Detailed description of the invention
The web of fiber that adds washing lotion, particularly tissue paper of the present invention, dry web of fiber, particularly tissue webs (not having washing lotion) are upper to be obtained by above-mentioned washing lotion composition is applied to usually. Preferably, the content of residual water of described web of fiber, particularly tissue webs is not more than 10% weight.
1. washing lotion
By making oil, (O/W) emulsifying agent or (O/W) emulsifier mixture mixing and homogenising, and obtain oil-in-water (O/W) emulsion.
At room temperature (23 ℃), this washing lotion composition can half-solid phase or viscous liquid.
In the first situation, 23 ℃ of its viscosity usually less than 30,000mPas (utilize the Brookfield-RVF viscosimeter to measure, spindle 5,10rpm). Therefore, the washing lotion composition mainly remains on the surface of fibre substrate, helps the soft surface degree of product, but less to the promotion of overall bulk softness.
In preferred embodiments, compare with being used for half-solid phase washing lotion composition tissue paper, known, this washing lotion has quite low viscosity. This low viscosity provides excellent permeance property and has prevented on its surface that is retained in web of fiber, particularly single or multiple lift tissue paper product. In the situation of individual layer paper web such as individual layer tissue paper, it will permeate this layer fully and make it softening. In the situation of multi-layered product, the washing lotion composition will arrive internal layer, and this will strengthen overall bulk softness widely. Above-mentioned low viscosity washing lotion is in the time of 23 ℃, and its viscosity is preferably less than 10,000mPas, and the representative value of half-solid phase washing lotion (utilizes the Brookfield-RVF viscosimeter to measure spindle 5,10rpm; Hereinafter, the viscosity number of final washing lotion composition always with Brookfield-RVF viscosimeter (spindle 5, measured value 10rpm) is relevant). Preferably, its in the viscosity of 23 ℃ of measurements less than 7,500mPas, more preferably from 1,500-5,000mPas, particularly 2000-3500mPas. In addition preferably, in the time of 30 ℃ its viscosity from 800-2500mPas, 1000-2200mPas particularly. Under 40 ℃ temperature, preferred viscosity number is 500-1500mPas, particularly 600-1200mPas. In the time of 50 ℃, the viscosity of low viscosity washing lotion is preferably less than 500, particularly less than 400mPas.
As known in the art, by utilizing the solid constituent of higher or lower amount, consistency modifiers cited below particularly can be regulated the viscosity of washing lotion. In addition, the homogenization of washing lotion (energy injection) can exert an influence to final viscosity. When measuring according to the dsc analysis of final washing lotion composition, the fusion temperature scope of the solid constituent that optionally exists is preferably at 25-70 ℃, particularly in the scope of 60 ℃ of 30-.
This washing lotion does not need to exist silicon-containing compound, and for example silicone oil or quaternary ammonium compound so that obtain its emollescence, but are not got rid of its use.
1.1. oil ingredient (A)
Term " oil " is used for oil water-insoluble, organic, natural and synthetic, that skin moisten is useful, preferably, at room temperature (23 ℃) it has liquid consistency.Preferably, the consumption of this oil ingredient is a 20-70% weight, more preferably from 30-65% weight, and 40 (or 50)-65% weight particularly.(below, except as otherwise noted, the % gravimetric value relates to the gross weight of washing lotion composition).
This oil ingredient suitably is selected from the known oil of plant source, mineral oil or artificial oil.
Preferably, this oil ingredient (A) comprises at least a oil that is selected from following kind:
1. glyceride, its be glycerine list-, two-and/or three esters (particularly two-and/or three esters).As known in the art, glyceride can obtain or derive from natural source (plant or animal) by chemical synthesis.Preferably, fatty acid component has 6-24, more preferably 6-18, a particularly 8-18 carbon atom.But this aliphatic acid branch or unbranched and saturated or unsaturated.According to the present invention, the preferred liquid glyceride that uses from plant source, particularly utilize modification the liquid coconut oil (the INCI name: coconut glyceride, with trade name myritol
331 derive from Cognis Deutschland GmbH), its comprise as main component, based on two of C8-C18 aliphatic acid-and the mixture of glyceryl ester.
2. can also comprise crude vegetal as the liquid glyceride of main component, as soybean oil, peanut oil, olive oil, sunflower oil, macademia nut oil or jojoba oil.
3. (each alkyl (thiazolinyl) group preferably has 12-24 carbon atom to have symmetrical or asymmetric, the linearity of 6-24 carbon atom or dialkyl group (thiazolinyl) ether of branch, as total carbon number), as two-just-Octyl Ether (two decoyl ether), two-(2-ethylhexyl) ethers, lauryl methyl ether, octylbutylether or docosyl ether wherein preferably use two-just-Octyl Ether (two decoyl ethers; Viscosity: at 20 ℃ is 2-5mPas, DGF method as described below).
4. dialkyl group (thiazolinyl) carbonic acid ester (preferred the total number of carbon atoms: no more than 45, comprise the carbon atom of carbonate unit) that preferably has at least one C6-C22 alkyl or alkenyl.Alkyl or alkenyl can be a straight or branched.Can there be the two keys more than the thiazolinyl unit.These carbonic acid esters can according to known method (cf.Chem.Rev.96,951 (1996)), obtain by the ester exchange of dimethyl carbonate or diethyl carbonate in the presence of the C6-C22 fatty alcohol.For the basic carbonic acid ester of dioxane (alkene), typical example is: Capron alcohol, octanol, 2-ethylhexanol, just-decyl alcohol, laruyl alcohol, different tridecanol, tetradecanol, cetanol, Palmitoleyl alcohol, octadecanol, isooctadecanol, arachidic alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and Brazilian enol with and (part) ester exchange offspring of technology mixture, they for example obtain by the high-pressure hydrogenation to methyl esters special on fat or the oil base.In view of its low viscosity 20 ℃ the time, specially suitablely be: dihexyl-, dioctyl-, two-(2-ethylhexyl)-or two oil base carbonic acid esters (viscosity of dioctyl carbonic acid ester: in the time of 20 ℃, be 7mPas, DGF method as described below).Therefore, preferably use short chain (C6-C10) alkyl or alkenyl carbonic acid ester.
