JP2018172801A - Cleaning sheet and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve deodorant effect in a cleaning sheet.SOLUTION: A cleaning sheet is obtained by impregnating a base paper sheet with an aqueous agent. The base paper sheet has a basis weight of 30-150 gsm, and contains cellulose nanofiber. The aqueous agent includes a deodorizer, and the cellulose nanofiber is contained in the base paper sheet so as to be in a state in which the content is increased from the thickness direction inside to the outside of the base paper sheet.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a cleaning sheet and a method for manufacturing the cleaning sheet.

In recent years, disposable paper cleaning sheets are widely used for the purpose of cleaning toilets. In general, the cleaning sheet is provided in a state of being impregnated with a cleaning agent, and can be processed by flowing into a toilet after use (see, for example, Patent Document 1).
In such a cleaning sheet, a deodorizing function is exhibited by adding a deodorant.

Japanese Patent No. 3865506

  However, the conventional cleaning sheet can deodorize the odor of dirt that has been wiped off and adsorbed, but it cannot deodorize the odor drifting around the dirt.

  This invention is made | formed in view of the said subject, Comprising: It aims at improving the deodorizing effect in the sheet | seat for cleaning.

In order to solve the above-mentioned problem, the invention described in claim 1
A cleaning sheet obtained by impregnating a base paper sheet with an aqueous drug,
The base paper sheet is
The basis weight is 30 to 150 gsm,
Contains cellulose nanofibers,
The aqueous drug contains a deodorant,
The cellulose nanofibers are contained in the base paper sheet so that the content of the cellulose nanofiber is increased from the inside to the outside in the thickness direction of the base paper sheet.
According to the present invention, the deodorizing effect can be improved efficiently.

Moreover, invention of Claim 2 is the sheet | seat for cleaning of Claim 1, Comprising:
The cellulose nanofiber is contained in the base paper sheet so that the content is increased from the center in the thickness direction of the base paper sheet toward the front and back surfaces.
According to the present invention, the deodorizing effect can be improved more efficiently.

The invention according to claim 3 is the cleaning sheet according to claim 1 or 2,
The base paper sheet is
Contains a water-soluble binder,
The aqueous drug contains a cross-linking agent that cross-links with the water-soluble binder.
According to the present invention, the strength of the cleaning sheet can be improved.

Moreover, invention of Claim 4 is a manufacturing method of the sheet | seat for cleaning,
A CNF applying step for applying cellulose nanofibers to the base paper sheet;
An aqueous drug application step for applying an aqueous drug containing a deodorant to the base paper sheet,
Have
In the CNF applying step, cellulose nanofibers are sprayed on the base paper sheet.
ADVANTAGE OF THE INVENTION According to this invention, the sheet | seat for cleaning made into the state which increased content of the cellulose nanofiber as it goes to the outer side from the thickness direction inner side of a base paper sheet | seat can be manufactured.

The invention according to claim 5 is a method for manufacturing the cleaning sheet according to claim 4,
A binder application step for applying a solution containing a water-soluble binder to the base paper sheet;
A drying step of drying the sheet provided with the water-soluble binder and the cellulose nanofibers;
Have
In the aqueous drug application step, the aqueous drug is applied to the sheet dried in the drying step.
According to the present invention, a cleaning sheet containing a water-soluble binder and cellulose nanofibers and impregnated with an aqueous drug can be produced.

  According to the present invention, the deodorizing effect can be improved in the cleaning sheet.

It is a top view which shows an example of the toilet cleaner which concerns on this embodiment. (A) is a figure which shows the fiber orientation of the conventional paper, (b) is a figure which shows the fiber orientation of this invention. It is the enlarged view and sectional drawing of the embossed part of a toilet cleaner. It is explanatory drawing which shows an example of the contact area of embossing. It is a flowchart which shows the manufacturing method of the toilet cleaner which concerns on this embodiment. It is a schematic diagram of the toilet cleaner manufacturing equipment (solution application equipment) according to the present embodiment. It is a schematic diagram of the manufacturing equipment (processing equipment) of the toilet cleaner which concerns on this embodiment. It is the schematic which shows an example of a papermaking apparatus. It is a top view which shows another example of the toilet cleaner which concerns on this embodiment. It is a top view which shows another example of the toilet cleaner which concerns on this embodiment. It is the AA partial enlarged view of FIG. (A) is a BB cut part end elevation of Drawing 11, and (b) is a CC cut part end elevation of Drawing 11.

Hereinafter, a water-decomposable sheet as a cleaning sheet according to an embodiment of the present invention will be described in detail with reference to the drawings. However, the scope of the invention is not limited to the illustrated examples.
The water-decomposable sheet will be described by taking a toilet cleaner as an example, but the water-decomposable sheet includes wet tissue impregnated with an aqueous chemical for wiping purposes other than the toilet cleaner. In addition, the paper conveyance direction at the time of manufacturing the toilet cleaner will be described as Y direction (vertical direction), and the direction orthogonal to the conveyance direction will be described as X direction (lateral direction).

[Description of toilet cleaner]
The toilet cleaner 100 is obtained by plying (stacking) a plurality of (for example, two) base paper sheets, and is impregnated with a predetermined aqueous medicine. The base paper sheet may be composed of a single base paper sheet that is not ply-processed.
The basis weight of the base paper sheet is about 30 to 150 gsm. The basis weight is based on JIS P8124.

[Base paper sheet]
The base paper sheet of the toilet cleaner 100 is made of a water-degradable fiber assembly so that it can be discarded as it is in the toilet bowl after the toilet is cleaned.

  Although it will not specifically limit as a fiber assembly if it is a fiber assembly which has water disintegration property, Single layer or multiple layers paper or a nonwoven fabric can be used suitably. The raw fiber may be natural fiber or synthetic fiber, and these may be mixed. Suitable raw material fibers include cellulose fibers such as wood pulp, non-wood pulp, rayon and cotton, biodegradable fibers made of polylactic acid, and the like. In addition, polyethylene fibers, polypropylene fibers, polyvinyl alcohol fibers, polyester fibers, polyacrylonitrile fibers, synthetic pulp, glass wool and the like can be used in combination with these fibers as a main component.

