CN101952505B - Tissue paper for domestic use - Google Patents
Tissue paper for domestic use Download PDFInfo
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- CN101952505B CN101952505B CN200980105855.8A CN200980105855A CN101952505B CN 101952505 B CN101952505 B CN 101952505B CN 200980105855 A CN200980105855 A CN 200980105855A CN 101952505 B CN101952505 B CN 101952505B
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- paper
- pulp
- cavitation erosion
- pressure
- paper pulp
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Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/002—Tissue paper; Absorbent paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
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- Paper (AREA)
Abstract
Provided is a tissue paper for domestic use, which is soft, is comfortable to the touch, and has excellent strength. The tissue paper for domestic use is characterized by containing a pulp obtained by applying, to pulp fibers, an impact force generating upon the collapse of bubbles generated by cavitation. Also provided is the tissue paper for domestic use which is composed of two or more paper layers and is characterized in that at least one of the paper layers contains a pulp obtained by applying, to pulp fibers, an impact force generating upon the collapse of bubbles generated by cavitation.
Description
Technical field
The present invention relates to the household tissue paper such as thin paper (tissue paper), paper handkerchief of toilet paper facial tissue etc., relate in particular to softness, the hand sense of touch is good and intensity is high household tissue paper.
Background technology
All the time, as the paper pulp that uses in the so-called household tissue papers such as the thin paper of toilet paper, facial tissue etc., paper handkerchief, use following material: the liquid paper pulp (slushed pulp) of the pulpous state attitude former state that the chemical pulp that is obtained by the timber smear metal of steam separating broad leaf tree, coniferous tree source is made, with this liquid paper pulp dewater, the universe is dry and the dry pulp (dry pulp) that obtains, perhaps waste paper is carried out that deinking is processed and the deinking paper pulp that obtains; These paper pulp can be with the state of unbleached pulp, bleached pulp, and the state of the paper pulp of perhaps not pulling an oar, pull an oar is used alone or as a mixture according to Quality Design.
for belong to the flexibility of thin paper important quality with raising, the hand sense of touch is that the technology of purpose is studied always, has for example proposed following various scheme: to stacked kind of copying paper paper pulp, its usage rate has carried out stacked thin paper and the manufacture method (patent documentation 1 thereof adjusted, patent documentation 2), by suitable selection fourdrinier wire, short net, two nets, the paper machine of circle shape net Yankee paper machine etc. is perhaps by adding softening agent for paper to liquid paper pulp, for example fatty acid ester is gentle softening agent (patent documentation 3), quaternary ammonium salt cationic surfactant (patent documentation 4), carbamate alcohol or its salt, or CATION compound (patent documentation 5), non-cationic type surfactant (patent documentation 6, patent documentation 7), Quadrafos (patent documentation 8), polysiloxanes (patent documentation 9, patent documentation 10) etc. interpolation medicament, thus improve the sliding compliance of liquid paper pulp itself and the hand sense of touch is improved, the method that limbers up, the after-applied mechanically milling of temporary transient thicken pulp are processed and are made fiber bending (patent documentation 11, patent documentation 12) etc.
Can access good soft effect although the method for medicament is added in above-mentioned use, because there is greatly worry itself that bring obstacle to copying the paper operation in foaming characteristic, sometimes have the problem that causes paper power and water imbibition to descend.In addition, when making fiber bending by mechanical treatment, with increasing unnecessary raw material enrichment process, so there is the problem of unfavorable grade on the energy.
In addition, in order to strengthen the moistening intensity of thin paper, mainly use the moistening paper power reinforcing agent of polyamide, polyamine, epoxy resin etc., but exist thin paper itself to anchylose, the problem of variation aspect flexibility, hand sense of touch.
In addition, in the past for surface smoothness is improved, use the chilled roll that 1 group or 2 groups fully grind by each a pair of quilt of 1 up and down, the calender that metallic roll consists of after the thin paper paper machine.Yet, when improving line pressure in order to strengthen flatness with this calender, there is the thickness attenuation and anchyloses, the hand sense of touch is the such problem of hardening also.
Patent documentation 1: Japanese kokai publication sho 54-46914 communique
Patent documentation 2: Japan opens flat 4-66992 communique in fact
Patent documentation 3: United States Patent (USP) 3,296, No. 065 communique
Patent documentation 4: Japanese kokai publication sho 48-22701 communique
Patent documentation 5: Japanese kokai publication sho 60-139897 communique
Patent documentation 6: Japanese kokai publication hei 2-99690 communique
Patent documentation 7: Japanese kokai publication hei 2-99691 communique
Patent documentation 8: Japanese kokai publication hei 2-36288 communique
Patent documentation 9: Japanese kokai publication hei 2-224626 communique
Patent documentation 10: Japanese kokai publication hei 3-900 communique
Patent documentation 11: Japanese kokai publication hei 5-23262 communique
Patent documentation 12: Japanese kokai publication hei 6-14848 communique
Summary of the invention
Problem of the present invention is for providing softness and hand sense of touch good, and the household tissue paper of good strength.
The processes such as the inventor study intensively, found that by containing the impulsive force that produces when the bubble that will generate because of cavitation erosion breaks and put on the paper pulp that paper pulp fiber obtains, just can access softness and the hand sense of touch is good, and the household tissue paper of good strength, and completed the present invention.
