</SP>)<SB>3</SB>and dialkoxysilane of formula (3): R<SP>1</SP><SB>2</SB>Si(OR<SP>2</SP>)<SB>2</SB>, the amount of water is ≥3 times mol of the amount of the alkoxysilane of formula (1), and the pH of the agent is 2-5 at 20°C. In the formulas, R<SP>1</SP>is a 1-6C alkyl or the like; R<SP>2</SP>is a 1-6C alkyl; and p is an integer of 1-3. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a method for producing paper having a basis weight of 5 to 30 g / m ² that is frequently used for household paper, and a pulp treatment agent for obtaining paper having excellent softness and smoothness.

  Conventionally, among papers made from pulp (hereinafter, also simply referred to as paper), development has been promoted to improve the feel of household paper such as toilet paper and tissue paper, that is, soft, smooth and comfortable to the touch. .

  For example, a method (Patent Document 1) for producing by changing the kind and composition of pulp, a method (Patent Document 2) for adding a quaternary ammonium salt type cationic activator as a softening agent, and the like have been proposed.

  On the other hand, a specific alkoxysilane is treated on paper to give various functions to the paper (Patent Document 3), or it is treated on pulp slurry to improve the water resistance, dimensional stability and friction resistance of the paper. (Patent Document 4) has been attempted.

JP 54-46914 A Japanese Patent Laid-Open No. 48-22701 JP 2003-319721 A JP 2001-181599 A

  In recent years, hay fever and influenza epidemics and a kind of externally irritating skin disease called sensitive skin tend to increase, and skin irritation has been taken up much more than before, The demand for softness and smoothness of paper is increasing more than ever.

INDUSTRIAL APPLICABILITY The present invention provides a pulp processing agent that can impart excellent softness and smoothness to paper having a basis weight of 5 to 30 g / m ² that is often used for household paper, and a suitable basis weight of 5 using the pulp processing agent. It is an object of the present invention to provide a method for producing paper of ˜30 g / m ² .

  As a result of examining the alkoxysilane-based treatment agent in more detail, the present inventors have found a pulp treatment agent that is superior to conventional treatment agents in terms of softness and smoothness, and a suitable paper manufacturing method using the agent. The headline and the present invention were completed.

This invention manufactures paper which has the process (I) which makes the pulp processing agent formed by mix | blending the alkoxysilane (a) represented by General formula (1), organic acid (b), and water with a pulp fiber. A method wherein 50% by weight or more in alkoxysilane (a) is selected from trialkoxysilane (a1) represented by general formula (2) and dialkoxysilane (a2) represented by general formula (3) The basis weight is 5 to 30 g / m. The basis weight is 5 to 30 g / m. ^{The present} invention relates to a method for producing paper ² .
R ¹ _p Si (OR ² ) _4-p (1)
R ¹ Si (OR ² ) ₃ (2)
R ¹ ₂ Si (OR ² ) ₂ (3)
Wherein, R ¹ represents a linear or branched alkyl group having 1 to 6 carbon atoms, a straight-chain or branched alkenyl group having a phenyl group, or 2 to 6 carbon atoms, R ² is 1 to the number of carbon atoms 6 linear or branched alkyl groups, p R ¹ and (4-p) R ² may be the same or different. p shows the integer of 1-3. ]

Moreover, this invention is a pulp processing agent formed by mix | blending the alkoxysilane (a) represented by the said General formula (1), organic acid (b), and water, Comprising: 50 in alkoxysilane (a) % By weight or more is at least one selected from trialkoxysilane (a1) represented by general formula (2) and dialkoxysilane (a2) represented by general formula (3), The present invention relates to a pulp treating agent for producing paper having a basis weight of 5 to 30 g / m ² , which is 3 times mol or more of the amount of alkoxysilane (a) and has a pH of 2 to 5 at 20 ° C.