5. hydrocarbon-the base oil that preferably has 8-30, a particularly 15-20 carbon atom, as saualane, squalene, paraffin oil, isohexadecane, Isoeicosane, poly decene or dialkyl cyclic hexane, or mineral oil.
6. the wax shape ester that preferably has following general formula (I):
R
1COO-R
2(I)
Wherein, R
1CO represents to have 6-22 carbon atom and 0,1,2, or acyl residue 3 two keys, linearity or branch, R
2Expression has alkyl or alkenyl residue 6-22 carbon atom, linearity or branch.Preferably, the sum of carbon atom is at least 20 in ester.The exemplary of wax shape ester is: myristic acid myristyl ester, palmitic acid myristyl ester, stearic acid myristyl ester, behenic acid myristyl ester, erucic acid myristyl ester, myristic acid spermaceti alcohol ester, isostearic acid cetyl ester, oleic acid cetyl ester, behenic acid cetyl ester, erucic acid cetyl ester, myristic acid (mystrate) stearyl ester, palmitic acid stearoyl ester, stearic acid stearoyl ester, isostearic acid stearoyl ester, oleic acid stearoyl ester, behenic acid stearoyl ester, erucic acid stearoyl ester, myristic acid isostearoyl ester, palmitic acid isostearoyl ester, stearic acid isostearoyl ester, isostearic acid isostearoyl ester, oleic acid isostearoyl ester, behenic acid isostearoyl ester, the myristic acid oleate, oleyl palmitate, stearic acid oil base ester, isostearic acid oil base ester, oleic acid oil base ester, behenic acid oil base ester, erucic acid oil base ester, myristic acid docosane ester, palmitic acid docosane ester, isostearic acid docosane ester, oleic acid docosane ester, behenic acid docosane ester, erucic acid docosane ester, myristic acid two dodecylene esters, palmitic acid two dodecylene esters, stearic acid two dodecylene esters, isostearic acid two dodecylene esters, oleic acid two dodecylene esters, behenic acid two dodecylene esters and erucic acid two dodecylene esters.Preferably, use unsaturated wax shape ester, as oleic acid oleic alcohol ester and erucic acid oil alcohol ester.
Following ester, owing to have similar character, so they are also counted " wax shape ester ": be derived from linear C
6-C
22Aliphatic acid and branched-chain alcoho be the ester of 2-Ethylhexyl Alcohol for example; C
18-C
38Alkyl hydroxy carboxylic acid and linearity or side chain C
6-C
22The ester of fatty alcohol; Or linear and/or the aliphatic acid of branch and the ester of polyalcohol (as propylene glycol, dimer diol or trimerization triol) and/or Guerbet alcohol, and C
6-C
22Fatty alcohol and/or Guerbet alcohol and aromatic carboxylic acids, particularly benzoic ester; C
2-C
12Dicarboxylic acids and have the linearity of 1-22 carbon atom or the alcohol of branch or have the ester, particularly malic acid dioctyl ester of the polyalcohol of 2-10 carbon atom and 2-6 hydroxyl.
7. the useful silicone oil of skin moisten (US-4 for example, those in 202,879 and US-5,069,897).
In addition, preferably oil ingredient is selected (according to chain length or esterification degree, this is well known in the prior art), be not more than 5, particularly be not more than 4Debey to cause its polarity.
In other embodiment preferred, in light viscosity oil, suitably select oil ingredient, described light viscosity oil promptly utilize the Huppler falling ball viscometer at (method " DeutscheGesellschaft fur Fettcheraie " the DGF C-IV 7) of 20 ℃ of measurements viscosity number from 1-100mPas, the oil of 1-50mPas (as 1-20mPas) particularly is so that particularly obtain the permeance property of hope on tissue paper at paper web.
Permeate paper web dearly if wish washing lotion, preferably, oil ingredient (a) comprises at least a following oil (in oil ingredient preferably, at least 20% weight, particularly at least 40% weight):
1. " oil (A ') ", be preferably selected from and utilize the Huppler falling ball viscometer to be lower than the oils of 30mPas at (the method DGFC-IV 7) of 20 ℃ of measurements viscosity number, and/or be selected from symmetry with 6-24 carbon atom (each alkyl group) and preferred 12-24 carbon atom (total) or the basic ether of asymmetric dioxane (alkene), or be derived from the C6-C22 fatty alcohol, the basic carbonic acid ester of dioxane (alkene) linearity or branch.As above measure, described oil viscosity preferably is lower than 20, more preferably less than 15, particularly is lower than 10mPas.
In other embodiment preferred, oil ingredient (a) comprises at least a following oil (in oil ingredient, preferably at least 20% weight, particularly at least 40% weight):
Oil (A "), when utilizing the Hoppler falling ball viscometer to measure (method DGF C-IV 7) for 20 ℃, its viscosity is preferably greater than oil (A '), particularly greater than 30mPas (preferably at least 40), and less than 100mPas; And/or at least a oil (A ") that is selected from wax shape ester, glyceride, natural oil and alkyl oils.
Preferred combination is used oil (A ') and (A "), the particularly basic ether of (A ') two-alkane (alkene) or the basic carbonic acid ester of dioxane (alkene) and (A ") wax shape ester, glyceride, the mixture of hydrocarbon-base oil or natural oil.Particularly preferably be and be used in combination basic carbonic acid ester of dioxane (alkene) and glyceride.
If with one of these oil as the part of oil ingredient (A), so, in its part by weight of total amount of oil ingredient preferably at least 20% weight, particularly at least 40% weight.
In particularly preferred embodiments, oil ingredient (A) comprises the liquid glyceride of 20-80%, particularly 40-60% weight and the basic carbonic acid ester of liquid dioxane (alkene) of 80-20%, particularly 60-40% weight.
1.2.O/W emulsifying agent
Preferred right and wrong-the ion-type of emulsifying agent or emulsifier combination (B) and mainly have a function that forms O/w emulsion.It can also promote the pliability of tissue paper.O/W emulsifying agent or its mixture that it can suitably be selected oneself and know.