According to the present invention, can obtain softness and the hand sense of touch is good, and also good household tissue paper of intensity.
Description of drawings
The synoptic diagram of the cavitation erosion jet flow treating apparatus that [Fig. 1] uses in an embodiment.
Symbol description
1: sample jar
2: nozzle
3: the cavitation erosion jet unit
4: plunger displacement pump
5: the upstream side pressure-control valve
6: the downstream pressure-control valve
7: the upstream side Pressure gauge
8: the downstream Pressure gauge
9: water-supply valve
10: circulating valve
11: draining valve
12: temperature sensor
13: agitator
The specific embodiment
Household tissue paper of the present invention is characterised in that, contains the impulsive force that produces when the bubble that will generate because of cavitation erosion breaks and puts on the paper pulp that paper pulp fiber obtains.The processing that the impulsive force that the below will produce in the time of breaking because of the bubble that cavitation erosion generates puts on paper pulp fiber is referred to as the cavitation erosion processing.
There is no particular limitation for the paper pulp of the object of processing as cavitation erosion of the present invention, can use ligno-cellulosic materials is steamed in alkalescence and steam the chemical pulp separating and obtain (acerose bleached kraft pulp (NBKP) or not the bleached kraft pulp (LBKP) of bleached kraft pulp (NUKP), broad leaf tree), mechanical pulp (groundwood pulp (GP), refiner mechanical paper pulp (RGP), thermomechanical paper pulp (TMP), CTMP (CTMP) etc.), de inked pulp (DIP) etc. in separating liquid.Can use kraft pulp, polysulfide paper pulp, caustic soda paper pulp, alkaline sulfite paper pulp, sodium carbonate paper pulp and oxygen-caustic soda paper pulp etc. as chemical pulp.
Above-mentioned chemical pulp can be to add to steam to separate after cyclic ketones compound (for example, anthraquinone, Isosorbide-5-Nitrae-dihydro-9,10-amerantrone etc.) and obtain as steaming enzymolysis auxiliary agent in above-mentioned steaming solution liquid.In addition, as above-mentioned chemical pulp the present invention kraft pulp preferably, this kraft pulp can be by being added by the segmentation of digester liquor and the following current of digester inside is steamed to separate with adverse current and steamed the paper pulp that so-called " improveing alkaline digestion process " of being deconstructed into obtains.Can be with unbleached pulp or bleached pulp state as these chemical pulps, perhaps not the making beating or the making beating paper pulp state, can be used alone or as a mixture aptly.
Process further describing for cavitation erosion, is that the impulsive force that the bubble that will occur because of cavitation erosion produces when breaking puts on paper pulp fiber, promotes the outside fibrillation of paper pulp, suppresses on the other hand inner fibrillation and adjusts the processing of freedom.Cavitation erosion is processed and is preferably the cavitation erosion jet flow processing of putting down in writing as the WO2005/012632 communique.
In addition, can also make up that cavitation erosion is processed and the machinery making beating is processed and make the outside fibrillation of paper pulp fiber.In pulp suspension, can also contain the contained filler of waste paper or paper piece, the inorganic particles of pigment provenance outside paper pulp fiber.Cavitation erosion is processed in the outside fibrillation that promotes paper pulp fiber and is suppressed inner fibrillation, so with the paper pulp that uses method in the past, namely use the paper pulp that the device of homogenate machine etc. utilizes the making beating of mechanical force to process to compare, can obtain also good paper pulp of the higher and intensity of bulking intensity when identical freedom (high).Contain the household tissue paper with outside fibriilar paper pulp of being processed gained by this cavitation erosion, not only more soft, and also also good on intensity.
Process the Canadian Standard Freeness of the paper pulp of modulating by cavitation erosion, preferred 50～650ml during chemical pulp, the scope of preferred 50～400ml during mechanical pulp or waste paper (deinking) slurry.In addition, when mixing above-mentioned paper pulp, be preferably total Canadian Standard Freeness in the scope of 100～550ml.
Then, describing cavitation erosion in detail processes.As add in the book (Ishikawajima-Harima Heavy Industries Co., Ltd. writes, new edition cavitation erosion basis and nearest progress, Maki bookstore, 1999) of rattan record, cavitation erosion causes the high impact forces that arrives number GPa in the regional area of several μ m levels when the breaking of cavitation bubbles, and when bubble breaks by the observation of adiabatic compression microcosmic temperature rise to thousands of ℃.Its result, generation will be attended by the rising of temperature when cavitating.Can find out that thus cavitation erosion has convection cell machinery to bring the harm face of damage, vibrations, hydraulic performance decline etc., is taken as the technical task that must control its generation always.In recent years, obtained development rapidly for the research of cavitating, by carrying out high accuracy to generation area, the impulsive force of cavitation erosion and control as operational elements with the hydrodynamic parameters of cavitation erosion jet flow.Its result can be expected effectively to utilize its powerful energy by controlling the breaking impulsive force of bubble.Therefore, by operation with adjust hydrodynamic parameters and high-precision control is carried out in cavitation erosion become possibility.This stability that shows maintenance technical role effect has become possibility, and the invention is characterized in and be not as the spontaneous bubble that produces and bring the cavitation erosion of uncontrollable harm to generate in former fluid machinery, but the bubble that the cavitation erosion that will carry out controlling generates, be directed in pulp suspension energetically, thereby effectively utilize its energy.