Moreover, this invention is a pulp processing kit for obtaining the pulp processing agent of this invention, Comprising: The alkoxysilane (a) represented by the said General formula (1) is contained, Organic acid (b) and water are contained. The first agent that does not contain, and the second agent that contains the organic acid (b) and water and does not contain the alkoxysilane (a), the amount of water in use is three times the amount of alkoxysilane (a) A pulp processing kit for producing paper having a basis weight of 5 to 30 g / m ² mixed so that the pH of the pulp processing agent at 20 ° C. is 2 to 5 (however, alkoxysilane (a ) Is at least one selected from trialkoxysilane (a1) represented by general formula (2) and dialkoxysilane (a2) represented by general formula (3). .

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for producing paper having a basis weight of 5 to 30 g / m ² excellent in softness and smoothness, and a pulp treating agent for obtaining such paper. Softness and smoothness can be imparted to paper of ˜30 g / m ² .

[Alkoxysilane (a)]
The alkoxysilane (a) used in the present invention is 50% by weight or more, preferably 60% by weight or more, more preferably 80% by weight or more, and still more preferably 100% by weight, from the viewpoint of softness and smoothness. % Is at least one selected from trialkoxysilane (a1) and dialkoxysilane (a2).

In the alkoxysilane (a), trialkoxysilane (a1), dialkoxysilane (a2), the alkyl groups represented by R ¹ and R ² are methyl, ethyl, propyl, butyl, isopropyl, isobutyl. Group, t-butyl group and the like. Examples of the alkenyl group represented by R ¹ include a vinyl group and allyl group, and examples of R ¹ include a phenyl group. R ¹ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably an alkyl group having 1 to 2 carbon atoms from the viewpoint of penetrability into the pulp fiber. . R ² is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, from the viewpoints of safety of by-products generated by hydrolysis, reactivity of the hydrolysis reaction, and the like. As for p, 1-2 are preferable.

  As the trialkoxysilane (a1), alkyl (C1-6) trimethoxysilane and alkyl (C1-6) triethoxysilane are preferable, and methyltrimethoxysilane, ethyltriethoxysilane, and propyltriethoxysilane are preferable. More preferred. As the dialkoxysilane (a2), dialkyl (C1-6) dimethoxysilane, dialkyl (C1-6) diethoxysilane and the like are preferable, and dimethyldimethoxysilane and diethyldiethoxysilane are more preferable.

  The weight ratio of the trialkoxysilane (a1) to the dialkoxysilane (a2) in the alkoxysilane (a) is preferably 9/1 to 0/10 from the viewpoint of softness and smoothness. ~ 0/10 is more preferable, 5/5 to 1/9 is more preferable, and when a surfactant is added to the pulp treating agent, a pulp slurry of trialkoxysilane (a1) and dialkoxysilane (a2), pulp It is particularly preferred when the amount of processing on the sheet or pulp web is large.

[Organic acid (b)]
Examples of the organic acid (b) used in the present invention include oxalic acid (pKa = 1.04, 3.82), maleic acid (pKa = 1.75, 5.83), tartaric acid (pKa = 2.82, 3 .96), fumaric acid (pKa = 2.85, 4.10), citric acid (pKa = 2.90, 4.34), malic acid (pKa = 3.24, 4.71), succinic acid (pKa = 4.00, 5.24), formic acid (pKa = 3.55), lactic acid (pKa = 3.66), adipic acid (pKa = 4.26, 5.03), acetic acid (pKa = 4.56) And propionic acid (pKa = 4.67) and the like. From the viewpoint of easy pH adjustment, an organic acid having a pKa in the range of 2.9 to 5.0 is preferable, and 3.5 to 5 is preferable. More preferred are organic acids in the range of 0.0. Among these, adipic acid, malic acid, acetic acid and propionic acid, which can easily control the hydrolysis reaction and polymerization reaction of alkoxysilane (a), are preferred, and adipic acid having a low odor is particularly preferred.
The dissociation constant pKa is based on “Revised 4th edition, Chemical Handbook II” 10.2.3. Dissociation constant of organic compounds in aqueous solution (P317).