In particular, it is preferable that the fiber aggregate includes at least pulp, and the pulp used as a raw material is preferably a mixture of hardwood bleached kraft pulp (LBKP) and softwood bleached kraft pulp (NBKP) at an appropriate ratio.
More preferably, the blending ratio of the hardwood bleached kraft pulp exceeds 50% by weight, that is, the blending ratio of the softwood bleached kraft pulp to the hardwood bleached kraft pulp is less than 1/1. By increasing the compounding ratio of hardwood bleached kraft pulp to softwood bleached kraft pulp, gaps between fibers are reduced and moisture transpiration is suppressed, so that the difficulty of drying can be improved.
Moreover, you may be comprised by the sheet | seat which consists of a pulverized pulp, and the sheet | seat which covered the pulverized pulp with the hydrolytic paper, or was pinched | interposed.

(Water-soluble binder)
In addition, a water-soluble binder for enhancing paper strength is applied to the base paper sheet of the toilet cleaner 100. Examples of water-soluble binders include carboxymethylcellulose, polyvinyl alcohol, starch or derivatives thereof, hydroxypropylcellulose, sodium alginate, tant gum, guar gum, xanthan gum, gum arabic, carrageenan, galactomannan, gelatin, casein, albumin, pull plan, polyethylene oxide, bis Examples thereof include binder components such as course, polyvinyl ethyl ether, polyacrylic acid soda, polymethacrylic acid soda, polyacrylamide, hydroxylated derivatives of polyacrylic acid, and polyvinylpyrrolidone / vinylpyrrolidone vinyl acetate copolymer.

In particular, it is preferable to use a water-soluble binder having a carboxyl group from the viewpoint of good water decomposability and the ability to express wet strength by a crosslinking reaction.
The water-soluble binder having a carboxyl group is an anionic water-soluble binder that easily forms a carboxylate in water. Examples thereof include polysaccharide derivatives, synthetic polymers, and natural products.

  Examples of the polysaccharide derivative include a salt of carboxymethyl cellulose, carboxyethyl cellulose or a salt thereof, carboxymethylated denven or a salt thereof, and an alkali metal salt of carboxymethyl cellulose (CMC) is particularly preferable.

Regarding CMC, the degree of etherification is desirably 0.6 to 2.0, particularly 0.9 to 1.8, and more preferably 1.0 to 1.5. This is because water disintegration and wet paper strength are very good.
Moreover, it is preferable to use a CMC that is water-swellable. This demonstrates the function of tying the fibers that make up the sheet while remaining unswelled by crosslinking with specific metal ions that are crosslinkers in aqueous chemicals, providing strength as a wiping sheet that can withstand cleaning and wiping operations. It is because it can express.
In the case of the toilet cleaner 100 of this embodiment, CMC is given as a water-soluble binder.

  Examples of the synthetic polymer include a salt of an unsaturated carboxylic acid polymer or copolymer, a salt of a copolymer of an unsaturated carboxylic acid and a monomer copolymerizable with the unsaturated carboxylic acid, and the like. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic anhydride, maleic acid, and fumaric acid. Examples of monomers that can be copolymerized with these include esters of these unsaturated carboxylic acids, vinyl acetate, ethylene, acrylamide, and vinyl ether. Particularly preferred synthetic polymers are those using acrylic acid or methacrylic acid as the unsaturated carboxylic acid, specifically polyacrylic acid, polymethacrylic acid, acrylic acid-methacrylic acid copolymer salt, acrylic acid or methacrylic acid. Examples thereof include a salt of a copolymer of an acid and an alkyl acrylate or an alkyl methacrylate. Examples of natural products include sodium alginate, xanthan gum, gellan gum, tarragant gum, pectin and the like.

[Cellulose nanofibers]
In addition, cellulose nanofiber (hereinafter referred to as CNF) is added to the toilet cleaner 100.
That is, CNF is added to the water-soluble binder (CMC in this embodiment).

  Here, CNF refers to fine cellulose fibers obtained by defibrating pulp fibers, and generally refers to cellulose fibers including cellulose fine fibers having a nano width (1 nm or more, 1000 nm or less). The average fiber width is preferably a fiber of 100 nm or less. The average fiber width is calculated using, for example, a certain number average, median, mode diameter (mode), and the like.

  Pulp fibers that can be used for the production of CNF include chemical pulps such as hardwood pulp (LBKP) and softwood pulp (NBKP), bleached thermomechanical pulp (BTMP), stone grand pulp (SGP), and pressed stone grand pulp (PGW). ), Refiner ground pulp (RGP), chemi ground pulp (CGP), thermo ground pulp (TGP), ground pulp (GP), thermo mechanical pulp (TMP), chemi thermo mechanical pulp (CTMP), refiner mechanical pulp (RMP) Waste paper made from mechanical pulp, tea waste paper, craft envelope waste paper, magazine waste paper, newspaper waste paper, flyer waste paper, office waste paper, corrugated waste paper, Kami white waste paper, Kent waste paper, imitation waste paper, land ticket waste paper, waste paper waste paper, etc. Deinked pulp made from pulp and wastepaper pulp Such as-flops (DIP), and the like. These may be used singly or may be used in combination of plural kinds as long as the effects of the present invention are not impaired.

Examples of the method for producing CNF include mechanical methods such as a high-pressure homogenizer method, a microfluidizer method, a grinder grinding method, a bead mill freeze grinding method, and an ultrasonic defibrating method, but are limited to these methods. is not.
For example, a pulp fiber that has been subjected to a mechanical method of defibrating treatment may be subjected to a chemical treatment such as carboxymethylation or an enzyme treatment.
Further, CNF subjected to chemical treatment or enzyme treatment may be subjected to a defibrating treatment by a mechanical method.

  Such toilet cleaner 100 may be in a state where CMC is uniformly impregnated in the thickness direction of the base paper sheet, but the content of CMC gradually increases from the center in the thickness direction of the base paper sheet toward the front and back surfaces. It is preferable that This is because the toilet cleaner 100 is less likely to be broken even if the edge of the toilet bowl is rubbed more strongly than a conventional product uniformly impregnated with the same amount of water-soluble binder.