As the means of the initiation in the present invention cavitation erosion, can enumerate method, the method for using ultrasonic oscillator, the method for using ultrasonic oscillator and horn shape amplifier of utilizing liquid jet, utilize the method for Ear Mucosa Treated by He Ne Laser Irradiation etc., but be not limited to this.Preferably use the method for liquid jet, its efficient that generates cavitation bubbles is high, can form the cavitation bubbles cloud with the more powerful impulsive force of breaking, so large to the action effect of paper pulp fiber.The cavitation erosion that is caused by above-mentioned method is different from significantly spontaneous generation in former fluid machinery and brings the cavitation erosion of uncontrollable harm.
As mentioned above, process preferably cavitation erosion jet flow processing as that put down in writing in the WO2005/012632 communique, that utilize liquid jet as cavitation erosion, the below is described in detail.
Liquid jet is liquid or the jet flow of disperseing in liquid or having mixed the fluid of solids or gas, refers to contain the liquid jet of paper pulp, inorganic particles slurry, bubble.Can contain at this said gas the bubble that produces because of cavitation erosion.
Accelerated and the locality pressure of cavitation erosion liquid causes when becoming lower than the vapour pressure of its liquid, so flow velocity and pressure particular importance.Thus, basic dimensionless number, cavitation number (Cavitation Number) σ of expression cavitation erosion state is defined as following (Ishikawajima-Harima Heavy Industries Co., Ltd. writes, new edition cavitation erosion basis and nearest progress, Maki bookstore, 1999).
[mathematical expression 1]
(p ∞: the pressure (absolute pressure), the U ∞ that usually flow: the flow velocity, the p that usually flow
v: the vapour pressure of fluid (absolute pressure), ρ: density)
At this, cavitation number means that greatly the institute flow field is in the state that is difficult to cavitate.Especially by as the cavitation erosion nozzle of jet flow or spray orifice when causing cavitation erosion, can be with nozzle upstream lateral pressure p
1(absolute pressure), nozzle downstream pressure p
2(absolute pressure), sample fit saturated vapor pressure p
v(absolute pressure) is rewritten into cavitation number σ as shown in the formula (2), and in the cavitation erosion jet flow, the pressure differential between p1, p2, pv is large, is p
1" p
2" p
vSo cavitation number σ can further be similar to following (H.Soyama, J.Soc.Mat.Sci.Japan, 47 (4), 3811998).
[mathematical expression 2]
So, cavitation number σ is represented by 2 values of the upstream side pressure of nozzle and downstream pressure.Wherein, the pressure of measuring in embodiments of the invention is gauge pressure, with the cavitation number σ in following formula (3) expression the present invention.
[mathematical expression 3]
σ＝p4/p3
(wherein, p3: nozzle upstream lateral pressure (gauge pressure), p4: nozzle downstream pressure (gauge pressure))
The condition of the cavitation erosion in the present invention preferably above-mentioned cavitation number σ is 0.001～0.5, more preferably 0.003～0.2, particularly preferably be 0.01～0.1.Cavitation number σ is less than 0.001 o'clock, and is low and effect is little with on every side pressure differential when breaking due to cavitation bubbles, greater than 0.5 o'clock, because low being difficult to of pressure differential of liquid stream cavitates.
In addition, jetting fluid is sprayed by nozzle or spray orifice cause when cavitation erosion, the pressure (nozzle upstream lateral pressure) of preferred jetting fluid is 0.01MPa (gauge pressure)～60MPa (gauge pressure), more preferably 0.7MPa (gauge pressure)～30MPa (gauge pressure), particularly preferably 2MPa (gauge pressure)～15MPa (gauge pressure).The nozzle upstream lateral pressure during less than 0.01MPa (gauge pressure) due to and nozzle downstream pressure between be difficult to generate pressure differential and action effect is little.In addition, the nozzle upstream lateral pressure needs special pump and pressure vessel during higher than 60MPa (gauge pressure), so that energy resource consumption will become will be unfavorable on large cost, and paper pulp fiber will be subject to excessive damage, and will be undesirable when being used as paper making raw material.On the other hand, the pressure in container (nozzle downstream pressure) (gauge pressure)～2.6MPa (gauge pressure) take static pressure as 0.05MPa preferably.The reason of also exerting pressure on the downstream is that the pressure in the zone that cavitation bubbles breaks is uprised, bubble and pressure differential on every side become large, thereby bubble breaks more intensely and make impulsive force become large.In addition, the hypertonia in container cavitates and self just is difficult to occur.In addition, the pressure ratio of container inner pressure and jetting fluid pressure ((gauge pressure)/(gauge pressure)) is preferably in 0.001～0.5 scope.
In addition, the jet speed of jetting fluid is preferably in the scope of second 1m/ second～200m/, more preferably in the scope of second 20m/ second～100m/.Jet speed is less than 1m/ during second, because pressure drop is difficult to cavitate, so a little less than its effect.On the other hand, during second, require high pressure to need special device greater than 200m/, unfavorable on cost.
Cavitation erosion in the present invention is processed and can be selected tank etc. arbitrarily in container or in pipe arrangement and carry out, but is not limited to this.In addition, although can be disposable process by (one-pass), the circulation by necessary number of times can further increase effect.And can use a plurality of initiation means to carry out side by side or processing successively.
Being used for causing the jet flow that cavitates can carry out at the container that opens at atmosphere as pulper, but preferably carries out in pressure vessel in order to control cavitation erosion.
In the present invention, for example in utilizing the cavitation erosion initiating method of liquid jet, stay the water again, the paper pulp that are recovered in water, running water, water for industrial use, paper operation processed to press water, paper waste, pulp suspension, alcohol etc. as atomizing of liquids such as spraying to steam to pulp suspension, but be not limited to this.Preferably by spraying pulp suspension self, thereby outside the action effect that obtains to cause because of the cavitation erosion that occurs around jet flow, also obtain the hydromechanical shearing force during with high-pressure injection from spray orifice, and then the larger action effect of performance.In addition, when using pulp suspension as atomizing of liquids, also can be with all amount circular treatment as the processing object.
Cause cavitation erosion when processing by liquid jet, be preferably below 5 % by weight as the solid component concentration of the pulp suspension of the processing object formation efficiency aspect from bubble, more preferably below 3 % by weight, the scope of 0.1～1.5 % by weight more preferably.
In addition, the pH of the pulp suspension during processing is preferably pH1～13, more preferably pH3～12, more preferably pH4～11.PH will become problem less than saprophage of 1 timer etc., and will be unfavorable from the viewpoint of material and maintenance etc.On the other hand, pH was greater than paper pulp fiber generation alkali burn in 13 o'clock, so whiteness decline is not preferred.Swelling due to paper pulp fiber during alkali condition is good, and the growing amount of the active free radical of OH increases, so preferred.
In the present invention, increase the flow velocity of jetting fluid by the expulsion pressure that improves liquid, cause more powerful cavitation erosion.And then uprise by the pressure that the container pressurization of taking in injected liquid is made the zone that cavitation bubbles breaks, make bubble and on every side pressure differential become large, so bubble breaks intensely, it is large that impulsive force also becomes.At this, jetting fluid refers to from the liquid of spray orifice with high-pressure injection, and injected liquid has referred to be injected in container or the liquid in pipe arrangement.The impact of the gas flow of cavitation erosion in liquid body is integrated the impact between gassing when gas is too much, so the impulsive force of breaking is absorbed by other bubble and produces buffering effect, thereby impulsive force dies down.Therefore, due to the impact that is subject to dissolved gas and vapour pressure, so its treatment temperature must be below the above boiling point of melting point.Liquid preferably is located at 0～80 ℃, more preferably is located at the scope of 10～60 ℃ and can obtains high effect during take water as medium.It is generally acknowledged that on the intermediate point of melting point and boiling point impulsive force is maximum, thus during the aqueous solution, 50 ℃ of left and right most preferably, but also can not be subject to the impact of vapour pressure during its following temperature, so as long as just can obtain high effect in above-mentioned scope.And during higher than the temperature of 80 ℃, the resistance to pressure that is used for causing the pressure vessel of cavitation erosion significantly descends, and easily causes the damage of container, so not preferred.
In the present invention, the material of the reduction surface tension of liquid by adding surfactant etc. and reducing is used for the initiation required energy that cavitates.Can exemplify known or novel surfactant as the material that adds, such as non-ionic surface active agent, anion surfactant, cationic surfactant, amphoteric surfactant or the organic solvent etc. of alkylene oxide adducts of soap, higher alkyl sulfates, alkylbenzenesulfonate, higher alcohol, alkylphenol, aliphatic acid etc. etc., but be not limited to this.The single component that can be these consists of, and can be also the mixture of composition more than 2 kinds.Addition is so long as make jetting fluid and/or injected liquid surface tension reduces required amount and gets final product.In addition, the position of interpolation can be any position of causing the position operation before of cavitation erosion, when making liquid-circulating, and can also be after the position of causing cavitation erosion.
In the present invention, with respect to the match ratio of the paper pulp of processing through cavitation erosion of total paper pulp amount, without limiting especially, but match ratio is got over Gao Yueneng and is obtained the high and soft household tissue paper of intensity.From this viewpoint, with respect to the absolute dry weight of full paper pulp preferably more than 5 % by weight, more preferably in 30～100 % by weight, further preferably in 60～100 % by weight.Match ratio does not change on flexibility, hand sense of touch during less than 5 % by weight, can't improve intensity.
Household tissue paper be with 1 layer or a plurality of layers consisted of, can copy separately paper with the cavitation erosion pulp treatment with 1 layer or a plurality of layers, also the cavitation erosion pulp treatment more than 2 kinds can be mixed and copy paper, can also mix existing liquid paper pulp, dry pulp, de inked pulp (DIP) and copy paper to the paper pulp of processing through cavitation erosion.
To be overlapped by the household tissue papers that a plurality of layer consists of 2 and carry out when stacked, the mode that makes the layer that contains the cavitation erosion pulp treatment become the outside overlaps, and the layer that touches of hand will be the layer that contains the pulp treatment that cavitates, so further strengthen the hand sense of touch.In addition, the lamination that will contain the pulp treatment that cavitates is connected to the Yang Ji drier, and to carry out the universe dry, is configured to can further strengthen the hand sense of touch when this face becomes the outside of 2 superimposed household tissue papers.
In addition, can also be with chemical pulp (acerose bleached kraft pulp (NBKP) or not the bleached kraft pulp (LBKP) of bleached kraft pulp (NUKP), broad leaf tree) or bleached kraft pulp (LUKP) etc. not), the paper pulp of mechanical pulp (groundwood pulp (GP), refiner mechanical paper pulp (RGP), thermomechanical paper pulp (TMP), CTMP (CTMP) etc.), de inked pulp (DIP) etc., mix with arbitrary proportion as the paper pulp beyond the paper pulp of processing through cavitation erosion and use.
The paper pulp processed through cavitation erosion is the paper pulp that outside fibrillation has been promoted, but sometimes can obtain having the outside fibriilar paper pulp of flakey, and the below will be explained.
Book (the bright work of rock shellfish " cellulosic materials chemistry ", Tokyo University publish meeting, p68,2001) according to rock shellfish etc., the making beating of paper pulp is that the paper pulp fiber to saturation state applies the mechanicalness shear stress, generate space (inner fibrillation) between the microfibril of paper pulp fiber inside, make the fibrillation in the paper pulp fiber outside play fine hair (outside fibrillation), increase specific area and strengthen paper pulp fiber to the swelling of water, the partial cut-out of fiber and the microfibre that the fiber outer peripheral face is peeled off also can occur simultaneously.
Because the making beating of paper pulp is processed, bonded area increase between formed fiber when making paper, various mechanics physical property, optics physical property, liquid-absorbent will change.But, when observing paper pulp fiber from molecular level, in the process that making beating is processed the decline of cellulosic molecular weight very little, degree of crystallinity changes hardly.Think that this may be because amorphism and hydrophilic hemicellulose part causes the mechanicalness energy just as absorbing as mat.
In addition, according to the book on island ground etc. (ground, island is modest wait collaborate, " tissue of timber ", gloomy northern publication, p55,1976), filament thing about wide 0.4～1 μ m that the outside fibrillation of seeing in the wood pulp with the usual method making beating refers to arrive with observation by light microscope, microfibril refers to exist in cell membrane wants the disposition construction unit, is the aggregate of cellulosic molecule with width of 9～37nm left and right.In the outside fibriilar paper pulp with flakey form that uses in the present invention, the outside fibrillation of characteristic flakey form refers to, having wide is more than 3 μ m, the wide fiber surface with the degree size that is preferably with paper pulp fiber peels off or rises fine hair, and be that above-mentioned microfibril laterally is connected and forms aggregate and become the layer of wide area, and the material that peels off under the state of retaining layer structure of the microfibril on fibre wall surface.In addition, take thickness in the scope of 9nm～2 μ m as feature.And, during with the electron microscope observation fiber, preferably stop hydrogen in conjunction with and carried out measuring under the dry state of the universe, this is simple when dry due to fiber is only carried out, because attracteding to fiber surface, the outside fibrillation of capillarity is difficult to be identified, so this fibrillation is difficult to carry out high-precision observation.
Outside fibriilar being characterized as of flakey in the present invention, the high molecular dyestuff with molecular weight more than 10,000 dyes.That is, outside fibrillation refers to adsorb the microfibril aggregate of the high molecular dyestuff of molecular weight more than 10,000.can enumerate document (F.L.Simons as Simon etc. as the dyestuff of molecular weight more than 10,000, Tappi, 33 (7), 312 (1950)), document (Y.Xiaochun et al. with Xiaochun etc., Tappi Journal, 78 (6), 175 (1995) .) in put down in writing contain direct orange 15 (old color index (CI) no, 621, the orange of CIConstitution no.40000 or CI Constitution no.40002/3)～40006 etc., just there is no particular limitation for the material of the fiber take cellulose as main body so long as can dye.
According to the document of Xiaochun etc., the dyestuff of above-mentioned molecular weight more than 10,000 is that the hydrodynamics size through determination of light scattering is the molecule more than 5nm, and it can't soak in the pore less than 5nm that is present in pulp fiber surface.On the other hand, because the fibrillation that is made of the microfibril aggregate of pulp fiber surface exposes the outside at paper pulp fiber, so the dye molecule of above-mentioned molecular weight more than 10,000 is easy to just can approach, so can partly optionally dye to fibrillation by absorption.
Emphasize the fibrillation part and observe for optical, can by direct blue 1 (old color index (CI) no.518 or the CI Constitution no.24410) that uses as above-mentioned document is put down in writing, direct blue 4, directly blue 15, directly blue 22, directly blue 151 etc. low molecular dye and all fibers are dyeed, observe thereby can give larger contrast.Although low molecular dye is adsorbed on all fibers, high molecular dye will replace low molecular dye because absorption affinity is strong.Its result, the fibrillation of energy adsorbed polymer dyestuff (orange) partly is colored as orange, the situation that fiber finer bore portion that can not the adsorbed polymer dyestuff is hanged down molecular dye (blue dyes) dyeing becomes possibility, thereby can emphasize the fibrillation part.Low molecular dyestuff contain more than 51%, molecular weight is less than 10000, preferably less than 2000, more preferably 300～1500 molecule.
Of the present invention have the outside fibriilar paper pulp of flakey and be preferably, and in its 1 fiber unit, the Area Ratio of the outside fibrillation part shown in following formula 4 is more than 20%, and the girth of the outside fibrillation part shown in following formula 5 is than more than 1.5.It is large that the outside fibrillation of the flakey of paper pulp of the present invention and common fibrillation are compared its surface area, so that these values can become is large.