[Pulp treatment agent]
The pulp treating agent used in the present invention comprises an alkoxysilane (a), an organic acid (b), and water.
In addition, when the pulp treatment agent of the present invention is produced by a two-component kit (hereinafter also referred to as a pulp treatment kit), it contains alkoxysilane (a), and does not contain organic acid (b) and water. And a second agent containing an organic acid (b) and water and not containing an alkoxysilane (a).

  In the pulp treating agent of the present invention, the compounding amount of alkoxysilane (a) is in the total amount of the treating agent of the present invention (in the case of a two-component system, in the total composition of the first agent and the second agent; the same applies hereinafter). It is preferably 2.5% by weight or more, more preferably 12% by weight or more, 85% by weight or less, further 60% by weight or less, further 50% by weight or less, and further preferably 25% by weight or less. Further, the content of the alkoxysilane (a) in the first agent is preferably 70 to 100% by weight, more preferably 80 to 100% by weight, and particularly preferably 90 to 100% by weight from the viewpoint of storage stability.

  The blending amount of the organic acid (b) in the pulp treating agent of the present invention is preferably 0.001 to 5% by weight from the viewpoint of suppressing the polymerization reaction of the hydrolyzate of the alkoxysilane (a). 1% by weight is more preferred. When the pulp treatment agent of the present invention is produced by a two-component pulp treatment kit, the organic acid (b) is incorporated in the second agent separately from the alkoxysilane (a) incorporated in the first agent. It is preferable from the viewpoint of solubility and storage stability.

  The blending amount of water in the pulp treating agent of the present invention is a silanol compound represented by the following formula (4) (hereinafter referred to as silanol compound ( 4)) is preferably 30% by weight or more, more preferably 50% by weight or more, and particularly preferably 70% by weight or more from the viewpoint of sufficiently contacting the pulp fiber. The upper limit is preferably 99.9% by weight or less, more preferably 98% by weight or less, and particularly preferably 90% by weight or less.

[Wherein, X represents a group represented by R ¹ , OR ² or OH, t represents an integer of 0 to 2, and (2t + 4) X may be the same or different, and at least one of these is OH. R ¹ and R ² have the above meanings. ]

  Moreover, the ratio of the alkoxysilane (a) and water in the pulp treating agent of the present invention is selected from the viewpoint of sufficiently contacting the silanol compound (4) generated by hydrolysis of the alkoxysilane (a) to the pulp fiber ( It is 3 times mol or more of the compounding quantity of a), 10-1000 times mol is preferable and 25-980 times mol is more preferable.

  In the pulp treatment agent of the present invention, water is blended in the second agent separately from the alkoxysilane (a) blended in the first agent in the case of the two-component pulp treatment kit of the present invention. .

  In the pulp treating agent of the present invention, the water is preferably ion-exchanged water from the viewpoint of softness and smoothness, but from the viewpoint of production efficiency, industrial water usually used in the paper industry can be preferably used. .

The pulp treating agent of the present invention improves the dispersion of the alkoxysilane (a) in the aqueous phase, promotes the hydrolysis reaction, and especially when the blending amount of the trialkoxysilane (a1) is large. From the viewpoint of smoothness, it is preferable to add the surfactant (c).
When the surfactant (c) is blended, the blending amount of the surfactant (c) in the pulp treating agent of the present invention is 0.1 to 20% by weight from the viewpoint of emulsification during mixing and acceleration of hydrolysis. Is preferable, 0.1 to 15% by weight is more preferable, and 0.1 to 5% by weight is further preferable.

  As the surfactant (c), any of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used, and two or more types can be used in combination. .

  Nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, higher fatty acid sucrose ester, polyglycerin fatty acid ester, higher fatty acid mono- or diethanolamide, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid Examples thereof include esters, polyoxyethylene sorbite fatty acid esters, alkyl saccharide surfactants, alkyl amine oxides, and alkyl amido amine oxides. Of these, polyoxyalkylene alkyl ether and polyoxyethylene hydrogenated castor oil are preferable, and polyoxyethylene alkyl ether is particularly preferable.