Moreover, it is preferable that the content of CNF is gradually increased from the center in the thickness direction of the base paper sheet toward the front and back surfaces. This is because the deodorizing effect can be improved efficiently as will be described later.
As described above, in this embodiment, since CNF is added to the water-soluble binder, the content of CMC gradually increases from the center in the thickness direction of the base paper sheet toward the front and back surfaces. At the same time, the CNF content gradually increases from the center in the thickness direction of the base paper sheet toward the front and back surfaces.

Moreover, although it does not specifically limit about the ratio (vertical / horizontal) of the fiber orientation of the toilet cleaner 100 in length and width, it is preferable that it is 0.8-2.0, and is 0.8-1.2. It is more preferable.
In the paper making process, which is a paper manufacturing process, fibers are spread on the wire of the paper machine and flow in the transport direction. Therefore, in general, the paper is lined with many fibers in the machine direction of the paper machine. (For example, vertical: horizontal = 2.3: 1, etc., see FIG. 2A). Therefore, the fiber density in the lateral direction is thin and the fiber is easy to tear. That is, it is easy to tear depending on the direction of wiping. Therefore, in the present embodiment, as shown in FIG. 2B, the vertical and horizontal fiber orientation ratio of the toilet cleaner 100 is set to 0.8 to 2.0, preferably 0.8 to 1.2. It is possible to provide a toilet cleaner 100 that is hard to tear when wiped from any direction. The ratio of the vertical and horizontal fiber orientations can be determined by the ratio of the wet strength in the MD and CD directions.

[Aqueous drug]
In addition, the toilet cleaner 100 according to the present embodiment is impregnated with a predetermined aqueous chemical that includes a water-soluble binder (CMC in the case of the toilet cleaner 100 according to the present embodiment) and a cross-linking agent and a deodorant. . In addition, the aqueous drug includes auxiliary agents such as an aqueous detergent, a fragrance, a preservative, a disinfectant, and an organic solvent.
The aqueous drug is impregnated into the dried base paper sheet after being impregnated with the water-soluble binder.
Further, the aqueous chemical is impregnated in an amount of 100 to 500% by weight, preferably 150 to 300% by weight, based on the weight of the base paper sheet that is the base material of the toilet cleaner 100.

  As the crosslinking agent, boric acid, various metal ions, and the like can be used, but when CMC is used as a water-soluble binder, it is preferable to use a polyvalent metal ion. In particular, the use of one or more polyvalent metal ions selected from the group consisting of alkaline earth metals, manganese, zinc, cobalt, and nickel allows the fibers to be sufficiently bonded to withstand use. It is preferable from the standpoint that strength is developed and water disintegration is sufficient. Of these metal ions, it is particularly preferable to use ions of calcium, strontium, barium, zinc, cobalt, and nickel.

  Examples of the deodorant according to the present invention include organic acids, organic acid salts, polyphenols, polyphenol derivatives, polyphenol analogs, amphoteric surfactants, citric acid, graft polymer-based deodorants, betaine compound-based deodorants, Examples include essential oils extracted from cedar and cypress. These can be used alone or in combination of two or more.

Application amount of deodorant is preferably from 0.0001~1.0g / m ^2, more preferably from 0.003~0.4g / m ^2. If it is less than 0.0001 g / m ² , the deodorizing effect is not sufficient. If it exceeds 1.0 g / m ² , the effect of improving the deodorizing effect is small even if more deodorizing agent is added, or the cost is reduced. Become high.

Polyphenol, polyphenol derivatives, and analogs exhibit a deodorizing effect by a chemical reaction with a malodorous component in the toilet space, and exhibit an extremely excellent deodorizing effect in the toilet space.
More preferred specific examples of the polyphenols and polyphenol derivatives and analogs according to the present invention are tannin, catechin, rutin, anthocyanin, ellagic acid, coumarin, flavone, and derivatives or precursors thereof.
Among the above polyphenols and the like, there are those having a deodorizing function that are reactive to hydrogen sulfide, methyl mercaptan, and trimethylamine in addition to ammonia. Of course, the deodorizer used in the present invention is such a deodorizer. It may be a thing.

Of the above specific examples, tannin and its derivatives are particularly preferable.
Tannin and tannin derivatives are excellent in deodorizing function because they have a large molecular weight and many phenolic hydroxyl groups. Tannin may be either condensed tannin or hydrolyzed tannin. Further, among tannins, cocoon tannins derived from cocoons have a very large molecular weight and are extremely excellent in deodorizing effects. Therefore, the deodorant component according to the present invention contains at least one of cocoon tannins and cocoon tannin derivatives. It is better to do so. Suitable application amount in the case of persimmon tannin, as described above, 0.0001~1.0g / m ^2, preferably 0.003~0.5g / m ^2. However, as tan tannin and tan tannin derivatives increase in concentration, the characteristic brownish brown color becomes more prominent, so if applied over 2.0 g / m ² , the cleaning sheet will be dyed brown and reduce cleanliness There is a risk of causing.

  As the aqueous detergent, for example, a surfactant or a lower or higher (aliphatic) alcohol can be used.

  As a fragrance | flavor, 1 type or several types can be suitably selected and used from oily fragrance | flavors, such as orange oil other than an aqueous | water-based fragrance | flavor, for example.

  As the preservative, for example, parabens such as methyl paraben, ethyl paraben, propyl paraben and the like can be used. As a disinfectant, for example, benzalkonium chloride, chlorhexidine gluconate, popidone iodine, ethanol, benzilium cetyl oxide, triclosan, chlorxylenol, isopropylmethylphenol and the like can be used. As the organic solvent, polyhydric alcohols such as glycol (divalent), glycerin (trivalent), and sorbitol (tetravalent) can be used.

  In addition, the above-mentioned auxiliary agent for the component of the aqueous drug can be appropriately selected, and if necessary, a component that performs another function may be included in the aqueous drug.