Emulsifying agent (mixture) can be relative polarity and can for example be selected from the surfactant of HLB value from 10-18.Above-mentioned surfactant is known according to prior art, and for example is set forth among the Enclypedia of Chemical Technology (third edition, 1979, the 8 volumes, the 913rd page) of Kirk-Othmer.Under the situation of ethoxylated product, the HLB value can be according to formula HLB=(100-L): 5 calculate, and L is the part by weight of lipophilic group in the formula, for example the fatty alkyl of fatty acyl group.
In addition, also may be in conjunction with the littler polarity as described below and the emulsifying agent of stronger polarity, as poly-(carboxyl ester) (B ") and alkyl (oligomeric) glucosides (B ') of polyalcohol.When according to the HLB value representation, the HLB value also is embodiment of the present invention from the surfactant mixture of 2.5-5 and 15-18.
Preferably, (O/W) content of emulsifying agent (mixture) is from 3-40% weight, more preferably from 5-30% weight, particularly 7-20%, and 8-15% weight for example.
Preferably, use liquid O/W emulsifying agent, still, depend on the viscosity that final washing lotion composition is wished, also may use the small amount of solid emulsifying agent.
Component (B) can suitably be selected from:
1. the fatty alcohol that has 8-24 carbon atom (particularly 12-22 carbon atom), the ethylene oxide or the propylene oxide adduct of (C8-C15 alkyl) phenol or polyalcohol comprise 2-50 moles of ethylene oxide unit and/or 0-5 mole propylene oxide units.
2. by glycerine, polysaccharide, compound sugar or monose, sugar alcohol or sugar alcohol acid anhydride (as sorbitan) and preferably have monoesters or diester (or its mixture) the 6-22 carbon atom, linearity or side chain, saturated or that unrighted acid is derived and obtained.These esters can also be by ethoxylation (→ EO unit), for example poly-sorbic acid list lauryl+20EO or poly-sorbic acid monoleate+20EO.If described ester is a liquid, so, aliphatic acid often can be selected from the short chain saturated fatty acid, for example the aliphatic acid in sorbitan monolaurate, perhaps be selected from the aliphatic acid that has a unrighted acid at least, as the aliphatic acid in NOFABLE SO-992.
3. alkyl (oligomeric) glycosides (in claims, being called B '), it is a nonionic surface active agent, wherein at least one hydroxyl of (oligomeric) glycosides (the normally C1 hydroxyl of first glycosyl) by at least one ehter bond (or ethylene oxide unit and/or propylene oxide units) with contain alkyl unit (preferably amounting to 6-28 carbon atom) and be connected.Preferably, alkyl (oligomeric) glycosides has following formula (II):
R
2O (C
nH
2nO)
t(glycosyl)
x(II) wherein, R
2Be selected from alkyl, alkyl phenyl, hydroxyalkyl, the hydroxyalkyl phenyl, and composition thereof, wherein alkyl group comprises 6-22 carbon atom, a particularly 8-16 carbon atom (for example 10-14 carbon atom); N is 2 or 3, and is preferred 2, and t is preferably 0 from 0 to about 10; X is at least 1, preferably from 1.1-5, and more preferably from 1.1-1.6,1.1-1.4 particularly, and " glycosyl " is monose.The value of X should be understood to the average content (the oligomeric degree of polymerization) of monosaccharide unit.
The production of the alkyl useful to the present invention (oligomeric) glycosides is known by prior art, and for example is described in US-4,011,389, US-3,598,865, US-3,721,633, US-3,772,269, US-3,640,998, US-3 is in 839,318, or US-4,223,129.
For preparing these compounds, at first form alcohol or alkyl-many ethoxy alcohols usually, then with the reaction of (oligomeric) glycosyl units, thereby form (low) glycosides (connecting) in the 1-position.Glycosyl units can be connected the C1 position of other glycosyl and contain 2-, 3-, 4-and/or the 6-position of the glycosyl unit of alkyl-group, between the preferred 6-position.
Preferred raw alcohol R
2OH is straight chain primary alcohol or the primary alconol with 2-methyl branch.Preferred alkyl residue R2 for example is: 1-octyl group, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl, particularly preferred the 1-octyl group that is to use, 1-decyl, 1-lauryl and 1-myristyl.
The alkyl useful to the present invention (oligomeric) glucosides can only comprise a specific alkyl residue.Usually, raw alcohol is by natural fat, oil or mineral oil production.In this case, raw alcohol is represented the mixture of various alkyl residue.
In four specific (preferably) embodiments, use alkyl (oligomeric) glucosides, wherein R
2Mainly by C8 and C10 alkyl, C12 and C14 alkyl group, the C8-C16 alkyl group, or the C12-C16 alkyl group is formed.
May use any monose or compound sugar with the form of saccharide residue " (glycosyl) x ".Usually, use sugar and corresponding compound sugar with 5 or 6 carbon atoms.Described sugar for example comprises: glucose, fructose, galactolipin, arabinose, ribose, wood sugar, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose.The preferred glucose that uses, fructose, galactolipin, arabinose, sucrose, with and compound sugar, wherein particularly preferably be (oligomeric) glucose.
In preferred embodiments, use " Plantacare APG 1200G ", C12-C16 fatty alcohol-glucosides (x=1.4), it is with trade name Plantacare
Derive from Cognis Deutschland GmbH.
4. its mixture.
Preferred use emulsifying agent as described below (B ') and (mixture of B "),
(B "): liquid polyester polyol wherein, has the polyalcohol of at least two hydroxyls and the condensation product esterification that at least one has 6-30 carbon atom (particularly 16-22 carbon atom) and has carboxylic acid or this hydroxy fatty acid of a hydroxyl at least.Polyalcohol comprises monose, disaccharides, and trisaccharide, sugar alcohol, other sugar derivatives, glycerine, and polyglycereol, for example diglycerol, triglycerin and higher glycerine.Above-mentioned polyalcohol preferably has 3-12, a particularly 3-8 hydroxyl and 2-12 carbon atom (if it is the polyglycereol mixture, being mean value).Preferably polyalcohol is a polyglycereol, those polyalcohols that particularly be described among the WO95/34528 (the 5th page), have specific oligomer distribution.