The Area Ratio (%) of outside fibrillation part=[(area of outside fibrillation part)/(total surface area of the area+paper pulp fiber of outside fibrillation part)] * 100 (formulas 4)
The girth ratio of outside fibrillation part=(the all-round length of enclosing of the girth+paper pulp fiber of outside fibrillation part)/(the all-round length of paper pulp fiber) (formula 5)
[effect]
Hand sense of touch and intensity about the thin paper that contains the paper pulp of processing through cavitation erosion all become good reason, are thought of as follows.
Generally, the hand sense of touch of thin paper will be improved when bulking intensity high (density is low), other surface smoothing.Yet as mentioned above, the paper pulp of processing through cavitation erosion is the paper pulp that outside fibrillation is promoted by specificity.Namely, also put down in writing as WO2006/085598, owing to having promoted outside fibrillation with the maintained former state of the stiffness of fiber, so compare with the former mechanical treatment of double disc refiner etc., intensity will improve when bulking intensity is equal, with intensity become equal mode modulate paper pulp bulking intensity uprise.
In addition, when using the paper pulp of processing through cavitation erosion, the even surface of metallic roll etc. easily is transferred, the cunning so paper easily flattens.
Due to these reasons, think that the thin paper that contains the paper pulp of processing through cavitation erosion has the hand sense of touch and intensity all becomes good tendency.
Embodiment
The below enumerates embodiment and comparative example illustrates the present invention, but the present invention can't be subject to any restriction because of these.In addition, the % in embodiment, comparative example all represents % by weight as long as no being particularly limited.The paper pulp of modulating in following embodiment and comparative example has been carried out copying paper with two net type 3 laminar Yang Ji paper machines.Wrinkle is to have realized dry crepe by the speed difference that arranges between drier and spool.As long as no being particularly limited, just become overlapping 2 of the mode in the outside (side that is touched by user's hand) with the face that contacts with the Yang Ji drier (YD face) of this thin paper body paper, the mode that becomes the outside with this face is carried out stacked, and will be contacted with the Yang Ji drier and by the dry face of the universe for processing in soft calender.In embodiment, comparative example, used all as paper pulp that to utilize the kraft pulp method be 84% bleached hardwood paper pulp from the broad leaf tree smear metal manufacturing of producing, through the Hunter whiteness of bleaching in Japan.
In addition, the evaluation assessment of using in embodiment and comparative example such as following.
＜hand sense of touch 〉
Carried out the evaluation of sense of touch and the skin feel of hand by 10 test mans.Represent with following classification.
Very good: ◎, good: zero, common: △, poor: *
The determination method of＜TENSILE STRENGTH (vertically) 〉
TENSILE STRENGTH: on MD direction, CD direction, sample is cut with the wide of 15mm, with 1 layer of TENSILE STRENGTH of measuring all directions, the value of being calculated by following formula is as TENSILE STRENGTH.TENSILE STRENGTH (g)=(MD TENSILE STRENGTH * CD TENSILE STRENGTH) 1/2
The determination method of＜bulking intensity 〉
Paper thick (mm) during with overlapping 10 layers of sample is as bulking intensity.
The mensuration of＜grammes per square metre 〉
Carry out according to JIS P 8124:1998 (ISO 536:1995).
The adjustment of＜cavitation erosion pulp treatment 〉
It is to carry out in cavitation erosion jet flow treating apparatus shown in Figure 1 that cavitation erosion is processed.In Fig. 1, take in not shown pulp suspension (concentration 1.1%) in sample jar 1, interior temperature sensor 12 and the agitator 13 of having inserted of sample jar 1.The pulp suspension of sample jar 1 will by be situated between by the pipe arrangement of regulation of plunger displacement pump 4 be directed to cavitation erosion jet unit 3 as jetting fluid.The bottom of cavitation erosion jet unit 3 is provided with nozzle 2, is described in more detail, and the pulp suspension of sample jar 1 is 3 interior injections from nozzle 2 to jet unit.And then the pipe arrangement from the sidepiece of sample jar 1 to jet unit 3 is provided with water-supply valve 9, circulating valve 10, and the pulp suspension in sample jar 1 is supplied in jet unit 3 as injected liquid.Other pipe arrangements from from the sidepiece of sample jar 1 to nozzle 2 are fitted with upstream side pressure-control valve 5.On the other hand, other pipe arrangements from the top of jet unit 3 to sample jar 1 are fitted with downstream pressure-control valve 6, by adjusting each valve 5,6, press for the injection of nozzle 2 and can adjust pulp suspension.In addition, the approaching side of nozzle 2 is provided with upstream side Pressure gauge 7, and the top of jet unit 3 is provided with downstream Pressure gauge 8.Be provided with draining valve 11 in the bottom of jet unit 3.
[embodiment 1]
The raw material of the upper and lower in 3 layers such as modulated.The pulpboard of bleached hardwood kraft pulp is dissociated in the low concentration pulper, after being adjusted into arbitrarily concentration, use cavitation erosion jet flow treating apparatus (nozzle diameter 1.5mm) shown in Figure 1, the pressure (nozzle upstream lateral pressure) of jetting fluid is made as 8MPa (the flow velocity 80m/ second of gauge pressure, jet flow), the pressure in injected container (nozzle downstream pressure) is made as 0.4MPa (gauge pressure), carried out disposable by processing.Wherein, having used concentration as jetting fluid is the pulp suspension of 3 % by weight, to the pulp suspension in container (the concentration 3 % by weight) processing of cavitating, Canadian Standard Freeness is made as 435mL, has obtained raw material A.Made thin paper by raw material A and middle level raw material B (pulpboard of bleached hardwood kraft pulp being dissociated, Canadian Standard Freeness 500mL) in the low concentration pulper.Become 16.6g/m with the grammes per square metre of copying the thin paper after paper
2Mode regulate.