  Anionic surfactants include alkyl benzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, Examples include α-sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphate mono- or diester type surfactants, and sulfosuccinate esters. As counter ions of the anionic surfactant, alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; 1 to 3 alkanol groups having 2 or 3 carbon atoms Examples thereof include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, and triisopropanolamine.

  Examples of the cationic surfactant include a quaternary ammonium salt represented by the general formula (5).

[In the formula, R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 28 carbon atoms or a benzyl group, and simultaneously become a hydrogen atom or a benzyl group; Except when it becomes an alkyl group. An ⁻ represents an anion. ]

In the general formula (5), one of R ³ and R ⁴ is preferably an alkyl group having 16 to 24 carbon atoms, more preferably 22 alkyl groups, particularly a linear alkyl group, and the other one having 1 to 3 carbon atoms. A lower alkyl group, particularly a methyl group is preferred. Examples of the anion An ⁻ include halide ions such as chloride ion, bromide ion and iodide ion; organic anions such as methyl sulfate ion, ethyl sulfate ion, methyl carbonate ion and saccharinate ion. In particular, chloride ions are preferred.

  As the cationic surfactant, mono long-chain alkyl quaternary ammonium salts are preferable, and specific examples include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, and behenyltrimethylammonium chloride. Stearyl trimethyl ammonium and behenyl trimethyl ammonium chloride are preferable.

  Examples of amphoteric surfactants include imidazoline series, carbobetaine series, amide betaine series, sulfobetaine series, hydroxysulfobetaine series, and amide sulfobetaine series.

  Among these surfactants (c), from the viewpoint of emulsifying ability (miscibility of alkoxysilane (a), organic acid (b), water and surfactant (c)), HLB 9-15, especially 11-14. Nonionic surfactants are preferred. In addition, HLB here shows the calculated value by the Griffin method.

  In the pulp treating agent of the present invention, for the purpose of dissolving the silanol compound (4) produced by hydrolysis of the alkoxysilane (a), lower monohydric alcohols having 1 to 3 carbon atoms such as methanol and ethanol, glycerin, etc. These water-soluble organic solvents can also be blended.

  In addition, the pulp treatment agent of the present invention is intended for pH adjusters, oil agents, silicone derivatives, cationic polymers, humectants, viscosity modifiers, fragrances, dyes, ultraviolet absorbers, antioxidants, antibacterial agents, etc. It can mix | blend suitably according to it.

In the case of using the water-soluble organic solvent in the pulp treating agent of the present invention, the blending amount is 35% by weight or less from the viewpoint of sufficiently swelling the pulp fiber and sufficiently bringing the silanol compound (4) into contact with the pulp fiber. Further, it is preferably 20% by weight or less. In addition to this, the pulp treatment agent after hydrolysis of the alkoxysilane (a) contains R ² OH as a by-product (R ² has the above meaning).

  The pulp treating agent of the present invention hydrolyzes alkoxysilane (a) to form silanol compound (4), and in order to bring silanol compound (4) into sufficient contact with pulp fibers, the pH at 20 ° C. is 2 -5, preferably 2-4. In the case of a two-component pulp treatment kit, the pH of the second agent at 20 ° C. is adjusted to the above range.

  The pulp treating agent of the present invention contains an alkoxysilane (a), an organic acid (b), and water, if necessary, a surfactant (c), or other optional components immediately before use, and a pH at 20 ° C. of 2 to 2. 5 may be prepared.

  The pulp treating agent of the present invention contains alkoxysilane (a) from the viewpoint of ensuring long-term stability, and 50% by weight or more of alkoxysilane (a) is trialkoxysilane (a1) and dialkoxysilane. A two-component pulp treatment comprising a first agent that is at least one selected from (a2), an organic acid (b) and water, and a second agent having a pH of 2 to 5 at 20 ° C. It is preferable that the kit is mixed.

  In the two-component pulp treatment kit of the present invention, the surfactant (c) is preferably contained in the second agent, but can also be contained in the first agent when the first agent does not contain moisture. Moreover, although it is preferable to contain other arbitrary components in the 2nd agent, if it is a non-aqueous liquid component and a solid component, it can also mix | blend in a 1st agent.