Thus, according to this invention, CNF is mix | blended with a base paper sheet, and the aqueous chemical | medical agent containing a deodorizer is impregnated.
As a result, the specific surface area of the base paper sheet is larger than that of the composition of only the pulp, so that the amount of transpiration of the aqueous chemical containing the deodorant increases, and the contact point between the deodorant and the malodorous substance increases. The deodorizing effect in space can be improved.

Also, when the content of CNF gradually increases from the center in the thickness direction of the base paper sheet toward the front and back surfaces, near the outermost surface portions of the front and back surfaces of the base paper sheet that will come into contact with malodorous substances In particular, the specific surface area can be increased, and the deodorizing effect can be improved efficiently.
The CNF content only needs to be gradually increased from the inner side toward the outer side in the thickness direction of the base paper sheet, and does not necessarily need to be increased toward both the front surface and the back surface. Therefore, for example, it may be increased toward the front surface or the back surface.

[Emboss]
Further, the surface of the toilet cleaner 100 may be a raw paper sheet, but is preferably embossed. In the case of the toilet cleaner 100, for example, two types of embosses EM11 and EM12 are embossed as shown in FIG. It is given by processing.

  The shape, number, area ratio, and the like of the emboss are arbitrary, but in the case of the toilet cleaner 100, the emboss EM11 is arranged to be a rhombus lattice, whereby the emboss EM11 is arranged in a square lattice or a rectangular lattice. The unevenness of wiping can be reduced as compared with the case where it is. Further, the embossing EM12 is disposed between the embossing EM11.

As shown in FIG. 3A, the embossed EM11 has a bulged portion PR21 having a curved shape.
Moreover, as shown in FIG.3 (b), the embossing EM12 has the planar shape in the bulging part PR22.

And since the embossing EM12 is arrange | positioned between embossing EM11, when the bulging part PR21 of embossing EM11 and the bulging part PR22 of EM12 adjoin and adjoin, they are connected as shown in FIG.3 (c). The embossed EM21 is formed.
Moreover, the case where the bulging part PR21 of the embossing EM11 and the bulging part PR22 of the embossing EM12 are only close to each other and may not be continuous may be used.

  Since the two types of embosses EM11 and EM12 formed in this way can increase the contact area with the object to be cleaned and the like, the hardness of the toilet cleaner 100 is reduced and the wiping performance is improved.

  That is, by forming the embossed EM11 whose bulged portion PR21 is a curved surface and the embossed EM12 whose bulged portion PR22 is a flat surface on the entire sheet surface of the toilet cleaner 100, the toilet cleaner 100 is powered during wiping work. When each emboss is deformed, the contact area is increased for the first time. Therefore, the contact area is increased, and the flexibility is improved due to the deformation of each emboss.

  For example, as shown in FIG. 4A, in the case of a single embossed EM11, the contact area CN31 generated by the deformation of the embossed EM11 due to the force applied to the toilet cleaner 100 during the wiping operation is discrete in the vicinity of the embossed EM11. Will occur. On the other hand, when two types of embossing EM11 and EM12 are combined, as shown in FIG.4 (b), the embossing EM11 and EM12 which deform | transform and generate | occur | produce by the force added to the toilet cleaner 100 at the time of wiping work It can be seen that the area SN32 increases as compared with the contact area CN31 of FIG.

  Moreover, the two types of embossing EM11 and EM12 can similarly obtain the effect of normal embossing, and can improve the texture, absorbability, bulkiness, and the like of the toilet cleaner. Furthermore, the continuous embossing EM21 can also obtain the effect of the appearance by giving embossing similarly to normal embossing.

  Further, the toilet cleaner 100 is folded into two at the center in the Y direction by being folded. Then, it is stored in a folded plastic case, packaging film, etc. in a folded state, and is expanded and used as needed during use. Note that the method of folding the toilet cleaner 100 is not limited to two, and may be, for example, four or eight.

[Manufacturing method of toilet cleaner]
Next, a method for manufacturing a toilet cleaner will be described. FIG. 5 is a flowchart showing a method for manufacturing a toilet cleaner. FIG. 6 is a schematic diagram of a solution application facility for applying a water-soluble binder solution to a toilet cleaner base paper sheet (papermaking sheet). FIG. 7 is a schematic diagram of processing equipment for processing a base paper sheet to which a water-soluble binder solution has been applied by the solution application equipment shown in FIG.

  In the toilet cleaner manufacturing method, as shown in FIG. 5, first, a paper making process (S1) is performed in which a paper as a base paper is made by a paper machine (not shown).

  Next, as shown in FIG. 5 and FIG. 6, in the solution application facility, continuous dry base paper 1 </ b> A fed out from a plurality of (for example, two) primary raw rolls 1, 1 each wound up the base paper that has been made. A ply processing step (S2) for plying 1A to make a ply continuous sheet 1B, a solution application step (S3) for applying a water-soluble binder solution to the ply continuous sheet 1B to make a continuous sheet 1C, and a continuous sheet 1C A drying step (S4) for drying and a slit / winding step (S5) for slitting and winding the dried continuous water-decomposable sheet 1D are performed. The number of primary rolls can be changed as long as there are two or more. However, in the following description, an example of using two primary rolls will be described.

Next, as shown in FIGS. 5 and 7, in the processing facility, the continuous water-decomposable sheet 1 </ b> D fed from the secondary raw roll 11 wound in the slit / winding step (S <b> 5) is embossed. An embossing process (S6) and a finishing process (S7) for finishing the embossed sheet 1E that has been embossed are performed.
Hereinafter, details of each step will be described in detail.

[Paper making process]
First, the paper making process (S1) according to the present embodiment will be described. In the papermaking step (S1) of the present invention, for example, a papermaking raw material is made by a known wet papermaking technique to form a base paper sheet. That is, after making the papermaking raw material into a wet paper state, it is dried by a dryer or the like to form a base paper sheet such as thin paper or crepe paper.
In addition to the pulp and the flocculant, papermaking chemicals such as a wet paper strength agent, an adhesive, and a release agent may be appropriately used for the base paper sheet.

Moreover, in embodiment of this invention, although a water-soluble binder solution is provided in the solution provision process of the solution provision equipment mentioned later, you may make it provide a water-soluble binder solution in the step of a papermaking process.
When a water-soluble binder solution is applied even in the papermaking process, the strength of the entire water-decomposable sheet can be increased, and by applying a water-soluble binder solution in the subsequent solution application process, the surface of the water-decomposable sheet can be obtained. The strength can be further increased.

  As a method for applying a water-soluble binder solution in a papermaking process, for example, a water-soluble binder and a fixing agent for pulp fibers of the water-soluble binder are added to a dispersion containing pulp as a papermaking raw material, and this is used as a raw material. A method for wet papermaking is known (Japanese Patent Laid-Open No. 3-193996). That is, it is a method of internally adding a water-soluble binder. Alternatively, a sheet made from a pulp-containing dispersion may be wet-papered, press dehydrated or semi-dried, and then a water-soluble binder may be spray-dried or coated and dried to produce a fiber sheet containing a predetermined amount of the water-soluble binder. Is possible. That is, it is a method of externally adding a water-soluble binder. In this case, a fiber sheet having a lower density and better water disintegration can be obtained by using a pre-drying system such as a hot-air passing dryer than performing press dewatering. Furthermore, instead of the above-mentioned wet papermaking method, it is also possible to produce a fiber sheet by drying fiber pulp dry without using water, forming a web, spraying a water-soluble binder, and then drying. . This is the so-called airlaid manufacturing method.

  FIG. 8 shows a schematic view of an example of a production apparatus preferably used for producing a fiber sheet when a water-soluble binder is used as the binder. The manufacturing apparatus (wet papermaking machine) shown in FIG. 8 includes a former 14, a wire part, a first dry part 17, a spray part, and a second dry part 24.

  The former 14 adjusts the furnish supplied from a preparation device (not shown) to a predetermined concentration and supplies it to the wire part. A preparation device (not shown) includes a device that beats and beats raw materials such as pulp fibers, and an addition device that adds additives such as sizing agents, pigments, paper strength enhancers, bleaching agents, and flocculants to the beaten and beaten raw materials. And a stock made of a raw material having a predetermined concentration according to the characteristics of hydrolyzed paper is prepared as a finished stock. It is also possible to mix a binder with the pulp slurry. The wire part is a wet paper that forms the paper stock supplied from the former as a wet paper. The first dry part 17 dries the wet paper formed in the wire part. The spray part sprays the binder onto the paper dried by the first dry part 17. The 2nd dry part 24 dries the paper which has been sprayed with the binder and is wet.

  The furnish supplied from the former 14 is made in the wire part, and a wet paper is formed on the wire 15. Water is removed from the wet paper by suction by a suction box 16 installed in the wire part, and the wet paper has a predetermined moisture content. Next, the wet paper is introduced into the first dry part 17 and dried. The first dry part 17 is composed of a through air dryer (hereinafter referred to as TAD). The TAD includes a rotating drum 18 having a breathable peripheral surface, and a hood 19 that covers the rotating drum 18 almost airtightly. In TAD, air heated to a predetermined temperature is supplied into the hood 19. The heated air flows from the outside of the rotating drum 18 toward the inside. The wet paper web is conveyed in a state of being held on the peripheral surface of the rotary drum 18 rotating in the direction of the arrow in FIG. While being transported in the TAD, the heated paper penetrates the wet paper in the thickness direction, whereby the wet paper is dried to become paper.

  The paper obtained in the first dry part 17 is sprayed with an aqueous solution containing a binder (water-soluble binder solution) in the spray part. The spray part is a position between the first and second dry parts 17 and 24. Both dry parts 17 and 24 are connected via a conveyor.

  The conveyor includes an upper conveyor belt 20 and a lower conveyor belt 21 that rotate in the directions indicated by the arrows. The conveyor 20 is configured to convey paper to the second dry part 24 while being dried by the TAD of the first dry part 17 and sandwiching the paper between the belts 20 and 21. A vacuum roll 22 is disposed at the folded end on the downstream side of the upper conveyor belt 20. The vacuum roll 22 adsorbs paper on the back surface of the upper conveyor belt 20 and conveys the upper conveyor belt 20 under the adsorbed state.

  As shown in FIG. 8, the spray part includes a spray nozzle 23. The spray nozzle 23 is disposed below the second dry part 24 and so as to face the vacuum roll 22. The spray nozzle 23 sprays a spray liquid containing a binder toward the vacuum roll 22 and adds (externally adds) the spray liquid to paper.

  After the binder is supplied in the spray part, the paper is conveyed to the second dry part 24. The second dry part 24 is composed of a Yankee dryer. The paper that has been sprayed with the spray liquid and is in a wet state is conveyed while being held on the peripheral surface of the rotary drum 25 of the Yankee dryer installed in the hood 26. The paper is dried while being held by the rotary drum 25 and conveyed.

  In addition, the position where the binder is supplied in the spray part may be a position between the first and second dry parts 17 and 24. For example, the position above the upper conveyor belt 20 (the first and second dry parts shown in FIG. 8). You may make it spray a binder from the arrow position between 17 and 24). Further, the binder may be sprayed from above (the arrow position on the right side of the second dry part 24 shown in FIG. 8) on the paper after being dried by the second dry part 24. In addition, the direction in which the binder is sprayed between the first and second dry parts 17 and 24 and after the second dry part 24 is not limited to the upper direction, and may be from the lower side or from the upper and lower sides.

  In the present embodiment, in the paper making process, adjustment is performed such that the ratio of vertical and horizontal fiber orientations (vertical / horizontal) of the base paper sheet is 0.8 to 2.0, preferably 0.8 to 1.2. The fiber orientation can be adjusted, for example, by adjusting the angle at which the papermaking raw material is supplied to the wire part in a paper machine. The angle at which the papermaking raw material is supplied can be determined, for example, by adjusting the slice opening degree of the head box. Or it is good also as adjusting fiber orientation by giving a vibration in the direction orthogonal to the conveyance direction (running direction) of a paper machine.

[Ply processing process]
Next, the ply processing step (S2) of this embodiment will be described. In the ply processing step (S2), as shown in FIG. 6, the continuous dry base papers 1A and 1A continuously fed from the raw roll 1 are ply processed along the continuous direction to form a ply continuous sheet 1B. It is supplied to the mating unit 2. The overlapping portion 2 is composed of a pair of rolls, and plies each continuous dry base paper 1A, 1A to form a ply-processed ply continuous sheet 1B. In addition, when the continuous dry base papers 1A and 1A are overlapped, the continuous dry base papers 1A and 1A may be lightly fastened with pin embossing (contact embossing) so that they are not easily displaced.

[Solution application process]
Next, the solution application step (S3) of this embodiment will be described. In the solution application step (S3), as shown in FIG. 6, both outer surfaces of the ply continuous sheet (paper making sheet) 1B (the surfaces where the continuous dry base papers 1A and 1A do not face each other when the continuous dry base papers 1A and 1A are plyed). ) By spraying the water-soluble binder solution with the two-fluid spray nozzles 3 and 3 to produce a continuous sheet 1C.

  The water-soluble binder solution contains carboxymethyl cellulose (CMC) as a water-soluble binder. The water-soluble binder solution contains CNF.

  In addition, as the spraying method of the water-soluble binder solution, the above-mentioned water-soluble binder solution may be sprayed on one outer surface of the ply continuous sheet 1B. Further, the above-described primary raw rolls 1 and 1 are fed from the two-fluid type spray nozzle to the outer surface (the surface where the sheets do not face each other) of at least one of the continuous dry base papers 1A and 1A fed from the primary raw rolls 1 and 1 respectively. You may make it produce | generate the sheet | seat equivalent to the above-mentioned continuous sheet 1C by spraying a water-soluble binder solution, and immediately plying the said continuous dry base paper 1A, 1A.

The two-fluid spray nozzle 3 is a spray nozzle that mixes and sprays compressed air and liquid divided into two systems, compared to a one-fluid spray nozzle that sprays compressed liquid alone, The liquid can be sprayed finely and uniformly.
The spray conditions can be set as appropriate. For example, the nozzle diameter of the spray nozzle 3 is 0.09 gal / min or less, the concentration of the water-soluble binder solution; 3.0 to 4.0%, the output temperature; 50 ˜70 ° C., liquid pressure; 2 MPa or more, air pressure; 0.05 to 0.2 MPs.

Thus, by spraying the water-soluble binder solution on the outer surface of the ply continuous sheet 1B, the toilet cleaner is in a state where the content of CMC gradually increases from the inside to the outside in the thickness direction. Thus, it is possible to improve the surface strength while securing the property, and it is possible to manufacture a toilet cleaner that is not easily damaged even when rubbed strongly.
At the same time, the toilet cleaner is in a state in which the content of CNF gradually increases from the inside toward the outside in the thickness direction. In particular, it can be increased and the deodorizing effect can be improved efficiently.
In addition, the inside and the outside in the thickness direction, when applied to both sides, the inside in the thickness direction is the inside and the outside is the outside. Moreover, when apply | coating to one side, let the non-application surface of a water-soluble binder solution be an inner side, and let an application surface be an outer side.

[Drying process]
Next, the drying step (S4) of this embodiment will be described. In the drying step (S4), as shown in FIG. 6, in the drying facility 4, the insoluble liquid in the water-soluble binder solution of the continuous sheet 1C is evaporated, and the active ingredient, particularly CMC, is applied to the fibers. Let it settle.
Here, since the amount of the water-soluble binder solution that permeates decreases from the outside in the thickness direction of the continuous sheet 1C toward the inside, the fixing amount of the CMC decreases as it goes in the thickness direction. Become. Therefore, when the aqueous drug is impregnated in the finishing step (S7) to be described later, the cross-linking reaction is less likely to occur toward the inner side in the thickness direction, and since there are many voids, the aqueous drug is confined inside the sheet. It can be. Thereby, the toilet cleaner obtained can be made hard to dry.
As the drying equipment 4, a hooded dryer equipment that blows hot air on the continuous sheet 1C to dry it can be used. In order to make the sheets more closely contact each other, a press roll or a turn roll may be installed, and the continuous sheet 1C may be passed through the press roll or the turn roll before the drying step (S4).

  Moreover, you may use the installation by infrared irradiation as said drying installation. In this case, a plurality of infrared irradiation units are arranged in parallel in the conveying direction of the continuous sheet 1C, and drying is performed by irradiating the continuous sheet 1C to be conveyed with infrared rays. Since moisture is generated by infrared rays and dried, uniform drying is possible as compared with a dryer using hot air, and wrinkles can be prevented from occurring in the subsequent slit / winding process.

[Slit and winding process]
Next, the slit / winding step (S5) of this embodiment will be described. In the slit / winding step (S5), in order to use the ply-processed continuous water-decomposable sheet 1D with an off-line processing machine, it is dried in the drying step (S4) and the CMC is fixed. The illustrated continuous water-decomposable sheet 1D is slit to a predetermined width by the slitter 5 while adjusting the tension, and wound by the winder facility 6. The winding speed is appropriately determined in consideration of the ply processing step (S2), the solution application step (S3), and the drying step (S4). Note that if it is too early, the sheet will break, and if it is too late, wrinkles will occur.
In the slit / winding step (S5), the continuous water-decomposable sheet 1D subjected to the ply process is pressure-bonded, whereby the continuous water-decomposable sheet 1D is more integrated and becomes a sheet corresponding to one sheet.

[Embossing process]
Next, the embossing process (S6) of this embodiment will be described. In the embossing step (S6), as shown in FIG. 7, the embossing roll 12 has an embossing process that forms a predetermined shape on the entire surface of the continuous water-decomposable sheet 1D fed from the secondary raw roll 11 by the embossing roll 12. Applied. This embossing is performed for the purpose of improving the strength, bulkiness, wiping property and the like of the sheet, as well as the design.