[comparative example 1]
The replacement cavitation erosion is processed and is used double disc refiner to carry out the making beating processing to the raw material of the upper and lower, and Canadian Standard Freeness is made as 470mL, has obtained raw material C.Made thin paper by raw material C and middle level raw material B.Become 16.6g/m with the grammes per square metre of copying the thin paper after paper
2Mode regulate.
[table 1]
| |
Comparative example 1 | |
| The hand sense of touch | △ | △ |
| Bulking intensity (mm/10 layer) | 0.88 | 0.91 |
| TENSILE STRENGTH (g) | 263 | 214 |
As shown in table 1, although the hand sense of touch in embodiment 1 and comparative example 1 is equal, the TENSILE STRENGTH of embodiment 1 is higher than comparative example 1 approximately 20%.Compare with comparative example 1, the intensity of embodiment 1 is greatly improved, and the decline of bulking intensity is very little.
[embodiment 2]
Raw material to the upper and lower carries out the processing identical with embodiment 1, and Canadian Standard Freeness is set as 420mL, has obtained raw material D.Add moistening paper power reinforcing agent 0.1% (with respect to the paper pulp absolute dry weight) to raw material D and middle level raw material B, made thin paper.Become 13.0g/m with the grammes per square metre of copying the thin paper after paper
2Mode regulate.
[comparative example 2]
Raw material to the upper and lower carries out the processing identical with comparative example 1, and Canadian Standard Freeness is set as 410mL, has obtained raw material E.Add moistening paper power reinforcing agent 0.1% (with respect to the paper pulp absolute dry weight) to raw material E and middle level raw material B, made thin paper.Become 13.0g/m with the grammes per square metre of copying the thin paper after paper
2Mode regulate.
[table 2]
| |
Comparative example 2 | |
| The hand sense of touch | ◎ | ○ |
| Bulking intensity (mm/10 layer) | 0.78 | 0.73 |
| TENSILE STRENGTH (g) | 155 | 160 |
As shown in table 2, the hand sense of touch of embodiment 2 is better than comparative example 2, the basic equal extent of TENSILE STRENGTH.And then the bulking intensity of embodiment 2 is compared with comparative example 2 and has been increased approximately 7%.
[embodiment 3]
Raw material with the upper and lower, use cavitation erosion jet flow treating apparatus (nozzle diameter 1.5mm), the pressure (nozzle upstream lateral pressure) of jetting fluid is set as 8MPa (the flow velocity 80m/ second of gauge pressure, jet flow), the pressure in injected container (nozzle downstream pressure) is set as 0.4MPa (gauge pressure), carried out outside 2 times (two pass) processing, carry out identical processing with embodiment 1, Canadian Standard Freeness is set as 390mL, has obtained raw material F.Add moistening paper power reinforcing agent 0.1% (with respect to the paper pulp absolute dry weight) to raw material F and middle level raw material B, made thin paper.Become 15.1g/m with the grammes per square metre of copying the thin paper after paper
2Mode regulate.
[comparative example 3]
The raw material of the upper and lower is carried out the processing identical with comparative example 1, Canadian Standard Freeness is made as 470mL, obtained raw material G.Add moistening paper power reinforcing agent 0.1% (with respect to the paper pulp absolute dry weight) to raw material G and middle level raw material B, made thin paper.Become 15.1g/m with the grammes per square metre of copying the thin paper after paper
2Mode regulate.
[table 3]
| |
Comparative example 3 | |
| The hand sense of touch | ◎ | ○ |
| Bulking intensity (mm/10 layer) | 0.85 | 0.87 |
| TENSILE STRENGTH (g) | 205 | 174 |
As shown in table 3, the hand sense of touch of embodiment 3 is better than comparative example 3, and TENSILE STRENGTH is approximately high by 20%.Embodiment 3 is greatly improved with comparative example 3 phase specific tensile strengths, and the decline of bulking intensity is very little.
[embodiment 4]
Though as the raw material of the upper and lower used intensity high have the hand sense of touch not good tendency, bleached hardwood brown paper pulpboard (moisture rate of pulpboard be approximately 50 % by weight (with respect to the paper pulp absolute dry weight)), carried out in addition the processing identical with embodiment 1, Canadian Standard Freeness is made as 440mL, has obtained raw material H.Add moistening paper power reinforcing agent 0.1% (with respect to the paper pulp absolute dry weight) to raw material H and middle level raw material B, made thin paper.Become 15.1g/m with the grammes per square metre of copying the thin paper after paper
2Mode regulate.
[comparative example 4]
Having used as the raw material of the upper and lower makes the hand sense of touch easily become good bleached hardwood brown paper pulpboard (moisture rate of pulpboard into approximately 10 % by weight (with respect to the paper pulp absolute dry weight)) usually, carry out in addition the processing identical with comparative example 1, Canadian Standard Freeness is made as 480mL, has obtained raw material I.Add moistening paper power reinforcing agent 0.1% (with respect to the paper pulp absolute dry weight) to raw material I and middle level raw material B, made thin paper.Become 15.1g/m with the grammes per square metre of copying the thin paper after paper
2Mode regulate.