  When the pulp treatment agent of the present invention is prepared by mixing alkoxysilane (a), organic acid (b), and water, if necessary, surfactant (c), or other optional components immediately before use, mix. Although the order is not particularly limited, in order to bring the silanol compound (4) produced by hydrolysis of the alkoxysilane (a) into sufficient contact with the pulp fiber, an organic acid (b), water, and optionally a surfactant (c). It is preferable to mix alkoxysilane (a) after mixing.

  Further, when both trialkoxysilane (a1) and dialkoxysilane (a2) are used as alkoxysilane (a), first, trialkoxysilane (a1), organic acid (b), and water are mixed, and then dial It is more preferable to mix the alkoxysilane (a2). It is preferable that at least a part of the trialkoxysilane (a1) is hydrolyzed after mixing the trialkoxysilane (a1), the organic acid (b), and water. The progress of hydrolysis can be judged by the increase in the transparency of the liquid.

[Paper manufacturing method]
The paper manufacturing method of the present invention is a method having the step (I) of bringing the pulp treating agent of the present invention into contact with pulp fibers.

In the step (I), examples of the method for bringing the pulp treating agent of the present invention into contact with pulp fibers include the following methods (i) to (iii), and the methods (i) and (ii) are preferable. Furthermore, the method (iii) is preferred.
(I) A method of bringing the pulp treating agent of the present invention into contact with pulp fibers in the pulp slurry.
(Ii) A method of bringing the pulp treating agent of the present invention into contact with a pulp sheet.
(Iii) A method of bringing the first pulp treating agent into contact with the pulp web.

  In the method (i), the pulp slurry is preferably a pulp dispersion having a pulp fiber weight of 0.1 to 10% by weight and a pulp treating agent or a diluted solution thereof as a medium. Specifically, before the papermaking process in which a dilute liquid of pulp raw material is filtered through the wire mesh to form a paper layer, a pulper, refiner or other disintegrator or beater, machine chest, head box or white water tank The pulp treating agent of the present invention may be added to a tank such as a tank or a pipe connected to these facilities, but the pulp treating agent of the present invention is uniformly added by a refiner, a machine chest, or a head box. A place where it can be blended with pulp raw materials is desirable.

  In the method (ii), examples of the method of bringing the pulp treatment agent of the present invention into contact with the pulp sheet include a method of immersing the pulp sheet in the pulp treatment agent of the present invention or spray spraying the pulp treatment agent of the present invention. .

  The pulp sheet used in the method (ii) preferably has a moisture content with respect to the pulp sheet of less than 50% by weight. In addition, a pulp sheet means the pulp fiber aggregate | assembly formed into a sheet form by combining pulp fibers with a hydrogen bond or a binder.

  In the method of (ii), in the pulp production process, the pulp treatment agent of the present invention is preferably sprayed, applied and / or immersed in the process from the drying process to the winding of the pulp sheet. Or it is more preferable to apply, and it is still more preferable to spray.

  In the method (iii), the pulp web refers to a sheet in which pulp fibers are intertwined with each other in a state where they are not sufficiently bonded with hydrogen bonds or binders. The moisture content of the pulp web with respect to the pulp is preferably 50 to 1000% by weight, more preferably 50 to 800% by weight, still more preferably 50 to 500% by weight, particularly preferably 100 to 500% by weight, and most preferably 150 to 500%. % By weight.

  In the method of (iii), in the pulp manufacturing process, the pulp web after the dehydration process after washing in the deinking process is used. In the paper manufacturing process, the pulp web is processed after the press process after paper making and before the drying process. The treatment agent is preferably applied by spraying or the like, and the latter is more preferred.

  When treating the pulp using the pulp treating agent of the present invention, after mixing the alkoxysilane, organic acid, water and surfactant, and other optional components before use, stirring and mixing by means such as shaking, After confirming that the transparency of the mixed solution has been increased visually, it is preferable to bring the pulp, pulp sheet or pulp web into contact with the obtained pulp treating agent.