[Finishing process]
Next, the finishing process (S7) of this embodiment will be described. In the finishing process (S7), as shown in FIG. 7, in the finishing equipment 13, the embossed sheet 1E is cut, the cut sheets are folded, and the aqueous chemical ( Including a cross-linking agent, deodorant, aqueous cleaning agent, fragrance, preservative, disinfectant, paper strength enhancer, organic solvent, etc.) and packaging of each sheet impregnated with the aqueous agent Do.
A toilet cleaner is manufactured through the above steps.

  Next, the results of evaluating the deodorizing effect of Examples and Comparative Examples of the present invention will be described.

<1. Sample creation>
First, a two-ply sheet of base paper (pulp blending; NBKP: LBKP = 40: 60) weighing 45 gsm was prepared in a dry state.
Subsequently, the aqueous solution (binder solution) adjusted on each condition was spray-coated on both surfaces with the water-soluble binder application | coating apparatus, and the sheet | seat of Example 1 and Comparative Example 1 was produced.
Subsequently, it was passed through a hot air dryer (temperature 180 ° C.) and dried until the moisture content was about 8%, and a raw sheet for processing a base paper sheet was prepared while slitting to a predetermined width.
Next, the dried base paper sheet was impregnated uniformly with a syringe with the following chemical solution (aqueous drug) so as to be 200% by weight of the sheet weight.
The aqueous drug contained Pancil FG-25 (manufactured by Release Science Industrial Co., Ltd.) as a deodorant and was adjusted to 0.018 g / m ² with respect to the sheet weight.
The sheets of Example 1 and Comparative Example 1 are as follows.

Example 1
A sheet in which a binder solution of 96% water, 3.7% CMC, and 0.3% CNF is applied to a dry two-ply sheet weighing 45 gsm (1.3% (dry coating amount)) (CNF is the thickness direction of the base paper sheet) The sheet is contained so that the content is increased from the inside toward the outside)
(Comparative Example 1)
Sheet coated with 1.3% (dry coating amount) of 96% water and 4.0% CMC binder solution on a dry 2-ply sheet weighing 45 gsm (Comparative Example 2)
Before applying the binder solution, the CNF aqueous solution was applied as a CNF to 0.0039% (dry coating amount) on a dry two-ply sheet weighing 45 gsm, and after drying, 96% water and CMC 4.0% A sheet obtained by applying 1.3% (dry coating amount) of a binder solution of 1 to a 2-ply sheet weighing 45 gsm in a dry state (sheet in which CNF is uniformly contained in the thickness direction of the base paper sheet)

The CMC used here is CMC1330 (Daicel).
Moreover, CNF used here is CNF of NBKP100%. CNF having an average fiber width (median diameter) of CNF of 49 nm was used. This CNF was obtained by subjecting NBKP to refiner treatment and rough defibrating, and then treating and defibrating four times using a high-pressure homogenizer.
The method for adding CNF to the binder solution was added to the binder solution as a CNF dispersion solution.

Here, a method for measuring the fiber width (average fiber width) of CNF will be described.
First, 100 ml of an aqueous dispersion of cellulose nanofibers having a solid content concentration of 0.01 to 0.1% by mass was filtered with a Teflon (registered trademark) membrane filter, and once with 100 ml of ethanol and three times with 20 ml of t-butanol. Replace.
Next, the sample is freeze-dried and coated with osmium. This sample is observed by an electron microscope SEM image at a magnification of 5000 times, 10000 times, or 30000 times (in this example, a magnification of 30000 times) depending on the width of the constituent fibers. Specifically, two diagonal lines are drawn on the observation image, and three straight lines passing through the intersections of the diagonal lines are arbitrarily drawn. Further, the total width of 100 fibers intersecting with the three straight lines is visually measured. The median diameter (median diameter) of the measured value is taken as the average fiber diameter. In addition, it is good also considering not only the median diameter of a measured value but a number average diameter and mode diameter (mode diameter) as an average fiber diameter, for example.

<2. Deodorization test>
Using the samples of Example 1 and Comparative Example 1, a deodorization test was performed according to the following procedure.
1) A nonwoven fabric cut out to a size of 30 mm × 30 mm is fixed to a wall surface in a desiccator, and the samples of Example 1 and Comparative Example 1 cut out to a size of 150 mm × 150 mm each have a large surface area at the bottom of the desiccator. Was installed.
2) 0.1 ml of ammonia water was dropped on the non-woven fabric, the desiccator was immediately sealed, and after 2 minutes had passed, it was confirmed that the ammonia concentration in the desiccator was 100 ppm.
3) After 1 minute, 2 minutes, 3 minutes, 4 minutes, and 5 minutes using an odor measuring device (Gastech Inc .; detector tube type gas measuring device gas sampling device set (GV-100S)) The odor (remaining rate of ammonia gas (%)) was measured.
The results are shown in Table I.

<Evaluation>
From Table I, the sample of Comparative Example 1 has a substantially constant ammonia gas remaining rate after 2 minutes, whereas the samples of Example 1 and Comparative Example 2 have ammonia gas remaining after 2 minutes. It can be seen that the rate decreases.
Thereby, it turns out that the sample of Example 1 and the comparative example 2 containing CNF has improved the deodorizing effect compared with the sample of the comparative example 1 which does not contain CNF.

Furthermore, the sample of Example 1 that contains CNF so that the content increases as it goes from the inside to the outside in the thickness direction of the base paper sheet is Comparative Example 2 that contains CNF uniformly in the thickness direction of the base paper sheet. It can be seen that the residual rate of ammonia gas is greatly reduced as compared with the sample.
Thereby, it turns out that a deodorizing effect can be improved efficiently by containing CNF so that it may be in the state which content increased as it went to the outer side from the thickness direction inside of a base paper sheet.

As described above, the cleaning sheet of the present embodiment is obtained by impregnating a base paper sheet containing CNF with an aqueous chemical containing a deodorant.
Thereby, the deodorizing effect can be improved.
Furthermore, the deodorizing effect can be improved efficiently by containing CNF so that the content increases as it goes from the inside to the outside in the thickness direction of the base paper sheet.