[table 4]
| Embodiment 4 | Comparative example 4 | |
| The hand sense of touch | ○ | ○ |
| Bulking intensity (mm/10 layer) | 0.79 | 0.84 |
| TENSILE STRENGTH (g) | 247 | 177 |
As shown in table 4, have the hand sense of touch not in the embodiment 4 of the bleached hardwood kraft pulp of good tendency in use, itself and the comparative example 4 that makes the hand sense of touch easily become good bleached hardwood brown paper pulpboard are compared, the hand sense of touch is also basic identical.In addition, the TENSILE STRENGTH of embodiment 4 is compared with comparative example 4 and has approximately been improved 40%.
Claims (3)
1. household tissue paper, it is the household tissue paper that is consisted of by the ply of paper more than 2 layers, it is characterized in that, the ply of paper of at least 1 layer contains that the impulsive force that produces when the bubble that will generate because of cavitation erosion breaks puts on paper pulp that paper pulp fiber obtains, pulp treatment cavitates, the ply of paper that will contain this cavitation erosion pulp treatment is crimped on the Yang Ji drier and carries out drying, and the mode that makes the ply of paper that contains the pulp treatment that cavitates become the outside is configured.
2. household tissue paper according to claim 1, is characterized in that, the cavitation erosion pulp treatment has lepidiod outside fibrillation.
3. household tissue paper according to claim 1 and 2, is characterized in that, the containing ratio of cavitation erosion pulp treatment is take the absolute dry weight of full paper pulp as benchmark as 30～100 % by weight.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008090510 | 2008-03-31 | ||
| JP2008-090510 | 2008-03-31 | ||
| PCT/JP2009/055988 WO2009122986A1 (en) | 2008-03-31 | 2009-03-25 | Tissue paper for domestic use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101952505A CN101952505A (en) | 2011-01-19 |
| CN101952505B true CN101952505B (en) | 2013-06-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200980105855.8A Expired - Fee Related CN101952505B (en) | 2008-03-31 | 2009-03-25 | Tissue paper for domestic use |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20110011550A1 (en) |
| EP (1) | EP2287396B1 (en) |
| JP (1) | JP5542356B2 (en) |
| CN (1) | CN101952505B (en) |
| CA (1) | CA2717923C (en) |
| TW (1) | TWI500838B (en) |
| WO (1) | WO2009122986A1 (en) |
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| EP2400054B1 (en) | 2005-02-09 | 2018-09-12 | Nippon Paper Industries Co., Ltd. | A method for treating process waters by cavitation |
| EP2287396B1 (en) * | 2008-03-31 | 2016-03-23 | Nippon Paper Industries Co., Ltd. | Tissue paper for domestic use |
| JP5463985B2 (en) * | 2010-03-17 | 2014-04-09 | 株式会社リコー | Image forming apparatus |
| JP5934497B2 (en) * | 2010-12-21 | 2016-06-15 | 花王株式会社 | Tissue paper |
| US9604388B2 (en) * | 2012-02-14 | 2017-03-28 | International Paper Company | Process for making composite polymer |
| CN102578945A (en) * | 2012-02-21 | 2012-07-18 | 金红叶纸业集团有限公司 | Multi-layer living paper |
| US11124920B2 (en) | 2019-09-16 | 2021-09-21 | Gpcp Ip Holdings Llc | Tissue with nanofibrillar cellulose surface layer |
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2009
- 2009-03-25 EP EP09726597.9A patent/EP2287396B1/en not_active Not-in-force
- 2009-03-25 WO PCT/JP2009/055988 patent/WO2009122986A1/en active Application Filing
- 2009-03-25 US US12/921,485 patent/US20110011550A1/en not_active Abandoned
- 2009-03-25 CN CN200980105855.8A patent/CN101952505B/en not_active Expired - Fee Related
- 2009-03-25 CA CA2717923A patent/CA2717923C/en not_active Expired - Fee Related
- 2009-03-26 JP JP2009076372A patent/JP5542356B2/en not_active Expired - Fee Related
- 2009-03-31 TW TW098110740A patent/TWI500838B/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389625A (en) * | 1996-11-26 | 2003-01-08 | 金伯利-克拉克环球有限公司 | Method for making toilet paper from recovered newspaper |
Non-Patent Citations (2)
| Title |
|---|
| JP平1-213491A 1989.08.28 |
| JP特开昭49-55908A 1974.05.30 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2717923A1 (en) | 2009-10-08 |
| EP2287396A1 (en) | 2011-02-23 |
| JP5542356B2 (en) | 2014-07-09 |
| TW201009165A (en) | 2010-03-01 |
| CN101952505A (en) | 2011-01-19 |
| US20110011550A1 (en) | 2011-01-20 |
| JP2009263844A (en) | 2009-11-12 |
| WO2009122986A1 (en) | 2009-10-08 |
| EP2287396B1 (en) | 2016-03-23 |
| CA2717923C (en) | 2017-04-25 |
| TWI500838B (en) | 2015-09-21 |
| EP2287396A4 (en) | 2013-03-27 |
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