  The obtained pulp treating agent is preferably brought into contact with the pulp, the pulp sheet or the pulp web within 30 minutes and further within 15 minutes.

  In order to fully infiltrate the pulp treating agent into the pulp, pulp sheet or pulp web, the time for contacting them is preferably 5 to 90 minutes, particularly preferably 20 to 60 minutes. It is considered that the hydrolyzate of alkoxysilane penetrates into the pulp by leaving it for a certain time after contact. Under the present circumstances, you may heat the pulp, pulp sheet, or pulp web which contacted the pulp processing agent to 40-120 degreeC, Preferably it is 60-120 degreeC, More preferably, it is 90-120 degreeC. Specifically, it is preferable to warm by hot air drying or press heating. Further, the polymerization can be promoted by adjusting the pH of the liquid to 5 to 8 without drying the fibers. The pH can be adjusted with an acid or base after the fibers are immersed in the liquid or after the excess liquid is removed.

  The paper making method using the pulp treating agent of the present invention may be a general paper machine. Examples of the paper machine include a long net type, a circular net type, a short net type, a twin wire type, and an inclined wire type paper machine. can give. In particular, the twin wire type is preferable from the viewpoint of reducing the difference between the front and the back of the paper. Wet crepes or dry crepes may be applied in the Yankee dryer process, or calendar treatment with a metal roll such as double-ply tissue or toilet paper may be performed. The paper making speed is preferably 200 m / min or more, more preferably 300 m / min or more, and particularly preferably 500 m / min or more in terms of productivity.

  In addition, a dye, a softening agent, a sizing agent, a filler, a yield improver, a drainage improver, a paper strength improver, and the like may be added during papermaking. In particular, in order for the pulp treating agent of the present invention to exhibit its function, it is important to fix to pulp fibers, and therefore an agent that promotes fixing (hereinafter referred to as a fixing accelerator) may be added. . Examples of the fixing accelerator include aluminum sulfate, a compound having an acrylamide group, and polyethyleneimine. The addition amount of the fixing accelerator is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the pulp raw material. The addition amount of the fixing accelerator in the pulp treating agent of the present invention is preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the alkoxysilane (a). Further, a fixing accelerator may be included in the pulp treating agent of the present invention.

  The processing amount of the pulp treating agent of the present invention is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 50 parts by weight, and more preferably 0.1 to 25 parts by weight as a solid content with respect to 100 parts by weight of the pulp fiber raw material. Part by weight is more preferred, 0.5 to 20 parts by weight is particularly preferred, and 1 to 20 parts by weight is most preferred.

The paper manufacturing method of the present invention is a paper having a basis weight of 5 to 30 g / m ² , preferably 10 to 30 g / m ² , and more preferably 10 to 25 g / m ² from the viewpoint of softness and smoothness. Applicable to.

In the present invention, the basis weight of paper is measured by the following method.
<Measurement method of basis weight>
The conditioned paper is cut into 150 mm × 150 mm, the weight of the paper is measured, and the basis weight (g / m ² ) is obtained by the following formula (6).

Basis weight (g / m ² ) = paper weight / 0.0225 (6)

  The production method of the present invention can be applied, for example, to the production of many household papers, specifically, preferably tissue paper, toilet paper, more preferably tissue paper. Not only general box-type tissue paper, but also widely applicable to tissue paper such as wet tissue, moisturizing tissue, lotion tissue and the like.

In the following examples,% is% by weight unless otherwise specified.
Production Example 1
9.6 g of methyltriethoxysilane (LS-1890 manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as alkoxysilane 1), 0.31 g of adipic acid and polyoxyethylene lauryl ether (Emalgen 108 manufactured by Kao Corporation), and so on ) 2.06 g was dissolved in water and added to 41.1 g of the first solution, stirred at room temperature for 20 minutes, and then 4.1 g of dimethyldiethoxysilane (LS-1370 manufactured by Shin-Etsu Chemical Co., Ltd.) (Hereinafter referred to as “alkoxysilane 2”) and further stirred for 20 minutes to obtain a pulp treating agent 1 of the present invention. The pH of this pulp treating agent 1 of the present invention at 20 ° C. was 3.7.