  As mentioned above, although this invention was concretely demonstrated based on embodiment, this invention is not limited to the said embodiment, It can change in the range which does not deviate from the summary.

  For example, in the description of the embodiment of the present invention, the configuration in which the crosslinking agent and CNF are blended with the aqueous drug is illustrated and described. However, the sheet containing the water-soluble binder is dried and crosslinked. It is good also as providing CNF aqueous solution after providing the aqueous | water-based chemical | medical agent containing an agent. Or it is good also as giving the aqueous | water-based chemical | medical agent containing a crosslinking agent after giving CNF aqueous solution to the said dried sheet | seat.

  For example, in the description of the embodiment of the present invention, a toilet cleaner is exemplified as a water-decomposable sheet. However, the present invention is not limited to this, and a toilet wipe after use such as a body wiping sheet and a hip wiping sheet for wiping the body is used. It can be applied to articles that need to be discarded with a large amount of water.

  In the description of the embodiment of the present invention, the embossed EM11 in which the bulging part PR21 has a curved shape and the embossed EM12 in which the bulging part PR22 has a flat shape are illustrated. However, it is not necessarily limited to this shape, and any shape of embossing is applicable.

  For example, in the description of the embodiment of the present invention, all the embosses EM11 and EM12 are convex in the front side of the drawing in FIG. 1, but the embossments EM11 and EM12 convex in the front side of the drawing and the front side in the drawing. Alternatively, the concave embosses EM11 and EM12 may be alternately arranged.

  Specifically, as shown in FIG. 9, embosses EM11 and EM12 (solid line portions) convex in the front direction of FIG. 9 and embossments EM11 and EM12 (broken line portions) concave in the front direction of FIG. By disposing in, it is possible to increase the surface strength of the water-decomposable sheet by embossing and to provide a water-decomposable sheet having high wiping performance on both sides of the toilet cleaner 101.

Moreover, the modification which changed only the embossing pattern of the toilet cleaner is shown in FIGS.
10-12, the recessed part e2 is the shape which reversed the convex part e1. The convex portions e1 and the concave portions e2 are alternately arranged as an example, and this row forms an emboss pattern in which the rows are arranged in multiple rows and the convex portions e1 and the concave portions e2 in adjacent rows are shifted from each other by a half pitch. . As described above, the convex portions e1 and the concave portions e2 are alternately formed both in the vertical direction and in the horizontal direction, so that the wiping property of dirt is improved compared to the embossed pattern in which the convex portions and the concave portions are arranged in a line. Can be made. In addition, the shape of the convex part e1 and the recessed part e2 is not specifically limited, Circular, an ellipse, a polygon etc. are used. It is good also as what combined each shape.

  In the description of the embodiment of the present invention, the water-soluble binder solution is applied by a spray method. However, the doctor is applied to the continuous dry base paper 1A continuously fed from the primary raw roll 1. Chamber system (transfer equipment with two plate rolls paired with one backup roll, anilox rolls paired with each plate roll, and a doctor chamber for applying a binder solution to each anilox roll) Or / and 3-roll system (two plate rolls paired with one backup roll, anilox roll paired with each plate roll, and a dip for applying a binder solution to each anilox roll Roll and a transfer facility comprising a pan for applying a binder solution to the dip roll). Nda solution may be granted. In other words, in the solution application step, the water-soluble binder solution is transferred to the corresponding base paper from a printing machine provided corresponding to at least one of the front and back surfaces of the water-decomposable sheet. Also good.

  Further, the water-soluble binder and CNF may be applied to the sheet at different timings. That is, a solution containing CNF may be separately applied to the sheet without adding CNF to the water-soluble binder. Also, CNF may be added to the aqueous drug and applied to the sheet.

100, 101 Toilet cleaner 1 Primary raw roll 1A Continuous dry base paper 1B Ply continuous sheet 1C Continuous sheet 1D Continuous water-decomposable sheet 1E Embossed sheet 2 Superposition part 3 Spray nozzle 4 First drying equipment 5 Slitter 6 Winder equipment 11 2 Next fabric roll 12 Embossing roll 13 Finishing processing equipment 14 Former 15 Wire 16 Suction box 17 First dry part 18 Rotary drum 19 Hood 20 Upper conveyor belt 21 Lower conveyor belt 22 Vacuum roll 23 Spray nozzle 24 Second dry part 25 Rotary drum 26 Hoods EM11, EM12, EM21 Embossed PR21, PR22 Swelling part HT21, HT22 Swelling part height CN31, SN32 Contact area e1 Convex part e2 Concave part

Claims (5)

A cleaning sheet obtained by impregnating a base paper sheet with an aqueous drug,
The base paper sheet is
The basis weight is 30 to 150 gsm,
Contains cellulose nanofibers,
The aqueous drug contains a deodorant,
The said cellulose nanofiber is contained in the said base paper sheet so that it may be in the state which increased content as it goes to the outer side from the thickness direction inside of the said base paper sheet, The sheet | seat for cleaning characterized by the above-mentioned.   The said cellulose nanofiber is contained in the said base paper sheet so that it may be in the state which increased content as it goes to the surface and the back surface from the center of the thickness direction of the said base paper sheet. Cleaning sheet. The base paper sheet is
Contains a water-soluble binder,
The cleaning sheet according to claim 1, wherein the aqueous drug contains a cross-linking agent that cross-links with the water-soluble binder. A method for producing a cleaning sheet, comprising:
A CNF applying step for applying cellulose nanofibers to the base paper sheet;
An aqueous drug application step for applying an aqueous drug containing a deodorant to the base paper sheet,
Have
In the said CNF provision process, the cellulose nanofiber is sprayed with respect to the said base paper sheet, The manufacturing method of the sheet | seat for cleaning characterized by the above-mentioned. A binder application step for applying a solution containing a water-soluble binder to the base paper sheet;
A drying step of drying the sheet provided with the water-soluble binder and the cellulose nanofibers;
Have
5. The method for producing a cleaning sheet according to claim 4, wherein in the aqueous chemical agent application step, the aqueous chemical agent is applied to the sheet dried in the drying step.

Images