CN100595379C - Sanitary thin paper and process for producing the same - Google Patents
Sanitary thin paper and process for producing the same Download PDFInfo
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- CN100595379C CN100595379C CN200580017964A CN200580017964A CN100595379C CN 100595379 C CN100595379 C CN 100595379C CN 200580017964 A CN200580017964 A CN 200580017964A CN 200580017964 A CN200580017964 A CN 200580017964A CN 100595379 C CN100595379 C CN 100595379C
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- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/22—Agents rendering paper porous, absorbent or bulky
- D21H21/24—Surfactants
-
- 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
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47K—SANITARY EQUIPMENT NOT OTHERWISE PROVIDED FOR; TOILET ACCESSORIES
- A47K10/00—Body-drying implements; Toilet paper; Holders therefor
- A47K10/24—Towel dispensers, e.g. for piled-up or folded textile towels; Toilet-paper dispensers; Dispensers for piled-up or folded textile towels provided or not with devices for taking-up soiled towels as far as not mechanically driven
- A47K10/32—Dispensers for paper towels or toilet-paper
- A47K2010/3266—Wet wipes
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/53—Polyethers; Polyesters
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
Abstract
A sanitary thin paper is provided which has an excellent pliability together with an excellent smoothness. Such a paper can be obtained by incorporating a fatty acid ester-based compound and a fatty acid amide-based compound internally and/or externally.
Description
Technical field
The present invention relates to home-use sanitary thin paper and the manufacture method thereof of waiting, particularly relate to and provide a kind of softness and smooth sanitary thin paper as this sanitary thin paper, can be enumerated paper handkerchief or toilet paper.
Background technology
In recent years, be accompanied by the variation of living environment, concerning the user, have the tendency of liking soft and smooth sanitary thin paper.Particularly in the paper handkerchief field, this tendency significantly.
In order to ensure flexibility, shown in patent documentation 1, for example, the known method that the interpolation quaternary ammonium salt is arranged.In addition, shown in patent documentation 2, the method for also known interpolation polysiloxanes material.
Yet when not having slickness when only giving flexibility, the skin sense of touch is poor.In order to obtain influencing " slickness " of skin sense of touch, the someone considers to add lubricant, but does not in fact also find its suitable lubricant.
Patent documentation 1: No. 3180916 communique of patent
Patent documentation 2: No. 2806974 communique of patent
Summary of the invention
Major subjects of the present invention provides significantly good sanitary thin paper and manufacture method thereof of a kind of flexibility, slickness both.
For solving above-mentioned problem, inventive point of the present invention is as follows.
[1] a kind of sanitary thin paper is characterized in that, makes raw material with paper pulp, and at least a kind of method of adding in the employing and adding outward contains fatty acid ester compound and fatty acyl amide compound.
[2] sanitary thin paper of record in [1] wherein, contains the content of the softener composition of above-mentioned fatty acid ester compound and above-mentioned fatty acyl amide compound, is benchmark with the dry mass, is 0.002～10 parts by mass to above-mentioned paper pulp raw material 100 parts by mass.
[3] sanitary thin paper of record in [1] or [2], wherein, adopt internal addition method to contain above-mentioned fatty acid ester compound, at least a kind of method of adding in the employing and adding outward contains above-mentioned fatty acyl amide compound, and contain the polyesters compound, adopt external addition method to contain this polyesters compound.
[4] sanitary thin paper of record in [3], wherein, as above-mentioned polyesters compound, contain the polyesters compound with following general formula (1) expression:
R in the formula
1Be HO-or HO (R
2O)
a-, R
2Be the alkylidene of carbon number 2～3, R
2O can only be a kind, 2 kinds R
2O also can add becomes random shape or block-wise, and a is 1～200, in a part, a both can be all identical also can be different, b is 2～100, R
3For hydrogen atom or with the base of general formula (2) expression.
[5] sanitary thin paper of record in [3] or [4], wherein, above-mentioned polyesters compound is a benchmark with the dry mass, and above-mentioned paper pulp raw material is added with the ratio of 0.05～30.0 quality %.
[6] sanitary thin paper of any one record in [1]～[5], wherein, per 1 layer level ground amount is 10～35g/m
2
[7] sanitary thin paper of any one record in [1]～[6] wherein, is given wrinkle copying the paper stage, the vertex distance of the flow direction that is shaped as wrinkle of this wrinkle below the 0.1mm, the lateral length of wrinkle is below the 0.5mm.
[8] sanitary thin paper of record in [7], wherein, in the horizontal section of paper between adjacent paper pulp fiber distance reach the above paper pulp fiber number of 1 μ m, shared ratio is more than 50% in whole paper pulp fiber numbers.
[9] sanitary thin paper of record in [7] or [8] wherein, is removed outside the area that paper pulp fiber occupies in the horizontal section of paper, and the area occupation ratio in space is more than 50%.
[10] a kind of manufacture method of sanitary thin paper is characterized in that, to the l Water Paper of paper pulp raw material, with interior add contain fatty acid ester compound and fatty acyl amide compound after, in this l Water Paper, add the polyesters compound outside with online mode.
[11] a kind of manufacture method of sanitary thin paper, it is characterized in that, l Water Paper to paper pulp raw material, after at least a kind of method of adding in the employing and adding contains fatty acid ester compound and fatty acyl amide compound, in above-mentioned paper pulp l Water Paper or the dried paper that is dried, add the polyesters compound outside with online mode outward.
According to the present invention, can make not only flexibility but also the also significantly excellent sanitary thin paper of flatness.It is as follows that its reason can be thought.That is, it is lax that fatty acid ester compound infiltrates into the interfibrous combination of fiber chien shih, and brought into play leavening effect, concerning the user, gives soft feeling.Fatty acyl amide compound not only encourages leavening effect, and gives the moist feeling of preserving moisture and smoothly feel.It is found that, these fatty acid ester compounds and fatty acyl amide compound both to be cationic person be particularly preferred.