Production Example 2
13.7 g of alkoxysilane 2 was added to a first solution in which 0.31 g of adipic acid and 2.06 g of polyoxyethylene lauryl ether were dissolved in water to make 41.1 g, and the mixture was stirred at room temperature for 20 minutes. Of pulp treating agent 2 was obtained. The pulp treating agent 2 of the present invention had a pH of 3.9 at 20 ° C.

Production Example 3
4.1 g of alkoxysilane 1 was added to a first solution in which 0.31 g of adipic acid and 2.06 g of polyoxyethylene lauryl ether were dissolved in water to make 41.1 g. After stirring for 20 minutes at room temperature, 9 g .6 g of alkoxysilane 2 was added and the mixture was further stirred for 20 minutes to obtain a pulp treating agent 3 of the present invention. The pulp treating agent 3 of the present invention had a pH at 20 ° C. of 3.3.

Production Example 4
13.7 g of alkoxysilane 1 was added to a first solution in which 0.31 g of adipic acid and 2.06 g of polyoxyethylene lauryl ether were dissolved in water to make 41.1 g, and the mixture was stirred at room temperature for 20 minutes. Pulp treating agent 4 was obtained. The pulp treating agent 4 of the present invention had a pH at 20 ° C. of 3.7.

Example 1
Hardwood bleached pulp (LBKP) was disaggregated and beaten with a beater at room temperature to make 2.2% LBKP slurry. The Canadian standard freeness of the slurry was 420 ml. The 2.2% LBKP slurry was weighed out so that the basis weight of the sheet after paper making was 30 g / m ² when it was absolutely dry, and immediately after the preparation of the pulp treatment agent 1 of Production Example 1 of the present invention, (Silane weight conversion) and after stirring for 40 minutes, dilute with water so that the pulp concentration is 0.5%, and after stirring, make paper with a 150 mesh wire with a square-type tappi paper machine, and perform coaching to obtain wet paper It was. The wet paper after paper making was pressed with a press at 3.5 kg / cm ² for 5 minutes and dried at 105 ° C. for 2 minutes using a drum dryer. The dried paper was conditioned at 23 ° C. and 50% humidity for 1 day to obtain the desired paper.

Example 2
A target paper was obtained in the same manner as in Example 1 except that the pulp treating agent 2 of the present invention was used instead of the pulp treating agent 1 of the present invention.

Example 3
A target paper was obtained in the same manner as in Example 1 except that the pulp treating agent 3 of the present invention was used instead of the pulp treating agent 1 of the present invention.

Example 4
A target paper was obtained in the same manner as in Example 1 except that the pulp treating agent 4 of the present invention was used instead of the pulp treating agent 1 of the present invention.

Comparative Example 1
Except not using the pulp treating agent 1 of this invention, it carried out similarly to Example 1 and obtained the target paper.

  The paper obtained in Examples 1 to 4 and Comparative Example 1 was evaluated for feel by the following method. The results are shown in Table 1.

<Evaluation method of touch>
The softness and smoothness were divided into 4 stages, and sensory evaluation was conducted by 20 men and women, and the average value was taken.
The softness was determined by grasping or squeezing the paper, and was determined to be 4: very soft, 3: soft, 2: normal, 1: hard.

The smoothness was determined by stroking the surface of the paper with the palm of the hand or rubbing it against the cheek, 4: very smooth, 3: smooth, 2: normal, 1: crisp.
In any evaluation, the paper not treated with the pulp treating agent of the present invention was evaluated as 2: normal.

Example 5
Immediately after preparing the pulp treatment agent 1 of the present invention of Production Example 1 using a spray gun on a commercially available tissue paper (basis weight of 1 ply 12 g / m ² ; double ply), 1.2 g on one side (in terms of weight of alkoxysilane) / M ² , and dried under reduced pressure at 80 ° C. and 150 mmHg for 3 hours.