Preferably, the carboxylic acid that in polyol polyester, uses be aliphatic acid with 6-30 carbon atom (below, except as otherwise noted, term " fatty acid " " be not limited to naturally occurring, even number, saturated or unsaturated long-chain carboxylic acid, but also comprise the homologue of its odd number or the derivative of its side chain).Aliphatic acid comprises a hydroxyl at least.It is the mixture of hydroxy fatty acid or its condensation product (poly-(hydroxy fatty acid)).The preferred carbon atom scope of above-mentioned hydroxy fatty acid is from 16-22, particularly 16-18.Particularly preferred poly-(hydroxy fatty acid) is hydroxy stearic acid, and particularly the condensation product of 12-hydroxy stearic acid is mixed with poly-(ricinoleic acid) wherein optionally, and described condensation product has the character of describing among the WO95/34528.
Preferred solvent comprises the polyalcohol poly-(hydroxy stearic acid ester) that is described among the WO95/34528, the polyglycereol poly-(hydroxy stearic acid ester) that particularly has the characteristic in the document of being disclosed in, for example polyglycereol gathers (1 2-hydroxystearic acid ester), and it is with trade name Dehymuls
PGPH derives from Cognis DeutschlandGmbH.
The preferred content of (B ') is a 1-15% weight, particularly 3-8% weight.(preferred content of B ") is a 2-15% weight, particularly 3-9% weight.
Preferably, B ' and B " weight ratio from 0.2-2.0, more preferably from 0.5-1.5, particularly from 0.8-1.2.
1.3. water
The washing lotion composition comprises 6-35% weight, more preferably 12-30% weight, the particularly water of 15-25% weight.Water will help to make user's skin to have the comfortable sensation of washing lotion-shape.In addition, water will suppress pure wetting agent (if present) is drawn water from application on human skin trend.On the other hand, because the mechanical strength of the tissue paper of handling may suffer the not loss of extend of hope, therefore, moisture should be apparently higher than 35% weight.Usually, the water of O/W emulsion comprises the water as main component.Yet, if moisture near the lower limit of claimed range, preferably the water-soluble water with respective amount forms component, preferred wetting agent is added in the washing lotion composition.In addition, discontinuous (oil) can be in very closely state of contact mutually, so that keep stable O/W emulsion.In view of the above, in the gross weight of washing lotion composition, the weight ratio of water is preferably greater than 20, more preferably at least 22, particularly at least 23, or at least 24% weight.
Measure by the water yield of carrying out Karl Fischer, might determine the moisture in the washing lotion composition.This also can be used for determining the moisture of the tissue paper handled.Therefore, whole washing lotion is extracted, determine moisture according to the ethanolic extract of Karl Fischer then with appropriate organic solvent (for example absolute ethyl alcohol).If necessary, should deduct the tissue paper content of residual water of handling.
1.4. wetting agent (optional)
Preferably, the washing lotion composition comprises 1-15% weight, particularly 3-8% weight (water-soluble) wetting agent.
This wetting agent is carried out multiple function.At first, its bound water and suppress the trend of water evaporation.In addition, wetting agent can with other washing lotion component interaction, so promote the pliability of tissue paper.Wetting agent can also influence the rheological characteristic of washing lotion composition.
Preferably, wetting agent is a poly hydroxyl compound, and it is interpreted as having the organic compound of at least two hydroxyls, and preferably, it only is made up of carbon, hydrogen, oxygen and nitrogen, and particularly only by C, H and O form.It is desirable for wetting agent in addition is not ion.
Although hydrophilic surfactant (have 10 or bigger hydrophilic lipophilic balance, referring to US4,764,418) have wet performance, according to the present invention, preferably, wetting agent does not have bigger hydrophobic molecular moiety, for example aliphatic acid or fatty alcohol residue.
In addition preferably, wetting agent has liquid consistency, although may use a small amount of solid phase, low melting point wetting agent, this depends on viscosity and permeance property that final washing lotion is wished.
If use the liquid wetting agent, so preferably, molecular weight is lower than 1,000, more preferably is lower than 800, particularly is not higher than 600.
The example of suitable wetting agent comprises: glycerine, and poly alkylene glycol, for example polyethylene glycol or polypropylene glycol, for example weight average molecular weight is from the polyethylene glycol of 200-600; Neopentyl alcohol is as pentaerythrite or neopentyl glycol; Sugar alcohol, as threitol, erythrite, adonitol (ribitol), arabitol, xylitol, dulcitol, mannitol and D-sorbite, carbohydrate such as D (+)-glucose, D (+)-fructose, D (+)-galactolipin, D (+)-mannose, the L-gulose, sucrose, galactolipin, maltose, polyglycereol, the polypropylene oxide adduct of glycerine, methoxy poly (ethylene glycol), the polyglycol ether of sugar alcohol, as D-sorbite, the polyglycol ether of glycerine, and composition thereof.Hyaluronic acid also can be used as wetting agent.
A kind of preferred humectants is a glycerine.
1.5. coemulsifier (optional)
In other embodiments, in the total amount of washing lotion composition, the washing lotion composition comprises at the most 15% weight, more preferably 1-10% weight, the particularly coemulsifier of 3-8% weight.In order to stablize the O/W emulsion, preferably use the nonionic coemulsifier, with regard to its ecotoxicological performance with on skin with regard to the soft sensation, they are excellent.Yet; although be not preferred; but also may use amphoteric surfactant (in molecule, have the C8-C18-alkyl or-acyl group; at least one free amino group and at least one COOK or-the SO3H-group and can form inner salt), zwitterionic surfactant (has at least one quaternary ammonium group and at least one COO in molecule
-Or SO
- 3Group), anion surfactant (have the anionic group that makes this surfactant water-soluble, as carboxylate, sulfate, sulfonate or phosphate group and lipophilic residue) and cationic surfactant (as quaternary ammonium compound).
Preferably, coemulsifier is selected from the HLB value for nonionic surface active agent 10-18, lipophilic.Above-mentioned surfactant is known in the prior art, and for example is set forth among the Enclypedia of Chemical Technology (third edition, 1979, the 8 volumes, the 913rd page) of Kirk-Othmer.In ethoxylated product, the HLB value can be according to formula HLB-(100-L): 5 calculate, and L is the weight ratio of lipophilic group in the formula, for example the fatty alkyl of fatty acyl group.
Be used in combination nonionic O/W emulsifying agent (B) and coemulsifier and can form very finely divided emulsion, therefore increased the stability of washing lotion composition.
Coemulsifier for example can be selected from:
1. the mixed ester that obtains of the esterification by following material
A) at least a have a 6-30, the aliphatic acid of preferred 6-22 carbon atom, and as cocinic acid,
B) neopentyl alcohol such as neopentyl glycol, dihydroxy methylpropane, or pentaerythrite preferably,
C) at least a fatty alcohol with 6-30 carbon atom, preferred 16-20 carbon atom, as stearyl alcohol and
D) have no more than 10 carbon atoms and the preferred tricarboxylic acids of at least one oh group, as citric acid,
Preferably, those among the DE-A-11 65 574, two coco group pentaerythrite base distearyl citrates for example, it is to be the solid shape.
2. demonstrate castor oil average 7-16 mole or 2-15 mole ethylene oxide unit, that ethoxylated castor oil and/or ethoxylation are solidified.
3. wool wax alcohol and composition thereof.
The consumption of above-mentioned optional component in the gross weight of washing lotion composition from 1.5-7.5% weight, 3.5-5% weight for example.
1.6. consistency modifiers (optional)
The viscosity of washing lotion can be regulated by the consistency modifiers of utilizing respective amount, and described conditioning agent is solid normally.Square and above, term " solid " or " liquid " refer at room temperature the physical state of (23 ℃).
The consumption of consistency modifiers depends on the viscosity that final washing lotion composition is wished.If obtain half-solid-state denseness, the consumption of consistency modifiers can be up to 30% weight, for example 5-20% weight.
On the other hand, if plan to produce the low viscosity washing lotion composition of the permeable fiber width of cloth fully, so, application consistency conditioning agent lower limit amount.In this case, comprise that the total content of the solid constituent of consistency modifiers preferably is lower than 15% weight,, particularly be lower than 5% weight more preferably less than 10% weight.
Consistency modifiers suitably is selected from: monoglyceride, diglyceride and triglycerides and composition thereof, solid fatty alcohol, wax, and metallic soap.Its embodiment preferred will be described below:
1. preferably, glyceride is glycerine and has 6-30, the particularly monoesters of the aliphatic acid of 16-30 carbon atom, diester and/or three esters, term " fatty acid " thus " be not limited to naturally occurring, even number, saturated and undersaturated carboxylic acid, but also comprise the homologue and the isomers thereof of its odd number.Those of skill in the art can suitably select in known glyceride (having the solid denseness at 23 ℃), and esterification degree and degree of unsaturation play an important role thus.Usually, preferably using wherein, fatty acid residue mainly is saturated glyceride.In a more preferred embodiment, use commercially available monoglyceride, diglyceride and/or triglycerides (mixture), it is with trade name Cutina
GMS or MD or Novata
AB derives from Cognis Deutschland GmbH.Also can use Syncrowax in addition
HGLC (deriving from Croda).Particularly preferably be tristerin (mainly being monoesters and diester, some three esters), its by Cognis Deutschland GmbH with trade name Cutina
MD appears on the market.
2. metallic soap:
Can use the metallic soap of following formula:
(R
1COO)
n-X wherein, R
1Expression has 6-22 carbon atom and at least one hydroxyl of optional ground, preferred 12-18 carbon atom, linear, saturated or undersaturated acyl residue, and X is alkali metal (for example Li); alkaline-earth metal (Ca for example; Mg), or Al or Zn, n is the chemical valence of X.The preferred example of metallic soap comprises zinc stearate, calcium, magnesium or aluminium.
3. wax:
Just as prior art, term " wax " is used for natural or suitable material, and it at room temperature has denseness that can mediate, solid phase or fragility, carefully to crystalline particulate, yet is non-glass-shape, and is clear to opaque.The fusion under the temperature more than 35 ℃ of useful wax is not but decomposed, and therefore (at a little higher than fusing point place) has quite low viscosity (being referred to as " lipophilic " wax sometimes).Useful wax is listed among the DE-A199 06 081.
4. fatty alcohol:
Preferred fatty alcohol is to have at least 12, those fatty alcohols, particularly its undersaturated embodiment of preferred 12-30 carbon atom (for example C12-C24 or C24-C30).Its example comprises: laruyl alcohol, tetradecanol, cetanol, octadecanol, erucyl alcohol, castor-oil plant alcohol, isooctadecanol, arachidic alcohol, behenyl alcohol, Brazilian enol, with and the Guerbet alcohol class.In addition, may use the fatty alcohol mixture that obtains by naturally occurring fat and oily reaction, described raw material such as tallow, peanut oil, rape seed oil, cotton seed oil, soybean oil, sunflower oil, palm oil, Linseed oil, castor oil, corn oil, sesame oil, cocoa butter and coca oil.Yet, also may use synthetic alcohols, as linearity, even number fatty alcohol (Alfole by the synthetic acquisition of Ziegler
), or synthesize the alcohol (Dobanole of the part branching that obtains by oxidation
).
1.7. additive (optional)
Optionally, the washing lotion composition can comprise 10% weight at the most, the particularly additive of 0.1-5% weight, as:
Stablize the preservative agent of washing lotion composition, as having methyl isothiazoline (ketone) as substituent chlorine, 5-chloro-2-methyl-4-isothiazoline-3-ketone or 2-methyl-4-isothiazoline-3-ketone for example; Phenoxyethanol or PHB ester, p-hydroxybenzoic acid preservative agent, pentanediol, sorbic acid or other the compound of in " Kosmetikverordnung, Anlage 4, Teil A und B ", mentioning.
Bactericide, for example those that describe among the DE-199 06 08l A.
Emollient preferably derives from natural source (plant extracts), for example has skin-console, anti-inflammatory (minimizing skin irritation), wound-healing, cell-regeneration, the anti--inflammatory and/or effect of resist-itching, as allantoin; Aloe corium extract; The Flos Chrysanthemi extract that comprises azulenes and x-bisabol; Echinacea; Dragosantanol; Panthenol; The licorice root extract that comprises the 18-enoxolone; Comprise quercetin and/or sweet-rutin sophorin; Marigold (marigold oil); Urea; The phytosterol of optional ground ethoxylation (deriving from Henkel, trade name " Generol "); Chitosan (acetylation chitin); Anthocyanidin; The ginkgo leaf extract that comprises quercetin and rutin sophorin; The horse chestnut extract that comprises quercetin and campherol; Vitamin or provitamin such as provitamin B5 or vitamin E; Avocado oil; The birch extract; Arnica; The extract of Sharon or St.John ' s wort rose; Tea oil; Cucumber; Hops; Or hamamelis extract or composition, ethoxylation quaternary amines (as the inhibitor of itching that adds the washing lotion toilet paper); Preferred α-the bisabol that uses.
Spices, for example those that describe among DE-199 06 081 A; And/or
Dyestuff that skin moisten is useful and pigment, for example be described in " Kosmetische Farbemittel " (skin moisten colouring agent) those, described document is by the Farbstoffkomrnission der DeutschenFarbstoff-gemeinschaft (Verlag Chemie, Weinheim, 1984, the 81-106 pages or leaves) publish.
Above-mentioned additive can use separately or use with the form of mixture.
1.8. most preferred washing lotion
Based on present knowledge, reflection implement best mode of the present invention, most preferred washing lotion composition comprises following component:
(A ') 20-40% weight, be derived from the basic carbonic acid ester of liquid dioxane (alkene) of C6-C22 fatty alcohol,
The liquid glyceride of (A ") 20-40% weight, wherein, glycerine is by at least a acid estersization with 6-24 carbon atom,
At least a alkyl-(oligomeric) glycosides of (B ') 1-15% weight,
The polyol polyester of (B ") 2-15% weight, wherein, the polyalcohol with at least two hydroxyls is by the acid of at least a 6-30 of having carbon atom and at least one hydroxyl or the condensation product esterification of this hydroxy fatty acid,
(C) water of 15-25% weight,
(D) wetting agent of 1-10% weight,
(E) at least a consistency modifiers of 1-5% weight optionally,
(F) additive of 0.1-5% weight optionally.
2. the preparation of washing lotion
Washing lotion composition (O/w emulsion) can be according to known method preparation (for example referring to KarlheinzSchrader, Grundlagen und Rezepturen der Kosmetika, Huthig Buch VerlagHeidelberg, second edition, 1989, the 906-912 pages or leaves).
If need fusion so that evenly distributions/dissolving without any solid constituent, unique applicable a kind of (low temperature) method comprises: in mixed at room temperature and evenly stir oil phase component such as oil ingredient (A) and emulsifying agent (B) and other dispensable oil phase component (common about 10 minutes).Water component such as water, wetting agent and possible water-soluble or not dispersed additive such as spices or preservative agent mixing separately at room temperature, and during continuous stirring, be added at leisure in the mixture of oil phase component.Afterwards, utilize suitable dispersal device such as Ultraturrax type supraton or stator-rotor homogenizer in continuous stirring (preferred about 10 minutes), to the mixture homogenization (about 10 minutes usually) that obtains.As well known in the prior art, the homogenizing condition can exert an influence to the viscosity of the emulsion that obtains.According to an embodiment, if the temperature that solid constituent such as Cutina MD need increase is so that evenly distribute/be dissolved in the oil phase, this embodiment is applicable, and the washing lotion composition prepares by the mixing with oil phase and water component by under higher temperature.For this reason, preferably individually oil phase and water component are heated to about 80-85 ℃.Then, under this temperature, when stirring, at leisure the water component is added in the oil phase component, wherein carries out or do not carry out homogenizing.After connecting stirring, after preferably stirring approximately 5 minutes, keep connecting the mode of moving with mixture, when stirring, make it to cool off.Simultaneously, should avoid introducing air.Then, preferably at 60-65 ℃, with suitable dispersal device such as Ultraturrax type supraton or stator-rotor homogenizer mixture is carried out homogenizing, so that improve stability and structure.After reaching uniform state, make composition cools to room temperature.
If viscosity is too high, for example, may during homogenization, may reduce energy and inject, particularly reduce energy and inject by the rotating speed that reduces the rotor/stator system.
3. pending web of fiber
Term " web of fiber " is interpreted as the two-dimensional fiber based substrate.It can be a single or multiple lift.Its paper web structure makes it porous and is absorbefacient for liquid such as water.It is quantitatively preferably from 10-100g/m
2
Preferably, paper web comprises as main component (particularly, web of fiber dry weight at least 80% weight with respect to no washing lotion) cellulose fibre, paper pulp particularly, but proportional use modified pulp fiber (for example with respect to total weight of fiber from 10-50% weight) or use the suitable fibers that is suitable for the paper web preparation (for example, with respect to total weight of fiber from 10-30% weight) also topped by the present invention.
Web of fiber can be " non-woven material " or " tissue paper ", and the latter is preferred.
German term " Vlies " and " Vliesstoffe " are used for product miscellaneous, according to its performance, they can be paper on the one hand, cardboard, and cardboard, they can be textiless on the other hand, and all are summarised in (referring to ISO 9092-EN 29092) in the term " non-woven material " at present.The present invention can use known nonwoven production method, as usually said dried shop and spunbond (spun-laid) technology, and wet-shop technology.
Non-woven material can also be called fabric-shape composite, its expression be not by graticule braiding or by the produced in conventional processes of running-on but winding by fiber and/or the pliable and tough porous fabric by poly-in it and/or bonding, wherein said fiber for example exists with the prefabricated fiber of fibers form or finite length for no reason, as synthetic fiber that produce or that be the staple fiber shape on the spot.Therefore can form by the mixture of synthetic fiber that are staple fiber and paper pulp according to non-woven material of the present invention.
If paper web is made up of " tissue paper ", so, can to by as " background technology " described in wet method transmit the wrinkling of acquisition in a hurry or " not wrinkling " tissue paper adds washing lotion, wherein preferably use wrinkling tissue paper.Tissue paper (or thus obtained final tissue paper product) can be single or multiple lift (being generally the 2-6 layer).The permeance property of low viscosity washing lotion is particularly suitable for multi-layered tissue paper (or tissue paper product), and particularly as being used for the embodiment of the 4-layer of toilet paper or handkerchief, this is because washing lotion almost is evenly distributed on skin and internal layer.
Tissue paper can be homogeneous or stratification, wet pressing or aeration-drying (TAD-drying).Tissue paper includes, but are not limited to: the tissue paper of woollen blanket-squeezing, the tissue paper of composition-densification, the tissue paper of uncompacted tissue paper or compacting.
The raw material that is used to produce tissue paper is fibrous cellulosic materials, particularly paper pulp normally.Yet, if cotton linter or cotton as the raw material of producing tissue paper does not need further slurrying step usually.Because due to the morphosis, cellulose exists with off-state.
Used raw material paper pulp relates to main fibrous material (magma) or relates to less important fibrous material, and thus, less important fibrous material is defined as the fibrous raw material that is reclaimed by cyclic process.Main fibrous material can relate to paper pulp and mechanical pulp such as thermomechanical pulp (TMP), CTMP (CTMP) or the high temeperature chemistry thermomechanical pulp (HTCTMP) of chemical steaming.Can also use the fiber that contains synthetic cellulose in addition.Yet, the paper pulp that preferably uses the plant that by vegetable material, particularly forms timber to obtain.For example, can use the fiber of needlebush (obtaining by coniferous tree usually), leaf wood (obtaining by deciduous tree usually) or cotton linter.From Spanish grass (Esparto) (alfa), bagasse (millet straw, straw, bamboo, hemp) is robbed flax fibre, flax, and the fiber in other wood fibres and cellulose fibre source also can be used as raw material.With manner known in the art, want performance according to final products, select corresponding fibre source.For example, be present in the fiber in the leaf wood, it is shorter than needle-leaved wood fibre, because therefore higher length provides higher stability to final products.If promote the pliability of product, pliability is important for tissue paper for example, and Eucalyptus is particularly suitable as fibre source so.
Consider the pliability of product, therefore the chemical magma of also preferred use, may use full bleaching, partial bleaching and unbleached fiber.The chemical magma suitable according to the present invention especially comprises: sulfite pulp, sulfate pulp (sulfate process).
Before magma is used for the tissue paper preparation process, in addition also advantageously, independently further carrying out delignification or adopting method for bleaching in the treatment step, so that after digestion process, remove delignification more widely, and obtain the paper pulp of complete boiling.
The tissue paper preferred production methods is used:
A comprise flow box and wet end shaping workshop section (slurries that are used for wet shop cellulosic fibre material, normally paper pulp) and
B also comprises the drying section (TAD on the Yang Keshi drying cylinder (impingement drying) or conventional drying) that is mainly used in the wrinkling process of tissue paper usually.
Usually, this step back is,
C monitoring and winding zone.
With orientation or at random mode, by fiber is arranged on two of paper machine continuous rotating online or between, remove the dilution water of main amount simultaneously, until obtain to do at 12-35% usually-solids content till, and form tissue paper.In paper furnish, may comprise additive, so that improve the wet-intensity or dried-intensity or other performance of final tissue paper.
By machinery and heating arrangements, with one or more steps the initial fiber width of cloth that is shaped is carried out drying, till the final doing-solids content that obtains usually about 93-97%.Under the situation of preparation tissue paper, this step is after wrinkling process, and described wrinkling step will have a strong impact on the performance of final tissue paper product in conventional method.Conventional dry crepe method relates to: by creping doctor, typically having a diameter from the drying cylinder of 4.5-6m, be on the so-called Yang Keshi drying cylinder wrinkling (, can use wet wrinkling so) of basis (" former the tissue paper ") tissue paper of above-mentioned final doing-solids content if only require lower tissue paper quality.Then, according to the present invention, basic tissue paper wrinkling, final drying can be processed into tissue paper product or tissue paper product.
Replace above-described conventional tissue paper preparation method, the present invention preferably adopts improved technology, wherein, obtained the improvement of specific volume by the drying of particular types in the processing b of workshop section, and also obtained the improvement of final tissue paper overall bulk softness in this mode.Should pre--dry run be called TAD (impingement drying) technology, it exists with multiple subclass.It is characterized in that, before final contact drying on the Yang Keshi drying cylinder, pass web of fiber by making hot-air, leaving " initially " web of fiber (being similar to non-woven material) that paper prepares workshop section will be by predrying to dried-solids content of about 80%.Web of fiber is supported by gas-permeable nets or band, and guides the surface by ventilative rotating cylindrical drum between its transmission period.Structurized supporting impression fabric or band make it and may produce: by making the deflection of fiber under hygrometric state, pre-then-dry (TAD step), and make the compacting that paper web obtains by the nip between pressure roll and the Yang Keshi dryer surface and the pattern of compacted region not, produce the average specific volume that increases thus and therefore increased overall bulk softness not having obviously to reduce under the situation of web of fiber intensity.
Basic tissue paper pliability and another possible influence of intensity are in the production process of stratification, wherein, the initial fiber width of cloth to be formed forms with physically different fibrous material layers by the flow box of ad hoc structure, and these layers replenish simultaneously with the form that is injected into shaping workshop section paper pulp.
Usually be described as " tissue paper " from paper machine and by common by the creping doctor individual layer intermediate products that dried wrinkling light weight papers is formed on the Yang Keshi drying cylinder, or be described as basic tissue paper more accurately.Individual layer basis tissue paper can by one deck or in turn a plurality of layers form.
By basic tissue paper form and according to end user's needs promptly according to all single or multiple lift final products of requirement preparation miscellaneous, all be referred to as " tissue paper product ".
When web of fiber or basic tissue paper are processed into final tissue paper product, usually use following process steps individually or in combination: cut into certain size (vertical and/or transverse cuts), produce a plurality of layers, produce machinery and/or chemical ply adhesion, volume and structure embossing, folding, impression, perforation, apply washing lotion, make smoothly, bank up, roll.
For producing multi-layered tissue paper products, as handkerchief, toilet paper, towel paper or wipe towel preferably, carries out intermediate steps, and promptly so-called coincidence step wherein, wants final products the basic tissue paper of the number of plies to be focused on the female roller of common multilayer usually.
Procedure of processing from the basic tissue paper optionally rolled with several layers to final tissue paper product, in processing equipment, carry out, described processing equipment comprises following operation, as make level and smooth that tissue paper repeats, edge embossed, make it to be bonded to so that produce the ply adhesion of each layer (basic tissue paper) with whole zone and/or topical application adhesive to a certain extent, and vertically cutting, folding, transverse cuts, to many other tissue papers and packing is placed and make it together, and make it bigger to form together around packing or bundle.The paper web of indivedual ply of papers also can carry out in advance-embossing, then according to pin to pin or nesting method, combination in roll gap.
In multi-layered tissue paper, embossing can be used for producing ply adhesion.In order to guarantee that washing lotion does not reduce ply adhesion, embossed area can keep and is untreated.In addition, by US-4,867,831 is known, can use the molten thermoplastic plastics, thereby obtain interlaminar bonding in adding the tissue paper of washing lotion.
Utilize the present invention to add the tissue paper product of the tissue paper of washing lotion, be preferably health product (particularly toilet paper), paper handkerchief, cosmetic wiping examination cloth (face tissue) or napkin/napkin.Particularly preferably be in having the toilet paper of preferred layer 2-4 and use.
According to the present invention, that utilizes tissue paper that washing lotion handles quantitatively is preferably 10-40, more preferably every square metre every layer of 12-20 gram, particularly the 13-17 gram is every square metre every layer, and total quantitative (comprising all layers that do not have washing lotion) restrains every square metre every layer from 10-80 usually.
4. the application of washing lotion on paper web, particularly tissue paper
As mentioned above, after the paper web drying, apply washing lotion usually.Proper time point for example just in time after to the paper web drying, before paper web is compounded to form multilayer soon or before multi-layer web is formed final tissue paper product.Yet preferential is, at first at least two individual layer paper webs is laminated into multi-layer web, applies washing lotion then.For tissue paper, on the washing lotion composition can be applied to every layer, or only be applied on one or two skin with two or more layers.In the preferred production process of the 4-layer (product) that adds washing lotion, 2-layer paper web only adds washing lotion separately on a side, then described 2-layer paper web untreated side is connected to together, obtains 4-layer product thus.Preferably, the washing lotion composition is applied at least one face of multilayer (tissue paper) paper web, on preferred two lateral surfaces, then, by obtain with respect to many-layer paper web, particularly tissue paper Z-direction (vertically) direction distributes as far as possible uniformly, the favourable permeance property of low viscosity washing lotion composition will be developed fully.Before or after applying the washing lotion composition, can make respective layer or sandwich construction carry out composition.Suitable coating technique comprises: spraying, and rotogravure printing, or be coated with by the roller with smooth surface.Preferably, before the washing lotion composition is applied on the paper web, it is heated, particularly is heated to 30-50 ℃ temperature slightly.
If two surfaces all add washing lotion, preferably, the amount that restrains every square metre of surface treated with 3-10 applies washing lotion, promptly uses double amount.The weight ratio of washing lotion composition/paper web (single or multiple lift, dry weight) is preferably 5-30%, more preferably from 9-25% weight.
5. method of testing
Utilize European Prenorm prENV 12625-8 " tissue paper and tissue paper product-part 8: absorbent time and absorbability are measured (artificial and automatic test method) ", go up the version of decision in CEN/TC 172 meetings (on June 14th, 2000), on-line determination adds the ability in the tissue paper sinking water of washing lotion, and is as described below:
Principle based on prenorm relates to: make it to immerse gradually in the test pieces of tissue paper product by tissue paper product is contacted with water.
Determine the required time of complete wetting sample (absorbent time), and with its measuring as sinking performance in water.The measurement of absorbent time (artificial version) is performed as follows.
Should select testpieces according to ENV 12625-2.
Should from sample, get five testpieces.
In the vertical wide and enough length of (76 ± 1) mm testpieces is cut,, and report the weight of each cutting member with piling up of obtaining that 5 (5.0 ± 0.2) restrain.
To be prepared piling up comprises: have the superimposed many pages of identical supine all independent sheets.
If some pages cut at once, before test, be necessary it is separated so.
Regulate testpieces according to ENV 12625-2.
For the basket that relies on its side sinking, water receptacle is big (suitable volume: 3 liters) enough.Be filled to the degree of depth of 100mm with enough demineralized waters.Liquid must be in room temperature.
As drainage equipment, with the cylindrical metal line basket that uses as shown in Figure 1.Height and diameter are made of suitable normal line, so that weigh (3 ± 0.1) gram.Should form a firm structure with welding or electrofuse.If utilize welding, they should be symmetrically distributed, so that keep the balance of basket.By making loop section ground dual, can the weight of bottom be compensated.Write down its weight (Mb).
Each testpieces of weighing is rolled into and cylindrical basket diameter loose winding much at one.Testpieces is placed basket, filling loosely, (particularly avoiding any hand), the parallel sided of its 76mm edge and basket, and utilize finger little by little to scatter, to cause, itself fashion into the profile (when utilizing square, will pile up and place basket, and not roll) of basket.
Basket will be fallen into to water receptacle along its side by the height of (25 ± 5) mm more than the water surface, begin simultaneously regularly.The time that record complete wetting testpieces needs.This refers to, in case testpieces fully sinks, stopwatch must stop.Utilize remaining sample to repeat this method four times.
According to 5 values that obtain to calculate average absorbent time second.