When adding the polyesters compound outside to this pulp based paper, can form polyester film, during contact skin, have the interfibrous friction function of the top layer part of reduction at pulp fiber surface.Therefore, resulting sanitary thin paper, owing to porous becomes moistening and soft, and the surface becomes level and smooth.
Like this, because the polyesters compound is to be used for forming polyester film at pulp fiber surface, preferably carry out outer adding.Owing to fatty acid ester compound is to be used for permeating between fiber making fiber combining lax, so add in preferably carrying out.It is found that, otherwise, although the effect that fatty acyl amide compound adds in adopting is big, carries out outer adding and also can.
On the other hand, it is found that flatness and wrinkle shape relation are big.That is, known, as shown in Figure 1, the vertex distance L of (use paper) of preferred wrinkle flow direction below the 0.1mm, wrinkle lateral length W is below 0.5mm.The vertex distance L that flows to when wrinkle is short, reaches 0.1mm and gives flatness when following.On the other hand, wrinkle lateral length W moves the flatness when hindering wiping during greater than 0.5mm towards flowing to when sanitary thin paper and contact skin.
Description of drawings
Fig. 1 is the key diagram of expression sanitary thin paper surface wrinkle, and (a) exterior view, (b) are the view of the B-B direction of arrow.
Fig. 2 is the transverse cross of paper.
Fig. 3 is the test method key diagram of MMD.
Symbol description
F... paper pulp fiber
The specific embodiment
The following describes embodiment of the present invention.Have again, as mentioned above,, can enumerate paper handkerchief or toilet paper etc. as sanitary thin paper.In addition, also can be used as cosmetic paper.
As this sanitary thin paper, be 7～40g/m with per 1 layer level ground amount (JIS P 8124)
2(preferred 10～35g/m
2, more preferably 11.0～17.0g/m
2) toilet paper during as object, characteristic of the present invention presents well.When being lower than 7g/m
2The time, the difficulty of manufacturing paper with pulp is when being lower than 10g/m
2The time, copying the paper stage, because paper is thin, the problem of the worry that generates hole is arranged.On the other hand, when greater than 40g/m
2The time, the thick increase of paper and hardening, in addition, when greater than 35g/m
2The time, when wrinkle is set, the wrinkle chap on paper surface, and superficiality variation.Therefore, the effect of softener is difficult to present.This sanitary thin paper can also be more than 3 layers except that 2 layers (2 overlapping is 1 group).In addition, the present invention demonstrates significant effect especially to the paper handkerchief that requires necessary paper intensity, also is like this to toilet paper.
This sanitary thin paper can adopt known equipment and manufacturing process to make.That is, paper pulp raw material is copied paper with paper machine, simultaneously, preferably adopt the manufacture method of implementing wrinkle processing and calendering processing to make.
Sanitary thin paper of the present invention is with as the soft imparting agent of sanitary thin paper, be added into sanitary thin paper in the paper pulp raw material with the polyesters compound of above-mentioned general formula (1) expression.
Because of the polyesters compound is water miscible, thus can dissolve or be dispersed in the water, but owing to be high molecular, so preferably be dissolved in back use in isopropyl alcohol, the dipropylene glycol equal solvent.
With the polyesters compound of general formula (1) expression, can adopt the aromatic dicarboxylic acid or derivatives thereof and use general formula HO-(R
2O)
aThe glycol that-H represents utilizes the known method manufacturing.As aromatic dicarboxylic acid, can enumerate terephthalic acid (TPA), M-phthalic acid, phthalic acid, as its derivative, for example, can enumerate the lower alkyl esters such as dimethyl ester, diethylester, dipropyl, dibutyl ester of these dicarboxylic acids, the chloride of these dicarboxylic acids etc., and phthalic anhydride etc.These aromatic dicarboxylic acid or derivatives thereofs both can use a kind separately, also can be used in combination more than 2 kinds.
As using general formula HO-(R
2O)
aThe glycol that-H represents for example, can be enumerated ethylene glycol, propylene glycol, diethylene glycol (DEG), dipropylene glycol, polyethylene glycol, polypropylene glycol, two terminal random shape or block-wise copolymers etc. for the oxirane of hydroxyl and expoxy propane.
These glycol both can use a kind separately, also can be used in combination more than 2 kinds.In general formula (1), a is 1～200, more preferably 1～150.When a surpassed 200, worry was too high with the viscosity of the polyesters compound of general formula (1) expression, and operation becomes and is not easy.In general formula (1), a both can be all identical in a part also can be different.The polyesters compound of general formula (1) expression that a is all identical, for example, dimethyl ester that can be by terephthalic acid (TPA), M-phthalic acid, phthalic acid etc. etc., react with the polyethylene glycol with certain molecular weight etc., be accompanied by separating methanol etc. and carry out ester exchange reaction, carry out polymerization and make.In with a part, the a that exists be 1 repetitive with, a is the polyesters compound of tens of～general formula (1) expression that hundreds of repetitives exist, for example, dihydroxy ethyl ester that can be by terephthalic acid (TPA), M-phthalic acid, phthalic acid etc. etc., react with the polyethylene glycol with certain molecular weight etc., be accompanied by and take off ethylene glycol etc. and carry out ester exchange reaction, carry out polymerization and make.In general formula (1), b is 2～100, more preferably 2～30.When b surpassed 100, the viscosity of the polyesters compound of general formula (1) expression was too high, and the worry of operating difficulties is arranged.
The matter average molecular weight preferred 1,000～200,000, more preferably 10,000～50,000 of the polyesters compound of general formula (1) expression.When the matter average molecular weight of polyesters compound is lower than at 1,000 o'clock, the worry of giving effect that can not give full play to flexibility is arranged.When the matter average molecular weight of polyesters compound greater than 200,000 o'clock, the viscosity of polyesters compound is too high, and the worry of operating difficulties is arranged.The matter average molecular weight of polyesters compound can disperse the known list of molecular weight polyethylene glycol as the bioassay standard material, obtains with gel permeation chromatography.
In this sanitary thin paper, the content (addition) of the polyesters compound of mutual-through type (1) expression is not particularly limited, but preferably with the dry mass is benchmark usually, paper pulp raw material is added 0.05～30.0 quality % outward, more preferably 0.5～5.0 quality %.When the content of the polyesters compound of general formula (1) expression is lower than 0.05 quality %, has and to give full play to the worry that flatness is given effect.When the content of the polyesters compound of general formula (1) expression is higher than 30.0 quality %, though giving effect, flatness strengthens, produce problems such as giving the sense of being clamminess.
The present invention as required, can contain the water soluble polyurethane resin of useful general formula (3) expression.Water soluble polyurethane resin is a benchmark with the dry mass, can add 0.05～7 quality % to paper pulp raw material.The mass ratio of polyesters compound and water soluble polyurethane resin is preferred 100/1～55/45, and especially preferably 100/1～70/30.That is, preferably make main body with polyesters compound of the present invention.As adding method, can adopt external addition methods such as spraying or print-on coating to carry out.
(in the formula, R
1The polyalkylene PTMEG chain of expression molecular weight 400～5000, R
2Expression:
Z is 3～300 integer).
In the present invention, also find when the above-mentioned polyesters compound of interpolation, do not influence paper pulp raw material hydrogen bond and attached on the paper pulp fiber, each paper pulp fiber that is covered probably, its result gives the effect of flatness.
In the present embodiment, as fatty acid ester compound, preferred cationic fatty acid ester compound and nonionic fatty acid ester compound both add.In addition, (a) a kind of or two kinds of fatty acid ester compounds in these adopt internal addition methods; (b) fatty acyl amide compound adds or external addition method adds by interior.The interpolation of additive also can consider to adopt external addition methods such as spraying or print-on coating to carry out.On the other hand, add in the employing, promptly sneak into to copy and copy paper behind the paper material and also can.
As the soup addition, preferably be benchmark with the dry mass, be 0.002～10 quality % to paper pulp raw material 100 parts by mass.Ratio in addition, (a)/(b) is preferably 0.1～500.
When the fatty acid ester compound of (a) attached to fiber on the time, infiltrate into fibrous inside, when drying, tube chamber (endoporus portion) inside produces hydrogen bond each other and prevents defeated and dispersedly, therefore, can generate bulk and light and soft papery.But when being not cationic, adhere to difficulty separately on fiber, effect is difficult to performance.
As fatty acid ester compound, preferred carbon number is the compound of the aliphatic acid of 6～24 alcohol and carbon number 7～25.As the alcohol of carbon number 6～24, can adopt straight chain alcohol, alcohol, saturated alcohols and unsaturated alcohol any of side chain arranged.In these various alcohol, the alcohol of preferred carbon number 10～22, especially preferably laruyl alcohol, myristyl alcohol, cetanol, stearyl alcohol, docosyl alcohol and oleyl alcohol.These both can use a kind also can more than 2 kinds and use separately.
As the aliphatic acid of carbon number 7～25, adopt any of straight chain fatty acid, the aliphatic acid that side chain is arranged, saturated fatty acid and unrighted acid.In these various aliphatic acid, the aliphatic acid of preferred carbon number 10～22, especially preferably laurate, myristic acid, palmitic acid, stearic acid, mountain Yu acid and oleic acid.These both can use a kind also can more than 2 kinds and use separately.
In addition, fatty acyl amide compound (b) 11 fiber surface coating, is given leavening effect, makes the surface produce flatness simultaneously, improves the flatness on paper surface.
Fatty acyl amide compound of the present invention makes by polyalkylene polyamine and carboxylic acid reaction.
The polyalkylene polyamine of using among the present invention has 3 amino at least in molecule, represent with following formula:
H
2N-(R
1-NH-)
n-R
1-NH
2...(4)
(in the formula, R
1Be the alkylidene of carbon number 1～4 independently respectively, n is 1～3 integer).
As R in the following formula (4)
1Object lesson, can enumerate methylene, ethylidene, trimethylene, tetramethylene, and butylidene.Both can there be different R in 1 molecule
1, also can adopt polyalkylene polyamine more than 2 kinds.Preferred R
1Be ethylidene.When the carbon number of alkylidene greater than 4 the time, operating difficulties.When adopting the amide compound that obtains with this compound, can make bulk and soft paper.
As the carboxylic acid that in amide compound is made, adopts, can adopt the carboxylic acid of carbon number 10～24.This carboxylic acid both can be any of saturated carboxylic acid, unsaturated carboxylic acid, can be the straight-chain carboxylic acid also, carboxylic acid any of side chain arranged.But wherein, at least 40 quality % must be at least a kind the carboxylic acids that has in unsaturated bond and the side chain.
As the object lesson of the carboxylic acid of carbon number 10～24, can enumerate following compounds: independent aliphatic acid such as capric acid, laurate, myristic acid, palmitic acid, palmitoleic acid, different palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, isostearic acid, arachidic acid, mountain Yu acid, erucic acid, carnaubic acid; And coco-nut oil fatty acid, palm oil fatty acid, tallow fatty acids, lard aliphatic acid, soya fatty acid, rape seed oil aliphatic acid, ready denier oil acid, olive oil aliphatic acid, the acid of cupu oil fat, the fatty acid of sesame oil, corn oil fatty acid, sunflower oil aliphatic acid, cottonseed oil fatty acid etc. are from the fatty acid mixed of natural oil and their hydrogenation thing etc.These can mix use more than 2 kinds.Wherein, the carboxylic acid of preferred carbon number 12～22, the carboxylic acid of special preferred carbon number 14～18.Less than 10 carboxylic acid, it is low that bulkiness that is caused by resulting amide compound and flexibility improve effect, surpasses 24 carboxylic acid, the operating difficulties of resulting amide compound about carbon number about carbon number.
Wherein,, oleic acid, linoleic acid, linolenic acid, erucic acid and palmitoleic acid can be enumerated,, different palmitic acid and isostearic acid can be enumerated as carboxylic acid with side chain as the example of the carboxylic acid with unsaturated bond (independent aliphatic acid).These aliphatic acid also contain other aliphatic acid as impurity sometimes, and this aliphatic acid also can utilize.As the natural fatty acid mixed that contains unsaturated carboxylic acid 40～100 quality %, can enumerate soya fatty acid, palm oil fatty acid, olive oil aliphatic acid, the acid of cupu oil fat, the fatty acid of sesame oil, corn oil fatty acid, sunflower oil aliphatic acid, cottonseed oil fatty acid, tallow fatty acids, lard aliphatic acid etc.Have in unsaturated bond and the side chain in the mixture of at least 1 carboxylic acid or this carboxylic acid and particularly preferably be soya fatty acid, oleic acid and erucic acid.
The fatty acyl amide compound of present embodiment can obtain by the polyalkylene polyamine and the above-mentioned carboxylic acid reaction of following formula (4) expression.This carboxylic acid is in being that 1.5～2.5 moles, preferred 1.8～2.2 moles ratio use to 1 mole of polyalkylene polyamine.When this amount is lower than 1.5 moles, then can not get bulk and soft paper fully, when greater than 2.5 moles, the amide compound operating difficulties of gained.
Above-mentioned amide compound can be directly uses as additive, but when using in inorganic acid or the organic acid and as salt, it is easier to operate.As above-mentioned inorganic acid, can enumerate hydrochloric acid, sulfuric acid, carbonic acid, nitric acid, phosphoric acid etc.As organic acid, can enumerate following compounds: formic acid, acetate, propionic acid, sad, butyric acid, oxalic acid, malonic acid, itaconic acid, adipic acid, butanedioic acid, decanedioic acid, citric acid, hydroxybenzoic acid, malic acid, tartronic acid, lactic acid, salicylic acid, hydroxypentanoic acid, aspartic acid, glutamic acid, taurine, sulfamic acid, laurate, myristic acid, palmitic acid, stearate acid, oleic acid etc.Wherein, preferred organic acid, wherein special preferable formic acid, acetate and lactic acid.
The acid amount that is used to form salt and uses is measured total amine value of the product that obtains by above-mentioned reaction, according to the necessary amount of purpose decision.The inorganic acid or the organic acid of preferred interpolation and total worthwhile amount of amine, the salt of generation amide compound.
The amide compound that obtains like this or its salt are handled easily, can make bulk and soft paper.In addition, this compound is added into is dispersed in the water with ratio arbitrarily with paper pulp fiber and the paper pulp that constitutes becomes silted up in the material, have the advantage that is difficult to bubble.
In addition, descend, add paper power agent such as starch, the paper power agent of polyacrylamide surface, polyvinyl alcohol in preferred, add starch in particularly because the use of soup produces paper power sometimes.
In the present embodiment, fatty acid ester compound and fatty acyl amide compound, after being contained in the paper pulp l Water Paper by internal addition method, in this l Water Paper, add the polyesters compound outside with online mode again, or add in adopting and after at least a kind of method of external addition method contains fatty acid ester compound and fatty acyl amide compound, in paper pulp l Water Paper or dried paper, add the polyesters compound outside with online mode, can add additives such as other suitable humectant or smooth agent by another operation.
As this humectant, can enumerate polyethylene glycol, glycerol, 1,3-butanediol, 1, humectant such as 2-pentanediol, pentaerythrite, D-sorbite, xylitol, maltitol, propylene glycol, dipropylene glycol, two glycerine, pyrrolidone sodium carboxylate, lactic acid, sodium lactate.
As smooth agent, can enumerate polysiloxanes such as silicone oil, silica flour etc.If desired, can make particulate to above-mentioned polyesters compound, use as powder particle by means such as emulsifications.The Si powder that the powder particle of special preferably average grain diameter 0.1～30 μ m constitutes.Or the aggregated particle of above-mentioned powder particle, the average grain diameter of this aggregated particle is that 10～100 μ m also can use.
As the paper pulp raw material of this sanitary thin paper, NBKP fit rate 30～80 quality %, the paper pulp fiber of preferred LBKP20～70 quality % is made main material.As required, can cooperate below the old paper 30 quality %, below the preferred 10 quality %,, preferably cooperate the former raw pulp of 100 quality % (virgin pulp) from the viewpoint of flexibility to paper pulp raw material.
On the other hand, in the sanitary thin paper of this programme, shown in Fig. 2 pattern, in the horizontal section of paper, it is preferred more than 50% to remove the outer void area rate of paper pulp fiber F area occupied (that is the area occupation ratio of removing the outer non-hatched area of paper pulp fiber F among Fig. 2 unit are S).When this area occupation ratio is high, give soft feeling.When this area occupation ratio is too high, causes intensity decreases, and do not have hardness.
Particularly, in the horizontal section of paper, apart from the paper pulp fiber number of D more than 1 μ m, shared radical ratio is preferably more than 50% in whole paper pulp fiber numbers between adjacent paper pulp fiber, and the best is preferably above the accounting for more than 50% of 5 μ m.To this, when this radical ratio is high, give soft feeling equally.When this radical ratio is too high, intensity decreases.
Shown in the following examples, in example, there are not the goods of embodiment of the present invention in the past.
As the MMD of surface characteristic index, preferred paper handkerchief is below 9.0, and particularly below 8.5, toilet paper is below 13, particularly below 11.
In this surface characteristic test, " the friction sense test instrument KESSE " that can adopt カ ト-テ Star Network Co., Ltd. to make carries out.When measuring, as shown in Figure 3, making the piano wire length that constitute, its contact-making surface of cross-sectional diameter 0.5mm on one side is friction of 5mm, contact pressure contact paper sample with 10g, apply on one side the tension force of 20g/cm, the coefficient of friction when the speed with 0.1cm/ second measured moves 2cm at moving direction paper feeding sample.Then, (make the change of the sub surface thickness when mobile of friction, promptly coefficient of friction is exactly MMD with frictional distance (displacement=2cm) remove value) to the average deviation of coefficient of friction.
As pliability, preferred paper handkerchief is below 1.5, and especially below 1.4, toilet paper is below 3.5, especially below 2.5.
In order to obtain the sanitary thin paper of the present embodiment, can obtain by selecting various key elements.That is, can be by adjusting as the kind that cooperates ratio, paper pulp of LBKP with the NBKP of paper pulp raw material (fibre coarseness or constitute the trees kind and the age of tree of raw material), degree of fragmentation, the interpolation and the amount thereof of copying paper moisture, calender clearance pressure material, soup.Preferably mismatch the paper pulp of old paper paper pulp.
In addition, interpolation that can be by TENSILE STRENGTH, aspect ratio, wrinkle shape (wrinkle rate, wrinkle difference of height etc.), moisture rate, density, the agent of paper power, the interpolation of soup and amount thereof etc. are adjusted.Surface characteristic can cooperate by paper pulp, the interpolation of the balance of calender condition, the point of a knife angle of copying paper moisture, scraper, blade angle, bonding peel strength, wrinkle rate, soup and amount thereof etc. adjust.
When making the wrinkle shape of this programme, influencing big is exactly to add additive.That is, preferably add cationic fatty acid ester compound (soup) and nonionic fatty acid ester compound (soup) two soups.
[softener composition]
Softener composition to fatty acids ester type compound and fatty acyl amide compound is described as follows.
As the softener that is added in the sanitary thin paper, the preferred cationic surfacant.Kind to this cationic surfactant is not particularly limited, but have at least in the preferred molecule amines of saturated or unsaturated alkyl of 1 carbon number 6～26 or its corrective or season thing or these mixture.Preferred amines or its corrective or season thing be described in more detail as followsly, these are to have 1, preferred 1～2,2 the alkyl of carbon number 6～26, preferred 14～22 saturated or undersaturated alkyl or alkenyl etc. most preferably in the molecule at least.This alkyl also can have ester group, anti-ester group (reversed ester group), amide groups, anti-amide groups (reversed amide group), ether in its chain.Also have, these alkyl, for example aliphatic acid that obtains from the not hydrogenated fatty acid of tallow or unsaturated partial hydrogenation or partial hydrogenation by using common industrial use, the aliphatic acid that obtains from the not hydrogenated fatty acids of plants such as palm coconut, coconut oil or fatty acid ester or unsaturated partial hydrogenation or partial hydrogenation or fatty acid ester etc. and imported.
In addition, it also is preferred using the compound of following general formula (5) expression:
(in the formula, R
3The alkyl of expression carbon number 6～24 or the alkenyl of carbon number 6～24, R
4With R
5Expression is selected from (EO)
m(PO)
nAt least a kind of the alkenyl of the alkyl of H, carbon number 1～24 and carbon number 1～24, and R
4With R
5Both can be identical also can be different, X
-The expression anion, above-mentioned E represents ethylidene, and above-mentioned P represents propylidene, and above-mentioned m and n add up to 1～60.Also have, m and n are average addition mole placate).
Here, it is preferred particularly having trimethyl one alkyl ammonium halide of alkyl of carbon number 6～24 and/or the dimethyl dialkyl ammonium halide with alkyl of carbon number 6～24.
In addition, can be quaternary ammonium salt with the imidazoline ring that contains alkyl and/or alkenyl.Here, the quaternary ammonium salt with imidazoline ring can be the compound with following general formula (6) expression:
(in the formula, R
6The alkyl of expression carbon number 6～24 or the alkenyl of carbon number 6～24, R
7The alkyl of expression carbon number 1～24 or the alkenyl of carbon number 1～24, X
-The expression anion).
Use oxyalkylated fatty acid ester in the present invention.
In addition, as operable cationic surfactant among the present invention, can enumerate and adopt R1R2R3R4N
+X
-The alkylammonium salt of expression.In the formula, R1 is selected from the alkyl with about 12～about 18 carbon atoms, or has the aromatic series aryl or the alkaryl of about 12～about 18 carbon atoms; R2, R3 and R4 be independently selected from hydrogen atom, have the alkyl of about 18 carbon atoms of about 1-or have the aromatic series aryl or the alkaryl of about 18 carbon atoms of about 12-; X is the anion that is selected from chloride, bromide, iodide, acetate, phosphate, nitrate, sulfate, Methylsulfate, sulfovinate, toluene fulfonate, lactate, paper レ one ト, glycollate and these mixture.In addition, alkyl can also contain ehter bond or hydroxyl or amino substituent (for example, alkyl can contain polyethylene glycol and polypropylene glycol part).
In addition, as other useful cationic surfactants, can enumerate that R1 changes R5CO-(CH in said structure
2)
n-(in the formula, R5 is the alkyl with about 12～about 18 carbon atoms; N is about 2～about 6, preferred about 2～about integer of 4, more preferably from about 2～about 3) amino amides.As the non-limiting example of these cationic emulsifiers, can enumerate stearamide propyl PG-chlorination phosphoric acid dimethyl ammonium, stearamide propyl ethyl ethoxy sulphite, stearamide propyl Dimethyl Ammonium (myristyl acetic acid esters) ammonium chloride, stearamide propyl dimethyl 16 octadecyl ammonium tosylates, stearamide propyl alkyl dimethyl ammonium chloride, stearamide propyl dimethyl ammonium lactate and their mixture.
As the non-limiting example of quaternary ammonium salt cationic surfacant, can enumerate and be selected from cetyl ammonium chloride, cetyl bromination ammonium, lauryl chlorination ammonium, lauryl bromination ammonium, stearyl chlorination ammonium, the stearyl ammonium bromide, the cetyl alkyl dimethyl ammonium chloride, cetyl dimethyl ammonium bromide, lauryl dimethyl ammonium chloride, the lauryl dimethyl ammonium bromide, the stearyl alkyl dimethyl ammonium chloride, stearyl dimethyl ammonium bromide, the cetyl trimethyl ammonium chloride, the cetyl trimethylammonium bromide, lauryl trimethyl ammonium chloride, the lauryl trimethylammonium bromide, the stearyl trimethyl ammonium chloride, the stearyl trimethylammonium bromide, lauryl dimethyl ammonium chloride, stearyl dimethyl cetyl Varisoft DHT, two cetyl ammonium chlorides, two cetyl bromination ammoniums, dilauryl ammonium chloride, the dilauryl ammonium bromide, distearyl ammonium chloride, the distearyl ammonium bromide, two cetyl ammonio methacrylates, two blubber ylmethyl ammonium bromides, the dilauryl ammonio methacrylate, dilauryl methyl ammonium bromide, the distearyl ammonio methacrylate, distearyl methyl ammonium bromide, and the quaternary ammonium salt cationic surfacant of these mixture.
As the quaternary ammonium salt of addition, can enumerate the salt of the alkyl chain of C12～C22 from tallow fatty acids or coconut fatty acid importing.Term " tallow " generally means the alkyl from the tallow fatty acids with the mixed alkyl chain in C12～C18 scope (being generally the hydrogenation tallow fatty acids).Term " coconut " generally means the alkyl from the coconut fatty acid with the mixed alkyl chain in C12～C18 scope (being generally the hydrogenation coconut fatty acid).As example, can enumerate Varisoft DHT from the quaternary ammonium salt in tallow and coconut source, two tallow base Dimethyl Ammonium Methylsulfates, two (hydrogenation tallow base) alkyl dimethyl ammonium chloride, two (hydrogenation tallow base) dimethyl acetic acid ammonium, two tallow base dipropyl ammonium phosphate, two tallow base dimethyl ammonium nitrate, two (coconut alkyl) alkyl dimethyl ammonium chloride, two (coconut alkyl) dimethyl ammonium bromide, tallow ammonium chloride, coconut ammonium chloride, stearamide propyl PG-dimethylammonium chloride phosphate, stearamide propyl ethyl Dimethyl Ammonium ethoxy sulfite, stearmide dimethyl (myristyl acetic acid esters) ammonium chloride, stearmide dipropyl methyl 16 octadecyl ammonium tosylates, the stearmide alkyl dimethyl ammonium chloride, stearmide dimethyl ammonium lactate, and their mixture.
Here, as useful preferred cation surfacant, can enumerate the cationic surfactant that is selected from dilauryl alkyl dimethyl ammonium chloride, VARISOFT TA100, myristyl alkyl dimethyl ammonium chloride, two palmityl alkyl dimethyl ammonium chlorides, VARISOFT TA100 and their mixture.
Except that above-mentioned, as softener, can enumerate quaternary ammonium salt cationic surfactants such as polyethylenepolyamine high fatty acid amide type cationic surfactant, imidazoline type cationic surfactant and alkyl-dimethyl ammonium chloride etc., wherein, preferred especially flexibility gives effect big polyethylenepolyamine high fatty acid amide type cationic surfactant.
As this polyethylenepolyamine high fatty acid amide type cationic surfactant, can enumerate polyethylenepolyamine high fatty acid amide (e1), polyoxyalkylene polyethylenepolyamine high fatty acid amide (e2), the urea condensate of polyethylenepolyamine high fatty acid amide (e3), the urea condensate (e4) of polyoxyalkylene polyethylenepolyamine high fatty acid amide, (e1)～(e4) epoxychloropropane addition product (e5), the alkyl chloride quaternary salt (e6) of polyethylenepolyamine high fatty acid amide, the chloroacetic acid addition amphoteric compound (e7) of polyethylenepolyamine high fatty acid amide and the part imidazoline salt (e8) of polyethylenepolyamine high fatty acid amide etc.
As the polyethylenepolyamine of these (e1)～(e8) constituents, can enumerate diethylenetriamines, trien, tetren etc.Wherein, preferably diethylenetriamines and trien.
Constitute (e2) or polyoxyalkylenes (e4), can enumerate epoxides addition base.As this epoxides, for example, can enumerate oxirane, expoxy propane and epoxy butane.Wherein, preferably oxirane and oxirane and expoxy propane and with (block or random addition).As the mixed weight ratio of oxirane with expoxy propane and time spent, preferred 1: (0.1～1.0).As epoxides addition molal quantity, be generally 1～10 mole, preferred 1～5 mole.
As the higher fatty acids of (e1)～(e8) constituent, can adopt the higher fatty acids from natural oil such as palm oil, tallow, rape seed oil, rice bran oil, fish oil usually, but the synthetic class higher fatty acids that also can adopt petrochemical plant to make.Wherein, the higher fatty acids of the carbon number 12～24 of iodine number below 50 preferably.
As the polyethylenepolyamine of another constituent of (e1)～(e8) or the mol ratio of polyoxyalkylene polyethylenepolyamine and higher fatty acids, be generally 1: 1.0～2.5, preferred 1: 1.2～1.8.Among above-mentioned (e1)～(e8) that enumerates preferably (e1)～(e5).
Embodiment 1
Embodiments of the invention are shown below.
To paper handkerchief with and the material used of toilet paper, according to the Different Results of the kind research and appraisal of additive.It the results are shown in table 1.Used additive is shown in table 1 in the lump.
Estimate, the KES testing machine that adopts カ ト-テ Star Network society to make is measured the MIU value relevant with coefficient of friction.This value heals little expression more smoothly.
In addition, under electron microscope, owing to only can not estimate by the MIU value, so the fibre pick state on finished paper surface is observed.
[table 1]
According to this result, goods of the present invention, when sensory evaluation, " flexibility ", " flatness " have all obtained high evaluation.Here, being expressed as that and fluffing 0.1mm more than total radical longer the fluffing combined length more than the 0.1mm is many is more level and smooth.Its reason is,, can infer from the example of feather when having the filoplume of many length on the surface of paper.
Embodiment 2
Paper handkerchief and paper handkerchief of the present invention to market sale carry out various comparisons.Any be 2 overlapping be 1 group (2 layers).The results are shown in table 2.
Flexibility composition used herein is as follows:
Softener A: nonionic class fatty acid ester (Japanese PMC society makes, " SFS1001 ")
Softener B: cationic fat acid esters (Japanese PMC society make " SFS1002 ")
Softener C: cationic fat acid esters (Japanese PMC society make " SFS1004 ")
Softener D: cationic fat acid amides (Japanese grease society make " leavening agent ")
Sensory evaluation is estimated according to 5.In addition, when void area rate and radical ratio measuring that 6 in sample is overlapping, under the state of overlapping OHP paper, use the razor blade of peak profit to cut off about it from the angles of 90 degree, the section of cut-out sample is taken a picture with 1000 times SEM, judges from this photo.
According to this result, goods of the present invention are carried out sensory evaluation, " flexibility ", " flatness " have all obtained high evaluation.
Industrial applicibility
The invention provides home-use etc. sanitary thin paper and the manufacturing side thereof such as a kind of paper handkerchief or toilet paper Method can be suitable for as special soft and level and smooth sanitary thin paper.
Claims (9)
1. sanitary thin paper, it is characterized in that, make raw material with paper pulp, contain fatty acid ester compound and fatty acid amide compound, wherein, adopt internal addition method to contain above-mentioned fatty acid ester compound, adopt at least a kind of method of internal addition method and external addition method to contain above-mentioned fatty acid amide compound, and contain petchem, adopt external addition method to contain above-mentioned petchem, as above-mentioned petchem, contain petchem with following general formula (1) expression:
R in the formula
1Be HO-or HO (R
2O)
a-, R
2Be the alkylidene of carbon number 2～3, R
2O is a kind or 2 kinds, 2 kinds R
2O adds becomes random shape or block-wise, and a is 1～200, and in a part, a is all identical or different, and b is 2～100, R
3For hydrogen atom or with the base of general formula (2) expression,
2. according to the sanitary thin paper of claim 1 record, wherein, containing the content of the softener composition of above-mentioned fatty acid ester compound and above-mentioned fatty acid amide compound, is benchmark with the dry mass, is 0.002～10 parts by mass to above-mentioned paper pulp raw material 100 parts by mass.
3. according to the sanitary thin paper of claim 1 or 2 records, wherein, above-mentioned petchem is a benchmark with the dry mass, and above-mentioned paper pulp raw material is added with the ratio of 0.05～30.0 quality %.
4. according to the sanitary thin paper of claim 1 record, wherein, per 1 layer level ground amount is 10～35g/m
2
5. according to the sanitary thin paper of claim 1 record, wherein, give wrinkle copying the paper stage, the vertex distance of the flow direction that is shaped as wrinkle of this wrinkle is below 0.1mm, and the lateral length of wrinkle is below the 0.5mm.
6. according to the sanitary thin paper of claim 5 record, wherein, in the horizontal section of paper between adjacent paper pulp fiber distance reach the above paper pulp fiber number of 1 μ m, shared ratio is more than 50% in whole paper pulp fiber numbers.
7. according to the sanitary thin papers of claim 5 or 6 records, wherein, remove outside the area that paper pulp fiber occupies in the horizontal section of paper, the area occupation ratio in space is more than 50%.
8. the manufacture method of a sanitary thin paper, it is characterized in that, l Water Paper to paper pulp raw material, after adopting internal addition method to contain fatty acid ester compound and fatty acid amide compound, in this l Water Paper, add petchem outside with online mode, as above-mentioned petchem, contain petchem with following general formula (1) expression:
R in the formula
1Be HO-or HO (R
2O)
a-, R
2Be the alkylidene of carbon number 2～3, R
2O is a kind or 2 kinds, 2 kinds R
2O adds becomes random shape or block-wise, and a is 1～200, and in a part, a is all identical or different, and b is 2～100, R
3For hydrogen atom or with the base of general formula (2) expression,
9. the manufacture method of a sanitary thin paper, it is characterized in that, l Water Paper to paper pulp raw material, after at least a kind of method of employing internal addition method and external addition method contains fatty acid ester compound and fatty acid amide compound, in above-mentioned paper pulp l Water Paper or the dried paper that is dried, add petchem outside with online mode, as above-mentioned petchem, contain petchem with following general formula (1) expression:
R in the formula
1Be HO-or HO (R
2O)
a-, R
2Be the alkylidene of carbon number 2～3, R
2O is a kind or 2 kinds, 2 kinds R
2O adds becomes random shape or block-wise, and a is 1～200, and in a part, a is all identical or different, and b is 2～100, R
3For hydrogen atom or with the base of general formula (2) expression,
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP165961/2004 | 2004-06-03 | ||
| JP2004165961 | 2004-06-03 | ||
| JP2004347116 | 2004-11-30 | ||
| JP347116/2004 | 2004-11-30 | ||
| PCT/JP2005/010257 WO2005118954A1 (en) | 2004-06-03 | 2005-06-03 | Sanitary thin paper and process for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1977082A CN1977082A (en) | 2007-06-06 |
| CN100595379C true CN100595379C (en) | 2010-03-24 |
Family
ID=35462944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200580017964A Active CN100595379C (en) | 2004-06-03 | 2005-06-03 | Sanitary thin paper and process for producing the same |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20070233024A1 (en) |
| EP (1) | EP1752580A4 (en) |
| JP (1) | JP4875488B2 (en) |
| CN (1) | CN100595379C (en) |
| WO (1) | WO2005118954A1 (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4928943B2 (en) * | 2004-08-31 | 2012-05-09 | 大王製紙株式会社 | Household hygiene tissue paper |
| JP2007307287A (en) * | 2006-05-22 | 2007-11-29 | Meiko Shoji Kk | Fiber body for cleaning body |
| JP4833936B2 (en) * | 2007-07-31 | 2011-12-07 | ライオン株式会社 | Tissue paper |
| JP5410026B2 (en) * | 2008-03-17 | 2014-02-05 | 大王製紙株式会社 | Sanitary tissue paper |
| JP2010084273A (en) * | 2008-09-30 | 2010-04-15 | Hakuto Co Ltd | Modifier and paper product containing the same |
| JP5479835B2 (en) * | 2009-09-30 | 2014-04-23 | 大王製紙株式会社 | Water-degradable sanitary thin paper and toilet paper roll |
| JP5445203B2 (en) * | 2010-02-16 | 2014-03-19 | 日油株式会社 | Additive for paper |
| CN105451621A (en) * | 2013-08-14 | 2016-03-30 | 爱速客乐株式会社 | Tissue base paper and tissue paper |
| JP6242018B2 (en) * | 2015-06-16 | 2017-12-06 | 大王製紙株式会社 | Tissue paper |
| JP6210567B2 (en) | 2015-09-14 | 2017-10-11 | 大王製紙株式会社 | Tissue paper |
| JP6069452B1 (en) | 2015-09-30 | 2017-02-01 | 大王製紙株式会社 | Toilet Paper |
| JP6583117B2 (en) * | 2016-04-18 | 2019-10-02 | 王子ホールディングス株式会社 | Hygienic thin paper and method for producing the same |
| JP6235674B1 (en) | 2016-09-30 | 2017-11-22 | 大王製紙株式会社 | Tissue paper |
| JP7163031B2 (en) * | 2018-01-31 | 2022-10-31 | 大王製紙株式会社 | Sanitary tissue paper and method for producing sanitary tissue paper |
| JP7133943B2 (en) | 2018-02-28 | 2022-09-09 | 大王製紙株式会社 | tissue paper |
| JP2021516295A (en) * | 2018-03-22 | 2021-07-01 | バックマン ラボラトリーズ インターナショナル，インコーポレイティド | Modified crepe adhesive formulation and crepe processing method using it |
| JP6689944B1 (en) * | 2018-11-30 | 2020-04-28 | 大王製紙株式会社 | Toilet Paper |
| JP7175801B2 (en) * | 2019-03-06 | 2022-11-21 | 大王製紙株式会社 | Toilet Paper |
| JP7169924B2 (en) * | 2019-03-27 | 2022-11-11 | 大王製紙株式会社 | TOILET PAPER AND TOILET PAPER MANUFACTURING METHOD |
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| EP0842327B1 (en) * | 1995-08-03 | 2002-02-13 | The Procter & Gamble Company | Lotioned tissue paper containing a liquid polyol polyester emollient and an immobilizing agent |
| CN1478166A (en) * | 2001-01-19 | 2004-02-25 | Sca������Ʒ����˾ | Lotioned fibrous web |
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| JP3786686B2 (en) * | 1993-12-13 | 2006-06-14 | ザ プロクター アンド ギャンブル カンパニー | Lotion composition for imparting a soft, smooth feel to tissue paper |
| JP4169783B2 (en) * | 1994-06-17 | 2008-10-22 | ザ プロクター アンド ギャンブル カンパニー | Tissue paper with lotion |
| ES2181896T3 (en) * | 1995-06-28 | 2003-03-01 | Procter & Gamble | PISEL TISU PLISADO SHOWING A UNIQUE COMBINATION OF PHYSICAL PROPERTIES. |
| ZA983401B (en) * | 1997-04-24 | 1998-10-27 | Procter & Gamble | Absorbent articles having lotioned leg cuffs containing a polysiloxane emollient |
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| WO2005060712A2 (en) * | 2003-12-19 | 2005-07-07 | The Procter & Gamble Company | Processes for foreshortening fibrous structures |
-
2005
- 2005-06-03 US US11/597,961 patent/US20070233024A1/en not_active Abandoned
- 2005-06-03 JP JP2006514144A patent/JP4875488B2/en active Active
- 2005-06-03 WO PCT/JP2005/010257 patent/WO2005118954A1/en not_active Application Discontinuation
- 2005-06-03 CN CN200580017964A patent/CN100595379C/en active Active
- 2005-06-03 EP EP05750808A patent/EP1752580A4/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0842327B1 (en) * | 1995-08-03 | 2002-02-13 | The Procter & Gamble Company | Lotioned tissue paper containing a liquid polyol polyester emollient and an immobilizing agent |
| CN1478166A (en) * | 2001-01-19 | 2004-02-25 | Sca������Ʒ����˾ | Lotioned fibrous web |
| CN1491306A (en) * | 2001-02-16 | 2004-04-21 | Lotioned and embossed tissuepaper |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1752580A1 (en) | 2007-02-14 |
| JPWO2005118954A1 (en) | 2008-04-03 |
| WO2005118954A1 (en) | 2005-12-15 |
| EP1752580A4 (en) | 2010-03-24 |
| US20070233024A1 (en) | 2007-10-04 |
| CN1977082A (en) | 2007-06-06 |
| JP4875488B2 (en) | 2012-02-15 |
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