Example 6
The same treatment as in Example 5 was performed, except that 0.8 g / m ² of the pulp treatment agent 2 of the present invention was applied instead of 1.2 g / m ² of the pulp treatment agent 1 of the present invention.

Example 7
The same treatment as in Example 5 was performed, except that 0.8 g / m ² of the pulp treatment agent 3 of the present invention was applied instead of 1.2 g / m ² of the pulp treatment agent 1 of the present invention.

Example 8
The same treatment as in Example 5 was performed except that the pulp treating agent 4 of the present invention was used instead of the pulp treating agent 1 of the present invention.

Comparative Example 2
The same treatment as in Example 5 was performed except that the pulp treating agent 1 of the present invention was not used.

  For the tissue papers obtained in Examples 5 to 8 and Comparative Example 2, the feel was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Claims (7)

A method for producing paper having a step (I) of bringing a pulp treating agent formed by blending an alkoxysilane (a) represented by the general formula (1), an organic acid (b), and water into contact with pulp fibers. And at least one selected from trialkoxysilane (a1) represented by the general formula (2) and dialkoxysilane (a2) represented by the general formula (3) in which 50% by weight or more in the alkoxysilane (a) is represented. The amount of water is 3 times mol or more of the amount of alkoxysilane (a) and the pH of the pulp treatment agent at 20 ° C. is 2 to 5, and the basis weight is 5 to 30 g / m ² . Production method.
R ¹ _p Si (OR ² ) _4-p (1)
R ¹ Si (OR ² ) ₃ (2)
R ¹ ₂ Si (OR ² ) ₂ (3)
Wherein, R ¹ represents a linear or branched alkyl group having 1 to 6 carbon atoms, a straight-chain or branched alkenyl group having a phenyl group, or 2 to 6 carbon atoms, R ² is 1 to the number of carbon atoms 6 linear or branched alkyl groups, p R ¹ and (4-p) R ² may be the same or different. p shows the integer of 1-3. ]   The method for producing paper according to claim 1, wherein in the step (I), the pulp treating agent is contacted in a pulp slurry having a pulp fiber weight of 0.1 to 10% by weight.   The method for producing paper according to claim 1, wherein in step (I), the pulp treating agent is brought into contact with a pulp sheet having a moisture content with respect to the pulp sheet of less than 50% by weight.   The paper manufacturing method in any one of Claims 1-3 in which a pulp processing agent mix | blends surfactant (c) further.   The pulp treatment agent is obtained by mixing trialkoxysilane (a1), organic acid (b) and water, and then mixing dialkoxysilane (a2). Production method. A pulp treatment agent comprising the alkoxysilane (a) represented by the general formula (1) according to claim 1, an organic acid (b), and water, wherein the pulp treatment agent is 50% by weight in the alkoxysilane (a). The above is at least one selected from trialkoxysilane (a1) represented by general formula (2) and dialkoxysilane (a2) represented by general formula (3) according to claim 1, A pulp treating agent for producing paper having a basis weight of 5 to 30 g / m ² , wherein the amount is 3 times mol or more of the compounding amount of alkoxysilane (a) and the pH at 20 ° C. is 2 to 5. It is a pulp processing kit for obtaining the pulp processing agent in any one of Claims 1-6, Comprising: The alkoxysilane (a) represented by General formula (1) of Claim 1 is contained, Organic acid ( b) and a first agent that does not contain water, and a second agent that contains an organic acid (b) and water, and does not contain alkoxysilane (a). A pulp treatment kit for producing a paper having a basis weight of 5 to 30 g / m ² mixed so that the pH of the pulp treatment agent at 20 ° C. is 2 to 5 or more and 3 times the molar amount of However, 50% by weight or more in the alkoxysilane (a) is a trialkoxysilane (a1) represented by the general formula (2) according to claim 1 and a dialkoxysilane (a2) represented by the general formula (3). At least one kind selected from: